TW201412777A - Alpha-olefin polymer - Google Patents

Abstract

To provide a highly reactive alpha-olefin polymer. An alpha-olefin polymer that satisfies the following conditions: (1) the 2,1-bonding fraction of said alpha-olefin polymer is less than 0.5 mol%; (2) the sum of the 1,3-bonding fraction and the 1,4-bonding fraction of said alpha-olefin polymer is less than 0.5 mol%; (3) the latent heat of fusion (DeltaHd) of said alpha-olefin polymer as measured by a differential scanning calorimeter (DSC) is less than 1.0 J/g; and (4) said alpha-olefin polymer is a propylene-based polymer or a butene-based polymer.

Description

Alpha-olefin polymer

This invention relates to alpha-olefin polymers and processes for their manufacture.

The high molecular weight polyolefin is widely used as an industrial member or the like because of its high chemical stability, excellent mechanical properties, and low cost. On the other hand, although the low molecular weight polyolefin is used as a wax, it is expected to be highly functional.

Although the functionalization of polyolefin has been carried out for many years, there is no efficient manufacturing technique in the low molecular weight to medium molecular weight region, and the addition technique for the polarity of the hydrocarbon polyolefin is also limited. In particular, attempts have been made to produce a low molecular weight to medium molecular weight polyolefin by a metallocene catalyst in recent years, and there is a limit to the technique of introducing a functional group or the like which is required to impart a high functional unsaturation.

Patent Documents 1 and 2 disclose that a high-molecular-weight polyolefin, particularly a thermally decomposable polypropylene, is thermally decomposed to introduce an unsaturated group (Patent Documents 1 and 2). Patent Document 1 discloses polypropylene in which isotactic polypropylene is thermally decomposed at 370 ° C (for example, 1.8 vinylidene groups per molecule), and Patent Document 2 discloses heat of thermal decomposition of polybutene at 370 ° C. break down Polybutene (for example, the number of vinylidene groups per molecule is from 1.53 to 1.75).

Further, Patent Document 3 describes a method of producing a terminally unsaturated α-olefin polymer by using a homopolymer or a copolymer of propylene or butene-1 as a raw material.

On the other hand, in applications such as adhesives, materials which are expected to have higher reactivity are reactive adhesives (epoxy resin, polyurethane, polyamide), sealing materials, and sealing materials. Among materials such as materials, adhesives, and plasticizers, materials with good handleability, high reactivity, and materials capable of controlling reactivity are expected. Further, from the viewpoint of improving heat resistance and improving water repellency, the demand for olefin-based materials is increasing.

On the other hand, for applications such as adhesives, materials with higher reactivity are expected, and reactive adhesives (epoxy resin, polyurethane, polyamide), sealing materials, and sealing materials are available. In the use of adhesives, plasticizers, etc., materials with good handleability, high reactivity, and materials capable of controlling reactivity are expected. Further, from the viewpoint of improving heat resistance and improving water repellency, the demand for olefin-based materials is increasing.

For example, Patent Document 4 discloses an α,ω-diene propylene polymer, a polypropylene-organopolyoxyalkylene copolymer obtained by hydroquinone alkylation of a polyoxyalkylene having a hydrogen-hydrazine bond at both terminals.

Further, Patent Document 5 discloses that (A) a saturated hydrocarbon polymer having a molecular weight of at least one alkenyl group having a molecular weight of 100,000 or less and (B) having a molecular weight of at least two hydroquinones in a molecule of 30,000 or less. a hardening agent, (C) a hydroquinone alkylation catalyst and (D) a hardening composition of the ceria bismuth fine powder.

In addition, in recent years, the environmental problems of the scale of the earth, the working environment of the operators, and safety. Health awareness events have increased. In this case, for example, in the field of hot-melt adhesives, in the past, the hot-melt adhesive has a melting point of 150 ° C or higher, and since heating is necessary, a material which can be used for a low-temperature coating can be expected.

For example, as disclosed in Patent Document 6, as a hot melt adhesive having a low melting point, a radical initiator is added to a polyolefin to form an alkoxysilane.

As the olefin-based material, Patent Document 7 discloses that a propylene-based polymer is used with a radical initiator and a horse for the purpose of producing a high-adhesion, high-strength, and soft-modified propylene-based polymer with high efficiency. A method of modifying a olefin-based compound containing a polar group such as an acid.

Further, Patent Document 8 discloses a useful material such as a polyolefin modifier, a dispersibility improver between dissimilar materials, and a compatibilizing agent, and a monomer such as maleic acid is allowed to be present in the presence of a radical initiator. The graft copolymer obtained by graft polymerization.

In addition, in recent years, the environmental problems of the scale of the earth, the working environment of the operators, and safety. Health awareness events have increased. In this case, for example, in the field of hot-melt adhesives, in the past, the hot-melt adhesive has a melting point of 150 ° C or higher, and since heating is necessary, a material which can be used for a low-temperature coating can be expected.

For applications such as adhesives, materials with higher reactivity are expected, such as reactive adhesives (epoxy resin, polyurethane, polyamide), sealing materials, sealing materials, and adhesives. Among materials such as plasticizers, materials with good handleability, high reactivity, and materials capable of controlling reactivity are expected. Again From the viewpoint of high heat resistance and improved water repellency, the demand for olefin-based materials is increasing.

As these olefin-based materials, Patent Documents 9 and 10 disclose that a terminal double bond having a double bond or a terminal double bond of a polypropylene having a double bond is subjected to hydroboration, and further, by oxidative decomposition, a hydroxyl group can be introduced and added. .

[Advanced technical literature] [Patent Literature]

[Patent Document 1] JP-A-2003-40921

[Patent Document 2] JP-A-2003-137927

[Patent Document 3] International Publication No. 2011/148586

[Patent Document 4] Patent No. 3579535

[Patent Document 5] JP-A-8-127683

[Patent Document 6] JP-A-2006-348153

[Patent Document 7] JP-A-2007-204700

[Patent Document 8] International Publication No. 2008/066168

[Patent Document 9] JP-A-2004-168803

[Patent Document 10] JP-A-2002-161142

When a polymerization of propylene or 1-butene is carried out using a metallocene catalyst, it is easy to cause abnormal insertion due to 2,1-insertion, 1,3-insertion, and 1,4-insertion. Into, the end structure does not completely change to a vinylidene structure, resulting in a vinyl or internal olefin. It is known that when these abnormally inserted α-olefin polymers are decomposed in the molecular chain to produce a low molecular weight to medium molecular weight polymer, a low reactivity can be obtained.

Accordingly, it is an object of the first invention to provide a highly reactive alpha-olefin polymer.

In Patent Documents 1 and 2, the vinylidene number can be increased by highly decomposing the high molecular weight body, but the yield is lowered due to the generation of a large amount of by-products. Moreover, it has a high melting point due to high regularity and is difficult to handle at normal temperature.

Further, in the field of an adhesive or a sealing material, it is necessary to have fluidity which can be used at normal temperature. In the adhesive using a high-melting-point polypropylene, the curing reaction must be at a temperature of 160 ° C or higher, which is inferior in handleability and difficult to apply. Further, the polyisobutylene-based adhesive has a problem in terms of adhesion to a polyolefin such as polypropylene or subsequent stability.

The problem to be solved by the second invention is to provide a polyolefin-based adhesive composition which is excellent in adhesion and adhesion to a polyolefin substrate, can be subjected to a curing reaction at a low temperature, and can be treated at a normal temperature.

Further, in the field of an adhesive or a sealing material, fluidity which is expected to be used at normal temperature is desired. In the adhesive using the high-melting-point polypropylene, the hardening reaction must be at a temperature of 160 ° C or higher, and the problem of poor handleability and difficulty in construction due to no fluidity at normal temperature.

The materials for the addition of alkoxydecane to polyolefins have been reported to date, but all are crystalline polyolefins, which are lower in temperature below 100 ° C. Hardening is difficult. Further, the site where the alkoxysilane is added is not specific, and when the curing reaction is carried out under moisture or the like in the air, all of the alkoxysilanes are not effectively used, and an efficient cured product cannot be obtained. problem.

The third object of the present invention is to provide a polyolefin-based adhesive which is excellent in adhesiveness and adhesion to a polyolefin substrate, has fluidity at a relatively low temperature, and can perform a curing reaction at a relatively low temperature.

In the field of adhesives or sealing materials, it is required to be at room temperature. Mobility (good handling). In the adhesive using a high-melting-point polypropylene, it is necessary to have a temperature of 160 ° C or higher in the hardening reaction, and it is difficult to carry out the work such as poor handleability.

Further, addition polymerization using a copolymerization or radical initiator In the case of the control, the amount of the carboxylic acid residue is difficult to control, and the difference between the larger portion and the smaller portion of the carboxylic acid residue is larger. As a result, molecules with strong polarity are mixed with molecules with weak polarities, and the function as a compatibilizing agent for polar materials and non-polar materials is lowered, or a large number of carboxylic acid residues are present in one molecular chain, so that The control of the crosslinking reaction of a compound such as an amine or a polyol becomes difficult.

A fourth object of the invention is to provide a polyolefin-based material which has fluidity at a relatively low temperature and can perform a curing reaction at a relatively low temperature.

When a polyolefin having a hydroxyl group only at one end is mixed with a polyisocyanate compound to obtain a cured product, the curing reaction proceeds slowly, and the obtained cured product has a problem of poor heat resistance.

The problem to be solved by the fifth invention is to provide a good hardening reactivity. The raw material of the cured product excellent in heat resistance is preferably a polyolefin-based substrate.

According to the first invention, the following invention is provided.

[1] An α-olefin polymer satisfying the following (1) to (4).

(1) The 2,1-binding fraction is less than 0.5 mol%.

(2) The total of the 1,3-binding fraction and the 1,4-binding fraction is less than 0.5 mol%.

(3) The melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) was less than 1.0 J/g.

(4) A propylene-based polymer or a butylene-based polymer.

[2] Further, the α-olefin polymer described in [1] of the following (5) to (8) is satisfied.

(5) The meso-penta unit [mmmm] fraction is less than 20 mol%.

(6) The fraction of the outer rotation of the five units [rrrr] is less than 20 mol%.

(7) The weight average molecular weight (Mw) is from 100 to 500,000.

(8) The molecular weight distribution (Mw/Mn) is 2.0 or less.

[3] Further, the α-olefin polymer described in [1] or [2] of the following (9) is satisfied.

(9) The number of terminal unsaturated groups per molecule is 0.5 to 2.5.

[4] The α-olefin polymer according to any one of [1] to [3], wherein the weight average molecular weight (Mw) is from 300 to 50,000.

[5] The α-olefin polymer according to any one of [1] to [4], wherein the number of terminal unsaturated groups per molecule is from 1.0 to 2.5.

[6] A functionalized α-olefin polymer obtained by functionalizing the α-olefin polymer according to any one of [1] to [5].

[7] A binder composition containing the functionalized α-olefin polymer described in [6].

[8] A sealing material composition containing the functionalized α-olefin polymer described in [6].

[9] A potting material composition containing the functionalized α-olefin polymer described in [6].

The second invention provides the following curable adhesive composition, cured product, adhesive, and sealant.

[1] A propylene-based polymer or a 1-butene-based polymer having (A) the following properties (a1) and (a2), and (B) a polyoxyalkylene having two or more hydrogen-hydrazine bonds, And (C) a sclerosing adhesive composition of a hydroquinone alkylation catalyst.

(a1) The heat of fusion ΔH-D measured by a differential scanning calorimeter (DSC) is less than 50 J/g.

(a2) The number of terminal unsaturated groups per molecule is from 0.5 to 2.5.

[2] The curable adhesive composition described in [1] of the melting heat absorption ΔH-D of less than 10 J/g.

[3] The polyoxyalkylene (B) is a curable adhesive composition as described in [1] or [2] of a polyoxyalkylene having a Si-H bond at a portion other than the terminal.

[4] The propylene-based polymer and the 1-butene-based polymer (A) are those in claims 1 to 3 which further have the following properties (a3) and (a4). A sclerosing adhesive composition as described.

(a3) The weight average molecular weight Mw is 1,000 to 500,000.

(a4) The molecular weight distribution Mw/Mn is 1.1 to 2.5.

[5] The propylene-based polymer and the 1-butene-based polymer (A) are curable adhesive compositions described in [4] which further have the following properties (a3').

The (a3') weight average molecular weight Mw is 5,000 to 20,000.

[6] The propylene-based polymer and the 1-butene-based polymer (A) are curable adhesives as described in any one of the following characteristics (a5) and (a6) [1] to [5]. Composition.

(a5) The 2,1-binding fraction is less than 0.5 mol%.

(a6) The total of the 1,3-binding fraction and the 1,4-binding fraction is less than 0.5 mol%.

[7] The curable adhesive composition according to any one of [1] to [6], which further comprises (D) an adhesion-imparting agent or a subsequent application agent, and (E) a diluent.

[8] The cured product obtained by subjecting the curable adhesive composition according to any one of [1] to [7] to a curing reaction at 100 ° C or lower.

[9] The adhesive comprising the curable adhesive composition according to any one of [1] to [7] or the cured product according to [8].

[10] A sealant comprising the curable adhesive composition according to any one of [1] to [7] or the cured product according to [8].

The third invention provides the following functionalized α-olefin polymer, a curable composition using the same, and a cured product.

[1] A functionalized α-olefin polymer having a ruthenium-containing group at the end of the α-olefin polymer main chain and satisfying the following (1) to (4).

(1) The number of ruthenium-containing groups per one molecule is 0.5 to 2.0.

(2) The melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) is 50 J/g or less.

(3) The weight average molecular weight (Mw) is 3,000 to 500,000.

(4) The aforementioned α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, or a propylene-1-butene copolymer.

[2] The functionalized α-olefin polymer described in [1] of the melting heat absorption ΔHD measured by a differential scanning calorimeter (DSC) of 10 J/g or less and having a molecular weight distribution (Mw/Mn) of less than 4.5 .

[3] The α-olefin polymer having 0.5 to 2.0 terminal unsaturated groups per molecule and reacting with a hydrazine compound having a hydrogen-hydrazine bond is characterized by [1] or [2]. A method of making a functionalized alpha-olefin polymer.

[4] A curable composition containing the functionalized α-olefin polymer described in (A) [1] or [2] and (B) a curing-promoting catalyst.

[5] Further comprising (C) an adhesiveness-imparting agent and (D) a diluent, the curable composition described in [4].

[6] A cured product obtained by curing the curable composition described in [4] or [5].

[7] The curable composition according to [4] or [5] is cured at a temperature of 100 ° C or lower to a cured product of [6]. Production method.

[8] The functionalized α-olefin polymer described in [1] or [2], which is used as an adhesive, a sealant, an adhesive, or a modifier.

[9] The cured product described in [6], which is used as an adhesive, a sealant, an adhesive, or a modifier.

The inventors of the present invention want to solve the above problems and conduct a detailed review. As a result, it has been found that a functionalized α-olefin polymer having an (anhydrous) carboxylic acid residue at the terminal can be obtained by adding an (anhydrous) carboxylic acid residue to an α-olefin polymer having an unsaturated group at the terminal. Solve the above problems.

That is, the fourth invention provides the following functionalized α-olefin polymer, a curable composition using the same, and a cured product.

[1] A functionalized α-olefin polymer having (anhydrous) carboxylic acid residue at the terminal of the α-olefin polymer and satisfying the following (1) to (6).

(1) The weight average molecular weight (Mw) is 1,000 to 500,000.

(2) The molecular weight distribution (Mw/Mn) is 4.5 or less.

(3) The melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) is 50 J/g or less.

(4) The aforementioned α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, a propylene-1-butene copolymer, a propylene-diene copolymer or a 1-butene-diene copolymer.

(5) The number of (anhydrous) carboxylic acid residues per molecule is from 0.5 to 2.5.

(6) The number of internal carboxylic acid residues per one molecule (anhydrous) - the number of internal double bonds is 0.5 to 2.5.

[2] The functionalized α-olefin polymer described in [1], wherein the heat of fusion ΔH-D measured by a differential scanning calorimeter (DSC) is 1 J/g or less.

[3] A curable composition containing the functionalized α-olefin polymer described in [1] or [2] and a crosslinking agent.

[4] A cured product obtained by curing the curable composition described in [3].

[5] The functionalized α-olefin described in [1] or [2] is obtained by reacting an α-olefin polymer satisfying the following (1') to (5') with an unsaturated (anhydrous) carboxylic acid. A method of producing a polymer.

The (1') weight average molecular weight (Mw) is from 1,000 to 500,000.

The (2') molecular weight distribution (Mw/Mn) is 4.5 or less.

(3') The heat of fusion ΔH-D measured by a differential scanning calorimeter (DSC) is 50 J/g or less.

(4') The aforementioned α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, a propylene-1-butene copolymer, a propylene-diene copolymer or a 1-butene-diene copolymer.

(5') The number of terminal unsaturated groups per molecule is from 0.5 to 2.5.

A fifth invention provides the following functionalized α-olefin polymer, a curable composition using the same, and a cured product.

[1] The α-olefin polymer has a hydroxyl group, and the α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, or a propylene-1-butene copolymer, and satisfies the following (1)~ (4) A functionalized alpha-olefin polymer.

(1) The weight average molecular weight (Mw) is 1,000 to 500,000.

(2) The molecular weight distribution (Mw/Mn) is 1.1 to 2.5.

(3) The number of the aforementioned hydroxyl groups per molecule is 1.1 to 4.5.

(4) The melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) is 50 J/g or less.

[2] The functionalized α-olefin polymer described in [1], wherein the heat of fusion ΔH-D measured by a differential scanning calorimeter (DSC) is 1 J/g or less.

[3] The number of the hydroxyl groups per molecule is 1.1 to 4.0, and the functionalized α-olefin polymer described in [1] or [2].

[4] Any of [1] to [3] of the above-mentioned α-olefin polymer having a meso-penta-unit (mmmm) fraction of 20 mol% or less of a propylene homopolymer or a 1-butene homopolymer; A functionalized alpha-olefin polymer as described.

[5] The above-mentioned α-olefin polymer is a propylene-1-butene copolymer having a meso-diad fraction (m) of 70 mol% or less, and [1] to [3] A functionalized alpha-olefin polymer as described.

[6] The functionalized α-olefin polymer according to any one of [1] to [5], which is used in the adhesive, the sealant, the adhesive, or the modifier.

[7] A curable composition comprising the functionalized α-olefin polymer according to any one of (1) to [6] and (B) a polyisocyanate compound.

[8] Further comprising (C) a curable composition as described in [7] of a curing-promoting catalyst.

[9] Hardening the curable composition described in [7] or [8] Hardened.

[10] The cured product described in [9], which is used as an adhesive, a sealant, an adhesive, or a modifier.

[11] Hydroxylation of a raw material α-olefin polymer having a number of terminal unsaturated groups of from 1.1 to 2.0 per molecule to the functionalized α-olefin described in any one of [1] to [6] A method of producing a polymer.

According to the first invention, a highly reactive α-olefin polymer can be provided.

The curable adhesive composition of the second invention is excellent in fluidity at room temperature and excellent in handleability, and can be subjected to a hardening reaction at room temperature. Further, since the polyoxyalkylene in the composition is added to the polyolefin substrate to improve the wettability, the adhesion to the polyolefin substrate and the adhesion are good.

The functionalized α-olefin polymer or the curable composition of the third invention is excellent in fluidity at a relatively low temperature and excellent in handleability, and can be subjected to a hardening reaction at a relatively low temperature. Further, since the wettability to the polyolefin substrate is excellent, the adhesion to the polyolefin substrate and the adhesion are good.

The functionalized α-olefin polymer according to the fourth aspect of the invention is a polyolefin material having excellent fluidity at a relatively low temperature, and is used as a curable composition by mixing with a crosslinking agent, so that the curing reaction can be carried out at a relatively low temperature.

The functionalized α-olefin polymer or the curable composition of the fifth invention is a polyolefin-based substrate which is excellent in curing reactivity and is applicable to a raw material of a cured product excellent in heat resistance.

[Formation of the Invention] <First invention> [α-olefin polymer]

The α-olefin polymer of the first invention satisfies the following (1) to (4), and preferably further satisfies the following (5) to (9).

(1) The 2,1-binding fraction is less than 0.5 mol%.

The α-olefin polymer of the first invention has a 2,1-binding fraction of less than 0.5 mol%, preferably less than 0.4 mol%, more preferably less than 0.2 mol%.

The control of the 2,1-binding fraction is carried out in accordance with the structure or polymerization conditions of the main catalyst. Specifically, due to the large influence of the structure of the main catalyst, the 2,1-binding can be controlled by narrowing the insertion of the monomer around the central metal of the main catalyst, and conversely, if the insertion is expanded, the addition can be increased. , 1-binding. For example, a catalyst called a semi-metallocene type has a structure in which a periphery of a center metal is wide, so that a structure such as a 2,1-bond or a long-chain branch is easily formed, and if it is a racemic type metallocene catalyst, it can be expected The 2,1-binding can be suppressed, but the stereoregularity becomes high in the case of the racemic type, and it is difficult to obtain an amorphous polymer as shown in the present invention. For example, even if it is a racemic type as described later, a metallocene catalyst crosslinked by two passes introduces a substituent at the third position, and under the insertion of the control center metal, amorphous or 2,1-bonding is extremely small. polymer.

(2) The total of the 1,3-binding fraction and the 1,4-binding fraction is less than 0.5 mol. %.

The α-olefin polymer of the first invention has a total of 1,3-binding fraction and a 1,4-binding fraction of less than 0.5 mol%, preferably less than 0.4 mol%, preferably less than 0.1 mol. ear%.

In the above-mentioned "the total of the 1,3-binding fraction and the 1,4-bonding fraction", when the α-olefin polymer of the first invention is a propylene-based polymer, it represents a 1,3-binding fraction and is butene. When the polymer is a polymer, it means a 1,4-binding fraction, and when it is a propylene-butene copolymer, it means a total of a 1,3-binding fraction and a 1,4-bonding fraction.

In addition, the propylene-based polymer is a propylene homopolymer or a propylene unit, and the copolymerization ratio is 50 mol% or more, preferably 70 mol% or more, and preferably 90 mol% or more. The butylene-based polymer has a copolymerization ratio of 1-butene homopolymer or 1-butene unit of 50 mol% or more, preferably 70 mol% or more, and preferably 90 mol% or more. The propylene-butene copolymer means that the total of the copolymerization ratio of the propylene unit and the copolymerization ratio of the 1-butene unit is 50 mol% or more, preferably 70 mol% or more, preferably 90 mol%. More than %.

The control of the 1,3-binding fraction and the 1,4-binding fraction is the same as the control of the above 2,1-binding fraction, and is carried out by the structure or polymerization conditions of the main catalyst.

(3) The melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) was less than 1.0 J/g.

The α-olefin polymer of the first invention has a melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) of less than 1.0 J/g. It is preferably 0.5 J/g, preferably less than 0.2 J/g.

When the melting heat absorption ΔH-D exceeds 1.0 J/g, the crystalline component is formed, and the fluidity at normal temperature is lowered.

Further, ΔH-D was determined by DSC measurement. Specifically, a differential scanning calorimeter (DSC-7 manufactured by Perkin-Elmer Co., Ltd.) was used, and 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then melted at a temperature of 10 ° C /min. The heat is taken as ΔHD.

In order to control the melting heat absorption to less than 1.0 J/g, the meso-five unit (mmmm) fraction of the stereoregularity index must be controlled to less than 20 mol%, which may be the structure or polymerization of the main catalyst. Conditions to control. For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is not easy to cause the insertion of the monomer to lower the activity, or if it is a racemic structure, a polymer having a high regularity can be obtained, and the heat of fusion is more than 1.0 J/g. If it is a meso-type structure, it is easy to obtain a polymer having a low regularity, and the heat of fusion can be as low as 1.0 J/g, but it is easy to cause the above 2,1-insertion, etc., and has a combination ratio and melting heat absorption. The synthesis of a balanced polymer becomes difficult. For example, by using a double crosslinked catalyst as described later, the coordination space of the monomer is controlled, so that the synthesis of the polymer having a balance between the binding ratio and the melting endotherm becomes possible.

(4) A propylene-based polymer or a butylene-based polymer.

The α-olefin polymer of the first invention is a propylene-based polymer or a butylene-based polymer, specifically, a propylene-based polymer having a propylene unit as a main component, and 1-butylene. The butene-based polymer having an olefin unit as a main component or a propylene-butene copolymer having a propylene unit and a 1-butene unit as a main component. The α-olefin polymer of the first invention may also be a comonomer containing ethylene or an α-olefin having 5 or more carbon atoms (preferably an α-olefin having 5 to 20 carbon atoms).

Specific examples of the α-olefin used as the comonomer include pentene-1, heptene-1, hexene-1, heptene-1, octene-1, decene-1, 4-methyl a diene such as pentene-1, 3-methylbutene-1, 1,3-butadiene, hexadiene, pentadiene, heptadiene or octadiene.

(5) The meso-penta unit [mmmm] fraction is less than 20 mol%.

The α-olefin polymer of the first invention has a mesogenic pentad fraction (mmmm) fraction of less than 20 mol%, preferably more than 1 mol% and less than 20 mol%, preferably more than 1 mol. % of ear and less than 15% by mole, more preferably more than 2% by mole and less than 15% by mole, most preferably more than 2% by mole and less than 10% by mole, particularly preferably more than 3% by mole And less than 10 mol%.

When the α-olefin polymer is a 1-butene-propylene copolymer, the meso-diad fraction [m] must be 1 to 50 mol%, preferably 2 to 45 mol%. It is better to use 2 to 40 mol%.

The control of the meso-penta-unit (mmmm) fraction and the meso-diad fraction [m] is carried out by the structure or polymerization conditions of the main catalyst.

If the meso-equivalent five-element [mmmm] fraction of the stereoregularity index is controlled to less than 20 mol%, it can be controlled by the structure or polymerization conditions of the main catalyst. For example, when it is controlled by the structure of the catalyst, it must be The catalyst center metal is designed to have an appropriate size for the space of the monomer coordination. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and only the structure of the racemic type, that is, the polymer having high regularity, the meso-penta-cell [mmmm] fraction becomes 20 m. %the above. If it is a meso-type structure, it is easy to obtain a polymer with low regularity, and the meso-penta-cell [mmmm] fraction may be less than 20 mol%, but the above-mentioned 2,1-insertion can be easily made. Etc., the synthesis of a polymer having a balance between the binding ratio and the stereoregularity is difficult. For example, when the double crosslinked catalyst described in the present invention is used, a polymer having a balance between a binding ratio and a stereoregularity can be synthesized under the coordination space of the control monomer.

(6) The fraction of the outer rotation of the five units [rrrr] is less than 20 mol%.

The α-olefin polymer of the first invention has a spine five unit [rrrr] fraction of less than 20 mol%, preferably more than 1 mol% and less than 20 mol%, and more than 2 mol%. Less than 18 mol% is preferred, preferably more than 2 mol% and less than 15 mol%, more than 3 mol% and less than 15 mol%, particularly preferably more than 3 mol% and less than 10 Moer%.

When the α-olefin polymer is a 1-butene-propylene copolymer, the racemo-diad fraction [r] must be 1 to 50 mol%, preferably 2 to 45 mol%. It is better to use 2 to 40 mol%.

The control of the rrrr fraction and the racemo-diad fraction [r] of the outer-rotating body is the same as the above-described meso-penta-unit (mmmm) fraction, depending on the structure of the main catalyst or The polymerization conditions are carried out.

In the first invention, the meso-equivalent five-unit [mmmm] fraction, the outer-rotating five-element [rrrr] fraction, the meso-diad fraction [m], and the 1,3-binding fraction The 1,4-binding fraction and the 2,1-binding fraction are reported by Chao Cang, "Polymer Journal, 16, 717 (1984)", reported by J. Randall, "Macromol. Chem. Phys., C29, 201 (1989) and obtained by the method proposed in "Macromol. Chem. Phys., 198, 1257 (1997)" reported by V. Busico. That is, using a ¹³ C nuclear magnetic resonance spectrum to measure the methyl and methine signals, the meso-pentameric unit (mmmm) fraction and the outer-rotating five-unit [rrrr] in the poly(1-butene) linkage are obtained. Fraction, meso-diad fraction [m], 1,3-binding fraction, 1,4-binding fraction, and 2,1-binding fraction.

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: mixed solvent of 1,2,4-trichlorobenzene and heavy benzene of 90:10 (capacity ratio)

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

<The case of propylene-based polymer>

The 1,3-binding fraction, the 1,4-binding fraction, and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,3-binding fraction = (D/2) / (A + B + C + D) × 100 (% by mole)

2,1-binding fraction = {(A+B)/2}/(A+B+C+D)×100 (mole%)

A: integral value of 15~15.5ppm

B: integral value of 17~18ppm

C: integral value of 19.5~22.5ppm

D: integral value of 27.6~27.8ppm

<The case of butene polymer>

The 1,4-binding fraction and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,4-binding fraction = E / (A + B + C + D + E) × 100 (% by mole)

2,1-binding fraction = {(a + b + d) / 3} / (a + b + c + d) × 100 (mole %)

A: integral value of 29.0~28.2ppm

B: integral value of 35.4~34.6ppm

C: integral value of 38.3~36.5ppm

D: integral value of 43.6~42.8ppm

E: integral value of 31.1 ppm

(7) The weight average molecular weight (Mw) is from 100 to 500,000.

The α-olefin polymer of the first invention preferably has a weight average molecular weight of 100 to 500,000 from the viewpoint of fluidity, preferably 200 to 100,000, preferably 300 to 50,000, and 400 to 10,000. Better, 500 to 5,000 are particularly good. Moreover, from the viewpoint of fluidity, the weight average molecular weight is preferably from 1,000 to 500,000, and from 2,000 to 50,000. The best is 3,000 to 20,000, 5,000 to 20,000 is preferred, 6,000 to 450,000 is preferred, 8,000 to 300,000 is preferred, and 10,000 to 70,000 is preferred.

(8) The molecular weight distribution (Mw/Mn) is 2.0 or less.

The α-olefin polymer of the first invention preferably has a molecular weight distribution (Mw/Mn) of 2.0 or less from the viewpoint of reactivity and reaction hardenability, and preferably 1.9 or less. From the viewpoint of reactivity and reaction hardenability, the molecular weight distribution (Mw/Mn) is preferably from 1.1 to 3.0, preferably from 1.4 to 3.0, more preferably from 1.4 to 2.6, and from 1.6 to 2.1. It is especially good, with 1.6~2.0 being the best.

And, the above weight average molecular weight (Mw) and the number average score The sub-quantity (Mn) is a polystyrene equivalent measured by the following apparatus and conditions, and the molecular weight distribution (Mw/Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).

GPC measuring device

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

Measuring condition

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0 ml / min

Sample concentration: 2.2 mg / ml

Injection volume: 160 microliters

Proofreading curve: Universal Calibration parser: HT-GPC (Ver.1.0)

(9) The number of terminal unsaturated groups per molecule is 0.5 to 2.5.

The α-olefin polymer of the first invention is preferably from 0.5 to 2.5 per molecule of the terminal unsaturated group, and preferably from 0.5 to 2.0, from the viewpoint of reactivity. When the α-olefin polymer of the first invention is used as a reactive plasticizer, the number of terminal unsaturated groups per molecule is preferably 0.5 to 1.5, preferably 0.5 to 1.2, and 0.8 to 1.2. The one is better, 0.5~1.0 is especially good, and 0.8~1.0 is the best. On the other hand, when the α-olefin polymer of the first invention is used as a reactive binder raw material, a sealing material raw material, a potting agent raw material or the like, it is important to have a curing property, and to obtain a crosslinked structure, each of the above molecules The number of unsaturation groups at the end is preferably 0.7 to 2.5, 0.7 to 2.3 is preferred, 0.7 to 2.1 is better, 1.0 to 2.5 is particularly good, and 1.0 to 2.2 is the most. good.

The number of unsaturation groups per one molecule can be controlled by the structure of the main catalyst, the type of the monomer or the polymerization conditions (polymerization temperature, hydrogen concentration, etc.).

The number of terminal unsaturation groups per molecule can be controlled by selecting the molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) in the presence of a catalyst.

For example, it can be obtained by carrying out a polymerization reaction in a range of 0 to 5000 in terms of a molar ratio of hydrogen to a transition metal compound (hydrogen/transition metal compound). To increase the selectivity of terminal unsaturation and the activity of the catalyst, in trace amounts It is preferred to carry out the polymerization in the presence of hydrogen.

Hydrogen is generally known as a chain shifting agent, and the end of the polymer chain becomes a saturated structure. In addition, it also has the function of reactivation of the temporary break and the activity of the catalyst. Although the effect of the trace amount of hydrogen catalyst is unclear, when hydrogen is used in a specific range, the terminal unsaturated group can be made highly selective and highly active.

The molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) is preferably from 200 to 4,500, more preferably from 300 to 4,000, most preferably from 400 to 3,000. When the molar ratio is 5,000 or less, the formation of an α-olefin polymer having an extremely low number of terminal unsaturated groups can be suppressed, and an α-olefin polymer having a desired number of terminal unsaturated groups can be obtained.

The α-olefin polymer of the first invention is reactive, at room temperature From the standpoint of workability, etc., it is preferable to have no melting point. It does not have a melting point, that is, the melting peak is less than 1.0 J/g, or may be represented by a fluidity (B viscosity) at 30 °C.

The production of an α-olefin polymer having no melting point can be controlled by the structure of the main catalyst, the monomer species, and the polymerization conditions. The α-olefin polymer of the first invention has a B viscosity (fluidity) of 5000 mPa at 30 ° C from the viewpoints of reactivity, workability at room temperature, and the like. s is better than the following, 2000mPa. The following are preferred.

Here, the above B viscosity means that it is measured in accordance with ASTM-D19860-91.

[Method for Producing α-Olefin Polymer]

The α-olefin polymer of the first invention can be produced, for example, by using a metallocene catalyst formed by using a combination of the following components (A), (B) and (C), and using hydrogen as a molecular weight modifier. Specifically, it can be manufactured according to the method disclosed in WO2008/047860.

(A) a transition metal compound containing a metal element of Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group, or a substituted fluorenyl group

(B) a compound obtained by reacting with a transition metal compound to form an ionic dislocation

(C) organoaluminum compound

The transition metal compound containing a metal element of Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group or a substituted fluorenyl group as the component (A) includes the following general A two-crosslinked complex represented by formula (I).

In the above general formula (I), M represents the 3~10 of the periodic table. Specific examples of the metal element of the group include titanium, zirconium, hafnium, tantalum, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid metals. Among them, titanium, zirconium and hafnium are preferred from the viewpoint of olefin polymerization activity and the like, and zirconium is preferred from the viewpoints of the yield of α-olefin polymer and catalyst activity.

E ¹ and E ² each represent a substituent selected from a substituted cyclopentadienyl group, a fluorenyl group, a substituted fluorenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, a decylamino group (-N<), a phosphino group ( -P<), a hydrocarbon group [>CR-, >C<] and a ruthenium-containing group [>SiR-, >Si<] (however, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group) The ligand in the form can form a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As the E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group and a substituted fluorenyl group are preferred, and at least one of E ¹ and E ² is a cyclopentadienyl group or a substituted cyclopentane group. Alkenyl, fluorenyl or substituted fluorenyl.

The substituent of the above-mentioned substituted cyclopentadienyl group, substituted fluorenyl group or substituted heterocyclopentadienyl group means a carbon number of 1 to 20 (preferably, a carbon number of 1 to 10, more preferably a carbon number of 1 to 6). A substituent such as a hydrocarbon group, a ruthenium-containing group or a hetero atom-containing group.

X represents a ligand for σ-binding, and when X is a complex number, the complex X may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of the X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a decylamine having 1 to 20 carbon atoms. The base, the ruthenium-containing group having 1 to 20 carbon atoms, the phosphide group having 1 to 20 carbon atoms, the sulfide group having 1 to 20 carbon atoms, and the fluorenyl group having 1 to 20 carbon atoms.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group; and an alkenyl group such as a vinyl group, a propenyl group or a cyclohexenyl group; Arylalkyl such as benzyl, phenylethyl or phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl , naphthyl, methylnaphthyl, anthracenyl, phenanthryl Etyl group and the like. Among them, an alkyl group such as a methyl group, an ethyl group or a propyl group or an aryl group such as a phenyl group is preferred.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group. An alkoxy group such as an ethoxy group, a propoxy group or a butoxy group, a phenylmethoxy group, a phenylethoxy group or the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the decylamino group having 1 to 20 carbon atoms include dimethyl decylamino group, diethyl decylamino group, dipropyl decylamino group, dibutyl decylamino group, dicyclohexyl decylamino group, and Alkenylamino group such as alkyl guanylamino group or alkyl sulfonylamino group or divinyl decylamino group, dipropylene decylamino group, dicyclohexenyl amide group; diphenylmethyl guanylamino group, benzene An arylalkylguanamine group such as a benzylaminoamine group or a phenylpropylguanamine group; an arylguanamine group such as a diphenylguanamine group or a dinaphthylguanamine group.

Examples of the fluorene-containing group having 1 to 20 carbon atoms include a monohydrocarbon-substituted fluorenyl group such as a methyl decyl group or a phenyl fluorenyl group; a dihydrocarbon-substituted decyl group such as a dimethyl decyl group or a diphenyl fluorenyl group; Methyl decyl, triethyl decyl, tripropyl decyl, tricyclohexyl decyl, triphenyl decyl, dimethylphenyl decyl, methyl diphenyl decyl, trimethyl decyl, a trihydrocarbon-substituted decyl group such as a trinaphthyl fluorenyl group; a hydrocarbon-substituted decyl ether group such as a trimethyl decyl alkyl ether group; a hydrazine-substituted alkyl group such as a trimethyl decylalkyl group; Aryl and the like. Among them, trimethyldecylmethyl group, phenyldimethyldecylethylethyl group and the like are preferred.

Examples of the phosphide group having 1 to 20 carbon atoms include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, and a octyl group. Alkyl sulfide Alkenyl sulfide group such as vinyl sulfide group, propylene sulfide group, cyclohexene sulfide group; benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group Isoarylalkyl sulfide group; phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl group An aryl sulfide group such as a sulfide group, a biphenyl sulfide group, a naphthyl sulfide group, a methylnaphthyl sulfide group, a sulfonium sulfide group, or a phenanthrene sulfide group.

As a sulfide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; An alkenyl sulfide group such as a propylene-based sulfide group or a cyclohexene sulfide group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; Phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide An aryl sulfide group such as a benzyl group, a naphthyl sulfide group, a methylnaphthyl sulfide group, an anthracene sulfide group, or a phenanthrene sulfide group.

Examples of the fluorenyl group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a palmitoyl group, a stearyl group, and an oil group. An aryl fluorenyl group such as a methyl sulfonyl group, a tolyl thiol group, a salicylidene group, a cinnamyl group, a naphthyl fluorenyl group, a phthalic acid group, or a dicarboxylic acid derived from a dicarboxylic acid such as oxalic acid, malonic acid or succinic acid. Didecyl, propylenediyl, amber thiol and the like.

On the other hand, Y represents a Lewis base, and Y represents a complex number, and the plural Ys may be the same or different and may be crosslinked with other Y or E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, and thioethers. The amine may, for example, be an amine having 1 to 20 carbon atoms, and specific examples thereof include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine and An alkylamine such as ethylamine, dipropylamine, dibutylamine, dicyclohexylamine or methylethylamine; vinylamine, propenylamine, cyclohexenamine, divinylamine, dipropylene An alkenylamine such as an amine or a dicyclohexenamine; an arylalkylamine such as a phenylamine, a phenylethylamine or a phenylpropylamine; or an arylamine such as a diphenylamine or a dinaphthylamine.

Examples of the ethers include methyl ether, ethyl ether, and propyl group. An aliphatic single ether compound such as ether, isopropyl ether, butyl ether, isobutyl ether, n-pentyl ether or isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl Ether, methyl-n-pentyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-pentyl An aliphatic mixed ether compound such as an ether or ethyl isoamyl ether; an aliphatic such as a vinyl ether, an allyl ether, a methyl vinyl ether, a methyl allyl ether, an ethyl vinyl ether or an ethyl allyl ether An unsaturated ether compound; an aromatic ether compound such as anisole, phenethyl ether, phenyl ether, benzyl ether, phenylbenzyl ether, α-naphthyl ether or β-naphthyl ether, ethylene oxide, A cyclic ether compound such as propylene oxide, epoxytrimethane, tetrahydrofuran, tetrahydropyran or dioxane.

Examples of the phosphine include a phosphine having 1 to 20 carbon atoms. Specific Illustrative of monohydrocarbon substituted phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, hexyl phosphine, cyclohexyl phosphine, octyl phosphine; dimethyl phosphine, diethyl phosphine, dipropyl phosphine, Dihydrocarbons such as butylphosphine, dihexylphosphine, dicyclohexylphosphine, dioctylphosphine a substituted phosphine; an alkylphosphine or a vinylphosphine such as a trihydrogen phosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine or trioctylphosphine; a diallylphosphine in which a hydrogen atom of a monoalkenylphosphine or a phosphine such as a propylene phosphine or a cyclohexene phosphine is substituted by two alkenyl groups; a trienylphosphine substituted with a hydrogen atom of a phosphine by three alkenyl groups; An arylalkylphosphine such as a phosphine, a phenylethylphosphine or a phenylpropylphosphine; a diarylalkylphosphine or an aryldialkylphosphine wherein the hydrogen atom of the phosphine is substituted by 3 aryl or alkenyl groups; Phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthylphosphine, phosphonium phosphine a phenanthroline; a bis(alkylaryl)phosphine in which a hydrogen atom of a phosphine is substituted by two alkylaryl groups; a tri((alkylaryl)phosphine substituted by three alkylaryl groups of a hydrogen atom of a phosphine; Arylphosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent cross-linking groups which combine two ligands, and represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group, and a ruthenium-containing group. , tin-containing groups, -O-, -CO-, -S-, -SO ₂ -, -Se-, -NR ¹ -, -PR ¹ -, -P(O)R ¹ -, -BR ¹ - Or -AlR ¹ -, R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the crosslinkable groups, at least one of them is a crosslinked group derived from a hydrocarbon group having 1 or more carbon atoms or a base containing ruthenium. Examples of such a crosslinking group include the following general formula (a), and examples of the specific examples include a methyl group, an ethyl group, an ethylene group, a propylene group, and an isopropylidene group. Cyclohexylene, 1,2-cycloxyl, vinylidene (CH ₂ =C=), dimethyldecyl, diphenylalkyl, methylphenylalkyl, dimethyldecenyl, Dimethyltirenyl, tetramethyldidecyl, diphenyldioxanyl, and the like. Among them, ethyl, isopropylidene and dimethylalkyl are preferred.

(D is a group 14 element of the periodic table, and examples thereof include carbon, ruthenium, osmium, and tin. R ² and R ^{3 are} each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different and each other Binding can form a ring structure. e represents an integer from 1 to 4).

As a transition metal compound of the general formula (I) Specific examples of WO2008/066168 can be mentioned as examples. Further, it may be a similar compound of a metal element of another group. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

Among the transition metal compounds represented by the above formula (I), a compound represented by the following general formula (II) is preferred.

In the above general formula (II), M represents a metal element of Groups 3 to 10 of the periodic table, and each of A ^1a and A ^2a represents a crosslinking group represented by the general formula (a) in the above general formula (I), and CH ₂ Further, CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C(CH ₃ ) ₂ C, (CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si are preferred. A ^1a and A ^2a may be the same or different from each other. R ⁴ to R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group or a hetero atom-containing group. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the ruthenium-containing group are the same as those described in the above general formula (I). Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, and 3,5-. Bis(trifluoro)phenyl, fluorobutyl, and the like. Examples of the hetero atom-containing group include a hetero atom-containing group having 1 to 20 carbon atoms, and specific examples thereof include a nitrogen group such as a dimethylamino group, a diethylamino group or a diphenylamino group; and a phenyl group; a sulfur-containing group such as a sulfide group or a methyl sulfide group; an anthracene group such as a dimethylphosphino group or a diphenylphosphino group; or an oxygen-containing group such as a methoxy group, an ethoxy group or a phenoxy group. Further, it is preferable that R ⁴ and R ⁵ are a group containing a hetero atom such as a halogen atom, oxygen or hydrazine, and a hydrocarbon having a carbon number of 1 to 20 is highly polymerizable. R ⁶ to R ^{13 are} preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as the general formula (I). q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the transition metal compounds represented by the above general formula (II), When the sulfhydryl groups of both of them are the same, a specific example described in WO2008/066168 is mentioned as a transition metal compound of Group 4 of the periodic table. Further, it may be a similar compound of a metal element of a group other than Group 4. Better It is a transition metal compound of Group 4 of the periodic table, and a compound of zirconium is also preferred.

On the other hand, in the transition metal compound represented by the above formula (II), when R ⁵ is a hydrogen atom and R ^{4 is} not a hydrogen atom, the transition metal compound of Group 4 of the periodic table includes WO2008/066168. Specific examples are described. Further, it may be a similar compound of a metal element of a group other than Group 4. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

(B) and the catalyst used as the first invention A compound obtained by reacting a transition metal compound to form an ionic dislocation, from the viewpoint of obtaining a relatively low molecular weight high-purity terminally unsaturated olefin-based polymer and a high activity of a catalyst, a boric acid ester compound is used. good. Specific examples of the boric acid ester compound described in WO2008/066168 are mentioned. These may be used alone or in combination of two or more. When the molar ratio of the hydrogen to the transition metal compound (hydrogen/transition metal compound) is 0, dimethyl phenyl quinolate (pentafluorophenyl) borate, triphenyl carbon quinone (pentafluorophenyl) borate Preferably, hydrazine and hydrazine (perfluorophenyl)boronic acid methylaniline are preferred.

The method for producing an α-olefin polymer of the first invention is used The catalyst may be a combination of the above components (A) and (B), and an organoaluminum compound as the component (C) may be used in addition to the components (A) and (B).

Examples of the organoaluminum compound as the component (C) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, and three-positive. Octyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl Aluminum hydride and ethyl aluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.

Among these, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, and tri-n-octyl aluminum is preferred, and triisobutyl aluminum is used. It is preferred that tri-n-hexyl aluminum and tri-n-octyl aluminum.

The amount of the component (A) to be used is generally 0.1 × 10 ^-6 to 1.5 × 10 ^-5 mol/L, preferably 0.15 × 10 ^-6 to 1.3 × 10 ^-5 mol/L, more preferably 0.2 × 10 ^{- 6} ~ 1.2 × 10 ^-5 mol / L, particularly preferably 0.3 × 10 ^-6 ~ 1.0 × 10 ^-5 mol / L. When the amount of the component (A) used is 0.1 × 10 ^-6 mol/L or more, the catalyst activity can be sufficiently exhibited, and when it is 1.5 × 10 ^-5 mol/L or less, the heat of polymerization can be easily removed.

When the ratio (A)/(B) of the component (A) to the component (B) is expressed by the molar ratio, it is preferably from 10/1 to 1/100, more preferably from 2/1 to 1/10. When (A)/(B) is in the range of 10/1 to 1/100, the effect as a catalyst can be obtained, and the catalyst cost per unit mass of the polymer can be suppressed. Further, there is a concern that a large amount of boron is present in the target α-olefin polymer.

When the ratio (A)/(C) of the component (A) to the component (C) is expressed by the molar ratio, it is preferably 1/1 to 1/10000, preferably 1/5 to 1/2000, more preferably It is 1/10~1/1000. By using the component (C), the polymerization activity per transition metal can be improved. (A)/(C) In the range of 1/1 to 1/10000, the balance between the addition effect of the component (C) and the economy is good, and the amount of aluminum present in the target-free α-olefin polymer is present. Concerns.

In the method for producing an α-olefin polymer according to the first aspect of the invention, the component (A) and the component (B), or the component (A), the component (B), and the component (C) may be used for preliminary contact. The preliminary contact may be carried out by, for example, bringing the component (B) into contact with the component (A). However, the method is not particularly limited, and a known method can be used. By such preparatory contact, it is effective in reducing the catalyst activity such as an increase in the activity of the catalyst or a decrease in the use ratio of the component (B) of the catalyst.

The α-olefin polymer of the first invention may be produced by the above The α-olefin polymer obtained by the method is used as a raw material, and further a terminally unsaturated α-olefin polymer obtained by thermal decomposition reaction.

The thermal decomposition reaction can be carried out by subjecting the raw material α-olefin polymer obtained by the above production method to heat treatment.

The heating temperature can be adjusted according to the molecular weight of the target set and the experimental results previously performed, preferably 300 to 400 ° C, more preferably 310 to 390 ° C. When the heating temperature is less than 300 ° C, there is a concern that the thermal decomposition reaction cannot be carried out. On the other hand, when the heating temperature exceeds 400 ° C, there is a concern that the resulting terminally unsaturated α-olefin polymer is deteriorated.

Further, the thermal decomposition time (heat treatment time) is preferably from 30 minutes to 10 hours, more preferably from 60 to 240 minutes. If the thermal decomposition time is less than 30 minutes, the amount of the terminal unsaturated α-olefin polymer produced may be too small. On the other hand, when the thermal decomposition time exceeds 10 hours, the resulting terminally unsaturated α-olefin polymer may be deteriorated.

The above thermal decomposition reaction, for example, is used as a thermal decomposition device A reaction vessel such as stainless steel, which is equipped with a stirring device, is filled with an inert gas such as nitrogen or argon, and is placed in a raw material α-olefin polymer and heated and melted to foam the molten polymer phase with an inert gas. The volatile product is removed and heated at a predetermined temperature for a predetermined period of time.

The free radical decomposition reaction can be carried out at a temperature of 160 to 300 ° C. The organic peroxide is added in an amount of 0.05 to 2.0% by weight based on the raw material α-olefin polymer.

The above decomposition temperature is preferably from 170 to 290 ° C, more preferably from 180 to 280 ° C. If the decomposition temperature is less than 160 ° C, there is a concern that the decomposition reaction cannot proceed. On the other hand, when the decomposition temperature exceeds 300 ° C, the decomposition proceeds intensely, and the decomposition of the organic peroxide is sufficiently completed before the homogeneous diffusion in the molten polymer, and there is a concern that the yield is lowered.

Of the organic peroxide to be added, preferably 1 minute An organic peroxide having a half-life temperature of 140 to 270 ° C, and specific examples of the organic peroxide include the following compounds: diisobutylphosphonium peroxide, cumene peroxypoxylate, and di-n -propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate , bis(4-t-butylcyclohexyl)peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate, t-hexylperoxy neodecanoate, t-butylperoxide Acid ester, t-hexyl peroxy valerate, t-butyl peroxy valerate, bis(3,5,5-trimethylhexyl) peroxide, lauric acid, 1,1,3 , 3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexyl) Oxy)hexane, t-hexylperoxy-2-ethylhexanoate, bis(4-methylbenzylidene) peroxide, t-butylperoxy-2-ethylhexanoic acid Ester, bis(3-methylbenzhydryl) peroxide, benzhydryl peroxide, 1,1-di(t-butylperoxy)-2-methylcyclohexane, 1 ,1-di(t-hexylpropylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di (t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarbonate , t-butyl peroxymaleate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butyl peroxidation Propyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 3,5-di-methyl-2,5-di(benzhydryl) Peroxy)hexane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl 4,4-di-(t-butylperoxy)trimethylacetate, bis(2-t-butylperoxyisopropyl)benzoate, dicumyl peroxide, di- T-hexyl , 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumene peroxide, di-t-butyl peroxide, p- Menthans hydrogen peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetra Methyl butyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide.

The amount of the organic peroxide added is preferably from 0.1 to 1.8% by weight, more preferably from 0.2 to 1.7% by weight, based on the raw material α-olefin polymer. When the amount added is less than 0.05% by weight, the decomposition reaction rate becomes slow, and there is a concern that the production efficiency is deteriorated. On the other hand, when the amount added exceeds 2.0% by weight, The odor caused by the decomposition of organic peroxides becomes a concern.

The decomposition time of the decomposition reaction, for example, 30 seconds to 10 hours, It is preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, the decomposition reaction is not sufficiently carried out, and there is a concern that a large amount of undecomposed organic peroxide remains. On the other hand, when the decomposition time exceeds 10 hours, the progress of the crosslinking reaction of the side reaction may become a problem, or there may be a concern that the obtained α-olefin polymer is yellowed.

The radical decomposition reaction can be carried out, for example, by any method which is decomposed by a batch method and decomposed by a melt continuous method.

When the radical decomposition reaction is carried out by a batch method, an inert gas such as nitrogen or argon is filled in a reaction vessel such as stainless steel equipped with a stirring device, and the α-olefin polymer of the raw material is placed in a molten material to be heated and melted, and melted. An organic oxide is dropped into the raw material α-olefin polymer, and heated at a predetermined temperature for a predetermined period of time to carry out a radical thermal decomposition reaction.

The dropping of the above organic peroxide may be carried out by dropping in the range of the above decomposition time, and the dropping may be either continuous dropping or batch dropping. Further, it is preferred that the reaction time from the end of the dropping time be set within the range of the above reaction time.

The organic peroxide can be dripped as a solution dissolved in a solvent.

The solvent is preferably a hydrocarbon solvent, and specific examples thereof include aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, hexadecane, and nonadecane; methylcyclopentane; , alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane, cyclododecane; and benzene, toluene, xylene, ethylbenzene, trimethyl An aromatic hydrocarbon such as benzene. Among these solvents, a solvent having a boiling point of 100 ° C or higher is also preferred.

In addition, the raw material α-olefin polymer can be dissolved in the decomposition. In the agent. The decomposition temperature at which the raw material α-olefin polymer is dissolved in a solvent to be decomposed is generally in the range of 100 to 250 ° C, preferably in the range of 120 to 200 ° C.

When the radical decomposition reaction is carried out by the melt continuous method, The reaction time in the average residence time, for example, 20 seconds to 10 minutes. The melt continuous method is compared with the batch method to make the mixed state good and the reaction time can be shortened.

The apparatus may use a single-axis or two-axis melt extruder, preferably an extruder having an injection port during the barreling process and capable of degassing under reduced pressure, which is an extruder having an L/D=10 or more.

Free radical decomposition reaction by melt continuous method The apparatus may be a method in which an organic peroxide is impregnated with a raw material α-olefin polymer, or a method in which a raw material α-olefin polymer and an organic peroxide are separately supplied and mixed.

The impregnation of the organic peroxide with the raw material α-olefin polymer, Specifically, the organic peroxide is added to the raw material α-olefin polymer in the presence of an inert gas such as nitrogen, and after being stirred at a temperature of from room temperature to 40° C., the raw material particles can be uniformly absorbed and impregnated. The obtained α-olefin polymer (impregnated particles) impregnated with an organic peroxide is decomposed by melt extrusion, or the impregnated particles are added as a mother particle to the raw material α-olefin polymer and decomposed to obtain terminal unsaturation. Alpha-olefin polymer. Further, when the organic peroxide is a solid or organic peroxide having low solubility to the raw material α-olefin polymer, the solution of the organic peroxide in the hydrocarbon solvent can be absorbed and impregnated with the raw material α-olefin polymer. .

The raw material α-olefin polymer and organic peroxide are separately supplied The mixture is mixed and supplied to the raw material α-olefin polymer and the organic peroxide at a constant flow rate in the hopper portion of the extruder, or may be supplied at a constant flow rate during the barreling of the organic peroxide.

[Functionalized α-olefin polymer]

The α-olefin polymer of the first invention can be used as a raw material to produce a functionalized α-olefin polymer having a functional group at the terminal. Examples of the functionalized α-olefin polymer having a functional group include a functionalized α-olefin polymer of the third invention (containing a ruthenium-containing group) and a functionalized α-olefin polymer of the fourth invention (including Specific examples of the (anhydrous) carboxylic acid residue) and the functionalized α-olefin polymer (containing a hydroxyl group) of the fifth invention.

The functionalized α-olefin polymer preferably has a functional group at 5 mol% or more of the terminal unsaturation, and more preferably 10 mol% or more of the terminal unsaturation has a functional group.

The functional group is selected from one or more functional groups preferably having a hydroxyl group, an epoxy group, an alkoxymethyl group, an alkyl group, a carboxyl group, an amine group, and an isocyanate group.

Further, the functionalized α-olefin polymer preferably has an acid anhydride structure. The acid anhydride structure is one in which one molecule of water is lost from two carboxyl groups of a carboxylic acid, and two sulfhydryl groups have a structure of one oxygen atom. R1COOCOR2 can generally be exemplified. For example, maleic anhydride, succinic anhydride, phthalic anhydride, etc. are mentioned.

By increasing the functional group by the α-olefin polymer, The compatibility and dispersibility of the polar compound make it easy to obtain a composition with various polymers. Further, since the functionalized α-olefin polymer has a functional group, it can improve solubility and dispersibility in a polar solvent such as water, and can be used as an emulsion-based adhesive or a coating material. When it is applied to a polyolefin-based material, it is possible to impart adhesiveness and coating properties, and it is desired to improve the surface state of the organic inorganic pigment, and it is also possible to manufacture the polyolefin-based masterbatch, in addition to the alkoxy fluorenyl group. Heat resistance is imparted by crosslinking.

As a method of introducing a functional group, for example, maleic acid can be mentioned. Alkene addition reaction of anhydride; introduction by hydroxyl group of formic acid/hydrogen peroxide; epoxidation by peracetic acid; by reaction with trimethoxydecane, triethoxydecane, triisopropoxydecane, methyl Introduction of an alkoxyfluorenyl group for the reaction of an alkoxydecane such as methoxydecane, ethyldiethoxydecane, phenyldimethoxydecane or phenyldiethoxydecane; with tri-n-hexyl Introduction of alkyl mercapto groups by reaction of alkyl decanes such as decane and tri-n-octyldecane; by carboxylation of copper bromide/peroxidized tert-butyl acetate; by anhydrous maleate and diamine Introduction of an amine group of a reaction of a compound; introduction of an isocyanate group by reaction of a anhydrous maleic compound with a diisocyanate compound, and the like.

The method of introducing the functional group can be carried out by using BH _{3 in addition to the above} . Hydroboration of THF; boronation by 9-borane bicyclo[3,3,1]nonane; metallation by isobutylaluminum hydride or the like; halogenation by dibromo or hydrogen bromide; Hydroformylation by a formic acid/cobalt-based catalyst; hydroformylation by a carbon monoxide/dicobalt octacarbonyl catalyst; sulfonation by acetic anhydride/sulfuric acid, and the like.

The functionalized alpha-olefin polymer of the first invention can be used for dense Sealing materials, potting materials, reactive hot melt adhesives, coatings, etc.

Examples of the above-mentioned bifunctional or higher polyfunctional compound include water; an isocyanate compound such as TDI or MDI; an amine compound such as hexamethylenediamine; a polyethylene glycol having a terminal hydroxyl group; and a polypropylene glycol; A polybutadiene modification of an oxy group; a polyacrylic acid and an acrylic copolymer, and the like.

Functionalized α-olefin polymer with more than 2 functional groups The reaction of the compound can be carried out according to a method generally used, for example, according to the method described in JP-A-2009-185171.

Specifically, when the functional group of the functionalized α-olefin polymer is a hydroxyl group, a bifunctional or higher polyfunctional compound which is suitable is a compound having an isocyanate group, a carboxylic acid group or an epoxy group. Similarly, in the case of an epoxy group, it is a compound having a hydroxyl group, an amine group, or an isocyanate group. In the case of an alkoxy fluorene, it has a hydroxyl group such as water. In the case of a carboxyl group, it is a compound having a hydroxyl group, an epoxy group, or an amine group. In the case of an amine group, an epoxy group, an isocyanate group, or a carboxyl group is used. In the case of an isocyanate group, a compound having an active hydrogen such as a hydroxyl group or an amine group is used. The acid anhydride structure is a hydroxyl group, an amine group, an epoxy group, or an isocyanate group.

The first invention containing an alkoxyfluorenyl group as a functional group The crosslinked body obtained by moisture-hardening the functionalized α-olefin polymer can be used for a sealing material, a potting material, a reactive hot melt adhesive, and the like.

Moisture hardening of a functionalized α-olefin polymer containing an alkoxyfluorenyl group as a functional group, generally by treatment with moisture or moisture Shi. As the hardening catalyst at this time, a decyl alcohol condensation catalyst can be used.

Examples of the sterol condensation catalyst include organometallic catalysts and tertiary amines. Examples of the organometallics include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate, tin octylate, lead octenoate, and lead naphthenate. Examples of the tertiary amines include N-triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl)ether, N,N,N',N",N",N. "-pentamethyldiethylideneamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N-methyl-N' - dimethylaminoethylpiperazine, an imidazole compound in which the second-order amine functional group of the imidazole ring is substituted with a cyanoethyl group, etc. These catalysts may be used alone or in combination of two or more.

Particularly preferred among the above catalysts are dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctanoate. These addition amounts are generally 0.005 to 2.0% by mass, preferably 0.01 to 0.5% by mass, based on the functionalized α-olefin polymer. The hardening reaction is also affected by the temperature, and the lower the temperature, the slower the temperature is, and it is necessary to have a ripening period of one week at room temperature.

The α-olefin polymer of the first invention may be used per molecule A hardened composition can be obtained by reacting two or more SiH-based organohydrogen polyoxyalkylenes with a catalyst (for example, a hydroquinone alkylation-promoting catalyst such as a platinum catalyst). The resulting hardened composition has high solvent solubility and heat resistance. An example of the hardening composition is a curable adhesive composition of the second invention.

The above organic hydrogen polyoxyalkylene preferably satisfies the following (a), (b) and (c) polyoxyalkylene residues:

(a) having a siloxane end (A unit) represented by formula (A) or a siloxane chain (B unit) represented by formula (B) or both structures

(b) having a repeating unit (C unit) of a oxoxane represented by the formula (C) in the main chain of the polyoxyalkylene molecule

(c) The number of A units is 0~2/molecule, the number of B units is 0~10/molecular, and A unit and B unit are not 0 at the same time. The total of the A unit, the B unit, and the C unit is 5 to 1,500, preferably 5 to 200, more preferably 10 to 150 per molecule, and the polyoxyalkylene end other than the binding site to the polyolefin is R ⁷ or OR ⁸ (R ⁷ and R ⁸ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms).

(wherein R ² to R ⁶ each represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms; *-Si represents a binding site to a polyolefin)

Examples of the unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R ² to R ⁸ include a methyl group, an ethyl group, an isopropyl group, and a phenyl group. In addition, examples of the substituted monovalent hydrocarbon group having 1 to 12 carbon atoms include a hydrocarbon group in which the above hydrocarbon group is substituted with a hydrogen atom, an alkoxy group or an amine group.

The above A unit is a group corresponding to the terminal of the reacted siloxane molecule, and the above unit B is a group existing in the main chain of the reacted siloxane molecule. The number of the above A unit, B unit, and C unit is an integer. but, When the polyoxyalkylene residue satisfying the above (a) to (c) has a molecular weight distribution, the number of the above-mentioned A unit, B unit, and C unit is represented by an average value, and is therefore a positive number.

As the above, it has two or more SiH groups per molecule. The organohydrogen polyoxyalkylene can be exemplified by a single-terminal hydride polydimethyl siloxane, a trimethyl methaloxy group at the two ends of the molecular chain, a methyl hydrogen polyoxyalkylene group, and a trimethyl group at both ends of the molecular chain. The methylalkoxy group blocks the dimethyloxane. The methylhydroquinone copolymer, the sterol group at both ends of the molecular chain blocks the methyl hydrogen polyoxyalkylene, and the sterol group at both ends of the molecular chain blocks the dimethyloxane. Methylhydroquinone copolymer, molecular end chain dimethyl hydroformyloxy group blocked dimethyl polyoxyalkylene, molecular chain two terminal dimethyl hydroformyloxy group blocked methyl hydrogen polyfluorene The oxyalkylene and the two ends of the molecular chain, dimethylhydroformamidooxy, block the dimethyloxane. A methylhydroquinone copolymer or the like.

Polyoxyalkylene residues can be combined with functionalized alpha-olefin polymers Use the purpose to make a suitable choice. When the functionalized α-olefin polymer is supplied to a resin for lubricity or abrasion resistance, a single terminal hydride polydimethyloxane residue is preferred. Further, when mechanical properties such as melt properties, flexibility, and impact resistance, and gas permeability are imparted to the resin, a polyoxyalkylene residue having 2 to 10 hydride-bonded residues is preferred. Further, when the functionalized α-olefin polymer is used in the treatment of the inorganic filler, the alkoxy group-containing polyoxyalkylene residue is preferred.

[The thermoplastic resin composition]

Polymerization of an α-olefin-containing polymer or a functionalized α-olefin of the first invention The thermoplastic resin composition of the article (hereinafter referred to as the composition of the first invention only) preferably contains a filler and/or a pigment.

The filler contains an inorganic filler and an organic filler.

Examples of the inorganic filler include talc, white carbon, cerium oxide, mica, bentonite, aluminum compound, magnesium compound, cerium compound, diatomaceous earth, glass beads or glass fibers, metal powder or metal fiber.

Examples of the organic filler include starch (for example, powdered starch), fibrous leather (for example, natural organic fibers made of cellulose such as cotton or hemp), and synthetic polymers such as nylon, polyester, and polyolefin. Made into fibers, etc.

Among the above pigments, there are inorganic pigments and organic pigments (for example, azo-based pigments and polycyclic pigments).

Examples of the inorganic pigment include oxides (titanium dioxide, zinc oxide (zinc oxide), iron oxide, chromium oxide, iron black, cobalt blue, etc., and examples of the hydroxides include hydrated alumina, iron oxide yellow, and chrome green. Etc.), sulfide (zinc sulfide, zinc antimony white, cadmium yellow, vermilion, cadmium red, etc.), chromate (yellow lead, molybdenum orange, zinc chromate, strontium chromate, etc.), citrate (white carbon, Clay, talc, ultramarine, etc.), sulfate (precipitated barium sulfate, barite powder, etc., as carbonate: calcium carbonate, lead white, etc.), in addition to ferricyanide (iron blue), phosphoric acid Salt (manganese violet), carbon (carbon black), and the like.

Examples of the azo-based pigment of the organic pigment include soluble azo (carmine 6B, lake red C, etc.), insoluble azo (disazo yellow, lake red 4R, etc.), and condensed azo (dyeing yellow 3G, Dyeing magenta RN, etc.), azo wrong salt (nickel azo yellow, etc.), benzimidazolone azo (permanent Orange HL, etc.). Examples of the polycyclic type pigment of the organic pigment include isoindolinone, isoporphyrin, quinophthalone, pyrazolone, anthraquinone yellow, anthracene, diketone-pyrrolo-pyrrole, and pyrrole. , pyrazolone, anthrone, anthrone, anthracene, quinacridone, anthracene, oxazine, imidazolinone, xanthene, normal carbon, purpurin, phthalocyanine, nitroso and the like.

The content of the filler and/or pigment is the filler and/or color The content of the material is (a), and when the content of the α-olefin polymer of the first invention is (b), it is, for example, (a)/(b)=0.005 to 20, preferably 0.01 to 10.

When (a)/(b) is less than 0.005, the wettability and adhesion of the surface of the filler or pigment are not sufficiently improved. For the masterbatch or the resin dispersion composition, the dispersibility and interfacial adhesion of the filler or pigment are present. Insufficient concerns. On the other hand, when (a)/(b) exceeds 20, there is a component (b) which is not related to the surface treatment, and the manufacturing cost is not improved.

The composition of the first invention can be used as an adhesive, a resin phase-solving agent, a dispersion or a coating agent.

The composition of the first invention can be used as a hot melt adhesive substrate. As other components of the hot-melt adhesive, an additive such as an oil, an adhesive imparting material, or an antioxidant can be used in a general range.

The composition of the first aspect of the invention can be used as a solvent-based adhesive which is dissolved in a solvent, and can be applied to a substrate to form a film on the surface of the substrate to be adhered to the object. Moreover, when the composition of the first invention is dispersed or emulsified in a polar solvent such as water, it can also be used as an adhesive. Further, the composition of the first invention is formed into a sheet shape or a film shape, sandwiched between the substrates, and heated to the next The agent can flow above the temperature and then can be cured by cooling.

The composition of the first invention can be used as a resin phase-solving agent when the resin composition containing polyolefin as an essential component is added in an amount of, for example, 0.005 to 15% by weight.

The composition of the first invention can be a dispersion in which the α-olefin polymer is slightly dispersed by dissolving the solvent at room temperature or under heating. The concentration of the α-olefin polymer is in the range of 5 to 30% by mass.

Examples of the solvent include aliphatic hydrocarbon compounds such as hexane, heptane, and decane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; and alicyclic hydrocarbon compounds such as cyclohexane and methylcyclohexane; a halogenated hydrocarbon such as chlorobenzene; an ether compound such as tetrahydrofuran or tetrahydropyran.

It can be emulsified by using a polar solvent as a solvent. Examples of the polar solvent include water; alcohols such as methanol, ethanol, and butanol; and carboxylic acid esters such as methyl acetate, ethyl acetate, and butyl acetate.

As a method of producing a dispersion, a solution in which a composition is dissolved in a solvent and added to the above-mentioned polar solvent to form a solid fine particle component, and then the solvent is distilled off to produce a dispersion of a polar solvent can be exemplified.

Specifically, a method in which a solution of 20 to 30% by mass of tetrahydrofuran is added in a small amount in 20 to 50° C., and then tetrahydrofuran is removed under reduced pressure to adjust the amount of water to a desired concentration can be exemplified. As another method, a known method such as a method of rapidly dispersing a high-speed stirring or a high-shear field in a polar solvent can be mentioned. Anion, a cation, an anionic surfactant or a water-soluble polymer compound may be added as necessary Use of the agent.

The above dispersion may be coated or sprayed on a substrate. The coating was carried out by removing the solvent. Further, the film or sheet may be placed on a substrate and coated by heating and cooling. In addition to this, the melted functionalized α-olefin polymer and the α-olefin polymer of the first invention may be uniformly coated on a substrate and cooled and solidified to be applied.

The functionalized α-olefin polymer of the first invention is the same as described above It can be used as a binder, a resin phase-solving agent, a dispersion, and a coating material, and can also be used as a reactive hot-melt adhesive, a sealing material, and a potting material.

Reactive hot melt adhesive will contain alkoxy quinone The α-olefin polymer and the α-olefin polymer of the first invention are contained as a main component, and if necessary, an oil, an adhesion-imparting agent, an inorganic filler, and a decyl alcohol-condensation catalyst are contained.

Examples of the oil include fine naphthalene oil and paraffin oil. An oil such as an aromatic oil and an oil mixed therewith, and a liquid rubber such as liquid polybutene or liquid isopolybutene. These may be used alone or in combination of two or more.

It can be used as an adhesion-imparting agent (adhesive imparting resin) Rosin and its derivatives, terpene resin and hydrogenated resin, styrene resin, coumarone-indene resin, dicyclopentadiene (DCPD) resin and hydrogenated resin, aliphatic system (C5 system) Petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9-based copolymerized petroleum resin and hydrogenated resin thereof are generally used in adhesion-imparting agents. Selecting compatible with functionalized alpha-olefin polymer Good sex. One type of these adhesiveness-imparting resins may be used alone or two or more types may be used as a mixture.

The preferred adhesiveness-imparting resin is selected from the group consisting of terpene-based resins and hydrogenated resins, styrene-based resins, and dicyclopentadiene from the viewpoint of balance between re-peelability and adhesion to curved surfaces and uneven surfaces. Alkene (DCPD) resin and its hydrogenated resin, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9 system One type of resin or a mixture of two or more types of the group of the polymerized petroleum resin and the hydrogenated resin is preferred.

As the inorganic filler, cerium oxide and oxidation are mentioned. Aluminum, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, zinc carbonate , strontium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium citrate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, sericite, glass fiber, glass beads , ruthenium dioxide is Ba Run, aluminum nitride, boron nitride, tantalum nitride, carbon black, graphite, carbon fiber, carbon paste, zinc borate, various magnetic powders, and the like.

Instead of inorganic fillers, inorganic fillers can be used, or The surface treatment is carried out with various coupling agents such as decane or titanate. Examples of the treatment method include a method of directly treating an inorganic filler with various coupling agents such as a dry method, a slurry method, or a spray method, or a collective mixing method such as a direct method or a master batch method, or a dry concentration method. And other methods.

The sterol condensation catalyst can be used after mixing. Add method is Pre-modulating the catalyst masterbatch into a high concentration sterol condensation catalyst, the catalyst It is preferred that the masterbatch is blended, kneaded or melted with other reactive hot melt components.

The sterol condensation catalyst is an organotin metal compound such as dibutyltin dilaurate, dibutyltin diacetate or dibutyltin dioctanoate; an organic acid such as an organic base or ethylamine; a fatty acid; Butyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate. These addition amounts are 0.005 to 2.0% by mass, preferably 0.01 to 0.5% by mass, based on the α-olefin polymer modified product.

As a hardening method for reactive hot melt adhesives, in sterol In the presence or absence of a condensation catalyst, it can be hardened by contact with moisture or moisture, followed by heat treatment or room temperature.

To be in contact with moisture or moisture, for example, a reactive hot melt adhesive may be placed in the air, immersed in a water tank, and steam introduced. Further, the temperature may be normal temperature, but if the high temperature is set, crosslinking may be carried out in a short time.

Functionalized alpha-olefin polymers can be used in closures, potting When the material is required to have crosslinking performance, it can be prepared in the same manner as the above reactive hot melt adhesive.

When the crosslinking property is not required, the melt of the functionalized α-olefin polymer and the α-olefin polymer of the first invention as a main component is used for blocking or potting, and is immobilized by cooling and solidification.

<Second invention> [Sclerosing adhesive composition]

The curable adhesive composition of the second invention contains (A) specific A propylene-based polymer or a 1-butene-based polymer, (B) a polyoxyalkylene having two or more hydrogen-hydrazine bonds, and (C) a hydroquinone alkylation catalyst. Further, it is preferred to contain (D) an adhesion-imparting agent or a subsequent-imparting agent, and (E) a diluent.

(A) propylene-based polymer or 1-butene-based polymer

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention has the following properties (a1) and (a2), and further preferably has the following properties (a3) and (a4), preferably. In order to further have the following characteristics (a5) and (a6), it is more preferable to further have the following characteristics (a7) and (a8).

(a1) The melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) is less than 50 J/g.

(a2) The number of terminal unsaturated groups per molecule is from 0.5 to 2.5.

(a3) The weight average molecular weight Mw is 1,000 to 500,000.

(a4) The molecular weight distribution Mw/Mn is 1.1 to 2.5.

(a5) The 2,1-binding fraction is less than 0.5 mol%.

(a6) The total of the 1,3-binding fraction and the 1,4-binding fraction is less than 0.5 mol%.

(a7) The meso-penta-unit [mmmm] fraction is less than 80 mol%.

(a8) The fraction of the outer rotation of the five units [rrrr] is less than 20 mol%.

A propylene-based polymer or a 1-butene system used in the second invention The polymer (A) is specifically a propylene-based polymer mainly composed of a propylene unit, a 1-butene polymer having a 1-butene unit as a main component, or a C-based polymer. A propylene-1-butene copolymer having an olefin unit and a 1-butene unit as a main component.

Here, the propylene-based polymer is a propylene homopolymer or a propylene unit having a copolymerization ratio of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, so-called 1-butene. The polymer is a 1-butene homopolymer or a 1-butene unit having a copolymerization ratio of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, so-called propylene- The total of the copolymerization ratio of the 1-butene copolymer to the propylene unit and the copolymerization ratio of the 1-butene unit is 50% by mole or more, preferably 70% by mole or more, and more preferably 90% by mole or more. .

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention contains ethylene or an α-olefin having 5 or more carbon atoms (preferably an α-olefin having 5 to 20 carbon atoms) as a copolymerization sheet. The body is better. Specific examples of the α-olefin used as a comonomer include pentene-1, heptene-1, hexene-1, heptene-1, octene-1, decene-1, 4-methyl a diene such as pentene-1, 3-methylbutene-1, 1,3-butadiene, hexadiene, pentadiene, heptadiene or octadiene.

(a1) melting heat absorption △H-D

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention has a melting heat absorption ΔHD measured by a differential scanning calorimeter (DSC) of less than 50 J/g, and is 40 J/g or less. Less than 40J/g, 30J/g or less, less than 30J/g, 15J/g or less, 10J/g or less, less than 10J/g, 1.0J/g or less, less than 1.0J/g, less than 0.5 The order of J/g, less than 0.2J/g, and 0J/g is preferred.

When the melting heat absorption ΔH-D exceeds 50 J/g, the presence of a crystalline component increases, and the fluidity at normal temperature is greatly lowered.

Further, ΔH-D was determined by DSC measurement. In other words, using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the melting heat absorbed by the temperature was raised at 10 ° C /min. As ΔHD.

In order to control the melting heat absorption to less than 50 J/g, the meso-five unit [mmmm] fraction of the stereoregularity index must be controlled to less than 80 mol%, which can be achieved by the structure or polymerization of the main catalyst. Conditional control. For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is not easy to cause the insertion of the monomer to lower the activity, or if it is a racemic structure, a polymer having a high regularity can be obtained, and the heat of fusion is more than 50 J/g. In the case of a meso-type structure, it is easy to obtain a polymer having a low regularity, and the heat of fusion is less than 50 J/g, and it is difficult to synthesize a polymer having a balance between the binding ratio and the heat of fusion. For example, when a double-crosslinked catalyst to be described later is used, even if it is a structure of either a meso-type or a racemic type, the coordination space of the control monomer can be synthesized, and the balance ratio and the heat of fusion can be balanced. polymer.

A propylene-based polymer or a 1-butene system used in the second invention The polymer (A) is preferably one having no melting point from the viewpoints of reactivity, workability at room temperature, and the like. The so-called melting point, that is, the melting peak is less than 1.0 J/g, or can be expressed by the fluidity (B viscosity) at 30 °C.

Manufacture of propylene-based or 1-butene-based polymers without melting point It can be controlled by the structure of the main catalyst, the monomer species and the polymerization conditions.

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention has a B-viscosity (flowability) at 30 ° C of 5000 mPa from the viewpoints of reactivity, workability at room temperature, and the like. . s is better than the following, 2000mPa. The following are preferred.

Here, the above B viscosity means that it is measured in accordance with ASTM-D19860-91.

(a2) Number of unsaturation groups per one molecule

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is preferably from 0.5 to 2.5 per molecule of the terminal unsaturated group from the viewpoint of reactivity, 0.5~ 2.0 is better, 0.5~1.5 is better, 1.1~1.5 is especially good, 1.1~1.2 is the best, on the other hand, from the point of hardening, 0.7~2.3 The one is better, 0.8~2.1 is better, 1.0~2.5 is better, 1.0~2.2 is especially good, and 1.1~2.0 is the best. The curable adhesive composition of the second invention can be used as an adhesive or a sealing material by the terminal unsaturated group.

When the number of terminal unsaturated groups per molecule is only the end of the main chain, the maximum is 2.0, and when it is 2.0 or more, the unsaturated group may be introduced at the end of the side chain by copolymerizing a diene or the like. Control the number of unsaturations per 1 molecule.

The number of unsaturation groups per one molecule can be controlled by the structure of the main catalyst, the type of monomer or the polymerization conditions (polymerization temperature, hydrogen concentration). Etc.).

The number of terminal unsaturation groups per molecule can be controlled by selecting the molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) in the presence of a catalyst.

For example, it can be obtained by carrying out a polymerization reaction in a range of 0 to 5000 in terms of a molar ratio of hydrogen to a transition metal compound (hydrogen/transition metal compound). In order to increase the selectivity of terminal unsaturation and the activity of the catalyst, it is preferred to carry out the polymerization in the presence of a trace amount of hydrogen.

Hydrogen is generally known as a chain shifting agent, and the end of the polymer chain becomes a saturated structure. In addition, it also has the function of reactivation of the temporary break and the activity of the catalyst. Although the effect of the trace amount of hydrogen catalyst is unclear, when hydrogen is used in a specific range, the terminal unsaturated group can be made highly selective and highly active.

The molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) is preferably from 200 to 4,500, more preferably from 300 to 4,000, most preferably from 400 to 3,000. When the molar ratio is 5,000 or less, the formation of a propylene-based polymer or a 1-butene-based polymer having an extremely low number of terminal unsaturated groups can be suppressed, and the desired number of terminal unsaturated groups can be obtained. Or 1-butene based polymer.

Further, as the terminal unsaturated group, a vinyl group or a sub A vinyl group, a trans(acetylene) group or the like, but a terminal unsaturated group as defined in the specification means a vinyl group and a vinylidene group. Vinyl and vinylidene are radically polymerizable, and various reactions are applicable to a wide range of applications.

A propylene-based polymer or a 1-butene-based polymer used in the second invention The terminal unsaturated group concentration and the terminal unsaturated group number in (A) represent the total concentration and number of vinyl and vinylidene groups. When only a vinyl group is present, it means only the concentration and number of vinyl groups, and when both vinyl and vinylidene are contained, the concentration and number of both sides are shown.

The terminal unsaturated group concentration or the number of terminal unsaturated groups per molecule can be determined by ¹ H-NMR measurement. Specifically, the terminal vinylidene group obtained by δ4.8 to 4.6 (2H) and the terminal vinyl group appearing at δ5.9 to 5.7 (1H) and δ1.05 were obtained by ¹ H-NMR measurement. The methyl group appearing at ~0.60 (3H) is used as the standard, and the terminal unsaturated group concentration (C) (% by mole) is calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturation concentration = [vinylidene amount] + [vinyl amount]

The terminal unsaturated group concentration (C, mol %) calculated by the above method and the number average molecular weight (Mn) and the monomer molecular weight (M) obtained by gel permeation chromatography (GPC) are The equation can calculate the number of unsaturation groups at the end of each molecule.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

(a3) Weight average molecular weight (Mw)

A propylene-based polymer or a 1-butene-based polymer used in the second invention (A) From the viewpoint of fluidity, the weight average molecular weight is preferably 1,000 to 500,000, 2,000 to 50,000 is preferred, 3,000 to 20,000 is preferred, 5,000 to 20,000 is preferred, and 6,000 to 450,000 is preferred. Preferably, 8,000 to 300,000 are preferred, and 10,000 to 17,000 are preferred. From the viewpoint of the strength of the subsequent strength, it is preferred that the weight average molecular weight is larger.

(a4) Molecular weight distribution (Mw/Mn)

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention has a molecular weight distribution (Mw/Mn) of preferably 1.1 to 2.5, from the viewpoint of reactivity and reaction hardenability, and 1.4~ 3.0 is better, 1.4 to 2.6 is better, 1.4 to 2.2 is better, 1.6 to 2.1 is better, and 1.6 to 2.0 is the best.

Further, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those in terms of polystyrene measured by the following apparatus and conditions, and the molecular weight distribution (Mw/Mn) is a weight average molecular weight (Mw) and a number The value calculated by the average molecular weight (Mn).

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0 ml / min

Sample concentration: 2.2 mg / ml

Injection volume: 160 microliters

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

(a5) 2,1-binding fraction

The 2,1-binding fraction of the propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, more preferably not Up to 0.2% by mole.

The control of the 2,1-binding fraction is carried out by the structure or polymerization conditions of the main catalyst. Specifically, due to the large influence of the structure of the main catalyst, the 2,1-binding can be controlled by narrowing the insertion of the monomer around the central metal of the main catalyst, and conversely, if the insertion is expanded, the addition can be increased. , 1-binding. For example, a catalyst called a semi-metallocene type has a structure in which a periphery of a center metal is wide, so that a structure such as a 2,1-bond or a long-chain branch is easily formed, and if it is a racemic type metallocene catalyst, it can be expected The 2,1-binding can be suppressed, but the stereoregularity becomes high in the case of the racemic type, and it is difficult to obtain the amorphous polymer as shown in the second invention. For example, even if it is a racemic type as described later, a metallocene catalyst crosslinked by two passes introduces a substituent at the third position, and under the insertion of the central metal, amorphous and 2,1-bonding are obtained. polymer.

(a6) 1,3-binding fraction and 1,4-binding fraction

The total of the 1,3-binding fraction and the 1,4-bonding fraction of the propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is preferably less than 0.5 mol%. Jiayida 0.4 mole%, better less than 0.1 mole%.

When the propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is a propylene-based polymer, the above-mentioned "the total of the 1,3-binding fraction and the 1,4-bonding fraction" is used. It represents a 1,3-binding fraction, and represents a 1,4-bonding fraction when it is a 1-butene-based polymer, and a 1,3-bonding fraction and a 1,4-bonding ratio when it is a propylene-1-butene copolymer. Combine the total scores.

The control of the 1,3-binding fraction and the 1,4-binding fraction is carried out by the structure of the main catalyst or the polymerization conditions as in the control of the above 2,1-binding fraction.

(a7) meso five unit [mmmm] fraction

The meso pentad fraction (mmmm) fraction of the propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is preferably less than 80 mol%, more preferably less than 60 mol%. %, preferably less than 40% by mole, more preferably less than 20% by mole, more preferably more than 1% by mole and less than 20% by mole, more than 1% by mole and less than 15% by mole, It is preferably more than 2 mol% and less than 15 mol%, more than 2 mol% and less than 10 mol%, more than 3 mol% and less than 10 mol%.

When the propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is a 1-butene-propylene copolymer, the meso-diad fraction [m] is 30~. 95% of the moles are preferred, preferably 30 to 80% by mole, and preferably 30 to 60% by mole.

Meso-five unit [mmmm] fraction and inner-rotational unit The (meso-diad) fraction [m] can be controlled by the structure or polymerization conditions of the main catalyst. For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and if it is a meso-type structure, it becomes easy to obtain a rule. Low polymer.

(a8) external rotation five unit [rrrr] fraction

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention preferably has an external rotation pentad fraction of less than 20 mol%, more preferably more than 1 mol%. Less than 20% by mole, more preferably more than 2% by mole and less than 18% by mole, more preferably more than 2% by mole and less than 15% by mole, especially preferably more than 3 moles % and less than 10 mol%, most preferably more than 3 mol% and less than 15 mol%.

When the propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is a 1-butene-propylene copolymer, the racemo-diad fraction [r] is 1~. 50% of the moles are preferred, preferably 2 to 45 moles, and preferably 2 to 40 mole%.

The control of the outer-rotator rrrr fraction and the racemo-diad fraction [r] is controlled by the structure of the main catalyst as well as the meso-penta-unit fraction (mmmm). The polymerization conditions are carried out.

In the second invention, the meso-penta-unit [mmmm] fraction, the outer-rotating five-element [rrrr] fraction, the meso-diad fraction [m], and the 1,3-binding fraction The 1,4-binding fraction and the 2,1-binding fraction are reported by Chao Cang, "Polymer Journal, 16, 717 (1984)", reported by J. Randall, "Macromol. Chem. Phys., C29, 201 (1989) and obtained by the method proposed in "Macromol. Chem. Phys., 198, 1257 (1997)" reported by V. Busico. That is, ¹³ C-nuclear magnetic resonance spectroscopy was used to measure the methyl and methine signals, and the meso-penta-unit (mmmm) fraction and the outer-rotor pentad in the poly(1-butene) linkage were obtained. 〕 fraction, meso-diad fraction [m], 1,3-binding fraction, 1,4-binding fraction and 2,1-binding fraction.

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

The 1,3-binding fraction and the 2,1-binding fraction of the propylene-based polymer and the propylene-1-butene copolymer can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,3-binding fraction = (D/2) / (A + B + C + D) × 100 (% by mole)

2,1-binding fraction = {(A+B)/2}/(A+B+C+D)×100 (mole%)

A: integral value of 15~15.5ppm

B: integral value of 17~18ppm

C: integral value of 19.5~22.5ppm

D: integral value of 27.6~27.8ppm

The 1,4-binding fraction of the propylene-1-butene copolymer, and the 1,4-binding fraction of the 1-butene polymer and the 2,1-binding fraction can be determined by the above ¹³ C-NMR The measurement result of the spectrum was calculated by the following formula.

1,4-binding fraction = E / (A + B + C + D + E) × 100 (% by mole)

2,1-binding fraction = {(A+B+D)/3}/(A+B+C+D)×100 (mole%)

A: integral value of 29.0~28.2ppm

B: integral value of 35.4~34.6ppm

C: integral value of 38.3~36.5ppm

D: integral value of 43.6~42.8ppm

E: integral value of 31.1 ppm

(Method for producing propylene polymer or 1-butene polymer)

The propylene-based polymer or the 1-butene-based polymer (A) used in the second invention is, for example, a metallocene catalyst formed by using a combination of the following components (Pa), (Pb) and (Pc). Hydrogen can be produced when used as a molecular weight regulator. Specifically, it can be manufactured according to the method disclosed in WO2008/047860.

(P-a) a transition metal compound containing a metal element of Group 3 to Group 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group, or a substituted fluorenyl group

(P-b) reacts with a transition metal compound to form an ionic error Compound obtained

(P-c) organoaluminum compound

<(P-a) component>

The transition metal compound containing a metal element of Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group or a substituted fluorenyl group as the component (Pa) includes the following general A two-crosslinked complex represented by formula (I).

In the above general formula (I), M represents the 3~10 of the periodic table. Specific examples of the metal element of the group include titanium, zirconium, hafnium, tantalum, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid metals. Among these, from the viewpoint of the polymerization activity of the olefin, etc., it is preferable to use the metal element of Group 4 of the periodic table, particularly preferably titanium, zirconium and hafnium, from the viewpoints of the yield of the α-olefin polymer and the catalytic activity. Zirconium is the best.

E ¹ and E ² each represent a substituent selected from a substituted cyclopentadienyl group, a fluorenyl group, a substituted fluorenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, a decylamino group (-N<), a phosphino group ( -P<), a hydrocarbon group [>CR-, >C<] and a ruthenium-containing group [>SiR-, >Si<] (however, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group) The ligand in the form can form a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As the E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group and a substituted fluorenyl group are preferred, and at least one of E ¹ and E ² is a cyclopentadienyl group or a substituted cyclopentane group. Alkenyl, fluorenyl or substituted fluorenyl.

The substituent of the above-mentioned substituted cyclopentadienyl group, substituted fluorenyl group or substituted heterocyclopentadienyl group means a carbon number of 1 to 20 (preferably, a carbon number of 1 to 10, more preferably a carbon number of 1 to 6). A substituent such as a hydrocarbon group, a ruthenium-containing group or a hetero atom-containing group.

X represents a ligand for σ-binding, and when X is a complex number, the complex X may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of the X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a decylamine having 1 to 20 carbon atoms. The base, the ruthenium-containing group having 1 to 20 carbon atoms, the phosphide group having 1 to 20 carbon atoms, the sulfide group having 1 to 20 carbon atoms, and the fluorenyl group having 1 to 20 carbon atoms.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group; and an alkenyl group such as a vinyl group, a propenyl group or a cyclohexenyl group; Arylalkyl such as benzyl, phenylethyl or phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl An aryl group such as a naphthyl group, a methylnaphthyl group, an anthracenyl group or a phenanthryl group. Among them, an alkyl group such as a methyl group, an ethyl group or a propyl group or an aryl group such as a phenyl group is preferred.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group. An alkoxy group such as an ethoxy group, a propoxy group or a butoxy group, a phenylmethoxy group, a phenylethoxy group or the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. As a guanamine group having a carbon number of 1 to 20, Examples thereof include alkyl decylamines such as dimethyl decylamino group, diethyl decylamino group, dipropyl decylamino group, dibutyl decylamino group, dicyclohexyl decylamino group, and methyl ethyl decylamino group. Or an alkenyl amidino group such as a divinylammonium group, a dipropylene decylamino group or a dicyclohexene fluorenylamine; a diphenylmethyl guanylamino group, a phenylethyl decylamino group, a phenylpropyl group An arylalkylguanamine group such as a guanamine group; an arylguanamine group such as a diphenylguanamine group or a dinaphthylguanamine group.

Examples of the fluorene-containing group having 1 to 20 carbon atoms include a monohydrocarbon-substituted fluorenyl group such as a methyl decyl group or a phenyl fluorenyl group; a dihydrocarbon-substituted decyl group such as a dimethyl decyl group or a diphenyl fluorenyl group; Methyl decyl, triethyl decyl, tripropyl decyl, tricyclohexyl decyl, triphenyl decyl, dimethylphenyl decyl, methyl diphenyl decyl, trimethyl decyl, a trihydrocarbon-substituted decyl group such as a trinaphthyl fluorenyl group; a hydrocarbon-substituted decyl ether group such as a trimethyl decyl alkyl ether group; a hydrazine-substituted alkyl group such as a trimethyl decylalkyl group; Aryl and the like. Among them, trimethyldecylmethyl group, phenyldimethyldecylethylethyl group and the like are preferred.

As a phosphide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; An alkenyl sulfide group such as a propylene-based sulfide group or a cyclohexene sulfide group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; Phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide Base, naphthyl sulfide group, methylnaphthyl sulfide group, bismuth sulfide An aryl sulfide group such as a phenanthrene group or a phenanthrene group.

As a sulfide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; An alkenyl sulfide group such as a propylene-based sulfide group or a cyclohexene sulfide group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; Phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide An aryl sulfide group such as a benzyl group, a naphthyl sulfide group, a methylnaphthyl sulfide group, an anthracene sulfide group, or a phenanthrene sulfide group.

Examples of the fluorenyl group having 1 to 20 carbon atoms include an alkyl fluorenyl group selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a palmitoyl group, a stearyl group, and an oil group. B, derived from benzamidine, toluene, salicylidene, cinnamyl, naphthyl, phthalic acid, aryl sulfhydryl, oxalic acid, malonic acid, succinic acid, etc. Di-decyl dicarboxylate, propylenedithiol, amber thiol and the like.

On the other hand, Y represents a Lewis base, and Y represents a complex number, and the plural Ys may be the same or different and may be crosslinked with other Y or E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, and thioethers. The amine may, for example, be an amine having 1 to 20 carbon atoms, and specific examples thereof include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine and An alkylamine such as ethylamine, dipropylamine, dibutylamine, dicyclohexylamine or methylethylamine; vinylamine, propenylamine, cyclohexenamine, divinylamine, dipropylene An alkenylamine such as an amine or a dicyclohexenamine; an arylalkylamine such as a phenylamine, a phenylethylamine or a phenylpropylamine; or an arylamine such as a diphenylamine or a dinaphthylamine.

Examples of the ethers include methyl ether, ethyl ether, and propyl group. An aliphatic single ether compound such as ether, isopropyl ether, butyl ether, isobutyl ether, n-pentyl ether or isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl Ether, methyl-n-pentyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-pentyl An aliphatic mixed ether compound such as an ether or ethyl isoamyl ether; an aliphatic such as a vinyl ether, an allyl ether, a methyl vinyl ether, a methyl allyl ether, an ethyl vinyl ether or an ethyl allyl ether An unsaturated ether compound; an aromatic ether compound such as anisole, phenethyl ether, phenyl ether, benzyl ether, phenylbenzyl ether, α-naphthyl ether or β-naphthyl ether, ethylene oxide, A cyclic ether compound such as propylene oxide, epoxytrimethane, tetrahydrofuran, tetrahydropyran or dioxane.

Examples of the phosphine include a phosphine having 1 to 20 carbon atoms. Specific Illustrative of monohydrocarbon substituted phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, hexyl phosphine, cyclohexyl phosphine, octyl phosphine; dimethyl phosphine, diethyl phosphine, dipropyl phosphine, Dihydrocarbon substituted phosphines such as butylphosphine, dihexylphosphine, dicyclohexylphosphine, dioctylphosphine; trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexyl An alkylphosphine such as a phosphine or a trioctylphosphine-substituted trihydrocarbon substituted phosphine, or a monoalkenylphosphine such as a vinylphosphine, a propenylphosphine or a cyclohexenephosphine or a dienylphosphine in which a hydrogen atom of a phosphine is substituted by two alkenyl groups. a trialkylenylphosphine in which a hydrogen atom of a phosphine is substituted by three alkenyl groups; an arylalkylphosphine such as benzylphosphine, phenylethylphosphine or phenylpropylphosphine; a hydrogen atom of a phosphine consists of three aryl groups Or diaryl substituted by alkenyl Alkylphosphine or aryldialkylphosphine; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, Naphthylphosphine, methylnaphthylphosphine, phosphonium phosphine, phenanthroline; aryl (alkylaryl)phosphine substituted by two alkyl aryl groups; hydrogen atom of phosphine consists of 3 alkyl aryl groups An arylphosphine such as a substituted tris(alkylaryl)phosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent cross-linking groups which combine two ligands, and represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group, and a ruthenium-containing group. , tin-containing groups, -O-, -CO-, -S-, -SO ₂ -, -Se-, -NR ¹ -, -PR ¹ -, -P(O)R ¹ -, -BR ¹ - Or -AlR ¹ -, R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the crosslinkable groups, at least one of them is a crosslinked group derived from a hydrocarbon group having 1 or more carbon atoms or a base containing ruthenium. Examples of such a crosslinking group include those shown in the following general formula (a).

(D is a group 14 element of the periodic table, and examples thereof include carbon, ruthenium, osmium, and tin. R ² and R ^{3 are} each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different and each other Binding can form a ring structure. e represents an integer from 1 to 4).

Specific examples of the structure represented by the above general formula (a) include a methyl group, an ethyl group, an ethylene group, a propylene group, an isopropylidene group, a cyclohexylene group, and a 1,2-cycloxyl group. , vinylidene (CH ₂ = C=), dimethyl decyl, diphenyl decyl, methyl phenyl decyl, dimethyl decenyl, dimethyl titanium alkenyl, tetramethyl dioxane Base, diphenyldidecyl and the like. Among them, an ethyl group, an isopropylidene group, a tetramethyldioxanyl group or a dimethyl decyl group is preferred.

Specific examples of the transition metal compound represented by the general formula (I) include specific examples described in WO2008/066168. Further, it may be a similar compound of a metal element of another group. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

Among the transition metal compounds represented by the above formula (I), a compound represented by the following general formula (II) or (III) is preferred.

In the above general formulas (II) and (III), M represents a metal element of Groups 3 to 10 of the periodic table, and each of A ^1a and A ^2a represents a crosslinking group represented by the general formula (a) in the above general formula (I). , CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C(CH ₃ ) ₂ C, (CH ₃ ) ₂ Si, (CH ₃ ) ₂ Si(CH ₃ ) ₂ Si and ( C ₆ H ₅ ) ₂ Si is preferred. A ^1a and A ^2a may be the same or different from each other. R ⁴ to R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group or a hetero atom-containing group. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the ruthenium-containing group are the same as those described in the above general formula (I). Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, and 3,5-. Bis(trifluoro)phenyl, fluorobutyl, and the like. Examples of the hetero atom-containing group include a hetero atom-containing group having 1 to 20 carbon atoms, and specific examples thereof include a nitrogen group such as a dimethylamino group, a diethylamino group or a diphenylamino group; and a phenyl group; a sulfur-containing group such as a sulfide group or a methyl sulfide group; a phosphorus-containing group such as a dimethylphosphino group or a diphenylphosphino group; or an oxygen-containing group such as a methoxy group, an ethoxy group or a phenoxy group. Among them, R ⁴ and R ^{5 are} preferably a group having a hetero atom such as a halogen atom, oxygen or hydrazine, and a hydrocarbon having a carbon number of 1 to 20 having a high polymerization activity. Further, from the viewpoint of synthesizing the coordination space of the monomer, it is possible to synthesize a polymer having a balance between the binding ratio and the heat of fusion, and R ⁴ and R ⁵ have a heterostructure such as an isopropyl group or an isopentyl group. The base is good. R ⁶ to R ^{13 are} preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as the general formula (I). q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

In the case of the transition metal compound represented by the above formula (II), when the sulfhydryl groups of the two groups are the same, a specific example described in WO2008/066168 is exemplified as the transition metal compound of Group 4 of the periodic table. Also A similar compound that may be a metal element of a group other than Group 4. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

On the other hand, in the transition metal compound represented by the above formula (II), when R ⁵ is a hydrogen atom and R ^{4 is a} non-hydrogen atom, the transition metal compound of Group 4 of the periodic table may be as described in WO2008/066168. Specific examples. Further, it may be a similar compound of a metal element of a group other than Group 4. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

<(P-b) component>

The compound obtained by reacting the above (Pb) with a transition metal compound to form an ionic dislocation is obtained from the viewpoint of obtaining a relatively low molecular weight high-purity terminally unsaturated olefin polymer and high catalyst activity. A borate compound is preferred. Specific examples of the boric acid ester compound described in WO2008/066168 are mentioned. These may be used alone or in combination of two or more. When the molar ratio of the hydrogen to the transition metal compound (hydrogen/transition metal compound) is 0, dimethyl phenyl quinolate (pentafluorophenyl) borate, triphenyl carbon quinone (pentafluorophenyl) borate Preferably, hydrazine and hydrazine (perfluorophenyl)boronic acid methylaniline are preferred.

<(P-c) component>

The catalyst of the method for producing a propylene-based polymer or a butene-based polymer (A) used in the second invention may be the same as the above (P-a) component and (P-b). In addition to the above-mentioned (P-a) component and (P-b) component, an organoaluminum compound can also be used as a (P-c) component.

Examples of the organoaluminum compound as the component (Pc) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and dimethyl aluminum. Chloride, diethylaluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum Semi-chloride, etc. These organoaluminum compounds may be used alone or in combination of two or more.

Among them, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum is preferred, and triisobutyl aluminum is used. It is preferred that tri-n-hexyl aluminum and tri-n-octyl aluminum.

The amount of the component (Pa) is usually 0.1 × 10 ^-6 to 1.5 × 10 ^-5 mol / L, preferably 0.15 × 10 ^-6 to 1.3 × 10 ^-5 mol / L, more preferably 0.2 × 10 ^{- 6} ~ 1.2 × 10 ^-5 mol / L, particularly preferably 0.3 × 10 ^-6 ~ 1.0 × 10 ^-5 mol / L. When the amount of the component (Pa) is 0.1 × 10 ^-6 mol/L or more, the catalyst activity can be sufficiently exhibited, and when it is 1.5 × 10 ^-5 mol/L or less, the heat of polymerization can be easily removed.

When the ratio (P-a)/(P-b) of the component (P-a) to the component (P-b) is expressed by the molar ratio, it is preferably from 10/1 to 1/100, more preferably from 2/1 to 1/10. When (P-a)/(P-b) is in the range of 10/1 to 1/100, the effect as a catalyst can be obtained, and the catalyst cost per unit mass of the polymer can be suppressed. Further, there is a concern that a large amount of boron is present in the target α-olefin polymer.

Use ratio of (P-a) component to (P-c) component (P-a)/(P- c) When expressed in molar ratio, it is preferably 1/1 to 1/10000, preferably 1/5 to 1/2000, more preferably 1/10 to 1/1000. By using the (P-c) component, the polymerization activity per transition metal can be improved. If (Pa)/(Pc) is in the range of 1/1 to 1/10000, the balance between the addition effect of the (Pc) component and the economy will be good, and the amount of aluminum present in the target-free α-olefin polymer will be present. Concerns.

A propylene-based polymer or a 1-butene system used in the second invention In the method for producing the polymer (A), the (P-a) component and the (P-b) component or the (P-a) component, the (P-b) component, and the (P-c) component can be used for preliminary contact. The preliminary contact can be carried out by bringing the (P-a) component into contact with the component (P-b), for example, and the method is not particularly limited, and a known method can be used. By such preparatory contact, it is effective in reducing the activity of the catalyst or reducing the catalyst cost such as a decrease in the use ratio of the (P-b) component of the catalyst.

A propylene-based polymer or a 1-butene system used in the second invention The polymer (A) may be a terminally unsaturated α-olefin polymer obtained by a thermal decomposition reaction using the α-olefin polymer obtained by the above production method as a raw material. The thermal decomposition reaction can be carried out by subjecting the raw material α-olefin polymer obtained by the above production method to heat treatment.

The heating temperature can be adjusted according to the molecular weight of the target set and the experimental results previously performed, preferably 300 to 400 ° C, more preferably 310 to 390 ° C. When the heating temperature is less than 300 ° C, there is a concern that the thermal decomposition reaction cannot be carried out. On the other hand, when the heating temperature exceeds 400 ° C, there is a concern that the resulting terminally unsaturated α-olefin polymer is deteriorated.

Further, the thermal decomposition time (heat treatment time) is preferably from 30 minutes to 10 hours, more preferably from 60 to 240 minutes. If the thermal decomposition time is less than 30 minutes, the amount of the terminal unsaturated α-olefin polymer produced may be too small. On the other hand, when the thermal decomposition time exceeds 10 hours, the resulting terminally unsaturated α-olefin polymer may be deteriorated.

The above thermal decomposition reaction, for example, is used as a thermal decomposition device A reaction vessel such as stainless steel, which is equipped with a stirring device, is filled with an inert gas such as nitrogen or argon, and is placed in a raw material α-olefin polymer and heated and melted to foam the molten polymer phase with an inert gas. The volatile product is removed and heated at a predetermined temperature for a predetermined period of time.

The free radical decomposition reaction can be carried out at a temperature of 160 to 300 ° C. The organic peroxide is added in an amount of 0.05 to 2.0% by mass based on the raw material α-olefin polymer.

The above decomposition temperature is preferably from 170 to 290 ° C, more preferably from 180 to 280 ° C. If the decomposition temperature is less than 160 ° C, there is a concern that the decomposition reaction cannot proceed. On the other hand, when the decomposition temperature exceeds 300 ° C, the decomposition proceeds intensely, and the decomposition of the organic peroxide is sufficiently completed before the homogeneous diffusion in the molten polymer, and there is a concern that the yield is lowered.

Of the organic peroxide to be added, preferably 1 minute An organic peroxide having a half-life temperature of 140 to 270 ° C, and specific examples of the organic peroxide include the following compounds: diisobutylphosphonium peroxide, cumene peroxypoxylate, and di-n -propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate , t-hexyl peroxy neodecanoate, t-butyl peroxy neoheptanoate, t-hexyl peroxy valerate, t-butyl peroxy valerate, di(3,5,5-three Methylhexyl) peroxide, dilaurate peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2, 5-bis(2-ethylhexylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, bis(4-methylbenzylidene) peroxide, t- Butylperoxy-2-ethylhexanoate, bis(3-methylbenzhydryl) peroxide, benzhydryl peroxide, 1,1-di(t-butylperoxy) 2-methylcyclohexane, 1,1-di(t-hexylpropylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexyl Oxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-(t-butylperoxy)cyclohexyl)propane , t-hexylperoxyisopropyl monocarbonate, t-butyl peroxy maleate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl Oxidized laurel Acid ester, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 3,5-di-methyl- 2,5-bis(benzimidylperoxy)hexane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butyl Oxidized benzoate, n-butyl 4,4-di-(t-butylperoxy)valerate, bis(2-t-butylperoxyisopropyl)benzoate, peroxidation Diisopropylbenzene, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumene peroxide, Di-t-butyl peroxide, p-Menthans hydrogen peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene Hydrogen peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide.

The amount of the organic peroxide to be added is preferably from 0.1 to 1.8% by mass, more preferably from 0.2 to 1.7% by mass, based on the raw material α-olefin polymer. When the amount added is less than 0.05% by mass, the decomposition reaction rate becomes slow, and there is a concern that the production efficiency is deteriorated. On the other hand, when the amount added exceeds 2.0% by mass, there is a concern that the odor caused by the decomposition of the organic peroxide becomes a problem.

The decomposition time of the decomposition reaction is, for example, 30 seconds to 10 hours, preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, the decomposition reaction is not sufficiently carried out, and there is a concern that a large amount of undecomposed organic peroxide remains. On the other hand, when the decomposition time exceeds 10 hours, the progress of the crosslinking reaction of the side reaction may become a problem, or there may be a concern that the obtained α-olefin polymer is yellowed.

The radical decomposition reaction can be carried out, for example, by any method which is decomposed by a batch method and decomposed by a melt continuous method.

When the radical decomposition reaction is carried out by a batch method, an inert gas such as nitrogen or argon is filled in a reaction vessel such as stainless steel equipped with a stirring device, and the α-olefin polymer of the raw material is placed in a molten material to be heated and melted, and melted. An organic oxide is dropped into the raw material α-olefin polymer, and heated at a predetermined temperature for a predetermined period of time to carry out a radical thermal decomposition reaction.

The dropping of the above organic peroxide may be carried out by dropping in the range of the above decomposition time, and the dropping may be either continuous dropping or batch dropping. Further, it is preferred that the reaction time from the end of the dropping time be set within the range of the above reaction time.

Organic peroxide can be used as a solution dissolved in a solvent under.

The solvent is preferably a hydrocarbon solvent, and specific examples thereof include aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, hexadecane, and nonadecane; methylcyclopentane; An alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, cyclooctane or cyclododecane; and an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene or trimethylbenzene. Among these solvents, a solvent having a boiling point of 100 ° C or higher is also preferred.

In addition, the raw material α-olefin polymer can be dissolved in the decomposition. In the agent. The decomposition temperature at which the raw material α-olefin polymer is dissolved in a solvent to be decomposed is generally in the range of 100 to 250 ° C, preferably in the range of 120 to 200 ° C.

When the radical decomposition reaction is carried out by the melt continuous method, The reaction time in the average residence time, for example, 20 seconds to 10 minutes. The melt continuous method is compared with the batch method to make the mixed state good and the reaction time can be shortened.

The apparatus may use a single-axis or two-axis melt extruder, preferably an extruder having an injection port during the barreling process and capable of degassing under reduced pressure, which is an extruder having an L/D=10 or more.

Free radical decomposition reaction by melt continuous method The apparatus may be a method in which an organic peroxide is impregnated with a raw material α-olefin polymer, or a method in which a raw material α-olefin polymer and an organic peroxide are separately supplied and mixed.

The impregnation of the organic peroxide with the raw material α-olefin polymer, Specifically, the organic peroxide is added to the raw material α-olefin polymer in the presence of an inert gas such as nitrogen, and after being stirred at a temperature of from room temperature to 40° C., the raw material particles can be uniformly absorbed and impregnated. The obtained α-olefin polymer (impregnated particles) impregnated with an organic peroxide is decomposed by melt extrusion, or the impregnated particles are added as a mother particle to the raw material α-olefin polymer and decomposed to obtain terminal unsaturation. Alpha-olefin polymer.

Further, when the organic peroxide is a solid or organic peroxide having low solubility to the raw material α-olefin polymer, the solution of the organic peroxide in the hydrocarbon solvent can be absorbed and impregnated with the raw material α-olefin polymer. .

The raw material α-olefin polymer and organic peroxide are separately supplied The mixture is mixed and supplied to the raw material α-olefin polymer and the organic peroxide at a constant flow rate in the hopper portion of the extruder, or may be supplied at a constant flow rate during the barreling of the organic peroxide.

(B) polyoxyalkylene oxide

The polyoxyalkylene (B) used in the second invention is an organic hydrogen polyoxyalkylene having two or more hydrogen-hydrazine bonds in the molecule and having two or more SiH groups per molecule, preferably A polyoxyalkylene having a Si-H bond in a portion other than the terminal. When the Si-H bond is present only at both ends, the molecular weight extends only to 1:1, that is, the hardening performance may not be deteriorated by crosslinking. Considering to become sticky. Then the strength is insufficient.

As the above, there are two or more SiH groups per molecule. Monohydrogenated polydimethyloxane The alkane, the end of the molecular chain, the trimethylmethaloxy group blocks the methyl hydrogen polyoxyalkylene, and the end of the molecular chain, the trimethylmethyl alkoxy group blocks the dimethyloxane. The methylhydroquinone copolymer, the sterol group at both ends of the molecular chain blocks the methyl hydrogen polyoxyalkylene, and the sterol group at both ends of the molecular chain blocks the dimethyloxane. Methylhydroquinone copolymer, molecular end chain dimethyl hydroformyloxy group blocked dimethyl polyoxyalkylene, molecular chain two terminal dimethyl hydroformyloxy group blocked methyl hydrogen polyfluorene The oxyalkylene and the two ends of the molecular chain, dimethylhydroformamidooxy, block the dimethyloxane. A methylhydroquinone copolymer or the like.

The above organohydrogen polyoxyalkylene (B) and propylene-based polymer or When the butene polymer (A) is reacted, it is preferred to form a polyoxyalkylene residue satisfying the following (a), (b) and (c).

(a) A oxoxane terminal (A unit) represented by the following formula (A) or a siloxane chain (B unit) represented by the following formula (B) or both.

(b) The repeating unit (C unit) of the oxoxane represented by the formula (C) in the main chain of the polyoxyalkylene molecule.

(c) The number of A units is 0~2/molecule, the number of B units is 0~10/molecular, and A unit and B unit are not 0 at the same time. The total of the A unit, the B unit, and the C unit is 5 to 1,500, preferably 5 to 200, more preferably 10 to 150 per molecule, and the polyoxyalkylene end other than the binding site to the polyolefin is R ⁷ or OR ⁸ (R ⁷ and R ⁸ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms).

(wherein R ² to R ⁶ each represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms; *-Si represents a binding site to a polyolefin).

Examples of the unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R ² to R ⁸ include a methyl group, an ethyl group, an isopropyl group, and a phenyl group. In addition, examples of the substituted monovalent hydrocarbon group having 1 to 12 carbon atoms include a hydrocarbon group in which the above hydrocarbon group is substituted with a hydrogen atom, an alkoxy group or an amine group.

The above A unit is equivalent to the end of the reacted oxirane molecule The terminal group B is the group present in the main chain of the reacted siloxane molecule. The number of the above A unit, B unit, and C unit is an integer. However, when the polyoxyalkylene residue satisfying the above (a) to (c) has a molecular weight distribution, the number of the above-mentioned A unit, B unit, and C unit is represented by an average value, and is therefore a positive number.

The polyoxyalkylene residue is a hardenable bond in combination with the second invention The purpose of use of the composition should be appropriate. When the curable adhesive composition of the second aspect of the invention is applied to a resin which imparts lubricity or abrasion resistance to the resin, the single terminal hydride polydimethyloxane residue is preferred. Further, when mechanical properties such as melt properties, flexibility, and impact resistance, and gas permeability are imparted to the resin, a polyoxyalkylene residue having 2 to 10 hydride-bonded residues is preferred. Further, when the curable adhesive composition of the second invention is used for the treatment of an inorganic filler, a polyoxyalkylene residue containing an alkoxy group is preferred.

The propylene system in the hardenable adhesive composition of the second invention The mass ratio (A)/(B) of the polymer or the 1-butene polymer (A) to the polyoxyalkylene (B) is from 10/0.001 to 10/ from the viewpoint of hardenability and crosslinking density. 5 is preferably, preferably 10/0.01 to 10/3, more preferably 10/0.05 to 10/2.

(C) hydroquinone alkylation catalyst

The hydroquinone alkylation catalyst (sterol condensation catalyst) used in the second invention may, for example, be an organometallic catalyst or a tertiary amine.

Examples of the organic metal include an organotin metal compound such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate or tin octylate, lead octenoate or lead naphthenate.

Examples of the tertiary amines include N-triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl)ether, N,N,N',N",N",N. "-pentamethyldiethylideneamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N-methyl-N' - an imidazole compound in which dimethylaminoethylpiperazine or a second-order amine functional group of the imidazole ring is substituted with a cyanoethyl group.

These catalysts may be used alone or in combination of two or more. Particularly preferred among the above catalysts are dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctanoate.

The content of the hydroquinone alkylation catalyst (C) in the curable adhesive composition of the second invention is generally 0.005 to 2.0% by mass based on 100% by mass of the curable adhesive composition of the second invention. Preferably, it is 0.01 to 0.5% by mass.

(D) adhesion imparting agent or subsequent imparting agent

Adhesive-imparting agent or adhesive-imparting agent (adhesive imparting resin or adhesive imparting resin), rosin and its derivatives, terpene-based resin and hydrogenated resin thereof, styrene resin, coumarone-indene resin, and Cyclopentadiene (DCPD) resin and hydrogenated resin thereof, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9 Among the adhesion-imparting agents which are generally used, such as a copolymerized petroleum resin and a hydrogenated resin thereof, are preferably selected to have good compatibility with a functionalized α-olefin polymer. One type of these adhesiveness-imparting resins may be used alone or two or more types may be used as a mixture.

The preferred adhesion-imparting agent or the subsequent-imparting agent is selected from the group consisting of terpene-based resins and hydrogenated resins, styrene-based resins, and the like, from the viewpoint of balance between re-peelability and adhesion to curved surfaces and uneven surfaces. Cyclopentadiene (DCPD) resin and hydrogenated resin thereof, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9 One type of resin or a mixture of two or more types of the copolymerized petroleum resin and the hydrogenated resin group is preferred.

The content of the adhesion-imparting agent or the adhesion-imparting agent (D) in the curable adhesive composition of the second invention is generally from 1 to 70% by mass based on 100% by mass of the curable adhesive composition of the second invention. It is preferably from 3 to 50% by mass.

(E) thinner

Examples of the diluent include oils such as naphthenic oils, paraffinic oils, and aromatic oils, and oils thereof, and liquid rubbers such as liquid polybutene and liquid isopolybutene. These may be used alone or in combination of two or more.

The content of the diluent (E) in the curable adhesive composition of the second invention is generally 0.5 to 50% by mass, preferably 1 to 1% by mass of the curable adhesive composition of the second invention. 30% by mass.

(other ingredients)

The curable adhesive composition of the second invention may contain an additive such as an inorganic filler or an antioxidant insofar as it does not inhibit the effects of the second invention.

Examples of the inorganic filler include cerium oxide, aluminum oxide, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, cerium oxide, ferrite, calcium hydroxide, magnesium hydroxide, and hydrogen. Alumina, basic magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium citrate, talc, clay, mica, montmorillonite, bentonite, sepiolite, Igne vermiculite, sericite, glass fiber, glass beads, cerium oxide system, barium, aluminum nitride, boron nitride, tantalum nitride, carbon black, graphite, carbon fiber, carbon bar, zinc borate, various magnetic powders Wait.

The curable adhesive composition of the second invention can be produced by mixing the above components by any method.

It is preferred that the hydroquinone alkylation catalyst (C) is used after mixing. Hydroquinone The method of adding the catalyst (C) is to prepare a catalyst masterbatch in which a high-concentration hydroquinone alkylation catalyst (C) is prepared in advance, and it is preferred that the catalyst masterbatch is blended with other components and then kneaded or melted. .

The composition of the second invention can be used as a hot melt adhesive. When it is used as a solvent-based adhesive dissolved in a solvent, it is applied and sprayed, and then a film is formed on the surface of the substrate to be adhered to the object. Moreover, when the composition of the second invention is dispersed or emulsified in a polar solvent such as water, it can also be used as an adhesive. Further, the composition of the second invention is formed into a sheet shape or a film shape, sandwiched between the substrates, heated to a temperature at which the adhesive agent can flow, and then cured by cooling and solidification.

The curable adhesive composition of the second invention can be used at low temperatures Apply a hardening reaction. Specifically, when the curable adhesive composition of the second invention is subjected to a curing reaction at 100 ° C or lower, a cured product can be obtained. The hardening reaction is carried out by contact with moisture or moisture, followed by heat treatment or ripening at room temperature. When moisture or moisture is brought into contact, for example, the curable adhesive composition of the second invention may be placed in the air, and may be immersed in a water tank to introduce steam. Further, the temperature may be room temperature (25 ° C), but if it is set to a high temperature, crosslinking may be carried out in a short time. The hardening speed and the crosslinking speed can be adjusted by the oxygen concentration.

The curable adhesive composition of the second invention can be used for the reverse Application of type adhesives, reactive hot melt adhesives, other adhesives, adhesives, sealing materials, sealing materials, potting materials, reactive plasticizers, and the like. Further, when the curable adhesive composition of the second invention is applied to a tape, a film, a sheet, or the like to be cured, it can also be used for an adhesive tape, an adhesive film, or a thin adhesive film. Tablets and other uses.

<Third invention> [Functionalized α-olefin polymer]

The functionalized alpha-olefin polymer of the third invention is a functionalized propylene homopolymer formed by functionalization of a propylene homopolymer, which will be selected from the group consisting of 1-butene homopolymer and propylene-1-butene copolymer. a functionalized 1-butene polymer obtained by functionalization of a 1-butene polymer, and a diene copolymer selected from the group consisting of a propylene-diene copolymer and a 1-butene-diene copolymer Three types of functionalized diene polymers formed by functionalization. The term "functionalization" in the present specification means that a hydrazine compound having a hydrogen-hydrazine bond is added to the terminal end of the α-olefin polymer.

Further, when copolymerization of a comonomer such as ethylene is carried out, since the crystal component is increased, there is no fluidity at room temperature, the handleability is deteriorated, or hardening at room temperature is difficult, so that it is difficult to use as an adhesive or adhesion. On the substrate of the agent or sealant.

The functionalized α-olefin polymer of the third invention exhibits fluidity at normal temperature. Specifically, the functionalized α-olefin polymer of the third invention exhibits fluidity at a relatively low temperature of 100 ° C or lower, and more preferably exhibits fluidity at a low temperature of 60 ° C or lower.

(functionalized propylene homopolymer)

The aforementioned functionalized propylene homopolymer has a ruthenium-containing group at the terminal end of the propylene homopolymer.

(functionalized 1-butene polymer)

The functionalized 1-butene polymer is a 1-butene-based polymer selected from the group consisting of a 1-butene homopolymer and a propylene-1-butene copolymer, and has a ruthenium-containing group at the terminal end of the main chain.

Further, when the main chain end of the polyisobutylene is functionalized, the polyisobutylene which is a raw material is synthesized by cationic polymerization of the isobutylene, and a reaction of introducing an unsaturated group is carried out to obtain a terminal unsaturated group, which is introduced into the polyisobutylene, and then introduced into the unsaturated group. Functional group. There are many steps for obtaining or functionalizing isobutylene, which is not desirable from the viewpoint of economy.

On the other hand, when the main chain end of poly-1-butene is functionalized, the poly-1-butene as a raw material is synthesized by coordinating anion polymerization of 1-butene of a general product by a metallocene catalyst. Further, after thermal decomposition or radical decomposition reaction to obtain a terminally unsaturated 1-butene, to introduce a functional group, an unsaturated group is easily introduced, and the functionalized isobutylene polymer is different in steps, for 1-butyl The economics such as the availability of the olefin and the production of raw materials are excellent.

(functionalized diene polymer)

The functionalized diene polymer has a ruthenium-containing group at the terminal end of the diene copolymer selected from the group consisting of a propylene-diene copolymer and a 1-butene-diene copolymer.

Here, the propylene-diene copolymer is a polymer which copolymerizes propylene and a diene, and a 1-butene-diene copolymer is a polymer which copolymerizes propylene and a diene.

Specific examples of the above diene include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene. 1,8-decadiene, 1,9-decadiene, 1,10-undecenediene, 1,11-dodecadiene, 1,13-tetradecadiene, divinyl Benzene, divinylcyclohexane, and the like.

The copolymerization ratio of the diene in the functionalized diene polymer is preferably 0.01 to 50 mol%, more preferably 0.1 to 30 mol%, still more preferably 0.5 to 20 mol%. When the copolymerization ratio of the diene is 50 mol% or less, the crosslinking reaction may be complicated in the production of the polymer, or the possibility of gelation may be lowered, and if it is 0.01 mol% or more, propylene or 1-butene The amount of the diene component in the olefin polymer increases, and the influence on the number of terminal unsaturation increases.

(a) terminal group containing ruthenium

The functionalized α-olefin polymer of the third invention has a ruthenium-containing group of from 0.5 to 2.5 per molecule of the functionalized diene polymer, but particularly has a ruthenium-containing group at the end of the main chain. In the functionalized propylene homopolymer or the functionalized 1-butene polymer, the number of ruthenium groups per one molecule of the main chain terminal is from 0.5 to 2.0. Further, when any of the functionalized propylene homopolymer, the functionalized 1-butene polymer, and the functionalized diene polymer is used as a compatibilizing agent, a group containing a ruthenium per molecule The number is 0.5 to 1.5, preferably 0.8 to 1.2, and when used in adhesives or sealing materials, the hardening property is important. From the viewpoint of obtaining a crosslinked structure, 1.2 The above is preferred, and more preferably 1.5 or more.

As a method of controlling the number of ruthenium-containing groups at the terminal, there are variations in the ratio of use of the ruthenium compound to the α-olefin polymer, reaction temperature, and reaction time. The method of between.

The above reaction temperature is preferably from 10 to 200 ° C, and more preferably from 20 to 180 ° C.

The above reaction time is preferably from 0.5 to 20 hours, preferably from 1 to 10 hours.

The ratio of the ruthenium compound to the α-olefin polymer is preferably from 1 to 20, more preferably from 1 to 10, in terms of the oxime compound/α-olefin polymer molar ratio.

Further, the maximum number of the terminal groups containing ruthenium depends on the number of terminal unsaturated groups per molecule of the α-olefin polymer to be described later.

The terminal ytterbium-containing group is preferably a substituted fluorenyl group, and specific examples thereof include an alkyl fluorenyl group, an aryl decyl group, an alkoxy fluorenyl group, and a halogenated fluorenyl group.

Specific examples of the above substituted fluorenylalkyl group include a trimethoxydecylalkyl group, a triethoxyalkylidene group, a triisopropoxydecylalkyl group, a methyldimethoxydecylalkyl group, and an ethyldiethoxydecylalkyl group. Phenyldiethoxydecylalkyl, tri-n-hexyldecylalkyl, tri-n-octyldecylalkyl, and the like.

The number of groups containing ruthenium at the end of each molecule described above can be determined by the measurement method shown below.

(A) The base concentration of the terminal ruthenium (% by mole) obtained by ¹³ C-NMR, and (B) the number of functionalized α-olefin polymers obtained by gel permeation chromatography (GPC) The average molecular weight (Mn), and (C) the average molecular weight (Mm) of the monomer unit = the unit ratio of propylene × 42.08 + 1-butene unit ratio × 56.11, and the basis of the ruthenium group per molecule is calculated by the following formula The number.

Number of groups containing ruthenium at the end of each molecule = (Mn/M) × [base concentration of ruthenium containing end groups] / 100

As the above end group concentration of the silicon-containing calculating method, side reactions by reducing the concentration of terminal unsaturation, it is as shown below, was calculated using ¹³ C-NMR at 20 ~ Si-CH CH ₂ appear from the vicinity of 22ppm ₂ Peak concentration.

CH ₂ (i) of Si-CH ₂ : integral value of 20-22 ppm

CH ₂ (ii) of propylene unit: peak integral value at 46.4 ppm

CH ₂ (iii) of butene units: peak integral value at 40.4 ppm

Base concentration of cerium at the end = [(i) / ((ii) + (iii))] × 100 (% by mole)

Further, the phrase "having a ruthenium-containing group at the end of the main chain" means that the ruthenium-containing group is at the end of the polymer main chain (preferably both ends), specifically, for the ¹³ C-NMR measurement, it means having the end from the main chain. The peak of 20~22ppm of the SiCH ₂ bond can be distinguished from the peak of 13-15ppm observed by the Si-C binding from the side chain.

The functionalized α-olefin polymer of the third invention has a ruthenium-containing group at the end of the main chain, so that when moisture is hardened, moisture in the air or the like easily permeates the ruthenium-containing group, and can be effectively used for the crosslinking reaction. Therefore, the cured product can be obtained with good efficiency.

(b) Melting heat absorption △H-D

The functionalized α-olefin polymer used in the third invention has a melting heat absorption ΔH-D of 50 J/g as measured by a differential scanning calorimeter (DSC). under.

In the functionalized propylene homopolymer, the melting heat absorption ΔH-D is preferably 30 J/g or less, more preferably 15 J/g or less, and particularly preferably 1 J/g or less.

In the functionalized 1-butene polymer, the melting heat absorption ΔH-D is preferably 40 J/g or less, more preferably 10 J/g or less, and particularly preferably 1 J/g or less.

When the heat of fusion ΔH-D is 50 J/g or less, the crystallinity component is small, and the fluidity at a relatively low temperature is improved, which is preferable from the viewpoint of energy saving during construction or a safe environment.

Moreover, ΔH-D can be determined by DSC measurement. Specifically, a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.) was used, and 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then melted at a temperature of 10 ° C /min. The heat is taken as ΔHD.

In order to control the melting heat absorption below 50 J/g, the meso-penta-unit (mmmm) fraction of the stereoregularity index must be controlled to be less than 80 mol%, which can be controlled by the structure or polymerization conditions of the main catalyst. . For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and the heat of fusion is more than 50 J/g. In the case of a meso-type structure, it is easy to obtain a polymer having a low regularity, and the heat of fusion may be 50 J/g or less, and it is difficult to synthesize a polymer having a balance between the binding ratio and the heat of fusion. For example, by using a double crosslinked catalyst as described later At this time, the coordination space of the monomer is controlled, so that the synthesis of the polymer having a balance of the binding ratio and the melting endotherm becomes possible.

(c) stereoregularity

The functionalized α-olefin polymer of the third invention preferably has a meso-penta-unit [mmmm] fraction of less than 80 mol%.

When the propylene homopolymer has a ruthenium-containing group at the end of the main chain, it is preferred that the meso-penta-unit (mmmm) fraction is less than 60 mol, and less than 40 mol% is better. The ear is especially good.

When the terminal group of the 1-butene homopolymer has a ruthenium-containing group, the meso-penta-unit [mmmm] fraction is less than 70 mol%, preferably less than 40 mol%. , less than 20% of the total is very good.

On the other hand, when the propylene-1-butene copolymer has a ruthenium-containing group at the terminal end of the main chain, the meso-diad fraction [m] is preferably 30 to 95 mol%. It is better to use 30 to 80 mol%, and 30 to 60 mol% is better.

The mesogenic five-unit [mmmm] fraction and the meso-diad fraction [m] are controlled to a low value to make it low-regular, completely amorphous and can be processed at room temperature. Hardening at lower temperatures is possible. Therefore, in the field of sealing and reactivity which has been difficult to use in the past, it is particularly possible to use it in the field of adhesion to a polyolefin-based substrate.

The structure of the meso-penta-unit [mmmm] and the meso-diad fraction [m] are controlled by the structure or polymerization of the main catalyst. When the conditions are controlled, for example, by controlling the structure of the catalyst, it is necessary to design the space of the metal coordination monomer in the catalyst center to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and if it is a meso-type structure, it becomes easy to obtain a rule. Low polymer.

The 2,1-binding fraction of the functionalized α-olefin polymer of the third invention is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, still more preferably less than 0.2 mol%.

The control of the 2,1-binding fraction is carried out by controlling the 2,1-binding fraction in the α-olefin polymer used as a raw material by the method described later.

The total of the 1,3-binding fraction and the 1,4-binding fraction of the functionalized α-olefin polymer of the third invention is preferably less than 0.5 mol%, preferably less than 0.4 mol%, more preferably Less than 0.1 mol%.

The above "the total of the 1,3-binding fraction and the 1,4-bonding fraction" is that the functionalized α-olefin polymer of the third invention has a propylene homopolymer main chain and represents a 1,3-binding component. The ratio, which has a butene homopolymer main chain, represents a 1,4-binding fraction, and when it has a propylene-1-butene copolymer main chain, it represents a total of a 1,3-binding fraction and a 1,4-bonding fraction. .

The control of the 1,3-binding fraction and the 1,4-binding fraction is carried out by the method described later by the 1,3-binding fraction and the 1,4-binding fraction in the α-olefin polymer used as a raw material. Controlled.

When the 2,1-binding fraction, the 1,3-binding fraction, and the 1,4-binding fraction are increased, the number of terminal unsaturation in the raw material is reduced, and since this is used as the starting point of the reaction, the end cannot be increased. The number of bases containing bismuth is not good.

In the third invention, the meso-equivalent five-element (mmmm) fraction and the meso-diad fraction are reported by the magazine "Polymer Journal, 16, 717 (1984)" and J. Randall. "Macromol. Chem. Phys., C29, 201 (1989)" and the "Macromol. Chem. Phys., 198, 1257 (1997)" reported by V. Busico. The method is obtained. And, using ¹³ C NMR spectroscopy to measure the methyl and methine signals, the meso-penta-unit (mmmm) fraction and the meso-diad fraction of the polymer linkage were obtained. m].

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: mixed solvent of 1,2,4-trichlorobenzene and heavy benzene of 90:10 (capacity ratio)

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

(d) Weight average molecular weight. The molecular weight distribution

The functionalized α-olefin polymer of the third invention is preferably from 3,000 to 500,000 in terms of fluidity, preferably from 4,000 to 450,000, and particularly preferably from 4,500 to 300,000.

The functionalized α-olefin polymer of the third invention is used for an adhesive In the meantime, the strength after hardening is strong, and from the viewpoint of not easily peeling off, it is preferred that the weight average molecular weight of the functionalized α-olefin polymer is 10,000 to 500,000.

The functionalized α-olefin polymer of the third invention preferably has a molecular weight distribution (Mw/Mn) of less than 4.5, and preferably 1.4 to 2.2, and 1.6 to 1.6, from the viewpoint of reactivity and reaction hardenability. 2.1 is better.

Further, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those in terms of polystyrene measured by the following apparatus and conditions, and the molecular weight distribution (Mw/Mn) is a weight average molecular weight (Mw) and a number The value calculated by the average molecular weight (Mn).

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0 ml / min

Sample concentration: 2.2 mg / ml

Injection volume: 160 microliters

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

(e) B viscosity

The functionalized α-olefin polymer of the third invention has a viscosity (fluidity) of 5000 mPa at 30 ° C from the viewpoints of reactivity, workability at room temperature, and the like. The following is better, at 2000mPa. The following is preferred.

Here, the above B viscosity means that it is measured in accordance with ASTM-D19860-91.

[Method for Producing Functionalized α-Olefin Polymer]

The functionalized α-olefin polymer of the third invention can be obtained by a production method in which an α-olefin polymer having a carbon-carbon double bond at the terminal end of the main chain and a ruthenium compound having a Si—H bond are reacted. It is necessary to use a hydroquinone alkylation catalyst. The α-olefin polymer used as the raw material may be selected from the group consisting of a propylene homopolymer, a 1-butene polymer, and a diene copolymer. The 1-butene-based polymer is selected from the group consisting of a 1-butene homopolymer and a propylene-1-butene copolymer, and the diene-based copolymer is selected from the group consisting of a propylene-diene copolymer and a 1-butene-II. Ene copolymer.

The hydroquinone alkylation catalyst is not particularly limited, and any one may be used. For example, chloroplatinic acid, platinum monomer, a platinum - vinyl siloxane silicon misprinted {e.g. _{Pt n (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) _{4] m};} platinum - phosphine misprinted {e.g. Pt(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ }; platinum-phosphite complex {eg Pt[P(OPh) ₃ ] ₄ , Pt[P(OBu) ₃ ] ₄ (wherein Me represents A The base, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, n and m represent an integer), Pt(acac) ₂ , a platinum-hydrocarbon complex, and a platinum alkoxide catalyst. Further, examples of the catalyst other than the platinum compound include RhCl(PPh ₃ ) ₃ , RhCl ₃ , Rh/Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , and PdCl ₂ . 2H ₂ O, NiCl ₂ , TiCl ₄ and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalyst activity, chloroplatinic acid, a platinum-olefin plastomer, a platinum-vinyl siloxane displacing body, Pt(acac) ₂ or the like is preferred. The amount of the catalyst is not particularly limited, and a range of from 1 to 1,000 ppm can be used for the functionalized olefin polymer. It is preferably used in the range of 10 to 500 ppm. Further, since the hydroquinone alkylation catalyst is generally expensive and corrosive, a large amount of hydrogen gas is generated to cause the cured product to foam and cause discoloration, so that it is preferably not used in a large amount.

(α-olefin polymer)

In the method for producing a functionalized α-olefin polymer according to the third aspect of the invention, the α-olefin polymer used as a raw material has the following properties (a') and preferably has the following properties (b') to (f').

(a') The number of terminal unsaturated groups per molecule is from 0.5 to 2.5.

(b') The heat of fusion ΔH-D measured by a differential scanning calorimeter (DSC) is 30 J/g or less.

(c') (c'-1) meso-diad fraction (m) of the meso-diad fraction (m) of the meso-penta unit (mmmm) fraction of less than 80 mol%, or (c'-2) 30~95% by mole.

The (d1') weight average molecular weight Mw is from 1,000 to 500,000.

The (d2') molecular weight distribution Mw/Mn was less than 4.5.

The (e') 2,1-binding fraction is less than 0.5 mol%.

The total of (f') 1,3-binding fraction and 1,4-binding fraction was less than 0.5 mol%.

(a') number of unsaturation groups per one molecule

In the case of the diene polymer, the α-olefin polymer used in the third invention has 0.5 to 2.5 terminal unsaturated groups per molecule. When the α-olefin polymer is a propylene homopolymer or a 1-butene polymer, the number of terminal unsaturated groups per molecule is preferably from 0.5 to 2.0, and is used as a compatibilizing agent. It is preferable that the number of terminal unsaturated groups per molecule is 0.5 to 1.5, preferably 0.8 to 1.2, and preferably 1.1 to 1.2, and is used for adhesive or sealing material. In the case of 1.2 or more, it is more preferable to use 1.5 or more.

When the α-olefin polymer is a diene copolymer, the number of terminal unsaturated groups per molecule is preferably from 0.5 to 2.5, and when it is used as a compatibilizing agent, the end of each molecule is not The number of saturated groups is preferably 0.5 to 1.0, and preferably 0.8 to 1.0. When used in adhesives or sealing materials, it is preferably 1.0 or more, and 1.1 to 1.5 is preferred. It is better to use 1.2 or more.

When the number of terminal unsaturated groups per molecule is only the end of the main chain, the maximum is 2.0. When 2.0 or more, the diene or the like is copolymerized, and the unsaturated group is introduced at the side of the side chain. Control the number of unsaturations per 1 molecule.

Control of the number of unsaturation groups per 1 molecule can be controlled by The structure of the main catalyst, the type of monomer, or the polymerization conditions (polymerization temperature, hydrogen concentration, etc.) are carried out.

In the presence of a catalyst, by selecting hydrogen and a transition metal compound The ear ratio (hydrogen/transition metal compound) controls the number of terminally unsaturated groups per molecule.

For example, it can be obtained by carrying out a polymerization reaction in a range of 0 to 5000 in terms of a molar ratio of hydrogen to a transition metal compound (hydrogen/transition metal compound). In order to increase the selectivity of terminal unsaturation and the activity of the catalyst, it is preferred to carry out the polymerization in the presence of a trace amount of hydrogen.

Hydrogen is generally known as a chain shifting agent, and the end of the polymer chain becomes a saturated structure. In addition, it also has the function of reactivation of the temporary break and the activity of the catalyst. Although the effect of the trace amount of hydrogen catalyst is unclear, when hydrogen is used in a specific range, the terminal unsaturated group can be made highly selective and highly active.

The molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) is preferably from 200 to 4,500, more preferably from 300 to 4,000, most preferably from 400 to 3,000. When the molar ratio is 5,000 or less, the formation of an α-olefin polymer having an extremely low number of terminal unsaturated groups can be suppressed, and an α-olefin polymer having a desired number of terminal unsaturated groups can be obtained.

Further, as the terminal unsaturated group, a vinyl group or a sub A vinyl group, a trans(acetylene) group or the like, but a terminal unsaturated group as defined in the specification means a vinyl group and a vinylidene group. Vinyl and vinylidene are radically polymerizable, and various reactions are applicable to a wide range of applications.

The terminal unsaturated group concentration and the terminal unsaturation group in the α-olefin polymer used in the third invention represent the total concentration and number of vinyl and vinylidene groups. When only a vinyl group is present, it means only the concentration and number of vinyl groups, and when both vinyl and vinylidene are contained, the concentration and number of both sides are shown.

The terminal unsaturated group concentration or the number of terminal unsaturated groups per molecule can be determined by ¹ H-NMR measurement. Specifically, the terminal vinylidene group obtained by δ4.8 to 4.6 (2H) and the terminal vinyl group appearing at δ5.9 to 5.7 (1H) and δ1.05 were obtained by ¹ H-NMR measurement. The methyl group appearing at ~0.60 (3H) is used as the standard, and the terminal unsaturated group concentration (C) (% by mole) is calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturation concentration = [vinylidene amount] + [vinyl amount]

The terminal unsaturated group concentration (C, mol %) calculated by the above method and the number average molecular weight (Mn) and the monomer molecular weight (M) obtained by gel permeation chromatography (GPC) are The equation can calculate the number of unsaturation groups at the end of each molecule.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

(b') melting heat absorption △H-D

The α-olefin polymer used in the third invention preferably has a melting heat absorption ΔH-D of 50 J/g or less as measured by a differential scanning calorimeter (DSC).

In the propylene homopolymer, the melting heat absorption ΔH-D is less than 50 J/g, less than 40 J/g, 30 J/g or less, less than 30 J/g, 15 J/g or less, and less than The order of 10 J/g, 1.0 J/g or less, less than 1.0 J/g, less than 0.5 J/g, less than 0.2 J/g, and 0 J/g is preferred.

The melting heat absorption ΔHD in the 1-butene homopolymer is preferably 40 J/g or less, preferably less than 30 J/g, more preferably 10 J/g or less, and preferably 1.0 J/g or less. .

The details of the melting heat absorption ΔH-D of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(c'-1) meso five unit [mmmm] fraction

The α-olefin polymer used in the third invention preferably has a meso-penta-unit fraction (mmmm) of less than 80 mol%.

In the propylene homopolymer, the meso-penta-unit [mmmm] fraction is preferably less than 60 mol%, preferably less than 40 mol%, and less than 20 mol%. good. And more than 1 mol% and less than 20 mol%, more than 1 mol% and less than 15 mol%, more than 2 mol% and less than 15 mol%, more than 2 mol% and less than 10 mo Ear %, more than 3 mole % and less than 10 mole % is preferred.

In the 1-butene homopolymer, the meso-penta-unit [mmmm] fraction is preferably less than 70 mol%, more preferably less than 40 mol%, and less than 20 mol%. It is especially good.

(c'-2) meso-diad fraction [m]

On the other hand, when the α-olefin polymer used in the third invention is a propylene-1-butene copolymer, the meso-diad fraction [m] It is preferably 30 to 95% by mole, preferably 30 to 80% by mole, and preferably 30 to 60% by mole.

The meso-penta-unit (mmmm) fraction and the meso-diad fraction [m] can be controlled by the structure or polymerization conditions of the main catalyst. For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and if it is a meso-type structure, it becomes easy to obtain a rule. Low polymer.

Further, the α-olefin polymer used in the third invention preferably has an external rotation pentad fraction of less than 20 mol%.

The excimer pentad fraction in the propylene homopolymer is preferably more than 1 mol% and less than 20 mol%, preferably more than 2 mol% and less than 18 mol%, more preferably It is more than 2 mol% and less than 15 mol%, particularly preferably more than 3 mol% and less than 15 mol%, most preferably more than 3 mol% and less than 10 mol%.

The excimer pentad fraction in the 1-butene homopolymer is preferably more than 1 mol% and less than 20 mol%, more preferably more than 2 mol% and less than 15 mol%. More preferably, it is more than 3 mol% and less than 10 mol%.

On the other hand, when the α-olefin polymer used in the third invention is a propylene-1-butene copolymer, the racemo-diad fraction [r] is 1 to 50 mol%. Preferably, 2 to 45 mol% is preferred, and 2 to 40 mol% is better.

(e') 2,1-binding fraction

The 2,1-binding fraction of the α-olefin polymer used in the third invention is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, still more preferably less than 0.2 mol%. When the 2,1-binding fraction of the α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction or the radical decomposition reaction described later is improved.

The control of the 2,1-binding fraction is carried out by the structure or polymerization conditions of the main catalyst. Specifically, due to the large influence of the structure of the main catalyst, the 2,1-binding can be controlled by narrowing the insertion of the monomer around the central metal of the main catalyst, and conversely, if the insertion is expanded, the addition can be increased. , 1-binding. For example, a catalyst called a semi-metallocene type has a structure in which a periphery of a center metal is wide, so that a structure such as a 2,1-bond or a long-chain branch is easily formed, and if it is a racemic type metallocene catalyst, it can be expected The 2,1-binding can be suppressed, but the stereoregularity becomes high in the case of the racemic type, and it is difficult to obtain the amorphous polymer as shown in the third invention. For example, even if it is a racemic type as described later, a metallocene catalyst crosslinked by two passes introduces a substituent at the third position, and under the insertion of the central metal, amorphous and 2,1-bonding are obtained. polymer.

(f') 1,3-binding fraction and 1,4-binding fraction

The α-olefin polymer used in the third invention preferably has a 1,3-binding fraction and a 1,4-binding fraction of less than 0.5 mol%, preferably less than 0.4 mol%, more preferably Less than 0.1 mol%. When the total of the 1,3-binding fraction and the 1,4-bonding fraction of the α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction or the radical decomposition reaction described later is improved.

The above "the total of the 1,3-binding fraction and the 1,4-binding fraction" The α-olefin polymer used in the third invention is a propylene homopolymer, which represents a 1,3-binding fraction, and when it is a butene homopolymer, it represents a 1,4-binding fraction, and is a propylene-1-butene. The olefin copolymer represents the total of the 1,3-binding fraction and the 1,4-binding fraction.

The control of the 1,3-binding fraction and the 1,4-binding fraction is carried out by the structure of the main catalyst or the polymerization conditions as in the control of the above 2,1-binding fraction.

In the third invention, the meso-equivalent five-unit [mmmm] fraction, the outer-rotating five-element [rrrr] fraction, the meso-diad fraction (m), and the outer-rotating di-unit (racemo) -diad) fraction [r], 1,3-binding fraction, 1,4-binding fraction, and 2,1-binding fraction are reported by Asakura, "Polymer Journal, 16, 717 (1984)" , as reported by J. Randall, "Macromol. Chem. Phys., C29, 201 (1989)" and by V. Busico, "Macromol. Chem. Phys., 198, 1257 (1997) ))). That is, using a ¹³ C nuclear magnetic resonance spectrum to measure the methyl and methine signals, the meso-pentameric unit (mmmm) fraction and the outer-rotating five-unit [rrrr] in the poly(1-butene) linkage are obtained. Fraction, meso-diad fraction [m], racemo-diad fraction [r], 1,3-binding fraction, 1,4-binding fraction And 2,1-binding fraction.

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

<The case of propylene homopolymer>

The 1,3-binding fraction and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,3-binding fraction = (D/2) / (A + B + C + D) × 100 (% by mole)

2,1-binding fraction = {(A+B)/2}/(A+B+C+D)×100 (mole%)

A: integral value of 15~15.5ppm

B: integral value of 17~18ppm

C: integral value of 19.5~22.5ppm

D: integral value of 27.6~27.8ppm

<The case of butene homopolymer>

The 1,4-binding fraction and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,4-binding fraction = E / (A + B + C + D + E) × 100 (% by mole)

2,1-binding fraction = {(A+B+D)/3}/(A+B+C+D)×100 (mole%)

A: integral value of 29.0~28.2ppm

B: integral value of 35.4~34.6ppm

C: integral value of 38.3~36.5ppm

D: integral value of 43.6~42.8ppm

E: integral value of 31.1 ppm

(d1') weight average molecular weight (Mw)

The α-olefin polymer used in the third invention is preferably from 1,000 to 500,000 in terms of fluidity, preferably from 2,000 to 50,000, more preferably from 3,000 to 20,000, and more preferably from 5,000 to 20,000. ~20,000 are particularly good, with 6000~450,000 being better, 8,000~300,000 being better, and 10,000~70,000 being better.

The details of the weight average molecular weight (Mw) of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(d2') molecular weight distribution (Mw/Mn)

The α-olefin polymer used in the third invention has a molecular weight distribution (Mw/Mn) of preferably less than 4.5, preferably 1.4 to 3.0, and 1.4 to 2.6, from the viewpoint of reactivity and reaction hardenability. It is better, 1.1 to 2.5 is better, 1.4 to 2.2 is better, 1.6 to 2.1 is better, and 1.6 to 2.0 is the best.

The details of the molecular weight distribution (Mw/Mn) of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(Method for producing α-olefin polymer)

The α-olefin polymer used in the third invention is, for example, a metallocene catalyst formed using a combination of the following components (P-a), (P-b) and (P-c). It can be produced when hydrogen is used as a molecular weight modifier. Specifically, it can be manufactured according to the method disclosed in WO2008/047860.

(P-a) a transition metal compound containing a metal element of Group 3 to Group 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group, or a substituted fluorenyl group

(P-b) a compound obtained by reacting with a transition metal compound to form an ionic dislocation

(P-c) organoaluminum compound

<(P-a) component>

The transition metal compound containing a metal element of Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group or a substituted fluorenyl group as the component (Pa) includes the following general A two-crosslinked complex represented by formula (I).

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, tantalum, vanadium, chromium, manganese, nickel, cobalt, palladium and lanthanide. Metal, etc. Among them, titanium, zirconium and hafnium are preferred from the viewpoint of olefin polymerization activity and the like, and zirconium is preferred from the viewpoints of the yield of α-olefin polymer and catalyst activity.

E ¹ and E ² each represent a substituent selected from a substituted cyclopentadienyl group, a fluorenyl group, a substituted fluorenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, a decylamino group (-N<), a phosphino group ( -P<), a hydrocarbon group [>CR-, >C<] and a ruthenium-containing group [>SiR-, >Si<] (however, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group) The ligand in the form can form a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As the E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group and a substituted fluorenyl group are preferred, and at least one of E ¹ and E ² is a cyclopentadienyl group or a substituted cyclopentane group. Alkenyl, fluorenyl or substituted fluorenyl.

The substituent of the above-mentioned substituted cyclopentadienyl group, substituted fluorenyl group or substituted heterocyclopentadienyl group means a carbon number of 1 to 20 (preferably, a carbon number of 1 to 10, more preferably a carbon number of 1 to 6). A substituent such as a hydrocarbon group, a ruthenium-containing group or a hetero atom-containing group.

X represents a ligand for σ-binding, and when X is a complex number, the complex X may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of the X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a decylamine having 1 to 20 carbon atoms. The base, the ruthenium-containing group having 1 to 20 carbon atoms, the phosphide group having 1 to 20 carbon atoms, the sulfide group having 1 to 20 carbon atoms, and the fluorenyl group having 1 to 20 carbon atoms.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group; and an alkenyl group such as a vinyl group, a propenyl group or a cyclohexenyl group; Arylalkyl such as benzyl, phenylethyl or phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl An aryl group such as a naphthyl group, a methylnaphthyl group, an anthracenyl group or a phenanthryl group. Among them, an alkyl group such as a methyl group, an ethyl group, a propyl group or a phenyl group The base is good.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group. An alkoxy group such as an ethoxy group, a propoxy group or a butoxy group, a phenylmethoxy group, a phenylethoxy group or the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the decylamino group having 1 to 20 carbon atoms include dimethyl decylamino group, diethyl decylamino group, dipropyl decylamino group, dibutyl decylamino group, dicyclohexyl decylamino group, and Alkenylamino group such as alkyl guanylamino group or alkyl sulfonylamino group or divinyl decylamino group, dipropylene decylamino group, dicyclohexenyl amide group; diphenylmethyl guanylamino group, benzene An arylalkylguanamine group such as a benzylaminoamine group or a phenylpropylguanamine group; an arylguanamine group such as a diphenylguanamine group or a dinaphthylguanamine group.

Examples of the fluorene-containing group having 1 to 20 carbon atoms include a monohydrocarbon-substituted fluorenyl group such as a methyl decyl group or a phenyl fluorenyl group; a dihydrocarbon-substituted decyl group such as a dimethyl decyl group or a diphenyl fluorenyl group; Methyl decyl, triethyl decyl, tripropyl decyl, tricyclohexyl decyl, triphenyl decyl, dimethylphenyl decyl, methyl diphenyl decyl, trimethyl decyl, a trihydrocarbon-substituted decyl group such as a trinaphthyl fluorenyl group; a hydrocarbon-substituted decyl ether group such as a trimethyl decyl alkyl ether group; a hydrazine-substituted alkyl group such as a trimethyl decylalkyl group; Aryl and the like. Among them, trimethyldecylmethyl group, phenyldimethyldecylethylethyl group and the like are preferred.

As a phosphide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; Propylene sulfide group, cyclohexene sulfide An alkenyl sulfide group such as an aryl group; a phenylalkyl sulfide group; a phenylethyl sulfide group; an arylalkyl sulfide group such as a phenylpropyl sulfide group; a phenyl sulfide group or a toluene sulfide group; , dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl group An aryl sulfide group such as a naphthyl sulfide group, a sulfonium sulfide group, or a phenanthrene sulfide group.

As a sulfide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; An alkenyl sulfide group such as a propylene-based sulfide group or a cyclohexene sulfide group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; Phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide An aryl sulfide group such as a benzyl group, a naphthyl sulfide group, a methylnaphthyl sulfide group, an anthracene sulfide group, or a phenanthrene sulfide group.

Examples of the fluorenyl group having 1 to 20 carbon atoms include an alkyl fluorenyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentamidine group, a palmitoyl group, a stearyl group or an oil group. An arylsulfonyl group such as benzamidine, tolylhydrazyl, salicylidene, cinnamyl, naphthylmethyl, phthalic acid, oxalic acid, malonic acid, succinic acid, etc. Didecyl, propylenediyl, amber thiol and the like.

On the other hand, Y represents a Lewis base, and Y represents a complex number, and the plural Ys may be the same or different and may be crosslinked with other Y or E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, and thioethers. The amine may, for example, be an amine having 1 to 20 carbon atoms, and specific examples thereof include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine and An alkylamine such as ethylamine, dipropylamine, dibutylamine, dicyclohexylamine or methylethylamine; vinylamine, propenylamine, cyclohexenamine, divinylamine, dipropylene An alkenylamine such as an amine or a dicyclohexenamine; an arylalkylamine such as a phenylamine, a phenylethylamine or a phenylpropylamine; or an arylamine such as a diphenylamine or a dinaphthylamine.

Examples of the ethers include methyl ether, ethyl ether, and propyl group. An aliphatic single ether compound such as ether, isopropyl ether, butyl ether, isobutyl ether, n-pentyl ether or isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl Ether, methyl-n-pentyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-pentyl An aliphatic mixed ether compound such as an ether or ethyl isoamyl ether; an aliphatic such as a vinyl ether, an allyl ether, a methyl vinyl ether, a methyl allyl ether, an ethyl vinyl ether or an ethyl allyl ether An unsaturated ether compound; an aromatic ether compound such as anisole, phenethyl ether, phenyl ether, benzyl ether, phenylbenzyl ether, α-naphthyl ether or β-naphthyl ether, ethylene oxide, A cyclic ether compound such as propylene oxide, epoxytrimethane, tetrahydrofuran, tetrahydropyran or dioxane.

Examples of the phosphine include a phosphine having 1 to 20 carbon atoms. Specific Illustrative of monohydrocarbon substituted phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, hexyl phosphine, cyclohexyl phosphine, octyl phosphine; dimethyl phosphine, diethyl phosphine, dipropyl phosphine, Dihydrocarbon substituted phosphines such as butylphosphine, dihexylphosphine, dicyclohexylphosphine, dioctylphosphine; trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, three An alkylphosphine such as a trihydrocarbon-substituted phosphine such as hexylphosphine, tricyclohexylphosphine or trioctylphosphine, or a hydrogen atom of a monoalkenylphosphine or a phosphine such as a vinylphosphine, a propenylphosphine or a cyclohexenephosphine; a substituted diallylphosphine; a trienylphosphine substituted by a hydrogen atom of a phosphine; an arylalkylphosphine such as benzylphosphine, phenylethylphosphine or phenylpropylphosphine; a diarylalkylphosphine or an aryldialkylphosphine in which a hydrogen atom is substituted by 3 aryl or alkenyl groups; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethyl Phenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthylphosphine, phosphonium phosphine, phenanthroline; the hydrogen atom of the phosphine is substituted by two alkyl aryl groups (alkyl aryl) Phosphine; an arylphosphine such as a tris(alkylaryl)phosphine substituted with three alkylaryl groups in the hydrogen atom of the phosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent cross-linking groups which combine two ligands, and represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group, and a ruthenium-containing group. , tin-containing groups, -O-, -CO-, -S-, -SO ₂ -, -Se-, -NR ¹ -, -PR ¹ -, -P(O)R ¹ -, -BR ¹ - Or -AlR ¹ -, R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the crosslinkable groups, at least one of them is a crosslinked group derived from a hydrocarbon group having 1 or more carbon atoms or a base containing ruthenium. Examples of such a crosslinking group include those shown in the following general formula (a).

(D is a group 14 element of the periodic table, and examples thereof include carbon, ruthenium, osmium, and tin. R ² and R ^{3 are} each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different and each other Binding can form a ring structure. e represents an integer from 1 to 4).

Specific examples of the structure represented by DR ² R ³ include a methyl group, an ethyl group, an ethylene group, a propylene group, an isopropylidene group, a cyclohexylene group, a 1,2-cyclodimethylene group, and a sub Vinyl (CH ₂ = C=), dimethyl decyl, diphenyl decyl, methyl phenyl decyl, dimethyl nonenyl, dimethyl titanium alkenyl, tetramethyl dinonyl, Diphenyldidecyl and the like. Among them, an ethyl group, an isopropylidene group, a tetramethyldidecyl group, and a dimethylalkyl group are preferred.

Specific examples of the transition metal compound represented by the general formula (I) include specific examples described in WO2008/066168. Further, it may be a similar compound of a metal element of another group. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

Among the transition metal compounds represented by the above general formula (I), a compound represented by the following general formula (II) is preferred.

In the above general formula (II), M represents a metal element of Groups 3 to 10 of the periodic table, and each of A ^1a and A ^2a represents a crosslinking group represented by the general formula (a) in the above general formula (I), and CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C(CH ₃ ) ₂ C, (CH ₃ ) ₂ Si, (CH ₃ ) ₂ Si(CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si is preferred. A ^1a and A ^2a may be the same or different from each other. R ⁴ to R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group or a hetero atom-containing group. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the ruthenium-containing group are the same as those described in the above general formula (I). Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, and 3,5-. Bis(trifluoro)phenyl, fluorobutyl, and the like. Examples of the hetero atom-containing group include a hetero atom-containing group having 1 to 20 carbon atoms, and specific examples thereof include a nitrogen group such as a dimethylamino group, a diethylamino group or a diphenylamino group; and a phenyl group; a sulfur-containing group such as a sulfide group or a methyl sulfide group; a phosphorus-containing group such as a dimethylphosphino group or a diphenylphosphino group; or an oxygen-containing group such as a methoxy group, an ethoxy group or a phenoxy group. Among them, R ⁴ and R ^{5 are} preferably a group having a hetero atom such as a halogen atom, oxygen or hydrazine, and a hydrocarbon having a carbon number of 1 to 20 having a high polymerization activity. Further, from the viewpoint of synthesizing the coordination space of the monomer, it is possible to synthesize a polymer having a balance between the binding ratio and the heat of fusion, and R ⁴ and R ⁵ have a heterostructure such as an isopropyl group or an isopentyl group. The base is good.

R ⁶ to R ^{13 are} preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as the general formula (I). q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the transition metal compounds represented by the above general formula (I), Specific examples of the transition metal compound of Group 4 of the periodic table include those described in WO2008/066168. Also, besides the 4th family A similar compound of the metal elements of other families. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

On the other hand, in the transition metal compound represented by the above formula (II), when R ⁵ is a hydrogen atom and R ^{4 is a} non-hydrogen atom, the transition metal compound of Group 4 of the periodic table may be as described in WO2008/066168. Specific examples. Further, it may be a similar compound of a metal element of a group other than Group 4. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

<(P-b) component>

The compound obtained by reacting the above (Pb) with a transition metal compound to form an ionic dislocation is obtained from the viewpoint of obtaining a relatively low molecular weight high-purity terminally unsaturated olefin polymer and high catalyst activity. A borate compound is preferred. Specific examples of the boric acid ester compound described in WO2008/066168 are mentioned. These may be used alone or in combination of two or more. When the molar ratio of the hydrogen to the transition metal compound (hydrogen/transition metal compound) is 0, dimethyl phenyl quinolate (pentafluorophenyl) borate, triphenyl carbon quinone (pentafluorophenyl) borate Preferably, hydrazine and hydrazine (perfluorophenyl)boronic acid methylaniline are preferred.

<(P-c) component>

The catalyst of the method for producing an α-olefin polymer used in the third invention may be combined with the component (Pa) and the component (Pb), and may be used as (Pc) in addition to the components (Pa) and (Pb). Ingredients Use an organoaluminum compound.

Examples of the organoaluminum compound as the component (Pc) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and dimethyl aluminum. Chloride, diethylaluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum Semi-chloride, etc. These organoaluminum compounds may be used alone or in combination of two or more.

Among them, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum is preferred, and triisobutyl aluminum is used. It is preferred that tri-n-hexyl aluminum and tri-n-octyl aluminum.

The amount of the component (Pa) is usually 0.1 × 10 ^-6 to 1.5 × 10 ^-5 mol / L, preferably 0.15 × 10 ^-6 to 1.3 × 10 ^-5 mol / L, more preferably 0.2 × 10 ^{- 6} ~ 1.2 × 10 ^-5 mol / L, particularly preferably 0.3 × 10 ^-6 ~ 1.0 × 10 ^-5 mol / L. When the amount of the component (Pa) is 0.1 × 10 ^-6 mol/L or more, the catalyst activity can be sufficiently exhibited, and when it is 1.5 × 10 ^-5 mol/L or less, the heat of polymerization can be easily removed.

When the ratio (P-a)/(P-b) of the component (P-a) to the component (P-b) is expressed by the molar ratio, it is preferably from 10/1 to 1/100, more preferably from 2/1 to 1/10. When (P-a)/(P-b) is in the range of 10/1 to 1/100, the effect as a catalyst can be obtained, and the catalyst cost per unit mass of the polymer can be suppressed. Further, there is a concern that a large amount of boron is present in the target α-olefin polymer.

When the ratio of use of (P-a) component to (P-c) component (P-a)/(P-c) is expressed by molar ratio, it is preferably 1/1 to 1/10000, preferably 1/5~. 1/2000, more preferably 1/10~1/1000. By using the (P-c) component, the polymerization activity per transition metal can be improved. If (Pa)/(Pc) is in the range of 1/1 to 1/10000, the balance between the addition effect of the (Pc) component and the economy will be good, and the amount of aluminum present in the target-free α-olefin polymer will be present. Concerns.

Method for producing α-olefin polymer used in the third invention In the above, the (P-a) component and the (P-b) component or the (P-a) component, the (P-b) component, and the (P-c) component can be used for preliminary contact. The preliminary contact can be carried out by bringing the (P-a) component into contact with the component (P-b), for example, and the method is not particularly limited, and a known method can be used. By such preparatory contact, it is effective in reducing the activity of the catalyst or reducing the catalyst cost such as a decrease in the use ratio of the (P-b) component of the catalyst.

The α-olefin polymer used in the third invention may be The α-olefin polymer (hereinafter referred to as "raw material α-olefin polymer (I)") obtained by the above production method is used as a raw material, and further contains an α-olefin polymer obtained by a thermal decomposition reaction or a radical decomposition reaction (hereinafter referred to as It is "raw material α-olefin polymer (II)"). By the thermal decomposition reaction or the radical decomposition reaction, the number of terminal unsaturated groups per molecule can be increased.

The thermal decomposition reaction is to add the raw material α-olefin polymer (I) The heat treatment is carried out, and the heating temperature can be adjusted according to the molecular weight of the target, and the experimental results are performed in advance, preferably 300 to 400 ° C, more preferably 310 to 390 ° C. When the heating temperature is less than 300 ° C, there is a concern that the thermal decomposition reaction cannot be carried out. On the other hand, when the heating temperature exceeds 400 ° C, there is a concern that the obtained raw material α-olefin polymer (II) is deteriorated.

Further, the thermal decomposition time (heat treatment time) is preferably from 30 minutes to 10 hours, more preferably from 60 to 240 minutes. If the thermal decomposition time is less than 30 minutes, the amount of the raw material α-olefin polymer (II) produced may be too small. On the other hand, when the thermal decomposition time exceeds 10 hours, the obtained raw material α-olefin polymer (II) may be deteriorated.

The above thermal decomposition reaction, for example, is used as a thermal decomposition device A reaction vessel such as stainless steel, which is equipped with a stirring device, is filled with an inert gas such as nitrogen or argon, placed in the raw material α-olefin polymer (I), and then heated and melted to foam the molten polymer phase with an inert gas. Thereafter, the volatile product is removed and heated at a predetermined temperature for a predetermined period of time.

The free radical decomposition reaction can be carried out at a temperature of 160 to 300 ° C. The organic peroxide is added in an amount of 0.05 to 2.0% by mass based on the raw material α-olefin polymer (I).

The above decomposition temperature is preferably from 170 to 290 ° C, more preferably from 180 to 280 ° C. If the decomposition temperature is less than 160 ° C, there is a concern that the decomposition reaction cannot proceed. On the other hand, when the decomposition temperature exceeds 300 ° C, the decomposition proceeds intensely, and the decomposition of the organic peroxide is sufficiently completed before the homogeneous diffusion in the molten polymer, and there is a concern that the yield is lowered.

Of the organic peroxide to be added, preferably 1 minute An organic peroxide having a half-life temperature of 140 to 270 ° C, and specific examples of the organic peroxide include the following compounds: diisobutylphosphonium peroxide, cumene peroxypoxylate, and di-n -propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate , t-hexyl peroxy neodecanoate, t-butyl peroxy neoheptanoate, t-hexyl peroxy valerate, t-butyl peroxy valerate, di(3,5,5-three Methylhexyl) peroxide, dilaurate peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2, 5-bis(2-ethylhexylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, bis(4-methylbenzylidene) peroxide, t- Butylperoxy-2-ethylhexanoate, bis(3-methylbenzhydryl) peroxide, benzhydryl peroxide, 1,1-di(t-butylperoxy) 2-methylcyclohexane, 1,1-di(t-hexylpropylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexyl Oxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-(t-butylperoxy)cyclohexyl)propane , t-hexylperoxyisopropyl monocarbonate, t-butyl peroxy maleate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl Oxidized laurel Acid ester, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 3,5-di-methyl- 2,5-bis(benzimidylperoxy)hexane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butyl Oxidized benzoate, n-butyl 4,4-di-(t-butylperoxy)valerate, bis(2-t-butylperoxyisopropyl)benzoate, peroxidation Diisopropylbenzene, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumene peroxide, Di-t-butyl peroxide, p-Menthans hydrogen peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene Hydrogen peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide.

The amount of the organic peroxide added is preferably the raw material α-ene The hydrocarbon polymer (I) is 0.1 to 1.8% by mass, more preferably 0.2 to 1.7% by mass. When the amount added is less than 0.05% by mass, the decomposition reaction rate becomes slow, and there is a concern that the production efficiency is deteriorated. On the other hand, when the amount added exceeds 2.0% by mass, there is a concern that the odor caused by the decomposition of the organic peroxide becomes a problem.

The decomposition time of the decomposition reaction, for example, 30 seconds to 10 hours, It is preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, the decomposition reaction is not sufficiently carried out, and there is a concern that a large amount of undecomposed organic peroxide remains. On the other hand, when the decomposition time exceeds 10 hours, the progress of the crosslinking reaction of the side reaction may become a problem, or the obtained α-olefin polymer (II) may become yellow.

Free radical decomposition reaction, for example, by batch method Decomposition and implementation by any method of decomposition by a melt continuous process.

When the radical decomposition reaction is carried out by a batch method, an inert gas such as nitrogen or argon is filled in a reaction vessel such as stainless steel equipped with a stirring device, and the α-olefin polymer (I) of the raw material is placed in a heating bath to be heated and melted. The organic oxide is dropped into the molten raw material α-olefin polymer (1), and heated at a predetermined temperature for a predetermined period of time to carry out a radical thermal decomposition reaction. The dropping of the above organic peroxide may be carried out by dropping in the range of the above decomposition time, and the dropping may be either continuous dropping or batch dropping. Moreover, the reaction time from the end of the dropping time is set as the range of the above reaction time. It is better inside.

Organic peroxide can be used as a solution dissolved in a solvent under.

The solvent is preferably a hydrocarbon solvent, and specific examples thereof include aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, hexadecane, and nonadecane; methylcyclopentane; An alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, cyclooctane or cyclododecane; and an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene or trimethylbenzene. Among these solvents, a solvent having a boiling point of 100 ° C or higher is also preferred.

Further, the raw material α-olefin polymer (I) can be dissolved during decomposition. In the solvent. The decomposition temperature at which the raw material α-olefin polymer (I) is dissolved in a solvent to be decomposed is generally in the range of 100 to 250 ° C, preferably in the range of 120 to 200 ° C.

When the radical decomposition reaction is carried out by the melt continuous method, The reaction time in the average residence time, for example, 20 seconds to 10 minutes. The melt continuous method is compared with the batch method to make the mixed state good and the reaction time can be shortened.

The apparatus may use a single-axis or two-axis melt extruder, preferably an extruder having an injection port during the barreling process and capable of degassing under reduced pressure, which is an extruder having an L/D=10 or more.

Free radical decomposition reaction by melt continuous method The apparatus may be a method in which an organic peroxide is impregnated with a raw material α-olefin polymer (I), or a method in which a raw material α-olefin polymer (I) and an organic peroxide are separately supplied and mixed.

Organic peroxide to raw material α-olefin polymer (I) In particular, the organic peroxide is added to the raw material α-olefin polymer (I) in the presence of an inert gas such as nitrogen, and is uniformly absorbed in the raw material particles after stirring at a temperature of from room temperature to 40 ° C. And impregnated. The obtained raw material α-olefin polymer (I) impregnated with an organic peroxide (hereinafter referred to as "dip particles") is decomposed by melt extrusion, or the impregnated particles are added as a master batch to the raw material α-olefin polymer. (I) and decomposed to obtain a terminally unsaturated ?-olefin polymer (II).

Further, when the organic peroxide is a solid or an organic peroxide having low solubility to the raw material α-olefin polymer (I), the solution of the organic peroxide in the hydrocarbon solvent may be absorbed and impregnated with the raw material α- Olefin polymer (I).

Raw material α-olefin polymer (I) and organic peroxide The mixture is not supplied, and the raw material α-olefin polymer and the organic peroxide are supplied to the hopper portion at a constant flow rate, or may be supplied at a constant flow rate during the barreling of the organic peroxide.

[Method for Producing Functionalized α-Olefin Polymer]

The functionalized α-olefin polymer of the third invention can be produced by reacting the above α-olefin polymer with a ruthenium compound having a hydrogen-hydrazine bond.

(矽 compound with hydrogen-矽 bond)

As the hydrazine compound having a hydrogen-hydrazine bond, a compound known in the past can be used without particular limitation, and an organic decane or an organic decane is preferable.

The organodecane is preferably represented by the following formula (1).

(wherein R ²¹ to R ²³ each independently represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon; 1 to 20 alkenyl groups, substituted or unsubstituted alkenyloxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 24 carbon atoms, substituted or unsubstituted carbon groups of 6 to 24 Alkoxy, substituted or unsubstituted decyloxy, substituted or unsubstituted anthracenyl, or substituted or unsubstituted methoxyalkyloxy).

The substituent in the above R ²¹ to R ²³ is preferably a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or a decyl group. .

Specific examples of the above organic decane include trimethoxy Alkoxy decanes such as decane, triethoxy decane, dimethoxymethyl decane, methoxy dimethyl decane, dimethoxyphenyl decane, trichloro decane, methyl dichloro decane, a halogenated decane such as methyl chlorodecane or trimethylmethane alkoxydioxane; a decyloxy decane such as methyldiethoxy decane or trimethylmethane alkoxymethyl ethoxy decane; Dimethylnonane or trimethylmethaneoxymethyl decane is equivalent to an alkenyloxy hydrazine such as a hydrohalo group having two or more Si-H bonds in the molecule or a methyl di(isopropenyloxy)decane. Alkane, etc., among them, methyl dichlorodecane, dimethoxymethyl decane, diethoxymethyl decane, trimethoxy decane, triethoxy decane, etc., preferably trimethoxy decane An alkoxy decane such as triethoxy decane or dimethoxymethyl decane is particularly preferred.

On the other hand, as the above organic decane, 1,1,3,3-tetramethyldioxane, 1,3,5-trimethylcyclotrioxane, 1,3,3,5 are used. 5,7,7-heptamethyl-1,1-dimethoxytetraoxane or the like is preferred.

For α-olefin polymers and ruthenium compounds having hydrogen-hydrazine bonds For the reaction, it is important to set the reaction temperature to 10 to 200 °C. When the reaction temperature is set to 10 ° C or more, the viscosity of the polymer can be lowered to an appropriate region, and at the same time, the shortening of the reaction time can be made possible. On the other hand, when the reaction temperature is high, the viscosity of the component polymer is preferably low, but when the reaction temperature is excessively increased, the main chain of the component polymer is cut. The above reaction temperature is preferably from 20 to 180 ° C, particularly preferably from 20 to 100 ° C.

The reaction time in the above reaction is preferably from 0.5 to 20 hours, preferably from 1 to 10 hours.

The ratio of the ruthenium compound to the α-olefin polymer described later is preferably from 1 to 20, more preferably from 1 to 10, in terms of the oxime compound/α-olefin polymer molar ratio.

Further, the reaction between the α-olefin polymer and the hydrazine compound having a hydrogen-hydrazine bond may be diluted with a hydrocarbon solvent or the like. By diluting, the viscosity at room temperature can be further lowered, and the efficiency of the reaction can be made and the reaction time can be shortened. In the case of diluting with a solvent, the total amount of the α-olefin polymer and the ruthenium compound having a hydrogen-hydrazine bond is 50% by mass or less from the viewpoint of VOC measures and the like. Preferably, it is preferably 30% by mass or less, and more preferably 10% by mass or less.

[sclerosing composition]

The curable composition of the third invention preferably contains (A) the functionalized α-olefin polymer and (B) a curing-promoting catalyst, and further contains (C) an adhesion-imparting agent and a (D) diluent.

(B) Hardening promoting catalyst

Examples of the curing-promoting catalyst used in the third invention include an organic metal catalyst, a tertiary amine, and the like.

Examples of the organic metal include an organotin metal compound such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate or tin octylate, lead octenoate or lead naphthenate.

Examples of the tertiary amines include N-triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl)ether, N,N,N',N",N",N. "-pentamethyldiethylideneamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N-methyl-N' An dimethylamine ethylpiperazine or an imidazole compound of an imidazole ring substituted with a cyanoethyl group of a second-order amine functional group.

These catalysts may be used alone or in combination of two or more. Particularly preferred among the above catalysts are dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctanoate.

(B) The content of the curing-promoting catalyst in the curable composition of the third invention is 100% by mass of the curable composition of the third invention, Generally, it is 0.005 to 2.0% by mass, preferably 0.01 to 0.5% by mass.

(C) Adhesive imparting agent

As the adhesion-imparting agent (adhesive-imparting resin), rosin and its derivatives, terpene-based resin and hydrogenated resin, styrene-based resin, coumarone-indene resin, and dicyclopentadiene (DCPD) resin can be used. And hydrogenated resin, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9 copolymerized petroleum resin and hydrogenated thereof Among the adhesion-imparting agents which are generally used, such as a resin, a compatibility with a functionalized α-olefin polymer is selected. One type of these adhesiveness-imparting resins may be used alone or two or more types may be used as a mixture.

The preferred adhesion imparting agent is selected from the group consisting of terpene resins and hydrogenated resins, styrene resins, and dicyclopentane from the viewpoint of balance between removability and adhesion to curved surfaces and irregularities. Alkene (DCPD) resin and its hydrogenated resin, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9 system One type of resin or a mixture of two or more types of the group of the polymerized petroleum resin and the hydrogenated resin is preferred.

The content of the (C) adhesiveness imparting agent in the curable composition of the third invention is generally 1 to 50% by mass, preferably 2 to 45% by mass based on 100% by mass of the curable composition of the third invention. %.

(D) thinner

Examples of the diluent include oils such as naphthenic oils, paraffinic oils, and aromatic oils, and oils thereof, and liquid rubbers such as liquid polybutene and liquid isopolybutene. These may be used alone or in combination of two or more.

The content of the (D) diluent in the curable composition of the third invention is generally from 1 to 50% by mass, preferably from 2 to 40% by mass, based on 100% by mass of the curable composition of the third invention.

(other ingredients)

The curable composition of the third invention may contain an additive such as a filler, a pigment or an antioxidant within a range that does not impair the effects of the third invention.

The filler contains an inorganic filler and an organic filler.

Examples of the inorganic filler include cerium oxide, aluminum oxide, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, cerium oxide, ferrite, calcium hydroxide, magnesium hydroxide, and hydrogen. Alumina, basic magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium citrate, talc, clay, mica, montmorillonite, bentonite, sepiolite, Igne vermiculite, sericite, glass fiber, glass beads, cerium oxide system, barium, aluminum nitride, boron nitride, tantalum nitride, carbon black, graphite, carbon fiber, carbon bar, zinc borate, various magnetic powders Wait.

An inorganic filler may be used instead of the inorganic filler, or a surface treatment may be carried out by various coupling agents such as a decane-based or titanate-based compound. Examples of the treatment method include a method in which an inorganic filler is directly treated with various coupling agents such as a dry method, a slurry method, or a spray method, or a collective method such as a direct method or a master batch method. Mixing method, or dry concentration method.

Examples of the organic filler include starch (for example, powdered starch), fibrous leather, natural organic fiber (for example, cellulose such as cotton or hemp), and synthetic polymers such as nylon, polyester, and polyolefin. Synthetic fibers and the like.

Among the above pigments, there are inorganic pigments and organic pigments (for example, azo-based pigments and polycyclic pigments).

Examples of the inorganic pigment include oxides (titanium dioxide, zinc oxide (zinc oxide), iron oxide, chromium oxide, iron black, cobalt blue, etc., and examples of the hydroxides include hydrated alumina, iron oxide yellow, and chrome green. Etc.), sulfide (zinc sulfide, zinc antimony white, cadmium yellow, vermilion, cadmium red, etc.), chromate (yellow lead, molybdenum orange, zinc chromate, strontium chromate, etc.), citrate (white carbon, Clay, talc, ultramarine, etc.), sulfate (precipitated barium sulfate, barite powder, etc., as carbonate: calcium carbonate, lead white, etc.), in addition to ferricyanide (iron blue), phosphate (manganese violet), carbon (carbon black), and the like.

Examples of the azo-based pigment of the organic pigment include soluble azo (carmine 6B, lake red C, etc.), insoluble azo (disazo yellow, lake red 4R, etc.), and condensed azo (dyeing yellow 3G, Dyeing magenta RN, etc.), azo wrong salt (nickel azo yellow, etc.), benzimidazolone azo (permanent orange HL, etc.). Examples of the polycyclic type pigment of the organic pigment include isoindolinone, isoporphyrin, quinophthalone, pyrazolone, anthraquinone yellow, anthracene, diketone-pyrrolo-pyrrole, and pyrrole. , pyrazolone, anthrone, purple ring ketone, hydrazine, quinacridone, anthracene, oxazine, imidazolinone, xanthene, normal carbon, purpurin, phthalocyanine, nitroso and the like.

The curable composition of the third invention can be produced by mixing the above components by any method.

(B) The hardening promoting catalyst can be used after mixing. (B) The method of adding the hardening-promoting catalyst is to pre-modulate the catalyst masterbatch with a high concentration (B) hardening-promoting catalyst, blending the catalyst masterbatch with other components, and then kneading or melting. .

Further, the curable composition of the third invention can be produced using a solvent.

When the curable composition of the third aspect of the invention is used as a solvent-based adhesive dissolved in a solvent, it can be applied and sprayed, and then formed on the surface of the substrate to be adhered to the object.

Moreover, when the composition of the third invention is dispersed or emulsified in a polar solvent such as water, it can also be used as an adhesive. Further, the composition of the third invention is formed into a sheet shape or a film shape, sandwiched between the substrates, heated to a temperature at which the adhesive agent can flow, and then cured by cooling and solidification.

[hardened matter]

The third invention further provides a cured product which hardens the above hardenable composition.

The curable composition of the third invention can be subjected to a hardening reaction at a low temperature. Specifically, when the curable composition of the third invention is subjected to a curing reaction at 100 ° C or lower, a cured product can be obtained. The hardening reaction is carried out by contact with moisture or moisture, followed by heat treatment or ripening at room temperature. When moisture or moisture is brought into contact, for example, the curable adhesive composition of the third invention may be placed in the air, and may be immersed in a water tank to introduce steam. Again, warm The degree can be room temperature (25 ° C), but if set to a high temperature, crosslinking can be carried out in a short time.

The hardenable composition of the third invention can be used for the phase of the resin Emulsifier, polyolefin emulsification, reactive adhesive, reactive hot melt adhesive, other adhesives, adhesives, sealing materials, sealing materials, potting materials, reactive plasticizers, modifiers, etc.

The cured product of the third invention can be used for a reactive adhesive, a reactive hot melt adhesive, other adhesives, an adhesive, a sealing material, a sealing material, a potting material, a reactive plasticizer, a modifier, and the like. . Further, since the cured product obtained by the above curing method has heat resistance, it can be used even in a high temperature environment.

<Fourth invention> [Functionalized α-olefin polymer]

The functionalized α-olefin polymer of the fourth invention has (anhydrous) carboxylic acid residue at the end of the α-olefin polymer and satisfies the following (1) to (6).

(1) The weight average molecular weight (Mw) is 1,000 to 500,000.

(2) The molecular weight distribution (Mw/Mn) is 4.5 or less.

(3) The melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) is 50 J/g or less.

(4) The aforementioned α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, a propylene-1-butene copolymer, a propylene-diene copolymer or a 1-butene-diene copolymer.

(5) The number of (anhydrous) carboxylic acid residues per molecule is 0.5 to 2.5 One.

(6) The number of internal carboxylic acid residues per one molecule (anhydrous) - the number of internal double bonds is 0.5 to 2.5.

(a) (anhydrous) carboxylic acid residue

In the functionalized α-olefin polymer of the fourth invention, as described above, the number of terminal (anhydrous) carboxylic acid residues per molecule is 0.5 to 2.5, and when used as a compatibilizing agent, 0.5 to 1.5 are used. Preferably, 0.8 to 1.2 is preferred, and when used in an adhesive or sealing material, the hardening property is important. From the viewpoint of obtaining a crosslinked structure, it is preferably 1.2 to 2.5, and 1.5. ~2.1 are better. When the number of terminal (anhydrous) carboxylic acid residues per molecule is less than 0.5, cross-linking hardening reaction with a crosslinking agent does not occur, and when it exceeds 2.5, cross-linking of a cured product obtained by using a crosslinking agent The molecular weight between the two becomes small, and a cured product showing rubber elasticity cannot be obtained.

The functionalized α-olefin polymer of the fourth invention can be produced by reacting an α-olefin polymer having a carbon-carbon double bond at the end of the main chain with an unsaturated (anhydrous) carboxylic acid olefin. The functionalized α-olefin polymer of the fourth invention obtained by the reaction has an (anhydrous) carboxylic acid residue at a single terminal or both ends of the main chain, so that the number of (anhydrous) carboxylic acid residues can be controlled. It is easy to carry out by controlling the number of terminal unsaturation groups of the α-olefin polymer of the raw material.

The terminal (anhydrous) carboxylic acid residue is not particularly limited as long as it is a substituent obtained by removing one hydrogen atom from a carboxylic acid or an anhydrous carboxylic acid, and is a residue of a (carboxylic acid) having 1 to 20 carbon atoms. The base is better, with the carbon number 1~10 as the comparison Preferably, it is more preferably 1 to 5 carbon atoms, and specific examples thereof include a propionic acid residue, a butyric acid residue or an (anhydrous) succinic acid residue.

The number of (anhydrous) carboxylic acid residues per molecule described above can be determined by the measurement method shown below.

The blend of the pre-modified α-olefin polymer and the unsaturated (anhydrous) carboxylic acid was subjected to infrared spectrometry (IR) using a 0.1 mm interval and applied by a carbonyl group (1700 to 1800 cm ^-1 ) having a characteristic oxime. The amount of absorption is compared with the amount of the unsaturated (anhydrous) carboxylic acid, and the IR measurement of the pressure-applying plate of the functionalized α-olefin polymer to be measured is performed, and each molecule is identified by the following formula. The number of (anhydrous) carboxylic acid residues.

Number of (anhydrous) carboxylic acid residues per molecule = [(anhydrous carboxylic acid residue concentration] / 100 × Mn / molecular weight of the monomer (unit)

Average molecular weight (Mm) of monomer units = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11

Number average molecular weight (Mn): number average molecular weight determined by gel permeation chromatography (GPC)

(anhydrous) carboxylic acid residue concentration: IR measurement of a pressure-sensitive adhesive plate of a functionalized α-olefin polymer to be measured, and calculation of (anhydrous) carboxylic acid residue by a relationship between a calibration curve and an absorption amount of 1700 to 1800 cm ^-1 The concentration of the base.

As the measuring instrument used for the above-described IR measurement, for example, "FT/IR-5300" manufactured by JASCO Corporation can be used.

Further, the phrase "having an (anhydrous) carboxylic acid residue at the terminal" means that the (anhydrous) carboxylic acid residue is based on the polymer main chain terminal (at least one end of the polymer main chain, preferably a polymer main chain). Both ends). Specifically, the peak of 1700 to 1750 cm ^{-1 was} observed by infrared absorption spectroscopy (IR), and it was found to have 4.85 to 5.50 ppm of a terminal (anhydrous) carboxylic acid residue-internal double bond structure for ¹ H-NMR measurement. crest.

The functionalized α-olefin polymer of the fourth invention has an advantage of improving the hardening efficiency in the curing reaction because it has an (anhydrous) carboxylic acid residue at the terminal. When the (anhydrous) carboxylic acid residue is present in the interior (side chain) of the polymer other than the end of the polymer, the number of (anhydrous) carboxylic acid residues per molecule may exceed 2.5, which results in cross-linking. When the cross-linking molecular weight (molecular weight between the cross-linking point and the cross-linking point) is decreased, the original properties of the polymer itself cannot be maintained, and the cured product after cross-linking becomes brittle. Further, when the (anhydrous) carboxylic acid residue is present at the terminal end, it is likely to come into contact with the crosslinking agent when it is cross-linked and hardened with the crosslinking agent, and has an advantage that the curing rate and the curing efficiency can be further improved.

(b) Melting heat absorption △H-D

The functionalized α-olefin polymer used in the fourth invention has a heat absorption ΔHD of 50 J/g or less as measured by a differential scanning calorimeter (DSC), preferably 30 J/g or less, and 10 J/g or less. It is preferred, and it is particularly preferable to be 1 J/g or less. When the melting heat absorption ΔH-D exceeds 50 J/g, the crystallinity component increases, and the fluidity at a relatively low temperature deteriorates, which causes a problem from the viewpoint of energy saving or safety environment at the time of construction.

Further, ΔH-D was determined by DSC measurement. In other words, a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.) was used, and 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the heat of melting was obtained at a temperature of 10 ° C /min. △ HD.

In order to control the melting heat absorption below 50 J/g, the meso-penta-unit (mmmm) fraction of the stereoregularity index must be controlled to be less than 80 mol%, which can be controlled by the structure or polymerization conditions of the main catalyst. . For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and the heat of fusion is more than 50 J/g. In the case of a meso-type structure, it is easy to obtain a polymer having a low regularity, and the heat of fusion may be 50 J/g or less, and it is difficult to synthesize a polymer having a balance between the binding ratio and the heat of fusion. For example, by using a double crosslinked catalyst as described later, the coordination space of the monomer is controlled, so that the synthesis of the polymer having a balance between the binding ratio and the melting endotherm becomes possible.

(c) stereoregularity

The functionalized α-olefin polymer of the fourth invention is a meso-penta unit [mmmm] when it has an (anhydrous) carboxylic acid residue at the end of the propylene homopolymer main chain or at the end of the 1-butene homopolymer main chain. The fraction is preferably less than 80% by mole, preferably less than 60% by mole, preferably less than 40% by mole, and less than 20% by mole.

On the other hand, at the end of the main chain of the propylene-1-butene copolymer When the (anhydrous) carboxylic acid residue is used, the meso-diad fraction [m] is preferably 30 to 95 mol%, and 30 to 80 mol% is preferred, and 40~ 80% of the moles are better.

Control the meso-penta-unit [mmmm] fraction to a lower value, or control the meso-diad fraction [m] to a moderate degree, by making it low-regular and completely amorphous. It is possible to carry out the treatment at room temperature and to perform hardening at a lower temperature. Therefore, in the field of sealing and reactivity which has been difficult to use in the past, it is particularly possible to use it in the field of adhesion to a polyolefin-based substrate.

The control of the meso-penta-unit (mmmm) fraction and the meso-diad fraction [m] is controlled by the structure or polymerization conditions of the main catalyst, for example, by the structure of the catalyst. The space of the metal coordination monomer at the catalyst center must be designed to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and if it is a meso-type structure, it becomes easy to obtain a rule. Low polymer.

The 2,1-binding fraction of the functionalized α-olefin polymer of the fourth invention is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, still more preferably less than 0.2 mol%.

The control of the 2,1-binding fraction is carried out by controlling the 2,1-binding fraction in the α-olefin polymer used as a raw material to be described later.

In the functionalized α-olefin polymer of the fourth invention, the total of the 1,3-binding fraction and the 1,4-binding fraction is preferably less than 0.5 mol%, preferably less than 0.4 mol%, more preferably Jia Wei Da 0.1 Mole%.

The above "the total of the 1,3-binding fraction and the 1,4-bonding fraction" is that the functionalized α-olefin polymer of the fourth invention has a propylene homopolymer main chain and represents a 1,3-binding component. The ratio, which has a butene homopolymer backbone, represents a 1,4-binding fraction, and when it has a propylene-1-butene copolymer backbone, it represents a 1,3-binding fraction and a 1,4-binding fraction. total.

The control of the 1,3-binding fraction and the 1,4-binding fraction is controlled by using a 1,3-binding fraction and a 1,4-binding fraction in an α-olefin polymer as a raw material. Controlled.

In the fourth invention, the meso-penta-unit [mmmm] fraction and the meso-diad fraction are reported by the magazine "Polymer Journal, 16, 717 (1984)" by the Asakura, by J. "Ranall's report "Macromol. Chem. Phys., C29, 201 (1989)" and by V. Busico's report "Macromol. Chem. Phys., 198, 1257 (1997)" The method of the proposal is obtained. That is, ¹³ C NMR spectroscopy was used to measure the methyl and methine signals, and the meso-penta-unit (mmmm) fraction, the outer-rotator pentad fraction, and the internal rotation in the polymer linkage were determined. Meso-diad fraction [m], racemo-diad fraction [r], 1,3-binding fraction, 1,4-binding fraction and 2,1- Combine the rate.

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: mixed solvent of 1,2,4-trichlorobenzene and heavy benzene of 90:10 (capacity ratio)

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

(d) Weight average molecular weight. The molecular weight distribution

The functionalized α-olefin polymer of the fourth invention has a weight average molecular weight of 1,000 to 500,000 from the viewpoint of fluidity, preferably 4,000 to 50,000, preferably 5,000 to 40,000, and 5,000 to 30,000. Very good. From the viewpoint of durability such as adhesion strength after hardening or difficulty in peeling off, the larger the molecular weight, the better.

The functionalized α-olefin polymer of the fourth invention preferably has a molecular weight distribution (Mw/Mn) of less than 4.5 and a preference of 1.4 to 3.0, and 1.6 to 1.6, from the viewpoint of reactivity and reaction hardenability. 2.5 is better.

Further, 'the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those in terms of polystyrene measured by the following apparatus and conditions, and the molecular weight distribution (Mw/Mn) is obtained by these weight average molecular weights (Mw) and The value calculated from the number average molecular weight (Mn).

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0 ml / min

Sample concentration: 2.2 mg / ml

Injection volume: 160 microliters

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

(e) B viscosity

The functionalized α-olefin polymer of the fourth invention has a viscosity (fluidity) of 5000 mPa at 30 ° C from the viewpoints of reactivity, workability at room temperature, and the like. The following is better, at 2000mPa. The following is preferred.

Here, the above B viscosity means that it is measured in accordance with ASTM-D19860-91.

(f) terminal (anhydrous) carboxylic acid residue - internal double bond structure

The functionalized α-olefin polymer of the fourth invention is produced by reacting an α-olefin polymer having a carbon-carbon double bond at the end of the main chain with an unsaturated (anhydrous) carboxylic acid olefin as described later. The functionalized α-olefin polymer of the fourth invention obtained by this reaction is formed by a terminal (anhydrous) carboxylic acid residue-internal double bond structure. The number of the internal double bonds is 0.5 to 2.5 per molecule, and when it is used as a compatibilizing agent, it is preferably 0.5 to 1.5, preferably 0.8 to 1.2, and is used for adhesion. Agent or sealant When it is 1.2 to 2.5, it is better, and 1.5 to 2.1 is better.

The number of internal double bonds per molecule described above can be determined by the measurement method shown below.

First, the resulting (4.8) to 5.50 ppm of the terminal (anhydrous) carboxylic acid residue-hydrogen atom of the internal double bond in the internal double bond structure, and the α-olefin main at 0.70 to 1.80 ppm were measured by ¹ H-NMR. Based on the hydrogen atom of the chain, the number of terminal (anhydrous) carboxylic acid residues - internal double bond structure is calculated.

Terminal (anhydrous) carboxylic acid residue - CH(i) of internal double bond in internal double bond structure: integral value of 4.85~5.50ppm

Hydrogen atom of the α-olefin main chain (ii): integral value of 0.70 to 1.80 ppm

Average molecular weight (Mm) of monomer units = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11

Average hydrogen number of monomer units (Hnum) = propylene unit ratio × 6 + 1 - butene unit ratio × 8

Internal double bond concentration = [(i) / ((ii) / (Hnum))]

The concentration of the internal double bond (% by mole) calculated by the above method, and the number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and the average molecular weight of the monomer unit (Mm) The number of internal double bonds per molecule was calculated by the following formula.

Number of internal double bonds (number) = (Mn) / (Mm) × [concentration of internal double bonds]

[Method for Producing Functionalized α-Olefin Polymer]

The functionalized α-olefin polymer of the fourth invention is an α-olefin polymer having a carbon-carbon double bond at the end of the main chain and an unsaturated (anhydrous) carboxylic acid. It is obtained by the production method of the reaction. The α-olefin polymer used as a raw material is selected from the group consisting of a propylene homopolymer, a 1-butene polymer, and a diene copolymer. The 1-butene-based polymer is selected from the group consisting of a 1-butene homopolymer and a propylene-1-butene copolymer, and the diene-based copolymer is selected from the group consisting of a propylene-diene copolymer and a 1-butene-II. Ene copolymer.

(α-olefin polymer)

In the method for producing a functionalized α-olefin polymer according to the fourth aspect of the invention, the α-olefin polymer used as a raw material has the following characteristics (1′) to (5′) and has the following characteristics (6′) to (8). ') is better.

The (1') weight average molecular weight (Mw) is from 1,000 to 500,000.

The (2') molecular weight distribution (Mw/Mn) is 4.5 or less.

(3') The heat of fusion ΔH-D measured by a differential scanning calorimeter (DSC) is 50 J/g or less.

(4') The aforementioned α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, a propylene-1-butene copolymer, a propylene-diene copolymer or a 1-butene-diene copolymer.

(5') The number of terminal unsaturated groups per molecule is from 0.5 to 2.5.

(6')(6'-1) meso-diad fraction (m) of meso-diad fraction (m) with a fraction of less than 80 mol%, or (6'-2) It is 30~95% by mole.

The (7') 2,1-binding fraction was less than 0.5 mol%.

The total of the (8') 1,3-binding fraction and the 1,4-binding fraction was less than 0.5 mol%.

(1') weight average molecular weight (Mw)

The α-olefin polymer used in the fourth invention preferably has a weight average molecular weight of 1,000 to 500,000, and preferably 6,000 to 450,000, 8,000 to 300,000, 10,000 to 70,000, and 2,000 to 50,000, from the viewpoint of fluidity. It is preferably 3,000 to 20,000 and 5,000 to 20,000.

The details of the weight average molecular weight (Mw) of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(2') molecular weight distribution (Mw/Mn)

The α-olefin polymer used in the fourth invention has a molecular weight distribution (Mw/Mn) of 4.5 or less from the viewpoint of reactivity and reaction hardenability, preferably less than 4.5, and preferably 1.1 to 3.0. 1.4 to 3.0 is better, 1.4 to 2.6 is better, 1.4 to 2.2 is better, 1.6 to 2.1 is better, and 1.6 to 2.0 is the best.

The details of the molecular weight distribution (Mw/Mn) of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(3') melting heat absorption △H-D

The α-olefin polymer used in the fourth invention has a melting heat absorption ΔHD measured by a differential scanning calorimeter (DSC) of 50 J/g or less, which is less than 50 J/g, 40 J/g or less, and less than 40 J. /g, 30J/g or less, less than 30J/g, 15J/g or less, 10J/g or less, less than 10J/g, 1.0J/g The order of less than 1.0 J/g, less than 0.5 J/g, less than 0.2 J/g, and 0 J/g is preferred.

The details of the melting heat absorption ΔH-D of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(4') α-olefin polymer

The α-olefin polymer used in the fourth invention is a propylene homopolymer, a 1-butene homopolymer, a propylene-1-butene copolymer, a propylene-diene copolymer or a 1-butene-diene copolymer. .

In the case of a propylene-1-butene copolymer, the structural unit derived from propylene is preferably 10 mol% or more, and more preferably 20 mol% or more.

In the case of the propylene-diene copolymer, the structural unit derived from propylene is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.

In the case of a 1-butene-diene copolymer, the structural unit derived from 1-butene is preferably 70 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more. good.

Among them, a propylene homopolymer and a 1-butene homopolymer are preferred from the viewpoint of compatibility when used as a binder composition or adhesion strength to a substrate.

(5') Number of unsaturation groups per one molecule

In the case of the diene polymer used in the α-olefin polymer used in the fourth invention, the number of terminal unsaturated groups per molecule is from 0.5 to 2.5. Further, even if the α-olefin polymer is a propylene homopolymer or a 1-butene polymer In any of the diene copolymers, the number of terminal unsaturated groups per molecule is preferably from 0.5 to 2.5, preferably from 0.7 to 2.5, and more preferably from 0.7 to 2.3. 0.8 to 2.1 are particularly preferred. When used as a compatibilizing agent, the number of ruthenium-containing groups per molecule is preferably 0.5 to 1.5, and 0.5 to 1.0 is preferred, and 1.1 to 1.1. 1.5 is better, 0.8 to 1.2 is the best, 1.1 to 1.2 is the best, and when used in adhesives or sealing materials, it is better to use 1.2 or more, more than 1.5 The better.

The number of unsaturation groups per molecule is only 2.0 at the end of the main chain, and when 2.0 or more, it is possible to control each molecule by introducing an unsaturated group at the end of the side chain by copolymerizing a diene or the like. The number of ends is not saturated.

The number of unsaturation groups per one molecule can be controlled by the structure of the main catalyst, the type of the monomer or the polymerization conditions (polymerization temperature, hydrogen concentration, etc.).

The number of terminal unsaturation groups per molecule can be controlled by selecting the molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) in the presence of a catalyst.

For example, it can be obtained by carrying out a polymerization reaction in a range of 0 to 5000 in terms of a molar ratio of hydrogen to a transition metal compound (hydrogen/transition metal compound). In order to increase the selectivity of terminal unsaturation and the activity of the catalyst, it is preferred to carry out the polymerization in the presence of a trace amount of hydrogen.

Hydrogen is generally known as a chain shifting agent, and the end of the polymer chain becomes a saturated structure. In addition, it also has the function of reactivation of the temporary break and the activity of the catalyst. Although the effect of the trace hydrogen performance of the catalyst is unknown Indeed, when hydrogen is used in a specific range, the terminal unsaturation group is highly selective and highly active.

The molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) is preferably from 200 to 4,500, more preferably from 300 to 4,000, most preferably from 400 to 3,000. When the molar ratio is 5,000 or less, the formation of an α-olefin polymer having an extremely low number of terminal unsaturated groups can be suppressed, and an α-olefin polymer having a desired number of terminal unsaturated groups can be obtained.

Further, examples of the terminal unsaturated group include a vinyl group, a vinylidene group, and a trans(acetylene) group. However, the terminal unsaturated group as defined in the specification means a vinyl group and a vinylidene group. Vinyl and vinylidene are radically polymerizable, and various reactions are applicable to a wide range of applications.

The terminal unsaturated group concentration and the terminal unsaturation group in the α-olefin polymer used in the fourth invention represent the total concentration and number of vinyl and vinylidene groups. When only a vinyl group is present, it means only the concentration and number of vinyl groups, and when both vinyl and vinylidene are contained, the concentration and number of both sides are shown.

The terminal unsaturated group concentration or the number of terminal unsaturated groups per molecule can be determined by ¹ H-NMR measurement. Specifically, the terminal vinylidene group obtained by δ4.8 to 4.6 (2H) and the terminal vinyl group appearing at δ5.9 to 5.7 (1H) and δ1.05 were obtained by ¹ H-NMR measurement. The methyl group appearing at ~0.60 (3H) is used as the standard, and the terminal unsaturated group concentration (C) (% by mole) is calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturation concentration = [vinylidene amount] + [vinyl amount]

The terminal unsaturated group concentration (C, mol %) calculated by the above method and the number average molecular weight (Mn) and the monomer molecular weight (M) obtained by gel permeation chromatography (GPC) are The equation can calculate the number of unsaturation groups at the end of each molecule.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

(6'-1) meso-penta unit [mmmm] fraction

When the α-olefin polymer used in the fourth invention is a propylene homopolymer or a 1-butene homopolymer, the meso-penta-unit [mmmm] fraction is preferably less than 80 mol%, and is not Up to 60% by mole is preferred, less than 40% by mole is better, and less than 20% by mole is particularly good. And more than 1 mol% and less than 20 mol%, more than 1 mol% and less than 15 mol%, more than 2 mol% and less than 15 mol%, more than 2 mol% and less than 10 mo Ear %, more than 3 mole % and less than 10 mole % is preferred.

(6'-2) meso-diad fraction [m]

On the other hand, when the α-olefin polymer used in the fourth invention is a propylene-1-butene copolymer, the meso-diad fraction [m] is 30 to 95 mol%. Good, 30~80% of the mole is better, 30~60%% is better.

Meso-five unit [mmmm] fraction and inner-rotational unit The (meso-diad) fraction [m] can be controlled by the structure or polymerization conditions of the main catalyst. For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and if it is a meso-type structure, it becomes easy to obtain a rule. Low polymer.

Further, when the α-olefin polymer used in the fourth invention is a propylene homopolymer or a 1-butene homopolymer, the outer-rotating penta unit [rrrr] fraction is preferably less than 20 mol%, more preferably More than 1% by mole and less than 20% by mole, more preferably more than 2% by mole and less than 18% by mole, further preferably more than 2% by mole and less than 15% by mole, particularly preferably More than 3 mol% and less than 15 mol%, most preferably more than 3 mol% and less than 10 mol%.

On the other hand, when the α-olefin polymer used in the fourth invention is a propylene-1-butene copolymer, the racemo-diad fraction [r] is 1 to 50 mol%. Preferably, 2 to 45 mol% is preferred, and 2 to 40 mol% is preferred.

(7') 2,1-binding fraction

The 2,1-binding fraction of the α-olefin polymer used in the fourth invention is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, still more preferably less than 0.2 mol%. When the 2,1-binding fraction of the α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction or the radical decomposition reaction to be described later can be improved.

The control of the 2,1-binding fraction is controlled by the structure or polymerization conditions of the main catalyst. get on. Specifically, due to the large influence of the structure of the main catalyst, the 2,1-binding can be controlled by narrowing the insertion of the monomer around the central metal of the main catalyst, and conversely, if the insertion is expanded, the addition can be increased. , 1-binding. For example, a catalyst called a semi-metallocene type has a structure in which a periphery of a center metal is wide, so that a structure such as a 2,1-bond or a long-chain branch is easily formed, and if it is a racemic type metallocene catalyst, it can be expected The 2,1-binding can be suppressed, but the stereoregularity becomes high in the case of the racemic type, and it is difficult to obtain the amorphous polymer as shown in the fourth invention. For example, even if it is a racemic type as described later, a metallocene catalyst crosslinked by two passes introduces a substituent at the third position, and under the insertion of the central metal, amorphous and 2,1-bonding are obtained. polymer.

(8') 1,3-binding fraction and 1,4-binding fraction

The α-olefin polymer used in the fourth invention preferably has a 1,3-binding fraction and a 1,4-binding fraction of less than 0.5 mol%, preferably less than 0.4 mol%, more preferably Less than 0.1 mol%. When the total of the 1,3-binding fraction and the 1,4-bonding fraction of the α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction or the radical decomposition reaction described later is improved.

The "the total of the 1,3-binding fraction and the 1,4-bonding fraction" is the 1,3-binding fraction when the α-olefin polymer used in the fourth invention is a propylene homopolymer. The butene homopolymer represents a 1,4-binding fraction, and when it is a propylene-1-butene copolymer, it represents a total of a 1,3-binding fraction and a 1,4-bonding fraction.

The control of the 1,3-binding fraction and the 1,4-binding fraction is carried out by the structure of the main catalyst or the polymerization conditions as in the control of the above 2,1-binding fraction.

In the fourth invention, the meso-penta-unit [mmmm] fraction, the outer-rotating five-element [rrrr] fraction, the meso-diad fraction [m], and the outer-rotating di-unit (racemo) -diad) fraction [r], 1,3-binding fraction, 1,4-binding fraction, and 2,1-binding fraction are reported by Asakura, "Polymer Journal, 16, 717 (1984)" , as reported by J. Randall, "Macromol. Chem. Phys., C29, 201 (1989)" and by V. Busico, "Macromol. Chem. Phys., 198, 1257 (1997) ))). That is, using ¹³ C nuclear magnetic resonance spectroscopy, the signals of methyl and methine groups were measured, and the meso-pentameric unit (mmmm) fraction and the outer-rotating five-unit [rrrr] in the poly(1-butene) linkage were determined. 〕 fraction, meso-diad fraction [m], racemo-diad fraction [r], 1,3-binding fraction, 1,4-binding fraction Rate and 2,1-binding fraction.

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

<The case of propylene homopolymer>

The 1,3-binding fraction, the 1,4-binding fraction, and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,3-binding fraction = (D/2) / (A + B + C + D) × 100 (% by mole)

2,1-binding fraction = {(A+B)/2}/(A+B+C+D)×100 (mole%)

A: integral value of 15~15.5ppm

B: integral value of 17~18ppm

C: integral value of 19.5~22.5ppm

D: integral value of 27.6~27.8ppm

<The case of butene homopolymer>

The 1,4-binding fraction and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,4-binding fraction = E / (A + B + C + D + E) × 100 (% by mole)

2,1-binding fraction = {(A+B+D)/3}/(A+B+C+D)×100 (mole%)

A: integral value of 29.0~28.2ppm

B: integral value of 35.4~34.6ppm

C: integral value of 38.3~36.5ppm

D: integral value of 43.6~42.8ppm

E: integral value of 31.1 ppm

(Method for producing α-olefin polymer)

The α-olefin polymer used in the fourth invention can be produced, for example, by using a metallocene catalyst formed by using a combination of the following components (P-a), (P-b) and (P-c), and using hydrogen as a molecular weight modifier. Specifically based on The method disclosed in WO 2008/047860 is manufactured.

(P-a) a transition metal compound containing a metal element of Group 3 to Group 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group, or a substituted fluorenyl group

(P-b) a compound obtained by reacting with a transition metal compound to form an ionic dislocation

(P-c) organoaluminum compound

<(P-a) component>

The transition metal compound containing a metal element of Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group or a substituted fluorenyl group as the component (Pa) includes the following general A two-crosslinked complex represented by formula (I).

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, tantalum, vanadium, chromium, manganese, nickel, cobalt, palladium and lanthanide. Metal, etc. In view of the olefin polymerization activity, etc., it is preferable to use the metal element of Group 4 of the periodic table, especially titanium, zirconium and hafnium, and the viewpoint of the yield and catalytic activity of the α-olefin polymer. From the point of view, zirconium is the best.

E ¹ and E ² each represent a substituent selected from a substituted cyclopentadienyl group, a fluorenyl group, a substituted fluorenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, a decylamino group (-N<), a phosphino group ( -P<), a hydrocarbon group [>CR-, >C<] and a ruthenium-containing group [>SiR-, >Si<] (however, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group) The ligand in the form can form a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As the E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group and a substituted fluorenyl group are preferred, and at least one of E ¹ and E ² is a cyclopentadienyl group or a substituted cyclopentane group. Alkenyl, fluorenyl or substituted fluorenyl.

The substituent of the above-mentioned substituted cyclopentadienyl group, substituted fluorenyl group or substituted heterocyclopentadienyl group means a carbon number of 1 to 20 (preferably, a carbon number of 1 to 10, more preferably a carbon number of 1 to 6). A substituent such as a hydrocarbon group, a ruthenium-containing group or a hetero atom-containing group.

X represents a ligand for σ-binding, and when X is a complex number, the complex X may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples thereof include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a decylamino group having 1 to 20 carbon atoms, and carbon. The number of bismuth-containing groups of 1 to 20, the phosphide group having 1 to 20 carbon atoms, the sulfide group having 1 to 20 carbon atoms, and the fluorenyl group having 1 to 20 carbon atoms.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group; and an alkenyl group such as a vinyl group, a propenyl group or a cyclohexenyl group; Arylalkyl such as benzyl, phenylethyl or phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl An aryl group such as a naphthyl group, a methylnaphthyl group, an anthracenyl group or a phenanthryl group. Among them, an alkyl group such as a methyl group, an ethyl group, a propyl group or a phenyl group The base is good.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group. An alkoxy group such as an ethoxy group, a propoxy group or a butoxy group, a phenylmethoxy group, a phenylethoxy group or the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the decylamino group having 1 to 20 carbon atoms include dimethyl decylamino group, diethyl decylamino group, dipropyl decylamino group, dibutyl decylamino group, dicyclohexyl decylamino group, and Alkenylamino group such as alkyl guanylamino group or alkyl sulfonylamino group or divinyl decylamino group, dipropylene decylamino group, dicyclohexenyl amide group; diphenylmethyl guanylamino group, benzene An arylalkylguanamine group such as a benzylaminoamine group or a phenylpropylguanamine group; an arylguanamine group such as a diphenylguanamine group or a dinaphthylguanamine group.

Examples of the fluorene-containing group having 1 to 20 carbon atoms include a monohydrocarbon-substituted fluorenyl group such as a methyl decyl group or a phenyl fluorenyl group; a dihydrocarbon-substituted decyl group such as a dimethyl decyl group or a diphenyl fluorenyl group; Methyl decyl, triethyl decyl, tripropyl decyl, tricyclohexyl decyl, triphenyl decyl, dimethylphenyl decyl, methyl diphenyl decyl, trimethyl decyl, a trihydrocarbon-substituted decyl group such as a trinaphthyl fluorenyl group; a hydrocarbon-substituted decyl ether group such as a trimethyl decyl alkyl ether group; a hydrazine-substituted alkyl group such as a trimethyl decylalkyl group; Aryl and the like. Among them, trimethyldecylmethyl group, phenyldimethyldecylethylethyl group and the like are preferred.

As a phosphide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; Propylene sulfide group, cyclohexene sulfide An alkenyl sulfide group such as an aryl group; a phenylalkyl sulfide group; a phenylethyl sulfide group; an arylalkyl sulfide group such as a phenylpropyl sulfide group; a phenyl sulfide group or a toluene sulfide group; , dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl group An aryl sulfide group such as a naphthyl sulfide group, a sulfonium sulfide group, or a phenanthrene sulfide group.

As a sulfide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; An alkenyl sulfide group such as a propylene-based sulfide group or a cyclohexene sulfide group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; Phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide An aryl sulfide group such as a benzyl group, a naphthyl sulfide group, a methylnaphthyl sulfide group, an anthracene sulfide group, or a phenanthrene sulfide group.

Examples of the fluorenyl group having 1 to 20 carbon atoms include alkyl fluorenyl groups such as a mercapto group, an ethyl group, a propyl group, a butyl group, a pentamidine group, a palmitoyl group, a stearyl group, and an oil group. B derived from a benzoic acid group such as a benzamidine group, a tolylylene group, a salicylidene group, a cinnamyl group, a naphthylmethyl group or a phthalic acid group, or a dicarboxylic acid such as oxalic acid, malonic acid or succinic acid. Di-decyl dicarboxylate, propylenedithiol, amber thiol and the like.

On the other hand, Y represents a Lewis base, and Y represents a complex number, and the plural Ys may be the same or different and may be crosslinked with other Y or E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, and thioethers. The amine may, for example, be an amine having 1 to 20 carbon atoms, and specific examples thereof include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine and An alkylamine such as ethylamine, dipropylamine, dibutylamine, dicyclohexylamine or methylethylamine; vinylamine, propenylamine, cyclohexenamine, divinylamine, dipropylene An alkenylamine such as an amine or a dicyclohexenamine; an arylalkylamine such as a phenylamine, a phenylethylamine or a phenylpropylamine; or an arylamine such as a diphenylamine or a dinaphthylamine.

Examples of the ethers include methyl ether, ethyl ether, and propyl group. An aliphatic single ether compound such as ether, isopropyl ether, butyl ether, isobutyl ether, n-pentyl ether or isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl Ether, methyl-n-pentyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-pentyl An aliphatic mixed ether compound such as an ether or ethyl isoamyl ether; an aliphatic such as a vinyl ether, an allyl ether, a methyl vinyl ether, a methyl allyl ether, an ethyl vinyl ether or an ethyl allyl ether An unsaturated ether compound; an aromatic ether compound such as anisole, phenethyl ether, phenyl ether, benzyl ether, phenylbenzyl ether, α-naphthyl ether or β-naphthyl ether, ethylene oxide, A cyclic ether compound such as propylene oxide, epoxytrimethane, tetrahydrofuran, tetrahydropyran or dioxane.

Examples of the phosphine include a phosphine having 1 to 20 carbon atoms. Specific Illustrative of monohydrocarbon substituted phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, hexyl phosphine, cyclohexyl phosphine, octyl phosphine; dimethyl phosphine, diethyl phosphine, dipropyl phosphine, Dihydrocarbon substituted phosphines such as butylphosphine, dihexylphosphine, dicyclohexylphosphine, dioctylphosphine; trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, three An alkylphosphine such as a trihydrocarbon-substituted phosphine such as hexylphosphine, tricyclohexylphosphine or trioctylphosphine, or a hydrogen atom of a monoalkenylphosphine or a phosphine such as a vinylphosphine, a propenylphosphine or a cyclohexenephosphine is a two-alkenyl group. Substituted dienylphosphine; a trienylphosphine substituted by a hydrogen atom of a phosphine; an arylalkylphosphine such as benzylphosphine, phenylethylphosphine or phenylpropylphosphine; hydrogen of a phosphine a diarylalkylphosphine or an aryldialkylphosphine having an atom substituted by 3 aryl or alkenyl groups; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylbenzene a phosphine, a propylphenylphosphine, a biphenylphosphine, a naphthylphosphine, a methylnaphthylphosphine, a phosphonium phosphine, a phenanthroline; a hydrogen atom of a phosphine substituted by two alkylaryl groups (alkylaryl) a phosphine; an arylphosphine such as a tris(alkylaryl)phosphine substituted with three alkylaryl groups of a hydrogen atom of a phosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent cross-linking groups which combine two ligands, and represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group, and a ruthenium-containing group. , tin-containing groups, -O-, -CO-, -S-, -SO ₂ -, -Se-, -NR ¹ -, -PR ¹ -, -P(O)R ¹ -, -BR ¹ - Or -AlR ¹ -, R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the crosslinkable groups, at least one of them is a crosslinked group derived from a hydrocarbon group having 1 or more carbon atoms or a base containing ruthenium. Examples of such a crosslinking group include those shown in the following general formula (a).

(D is a group 14 element of the periodic table, and examples thereof include carbon, ruthenium, osmium, and tin. R ² and R ^{3 are} each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different and each other Binding can form a ring structure. e represents an integer from 1 to 4).

Specific examples of the structure represented by the above general formula (a) include a methyl group, an ethyl group, an ethylene group, a propylene group, an isopropylidene group, a cyclohexylene group, and a 1,2-cycloxyl group. , vinylidene (CH ₂ = C=), dimethyl decyl, diphenyl decyl, methyl phenyl decyl, dimethyl decenyl, dimethyl titanium alkenyl, tetramethyl dioxane Base, diphenyldidecyl and the like. Among them, ethyl, isopropylidene and dimethylalkyl are preferred.

Specific examples of the transition metal compound represented by the general formula (I) include specific examples described in WO2008/066168. Further, it may be a similar compound of other metal elements. Preferred is a transition metal compound of Group 4 of the periodic table, wherein a compound of zirconium is preferred.

Among the transition metal compounds represented by the above general formula (I), a compound represented by the following general formula (II) is preferred.

In the above general formula (II), M represents a metal element of Groups 3 to 10 of the periodic table, and each of A ^1a and A ^2a represents a crosslinking group represented by the general formula (a) in the above general formula (1), and CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C(CH ₃ ) ₂ C, (CH ₃ ) ₂ Si, (CH ₃ ) ₂ Si(CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si is preferred. A ^1a and A ^2a may be the same or different from each other. R ⁴ to R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group or a hetero atom-containing group. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the ruthenium-containing group are the same as those described in the above general formula (I). As a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, it can be combined with p-fluorophenyl, 3,5-difluorophenyl, 3,4,5-trifluorophenyl, pentafluorophenyl, 3,5- Bis(trifluoro)phenyl, fluorobutyl, and the like. Examples of the hetero atom-containing group include a hetero atom-containing group having 1 to 20 carbon atoms, and specific examples thereof include a nitrogen group such as a dimethylamino group, a diethylamino group or a diphenylamino group; and a phenyl group; a sulfur-containing group such as a sulfide group or a methyl sulfide group; a phosphorus-containing group such as a dimethylphosphino group or a diphenylphosphino group; or an oxygen-containing group such as a methoxy group, an ethoxy group or a phenoxy group. Among them, R ⁴ and R ^{5 are} preferably a group having a hydrogen atom, a halogen atom, a hetero atom such as oxygen or hydrazine, and a hydrocarbon having a carbon number of 1 to 20 having a high polymerization activity. Further, from the viewpoint of synthesizing a coordination space of a monomer and synthesizing a polymer having a balance between a binding ratio and a melting endotherm, R ⁴ and R ^{5 are} a hydrogen atom, an ethyl group, an n-propyl group, and an i-propyl group. The group is preferably n-butyl, trimethyldecylmethyl or phenyl. R ⁶ to R ^{13 are} preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as the general formula (I). q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the transition metal compounds represented by the above formula (I), specific examples of the transition metal compound of Group 4 of the periodic table include those described in WO2008/066168. Also, besides the 4th family A similar compound of the metal elements of other families. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

On the other hand, in the transition metal compound represented by the above formula (II), when R ⁵ is a hydrogen atom and R ^{4 is a} non-hydrogen atom, the transition metal compound of Group 4 of the periodic table may be as described in WO2008/066168. Specific examples. Further, it may be a similar compound of a metal element of a group other than Group 4. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

<(P-b) component>

The compound obtained by reacting the above (Pb) with a transition metal compound to form an ionic dislocation is obtained from the viewpoint of obtaining a relatively low molecular weight high-purity terminally unsaturated olefin polymer and high catalyst activity. A borate compound is preferred. Specific examples of the boric acid ester compound described in WO2008/066168 are mentioned. These may be used alone or in combination of two or more. When the molar ratio of the hydrogen to the transition metal compound (hydrogen/transition metal compound) is 0, dimethyl phenyl quinolate (pentafluorophenyl) borate, triphenyl carbon quinone (pentafluorophenyl) borate Preferably, hydrazine and hydrazine (perfluorophenyl)boronic acid methylaniline are preferred.

<(P-c) component>

The catalyst of the method for producing an α-olefin polymer used in the fourth invention may be combined with the component (Pa) and the component (Pb), and may be used as (Pc) in addition to the components (Pa) and (Pb). Ingredients Use an organoaluminum compound.

Examples of the organoaluminum compound as the component (Pc) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and dimethyl aluminum. Chloride, diethylaluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum Semi-chloride, etc. These organoaluminum compounds may be used alone or in combination of two or more.

Among them, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum is preferred, and triisobutyl group is preferred. Aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum are preferred.

The amount of the component (Pa) is usually 0.1 × 10 ^-6 to 1.5 × 10 ^-5 mol / L, preferably 0.15 × 10 ^-6 to 1.3 × 10 ^-5 mol / L, more preferably 0.2 × 10 ^{- 6} ~ 1.2 × 10 ^-5 mol / L, particularly preferably 0.3 × 10 ^-6 ~ 1.0 × 10 ^-5 mol / L. When the amount of the component (Pa) is 0.1 × 10 ^-6 mol/L or more, the catalyst activity can be sufficiently exhibited, and when it is 1.5 × 10 ^-5 mol/L or less, the heat of polymerization can be easily removed.

When the ratio (P-a)/(P-b) of the component (P-a) to the component (P-b) is expressed by the molar ratio, it is preferably from 10/1 to 1/100, more preferably from 2/1 to 1/10. When (P-a)/(P-b) is in the range of 10/1 to 1/100, the effect as a catalyst can be obtained, and the catalyst cost per unit mass of the polymer can be suppressed. Further, there is a concern that a large amount of boron is present in the target α-olefin polymer.

When the ratio of use of (P-a) component to (P-c) component (P-a)/(P-c) is expressed by molar ratio, it is preferably 1/1 to 1/10000, preferably 1/5~. 1/2000, more preferably 1/10~1/1000. By using the (P-c) component, the polymerization activity per transition metal can be improved. If (Pa)/(Pc) is in the range of 1/1 to 1/10000, the balance between the addition effect of the (Pc) component and the economy will be good, and the amount of aluminum present in the target-free α-olefin polymer will be present. Concerns.

Method for producing α-olefin polymer used in the fourth invention In the above, the (P-a) component and the (P-b) component or the (P-a) component, the (P-b) component, and the (P-c) component can be used for preliminary contact. The preliminary contact can be carried out by bringing the (P-a) component into contact with the component (P-b), for example, and the method is not particularly limited, and a known method can be used. By such preparatory contact, it is effective in reducing the activity of the catalyst or reducing the catalyst cost such as a decrease in the use ratio of the (P-b) component of the catalyst.

The α-olefin polymer used in the fourth invention may also be borrowed The α-olefin polymer obtained by the above production method is used as a raw material, and further a terminally unsaturated α-olefin polymer obtained by a thermal decomposition reaction or a radical decomposition reaction. By the thermal decomposition reaction or the radical decomposition reaction, the number of terminal unsaturated groups per molecule can be increased.

The thermal decomposition reaction can be carried out by subjecting the raw material α-olefin polymer obtained by the above production method to heat treatment.

The heating temperature can be adjusted according to the molecular weight of the target set and the experimental results previously performed, preferably 300 to 400 ° C, more preferably 310 to 390 ° C. When the heating temperature is less than 300 ° C, there is a concern that the thermal decomposition reaction cannot be carried out. On the other hand, when the heating temperature exceeds 400 ° C, there is a concern that the resulting terminally unsaturated α-olefin polymer is deteriorated.

Further, the thermal decomposition time (heat treatment time) is preferably from 30 minutes to 10 hours, more preferably from 60 to 240 minutes. If the thermal decomposition time is less than 30 minutes, the amount of the terminal unsaturated α-olefin polymer produced may be too small. On the other hand, when the thermal decomposition time exceeds 10 hours, the resulting terminally unsaturated α-olefin polymer may be deteriorated.

The above thermal decomposition reaction, for example, is used as a thermal decomposition device A reaction vessel such as stainless steel, which is equipped with a stirring device, is filled with an inert gas such as nitrogen or argon, and is placed in a raw material α-olefin polymer and heated and melted to foam the molten polymer phase with an inert gas. The volatile product is removed and heated at a predetermined temperature for a predetermined period of time.

The free radical decomposition reaction can be carried out at a temperature of 160 to 300 ° C. The organic peroxide is added in an amount of 0.05 to 2.0% by mass based on the raw material α-olefin polymer.

The above decomposition temperature is preferably from 170 to 290 ° C, more preferably from 180 to 280 ° C. If the decomposition temperature is less than 160 ° C, there is a concern that the decomposition reaction cannot proceed. On the other hand, when the decomposition temperature exceeds 300 ° C, the decomposition proceeds intensely, and the decomposition of the organic peroxide is sufficiently completed before the homogeneous diffusion in the molten polymer, and there is a concern that the yield is lowered.

Among the organic peroxides to be added, an organic peroxide having a one-minute half-life temperature of 140 to 270 ° C is preferable, and specific examples of the organic peroxide include the following compounds: diisobutylphosphonium peroxide; Propyl phenyl neodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate , t-hexyl peroxy neodecanoate, t-butyl peroxy neoheptanoate, t-hexyl peroxy valerate, t-butyl peroxy valerate, di(3,5,5-three Methylhexyl) peroxide, dilaurate peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2, 5-bis(2-ethylhexylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, bis(4-methylbenzylidene) peroxide, t- Butylperoxy-2-ethylhexanoate, bis(3-methylbenzhydryl) peroxide, benzhydryl peroxide, 1,1-di(t-butylperoxy) 2-methylcyclohexane, 1,1-di(t-hexylpropylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexyl Oxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-(t-butylperoxy)cyclohexyl)propane , t-hexylperoxyisopropyl monocarbonate, t-butyl peroxy maleate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl Oxidized laurel Acid ester, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 3,5-di-methyl- 2,5-bis(benzimidylperoxy)hexane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butyl Oxidized benzoate, n-butyl 4,4-di-(t-butylperoxy)valerate, bis(2-t-butylperoxyisopropyl)benzoate, peroxidation Diisopropylbenzene, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumene peroxide, Di-t-butyl peroxide, p-Menthans hydrogen peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene Hydrogen peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide.

The amount of the organic peroxide added is preferably the raw material α-ene The hydrocarbon polymer is 0.05 to 2.0% by mass, preferably 0.1 to 1.8% by mass, more preferably 0.2 to 1.7% by mass. When the amount added is 0.05% by mass or more, the decomposition reaction rate is promoted and the production efficiency is improved. On the other hand, when the amount of addition is 2.0% by mass or less, odor due to decomposition of the organic peroxide is less likely to occur.

The decomposition time of the decomposition reaction, for example, 30 seconds to 10 hours, It is preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, the decomposition reaction is not sufficiently carried out, and there is a concern that a large amount of undecomposed organic peroxide remains. On the other hand, when the decomposition time exceeds 10 hours, the progress of the crosslinking reaction of the side reaction may become a problem, or there may be a concern that the obtained α-olefin polymer is yellowed.

The radical decomposition reaction can be carried out, for example, by any method which is decomposed by a batch method and decomposed by a melt continuous method.

When the radical decomposition reaction is carried out by a batch method, an inert gas such as nitrogen or argon is filled in a reaction vessel such as stainless steel equipped with a stirring device, and the α-olefin polymer of the raw material is placed in a molten material to be heated and melted, and melted. An organic oxide is dropped into the raw material α-olefin polymer, and heated at a predetermined temperature for a predetermined period of time to carry out a radical thermal decomposition reaction.

The dropping of the above organic peroxide may be carried out by dropping in the range of the above decomposition time, and the dropping may be either continuous dropping or batch dropping. Moreover, the reaction time from the end of the dropping time is set as the range of the above reaction time. It is better inside.

The organic peroxide can be dripped as a solution dissolved in a solvent.

The solvent is preferably a hydrocarbon solvent, and specific examples thereof include aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, hexadecane, and nonadecane; methylcyclopentane; An alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, cyclooctane or cyclododecane; and an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene or trimethylbenzene. Among these solvents, a solvent having a boiling point of 100 ° C or higher is also preferred.

Further, the raw material α-olefin polymer can be dissolved in a solvent at the time of decomposition. The decomposition temperature at which the raw material α-olefin polymer is dissolved in a solvent to be decomposed is generally in the range of 100 to 250 ° C, preferably in the range of 120 to 200 ° C.

When the radical decomposition reaction is carried out by the melt continuous method, the reaction time in the average residence time is, for example, 20 seconds to 10 minutes. The melt continuous method is compared with the batch method to make the mixed state good and the reaction time can be shortened.

The apparatus may use a single-axis or two-axis melt extruder, preferably an extruder having an injection port during the barreling process and capable of degassing under reduced pressure, which is an extruder having an L/D=10 or more.

The radical decomposition reaction by the melt continuous method is a method of impregnating the raw material α-olefin polymer with the above-mentioned apparatus, or the raw material α-olefin polymer and the organic peroxide are separately supplied and mixed. The method is applicable.

The impregnation of the organic peroxide with the raw material α-olefin polymer, Specifically, the organic peroxide is added to the raw material α-olefin polymer in the presence of an inert gas such as nitrogen, and after being stirred at a temperature of from room temperature to 40° C., the raw material particles can be uniformly absorbed and impregnated. The obtained α-olefin polymer (impregnated particles) impregnated with an organic peroxide is decomposed by melt extrusion, or the impregnated particles are added as a mother particle to the raw material α-olefin polymer and decomposed to obtain terminal unsaturation. Alpha-olefin polymer.

Further, when the organic peroxide is a solid or organic peroxide having low solubility to the raw material α-olefin polymer, the solution of the organic peroxide in the hydrocarbon solvent can be absorbed and impregnated with the raw material α-olefin polymer. .

The raw material α-olefin polymer and the organic peroxide are separately supplied and mixed, and the raw material α-olefin polymer and the organic peroxide are supplied to the hopper portion at a certain flow rate, or the organic peroxide may be barreled. It is implemented on the way with a constant flow of supply.

[Method for Producing Functionalized α-Olefin Polymer]

The functionalized α-olefin polymer of the fourth invention can be produced by reacting the above α-olefin polymer with an unsaturated (anhydrous) carboxylic acid.

(unsaturated (anhydrous) carboxylic acid)

As the unsaturated (anhydrous) carboxylic acid, those having a carbon number of 1 to 20 are preferred, and those having a carbon number of 1 to 10 are preferred, and specific examples thereof include maleic acid, maleic anhydride, acrylic acid, acrylate, and methacrylate. Wait.

For alpha-olefin polymers and unsaturated (anhydrous) carboxylic acids It is important to set the reaction temperature to 50 to 230 ° C. By setting the reaction temperature to 50 ° C or higher, the viscosity of the polymer can be lowered to an appropriate region, and at the same time, the shortening of the reaction time can be made possible. On the other hand, when the reaction temperature is high, the viscosity of the component polymer is preferably low, but when the reaction temperature is excessively increased, the main chain of the component polymer is cut. The above reaction temperature is preferably 70 to 210 ° C, and particularly preferably 80 to 200 ° C.

The reaction time in the above reaction is preferably from 0.5 to 12 hours, preferably from 2 to 8 hours.

Further, in the reaction between the α-olefin polymer and the unsaturated (anhydrous) carboxylic acid, it may be diluted by a hydrocarbon solvent or the like. After dilution, the viscosity at room temperature can be further reduced, the efficiency of the reaction, and the shortening of the reaction time become possible. When the solvent is diluted with a solvent, the amount of the solvent is preferably 50% by mass or less, preferably 30% by mass, based on the total amount of the α-olefin polymer and the unsaturated (anhydrous) carboxylic acid. Hereinafter, it is more preferably 10% by mass or less.

[sclerosing composition]

The curable composition of the fourth invention contains (A) the functionalized α-olefin polymer and (B) a crosslinking agent, and may further contain (C) a polymerization accelerator, (D) an adhesion-imparting agent, and (E) a dilution. Agent.

(B) Crosslinker

As a cross-linking agent, (anhydrous) carboxy with a functionalized α-olefin polymer The acid residue may be reacted and hardened by crosslinking, and examples thereof include a polyamine and a polyhydric alcohol.

Examples of the polyamine include methyl diamine, ethyl diamine, diamino propane, diaminobutane, trimethylamine, trimethylhexamethylenediamine, and hexamethyl. Aliphatic polyamines such as bisamine, octamethylamine, polyoxypropylenediamine and polyoxypropylenetriamine, phenyldiamine, 3,3'-dichloro-4,4'-diamino Aromatic polyamines such as diphenylmethane, 4,4'-methyl bis(phenylamine), 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylphosphonium , cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, bis-aminopropylpiperazine, thiourea, methyl amide An alicyclic diamine such as an amine bispropylamine, a norbornane diamine or an isophorone diamine. Further, examples thereof include hydrazine, carbonium, bismuth adipic acid, diterpene sebacate, and bismuth phthalate, or melamine, spermine, spermidine, putrescine, and the like.

Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol. Neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3- Methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl -1,3-propanediol, polyethylene glycol, polypropylene glycol, polybutylene glycol or hydrogenated diphenol A and ethylene oxide of diphenol A, or propylene oxide adduct, trimethylolethane , trimethylolpropane, glycerin, erythritol, pentaerythritol, glucose, polytetrahydrofuran, and the like.

The content of the (B) crosslinking agent in the curable composition of the fourth invention is generally 1 for the curable composition of the fourth invention of 100% by mass. ~50% by mass, preferably 10 to 30% by mass.

(C) polymerization accelerator

As the polymerization accelerator, a heteropoly acid, a heteropoly acid salt, benzenesulfonic acid, toluenesulfonic acid, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate or the like can be used.

The content of the (C) polymerization accelerator in the curable composition of the fourth invention is generally 0.1 to 5% by mass, preferably 0.5 to 3% by mass, based on 100% by mass of the curable composition of the fourth invention. .

(D) Adhesive imparting agent

As the adhesion imparting agent (adhesive imparting resin), rosin and its derivatives, terpene resin and hydrogenated resin thereof, styrene resin, coumarone-indene resin, and dicyclopentadiene (DCPD) system can be used. Resin and its hydrogenated resin, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9 copolymerized petroleum resin and Among the adhesion-imparting agents which are generally used, such as a hydrogenated resin, those having good compatibility with the functionalized α-olefin polymer are selected. One type of these adhesiveness-imparting resins may be used alone or two or more types may be used as a mixture.

The preferred adhesion imparting agent is selected from the group consisting of terpene resins and hydrogenated resins, styrene resins, and dicyclopentane from the viewpoint of balance between removability and adhesion to curved surfaces and irregularities. Alkene (DCPD) resin and hydrogenated resin thereof, aliphatic (C5) petroleum resin and hydrogen thereof A resin, an aromatic (C9) petroleum resin and a hydrogenated resin thereof, and a resin of a C5-C9-based copolymerized petroleum resin and a hydrogenated resin thereof, or a mixture of two or more kinds thereof are preferred.

The content of the (D) adhesiveness imparting agent in the curable composition of the fourth invention is generally 0 to 20% by mass, preferably 0 to 10% by mass based on 100% by mass of the curable composition of the fourth invention. %.

(E) thinner

Examples of the diluent include oils such as naphthenic oils, paraffinic oils, and aromatic oils, and oils thereof, and liquid rubbers such as liquid polybutene and liquid isopolybutene. These may be used alone or in combination of two or more.

The content of the (E) diluent in the curable composition of the fourth invention is generally from 1 to 30% by mass, preferably from 1 to 20% by mass, based on 100% by mass of the curable composition of the fourth invention.

(other ingredients)

The curable composition of the fourth invention may contain an additive such as a filler, a pigment or an antioxidant within a range that does not impair the effects of the fourth invention.

The filler contains an inorganic filler and an organic filler.

Examples of the inorganic filler include talc, white carbon, cerium oxide, mica, bentonite, aluminum compound, magnesium compound, cerium compound, diatomaceous earth, glass beads or glass fibers, metal powder or metal fiber.

As the organic filler, starch (for example, powdery starch) may be mentioned. Fibrous leather (for example, made of cellulose such as cotton or hemp), and fibers made of synthetic polymers such as nylon, polyester, and polyolefin.

Among the above pigments, there are inorganic pigments and organic pigments (for example, azo-based pigments and polycyclic pigments).

Examples of the inorganic pigment include oxides (titanium dioxide, zinc oxide (zinc oxide), iron oxide, chromium oxide, iron black, cobalt blue, etc., and examples of the hydroxides include hydrated alumina, iron oxide yellow, and chrome green. Etc.), sulfide (zinc sulfide, zinc antimony white, cadmium yellow, vermilion, cadmium red, etc.), chromate (yellow lead, molybdenum orange, zinc chromate, strontium chromate, etc.), citrate (white carbon, Clay, talc, ultramarine, etc.), sulfate (precipitated barium sulfate, barite powder, etc., as carbonate, calcium carbonate, lead white, etc.), in addition to ferricyanide (iron blue), phosphate (manganese violet), carbon (carbon black), and the like.

Examples of the azo-based pigment of the organic pigment include soluble azo (carmine 6B, lake red C, etc.), insoluble azo (disazo yellow, lake red 4R, etc.), and condensed azo (dyeing yellow 3G, Dyeing magenta RN, etc.), azo wrong salt (nickel azo yellow, etc.), benzimidazolone azo (permanent orange HL, etc.). Examples of the polycyclic type pigment as the organic pigment include isoindolinone, isoporphyrin, quinophthalone, pyrazolone, anthraquinone yellow, furfural, diketone-pyrrolo-pyrrole, and pyrrole. , pyrazolone, anthrone, purple ring ketone, hydrazine, quinacridone, anthracene, oxazine, imidazolinone, xanthene, normal carbon, purpurin, phthalocyanine, nitroso and the like.

The content of the filler and/or the pigment is (a), and when the content of the functionalized α-olefin polymer of the fourth invention is (b), for example, (a) ) / (b) = 0.005~ 20, preferably 0.01 to 10.

When (a)/(b) is less than 0.005, the wettability and adhesion of the surface of the filler or the pigment are not sufficiently improved. For the curable composition, there are concerns about the dispersibility of the filler or the pigment and insufficient interfacial adhesion. . On the other hand, when (a)/(b) exceeds 20, there is a component (b) which is not related to the surface treatment, and the manufacturing cost is not improved.

The curable composition of the fourth invention can be used as an adhesive, a resin phase-solving agent, a dispersion, or a coating agent.

The curable composition of the fourth invention can be used as a hot melt adhesive substrate. As other components of the hot-melt adhesive, an additive such as an oil, an adhesive imparting material, or an antioxidant can be used in a general range.

The curable composition of the fourth aspect of the invention can be used as a solvent-based adhesive which is dissolved in a solvent, and can be applied to a substrate to form a film on the surface of the substrate, followed by coating. Moreover, when the curable composition of the fourth invention is dispersed or emulsified in a polar solvent such as water, it can also be used as an adhesive. Further, the curable composition of the fourth invention is formed into a sheet shape or a film shape, sandwiched between the substrates, heated to a temperature at which the adhesive agent can flow, and then cured by cooling and solidification.

The curable composition of the fourth invention can be used as a resin phase-solving agent when the resin composition containing polyolefin as an essential component is added in an amount of, for example, 0.005 to 15% by weight.

The curable composition of the fourth invention is a dispersion of a finely dispersed functionalized α-olefin polymer by dissolving the solvent at room temperature or by heating. The concentration of the functionalized α-olefin polymer is 5 to 30% by mass range.

Examples of the solvent include aliphatic hydrocarbon compounds such as hexane, heptane, and decane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; and alicyclic hydrocarbon compounds such as cyclohexane and methylcyclohexane; a halogenated hydrocarbon such as chlorobenzene; an ether compound such as tetrahydrofuran or tetrahydropyran.

It can be emulsified by using a polar solvent as a solvent. Examples of the polar solvent include water; alcohols such as methanol, ethanol, and butanol; and carboxylic acid esters such as methyl acetate, ethyl acetate, and butyl acetate.

As a method of producing a dispersion, a curability group can be exemplified An example in which a solution in which a solution is dissolved in a solvent is added to the above-mentioned polar solvent to form a solid fine particle component, and the solvent is distilled off to produce a dispersion of a polar solvent.

Specifically, a method in which a solution of 20 to 30% by mass of tetrahydrofuran is added in a small amount in 20 to 50° C., and then tetrahydrofuran is removed under reduced pressure to adjust the amount of water to a desired concentration can be exemplified. As another method, a known method such as a method of rapidly dispersing a high-speed stirring or a high-shear field in a polar solvent can be mentioned. An anion, a cation, an anionic surfactant or a water-soluble polymer compound may be used as an additive as necessary.

The above dispersion may be coated or sprayed on a substrate. The coating was carried out by removing the solvent. Further, the film or sheet may be placed on a substrate and coated by heating and cooling. In addition to this, the molten functionalized α-olefin polymer is uniformly coated on the substrate and applied by a cooling and solidifying step.

The functionalized α-olefin polymer of the fourth invention is the same as described above It can be used as a binder, a resin phase-solving agent, a dispersion, and a coating material, and can also be used as a reactive hot-melt adhesive, a sealing material, and a potting material.

Reactive hot melt adhesive will contain alkoxy quinone The α-olefin polymer and the α-olefin polymer of the fourth invention contain, as necessary, an oil, an adhesion-imparting agent, an inorganic filler, and a decyl alcohol condensation catalyst.

Examples of the oil include naphthenic oils and paraffin oils. An oil such as an aromatic oil and an oil mixed therewith, and a liquid rubber such as liquid polybutene or liquid isopolybutene. These may be used alone or in combination of two or more.

It can be used as an adhesion-imparting agent (adhesive imparting resin) Rosin and its derivatives, terpene resin and hydrogenated resin, styrene resin, coumarone-indene resin, dicyclopentadiene (DCPD) resin and hydrogenated resin, aliphatic system (C5 system) Petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9-based copolymerized petroleum resin and hydrogenated resin thereof are generally used in adhesion-imparting agents. The compatibility with the functionalized α-olefin polymer is selected to be good. One type of these adhesiveness-imparting resins may be used alone or two or more types may be used as a mixture.

The preferred adhesiveness-imparting resin is selected from the group consisting of terpene-based resins and hydrogenated resins, styrene-based resins, and dicyclopentadiene from the viewpoint of balance between re-peelability and adhesion to curved surfaces and uneven surfaces. Alkene (DCPD) resin and its hydrogenated resin, aliphatic (C5) petroleum resin and A hydrogenated resin, an aromatic (C9-based) petroleum resin, a hydrogenated resin thereof, and a C5-C9-based copolymerized petroleum resin and a hydrogenated resin group thereof are preferably one type of resin or a mixture of two or more types.

As the inorganic filler, cerium oxide and oxidation are mentioned. Aluminum, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, zinc carbonate , strontium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium citrate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, sericite, glass fiber, glass beads , ruthenium dioxide is Ba Run, aluminum nitride, boron nitride, tantalum nitride, carbon black, graphite, carbon fiber, carbon paste, zinc borate, various magnetic powders, and the like.

Instead of inorganic fillers, inorganic fillers can be used, or The surface treatment is carried out with various coupling agents such as decane or titanate. Examples of the treatment method include a method of directly treating an inorganic filler by various coupling agents such as a dry method, a slurry method, or a spray method, or a collective mixing method such as a direct method or a master batch method, or a dry concentration method. And other methods.

The sterol condensation catalyst can be used after mixing. Add method is It is preferred to prepare a catalyst master batch into which a high concentration sterol condensation catalyst is placed, and to mix, knead or melt the catalyst master batch with other reactive hot melt components.

The sterol condensation catalyst is an organotin metal compound such as dibutyltin dilaurate, dibutyltin diacetate or dibutyltin dioctanoate; an organic acid such as an organic base or ethylamine; a fatty acid; Butyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate. These additions The amount of addition is 0.005 to 2.0% by mass, preferably 0.01 to 0.5% by mass, based on the α-olefin polymer modified product.

As a curing method of the reactive hot-melt adhesive, it can be hardened by contact with moisture or moisture in the presence or absence of sterol condensation catalyst, followed by heat treatment or room temperature.

In order to contact with moisture or moisture, for example, a reactive hot melt adhesive may be placed in the air, and the steam may be immersed in the water tank or introduced into the steam. Further, the temperature may be normal temperature, but if the high temperature is set, crosslinking may be carried out in a short time.

The functionalized α-olefin polymer can be used in the same manner as the above-mentioned reactive hot-melt adhesive when it is used for a sealing material or a potting material and requires crosslinking performance.

When the crosslinking performance is not required, the melt of the functionalized α-olefin polymer and the α-olefin polymer of the fourth invention as a main component is used for blocking or potting, and is immobilized by cooling and solidification.

[hardened matter]

The fourth invention also provides a cured product obtained by curing the curable composition.

The curable composition of the fourth invention can be subjected to a hardening reaction at a relatively low temperature. Specifically, the curable composition of the fourth invention is subjected to a curing reaction at a relatively low temperature of 100 ° C or lower to obtain a cured product. The hardening reaction is carried out by mixing with a crosslinking agent, and the curable composition is cured by heat treatment or aging at room temperature.

[modified body]

The fourth invention further provides a modified body obtained by modifying a terminal (anhydrous) carboxylic acid group of the above functionalized α-olefin polymer.

Specific examples of the modified product include an acid halide formed by halogenation, an ester formed by reacting with an alcohol, and a guanamine formed by reacting with an amine.

The hardenable composition of the fourth invention can be used for the phase of the resin Emulsifier, polyolefin emulsification, reactive adhesive, reactive hot melt adhesive, other adhesives, adhesives, sealing materials, sealing materials, potting materials, reactive plasticizers, modifiers, etc.

<Fifth invention> [Functionalized α-olefin polymer]

The functionalized α-olefin polymer of the fifth invention is a functionalized propylene homopolymer formed by functionalizing a propylene homopolymer, and a functionalized 1-butyl group obtained by functionalizing a 1-butene homopolymer. There are three types of olefin homopolymers and functionalized propylene-1-butene copolymers obtained by functionalizing propylene-1-butene copolymers. The term "functionalization" as used in the specification means an addition of a hydroxyl group to an α-olefin polymer.

Further, when copolymerization of a comonomer such as ethylene is carried out, the crystal component is increased, fluidity is not observed at room temperature, handling property is deteriorated, and hardening at room temperature is difficult, so that it is difficult to serve as a base for an adhesive, an adhesive or a sealing material. Material use.

The functionalized α-olefin polymer of the fifth invention exhibits fluidity at normal temperature. Specifically, the functionalized α-olefin polymer of the fifth invention is at 100 ° C The following comparison shows fluidity at a low temperature, and more preferably shows fluidity at a low temperature of 60 ° C or lower.

(a) hydroxyl

In the functionalized α-olefin polymer according to the fifth aspect of the invention, the number of hydroxyl groups per molecule is 1.1 to 4.5, and when used as a compatibilizing agent, the number of hydroxyl groups per molecule is 1.1 to 1.5. Preferably, 1.1 to 1.2 are preferred, and when used in an adhesive or a sealing material, the hardening property is important, and from the viewpoint of obtaining a crosslinked structure, the number of hydroxyl groups per molecule is 1.2 or more. It is better, with 1.5 or more being better.

Further, since the maximum number of hydroxyl groups depends on the number of unsaturated groups per molecule of the α-olefin polymer described later, the functionalization can be controlled by controlling the number of terminal unsaturated groups of the α-olefin polymer. The number of hydroxyl groups of the α-olefin polymer.

The number of hydroxyl groups per molecule described above can be determined by the measurement method shown below.

(A) The terminal hydroxyl group concentration (mol%) obtained by ¹³ C-NMR, (B) the number average of the functionalized α-olefin polymer obtained by gel permeation chromatography (GPC) The molecular weight (Mn) and (C) are calculated from the average molecular weight (Mm) of the monomer unit = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11, and the number of hydroxyl groups per molecule is calculated by the following formula.

Number of hydroxyl groups per molecule = (Mn/M) × [hydroxyl concentration] / 100

As a method of calculating the hydroxyl group concentration, the unsaturated concentration may be reduced by the side reaction. Therefore, as shown below, the peak concentration from OH-CH _{2 which} is present in the vicinity of 68 to 70 ppm is calculated by ¹³ C-NMR.

CH ₂ (i) of OH-CH ₂ : integral value of 68-70 ppm

CH ₂ (ii) of propylene units: integral value of peaks occurring at 46.4 ppm

CH ₂ (iii) of butene units: integral value of peaks appearing at 40.4 ppm

Hydroxyl concentration = [(i) / ((ii) + (iii))] × 100 (% by mole)

(b) Melting heat absorption △H-D

The functionalized α-olefin polymer used in the fifth invention has a melting heat absorption ΔH-D of 50 J/g or less as measured by a differential scanning calorimeter (DSC). When the melting heat absorption ΔH-D of the functionalized α-olefin polymer exceeds 50 J/g, the crystal component increases, and the fluidity at normal temperature is lost. Further, the melting heat absorption ΔHD is 10 J/g or less, and the fluidity at normal temperature depends on the molecular weight, but the fluidity can be expressed at a relatively low temperature (40 to 50 ° C), and the energy saving and safety environment at the time of construction come up. Look good.

Further, ΔH-D was determined by DSC measurement. Specifically, a differential scanning calorimeter (manufactured by Perkin-Elmer Co., Ltd., DSC-7) was used, and 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the temperature was increased at 10 ° C / min. As ΔHD.

In order to control the melting heat absorption to less than 50 J/g, the meso-equivalent five-element [mmmm] fraction of the stereoregularity index must be controlled to be less than 80 mol%, which may be caused by the structure or polymerization condition of the main catalyst. And control. For example, when the control is carried out by the structure of the catalyst, the metal coordination monomer at the catalyst center must be The space is designed to the appropriate size. By the size of the coordination space, it is not easy to cause the insertion of the monomer to lower the activity, or if it is a racemic structure, a polymer having a high regularity can be obtained, and the heat of fusion is more than 50 J/g. In the case of a meso-type structure, it is easy to obtain a polymer having a low regularity, and the heat of fusion is 50 J/g or less, and it is difficult to synthesize a polymer having a balance between the binding ratio and the heat of fusion. For example, when a double-crosslinked catalyst to be described later is used, a coordination space for controlling a monomer can be synthesized, and a polymer having a balance between a binding ratio and a melting endothermic amount can be obtained.

(c) stereoregularity

The functionalized α-olefin polymer of the fifth invention is a propylene homopolymer main chain, or the 1-butene homopolymer main chain has a hydroxyl group, and the meso-penta-unit [mmmm] fraction is 80 mol% or less. Preferably, it is preferably 60 mol% or less, more preferably 40 mol% or less, and most preferably 20 mol% or less.

On the other hand, when the main chain of the propylene-1-butene copolymer has a hydroxyl group, the meso-diad fraction [m] is preferably 30 to 95 mol%, and 30 to 80. Most of the moles are preferred, preferably 30 to 60 mole%.

The mesogenic five-unit [mmmm] fraction and the meso-diad fraction [m] are controlled to a lower value, making it possible to treat at room temperature with low regularity and complete amorphousness. Hardening at lower temperatures is also possible. Therefore, in the field of sealing and reactivity which has been difficult to use in the past, it is particularly required to be in close contact with a polyolefin-based substrate. Use in the middle is possible.

The control of the meso-penta-unit (mmmm) fraction and the meso-diad fraction [m] is controlled by the structure or polymerization conditions of the main catalyst, for example, by the structure of the catalyst. The space of the metal coordination monomer at the catalyst center must be designed to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and if it is a meso-type structure, it becomes easy to obtain a rule. Low polymer.

The 2,1-binding fraction of the functionalized α-olefin polymer of the fifth invention is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, still more preferably less than 0.2 mol%.

The control of the 2,1-binding fraction is carried out by controlling the 2,1-binding fraction in the α-olefin polymer used as a raw material to be described later.

The total of the 1,3-binding fraction and the 1,4-binding fraction of the functionalized α-olefin polymer of the fifth invention is preferably less than 0.5 mol%, preferably less than 0.4 mol%, more preferably Jia is less than 0.1% of the total.

The above "the total of the 1,3-binding fraction and the 1,4-bonding fraction" is that the functionalized α-olefin polymer of the fifth invention has a propylene homopolymer main chain and represents a 1,3-binding component. The ratio, which has a butene homopolymer backbone, represents a 1,4-binding fraction, and when it has a propylene-1-butene copolymer backbone, it represents a 1,3-binding fraction and a 1,4-binding fraction. total.

The control of the 1,3-binding fraction and the 1,4-binding fraction is controlled by using a 1,3-binding fraction and a 1,4-binding fraction in an α-olefin polymer as a raw material. Controlled.

When the 2,1-binding fraction, the 1,3-binding fraction, and the 1,4-binding fraction are increased, the number of terminal unsaturation in the raw material is reduced. From the viewpoint of the starting point of the reaction, It is preferred not to increase the number of terminal hydroxyl groups.

In the fifth invention, the meso-penta-unit (mmmm) fraction and the meso-diad fraction are reported by the "Polymer Journal, 16, 717 (1984)" by the Asakura, by J. "Ranall's report "Macromol. Chem. Phys., C29, 201 (1989)" and by V. Busico's report "Macromol. Chem. Phys., 198, 1257 (1997)" The method of the proposal is obtained. That is, the signal of methyl group and methine group was measured by ¹³ C nuclear magnetic resonance spectroscopy, and the meso-penta-unit (mmmm) fraction and the meso-diad fraction of the polymer linkage were obtained. m].

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: mixed solvent of 1,2,4-trichlorobenzene and heavy benzene of 90:10 (capacity ratio)

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

(d) Weight average molecular weight. The molecular weight distribution

The functionalized α-olefin polymer of the fifth invention is from the viewpoint of fluidity It is preferable that the weight average molecular weight is 3,000 to 500,000, preferably 4,000 to 450,000, and 4,500 to 300,000.

When the functionalized α-olefin polymer of the fifth invention is used for an adhesive application, the weight average molecular weight of the functionalized α-olefin polymer is 10,000~ from the viewpoint that the strength after hardening is strong and the peeling is not easily peeled off. 500,000 is preferred.

The functionalized α-olefin polymer of the fifth invention is reactive and From the viewpoint of reaction hardenability, the molecular weight distribution (Mw/Mn) is preferably less than 4.5, preferably 1.4 to 3.0, and more preferably 1.5 to 2.6.

And, the above weight average molecular weight (Mw) and the number average score The sub-quantity (Mn) is a polystyrene equivalent measured by the following apparatus and conditions, and the molecular weight distribution (Mw/Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0 ml / min

Sample concentration: 2.2 mg / ml

Injection volume: 160 microliters

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

(e) B viscosity

The functionalized α-olefin polymer of the fifth invention has a viscosity (fluidity) of 5000 mPa at 30 ° C from the viewpoints of reactivity, workability at room temperature, and the like. The following is better, at 2000mPa. The following is preferred.

Here, the above B viscosity is a value measured in accordance with ASTM-D19860-91.

[Method for Producing Functionalized α-Olefin Polymer]

The functionalized α-olefin polymer of the fifth invention can be produced by hydroxylating a terminal α-unsaturated α-olefin polymer to be described later.

Specific examples of the hydroxylation of the terminal α-unsaturated α-olefin include a hydration reaction of an olefin in the presence of an acid catalyst such as concentrated sulfuric acid or sulphuric acid, and an addition of maleic anhydride by an olefin reaction. Reaction, reduction reaction by lithium aluminum hydride or the like, oxidation reaction of an organic peroxide such as performic acid or peracetic acid, hydroboration by treatment of an oxide and a base by borohydride of borane - Oxidation reaction, etc.

Examples of the hydration reaction include the presence of a raw material α-olefin polymer in the presence of an acid catalyst such as sulfuric acid or phosphoric acid, a solid acid catalyst carrying zeolite, phosphoric acid or an ion exchange resin, or a magnesium salt such as magnesium sulfate or magnesium chloride. Under the temperature of 100~300 °C in the water system for 10 minutes to 10 hours method.

The olefin reaction can be carried out, for example, by contacting the raw material α-olefin polymer with an excess amount of maleic anhydride at a temperature of from 100 ° C to 250 ° C for 10 minutes to 10 hours. Further, the reaction of the olefin is preferably carried out in the presence of oxalic acid or maleic acid.

The reduction reaction may, for example, be a contact between a raw material α-olefin polymer in the presence of a solvent such as tetrahydrofuran (THF) or a reducing agent such as lithium aluminum hydride at room temperature to reflux for 30 minutes to 5 hours. The method.

As the borohydride, for example, the raw material α-olefin polymer is present in a solvent such as tetrahydrofuran (THF), second-order isoamylborane ((Sia) ₂ BH), Thexyl borone ((Thx) BH ₂ ), 9- A method of contacting a boron compound such as boronated bicyclo[3.3.1]nonane in the presence of a solvent such as THF at 0 ° C to reflux is exemplified. The oxidation reaction to be carried out is carried out by subjecting the reactant obtained by the above-described hydroboration to a treatment such as a peroxide such as hydrogen peroxide and a base such as sodium hydroxide at room temperature for 1 to 10 hours.

(Two-end unsaturated α-olefin polymer)

In the method for producing a functionalized α-olefin polymer according to the fifth aspect of the invention, the both terminal unsaturated α-olefin polymer used as a raw material has the following property (a′) and has the following characteristics (b′) to (f′). ) is better.

(a') The number of terminal unsaturated groups per molecule is 1.1 to 2.0.

(b') Melting endotherm measured by differential scanning calorimeter (DSC) The amount ΔH-D is 50 J/g or less.

(c') (c'-1) meso-diad fraction (m) is a meso-diad fraction (m) of (5), or (c'-2) 30~95% or less.

The (d1') weight average molecular weight Mw is from 1,000 to 500,000.

The (d2') molecular weight distribution Mw/Mn was less than 4.5.

The (e') 2,1-binding fraction is less than 0.5 mol%.

The total of (f') 1,3-binding fraction and 1,4-binding fraction was less than 0.5 mol%.

(a') number of unsaturation groups per one molecule

In the terminal-end unsaturated α-olefin polymer used in the fifth invention, the number of terminal unsaturated groups per molecule is 1.1 to 2.0. Further, when the both terminal unsaturated α-olefin polymer is used as a compatibilizing agent, the number of terminal unsaturated groups per molecule is preferably 1.1 to 1.5, and preferably 1.1 to 1.2. When it is used for an adhesive or a sealing material, it is preferably 1.2 or more, more preferably 1.5 or more.

The control of the number of terminal unsaturated groups per molecule of the terminal-end unsaturated α-olefin polymer can be carried out by the structure of the main catalyst, the type of the monomer or the polymerization conditions (polymerization temperature, hydrogen concentration, etc.).

In the presence of a catalyst, the number of terminally unsaturated groups per molecule can be controlled by selecting the molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound).

For example, by the molar ratio of hydrogen to the transition metal compound (hydrogen / The transition metal compound is obtained by carrying out a polymerization reaction in the range of 0 to 5,000. In order to increase the selectivity of terminal unsaturation and the activity of the catalyst, it is preferred to carry out the polymerization in the presence of a trace amount of hydrogen.

Hydrogen is generally known as a chain shifting agent, and the end of the polymer chain becomes a saturated structure. In addition, it also has the function of reactivation of the temporary break and the activity of the catalyst. Although the effect of the trace amount of hydrogen catalyst is unclear, when hydrogen is used in a specific range, the terminal unsaturated group can be made highly selective and highly active.

The molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) is preferably from 200 to 4,500, more preferably from 300 to 4,000, most preferably from 400 to 3,000. When the molar ratio is 5,000 or less, the formation of an α-olefin polymer having an extremely low number of terminal unsaturated groups can be suppressed, and an α-olefin polymer having a desired number of terminal unsaturated groups can be obtained.

Further, examples of the terminal unsaturated group include a vinyl group, a vinylidene group, and a trans(acetylene) group. However, the terminal unsaturated group as defined in the specification means a vinyl group and a vinylidene group. Vinyl and vinylidene are radically polymerizable, and various reactions are applicable to a wide range of applications.

The terminal unsaturated group concentration and the terminal unsaturation group in the both terminal unsaturated α-olefin polymer used in the fifth invention represent the total concentration and number of vinyl and vinylidene groups. When only a vinyl group is present, it means only the concentration and number of vinyl groups, and when both vinyl and vinylidene are contained, the concentration and number of both sides are shown.

The terminal unsaturated group concentration or the number of terminal unsaturated groups per molecule can be determined by ¹ H-NMR measurement. Specifically, the terminal vinylidene group obtained by δ4.8 to 4.6 (2H) and the terminal vinyl group appearing at δ5.9 to 5.7 (1H) and δ1.05 were obtained by ¹ H-NMR measurement. The methyl group appearing at ~0.60 (3H) is used as the standard, and the terminal unsaturated group concentration (C) (% by mole) is calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturation concentration = [vinylidene amount] + [vinyl amount]

The terminal unsaturated group concentration (C, mol %) calculated by the above method and the number average molecular weight (Mn) and the monomer molecular weight (M) obtained by gel permeation chromatography (GPC) are The equation can calculate the number of unsaturation groups at the end of each molecule.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

(b') melting heat absorption △H-D

The both-end unsaturated α-olefin polymer used in the fifth invention has a melting heat absorption ΔH-D of 50 J/g or less as measured by a differential scanning calorimeter (DSC), preferably less than 50 J/g.

For propylene homopolymer, the melting heat absorption ΔHD is 30 J/g or less, less than 30 J/g, 15 J/g or less, 1.0 J/g or less, less than 1.0 J/g, less than 0.5 J/g, and less than The order of 0.2 J/g and 0 J/g is preferred.

The melting heat absorption ΔH-D in the 1-butene homopolymer is 40 J/g or less. Less than 40 J/g, less than 30 J/g is preferred, less than 10 J/g, less than 10 J/g is better, less than 1.0 J/g, less than 1.0 J/g, less than 0.5 J/g It is especially good if it is less than 0.2J/g and 0J/g.

The details of the melting heat absorption ΔH-D of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(c'-1) meso five unit [mmmm] fraction

The meso-penta-membered unit (mmmm) fraction of the both-end unsaturated α-olefin polymer used in the fifth invention is preferably less than 80 mol%. And more than 1 mol% and less than 20 mol%, more than 1 mol% and less than 15 mol%, more than 2 mol% and less than 15 mol%, more than 2 mol% and less than 10 mo The order of % ear, more than 3 mol%, and less than 10 mol% is preferred.

For propylene homopolymers, the meso-penta-unit [mmmm] fraction is preferably less than 60 mol%, preferably less than 40 mol%, and less than 20 mol%. good.

In the case of a 1-butene homopolymer, the meso-penta-unit [mmmm] fraction is preferably less than 70 mol%, and less than 40 mol% is more preferably less than 20 mol. The ear is especially good.

(c'-2) meso-diad fraction [m]

On the other hand, when the both terminal unsaturated α-olefin polymer used in the fifth invention is a propylene-1-butene copolymer, the meso-diad fraction [m] is 30 to 95 moles. Ear% are better, to 30~80 The ear percentage is preferably, preferably 30 to 60 mol%.

The meso-penta-unit (mmmm) fraction and the meso-diad fraction [m] can be controlled by the structure or polymerization conditions of the main catalyst. For example, when controlling by the structure of the catalyst, it is necessary to design the space of the metal coordination unit in the catalyst center to an appropriate size. By the size of the coordination space, it is difficult to cause the insertion of the monomer and the activity is lowered, and it is only a racemic type structure, that is, a polymer having a high regularity is obtained, and if it is a meso-type structure, it becomes easy to obtain a rule. Low polymer.

Further, the outer-end five-unit [rrrr] fraction of the terminal-end unsaturated α-olefin polymer used in the fifth invention is preferably less than 20 mol%.

The excimer pentad fraction in the propylene homopolymer is preferably more than 1 mol% and less than 20 mol%, preferably more than 2 mol% and less than 18 mol%, more preferably It is more than 2 mol% and less than 15 mol%, particularly preferably more than 3 mol% and less than 15 mol%, most preferably more than 3 mol% and less than 10 mol%.

The excimer pentad fraction in the 1-butene homopolymer is preferably more than 1 mol% and less than 20 mol%, more than 2 mol% and less than 18 mol%. Preferably, more than 2% by mole and less than 15% by mole is more preferably, more preferably more than 3% by mole and less than 15% by mole, most preferably more than 3% by mole and less than 10% by mole. .

On the other hand, when the α-olefin polymer used in the fifth invention is a propylene-1-butene copolymer, the racemo-diad fraction [r] is 1 to 50 mol%. Preferably, 2 to 45 mol% is preferred, and 2 to 40 mol% is better.

(e') 2,1-binding fraction

In the two-terminal unsaturated α-olefin polymer used in the fifth invention, the 2,1-binding fraction is preferably less than 0.5 mol%, preferably less than 0.4 mol%, and less than 0.2 mol. Ear % is better. When the 2,1-binding fraction of the both terminal unsaturated α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction or the radical decomposition reaction described later can be improved.

The control of the 2,1-binding fraction is carried out by the structure or polymerization conditions of the main catalyst. Specifically, due to the large influence of the structure of the main catalyst, the 2,1-binding can be controlled by narrowing the insertion of the monomer around the central metal of the main catalyst, and conversely, if the insertion is expanded, the addition can be increased. , 1-binding. For example, a catalyst called a semi-metallocene type has a structure in which a periphery of a center metal is wide, so that a structure such as a 2,1-bond or a long-chain branch is easily formed, and if it is a racemic type metallocene catalyst, it can be expected The 2,1-binding can be suppressed, but in the case of the racemic type, the stereoregularity becomes high, and it is difficult to obtain the amorphous polymer as shown in the fifth invention. For example, even if it is a racemic type as described later, a metallocene catalyst crosslinked by two passes introduces a substituent at the third position, and under the insertion of the central metal, amorphous and 2,1-bonding are obtained. polymer.

(f') 1,3-binding fraction and 1,4-binding fraction

In the two-terminal unsaturated α-olefin polymer used in the fifth invention, the total of the 1,3-binding fraction and the 1,4-binding fraction is preferably less than 0.5 mol%, and less than 0.4 mol. % is preferably, preferably less than 0.1 mol%. The total of the 1,3-binding fraction and the 1,4-binding fraction of the α-olefin polymer is When the above range is within the range, the decomposition efficiency in the thermal decomposition reaction or the radical decomposition reaction to be described later can be improved.

The above "the total of the 1,3-binding fraction and the 1,4-bonding fraction" is that the two-terminal unsaturated α-olefin polymer used in the fifth invention is a propylene homopolymer and represents a 1,3-bond. The fraction is a 1,4-bonding fraction when it is a butene homopolymer, and is a total of a 1,3-bonding fraction and a 1,4-bonding fraction when it is a propylene-1-butene copolymer.

The control of the 1,3-binding fraction and the 1,4-binding fraction is carried out by the structure of the main catalyst or the polymerization conditions as in the control of the above 2,1-binding fraction.

In the fifth invention, the meso-penta-unit [mmmm] fraction, the outer-rotating five-element [rrrr] fraction, the meso-diad fraction [m], and the outer-rotating di-unit (racemo) -diad) fraction [r], 1,3-binding fraction, 1,4-binding fraction, and 2,1-binding fraction are reported by Asakura, "Polymer Journal, 16, 717 (1984)" , as reported by J. Randall, "Macromol. Chem. Phys., C29, 201 (1989)" and by V. Busico, "Macromol. Chem. Phys., 198, 1257 (1997) ))). That is, the signal of methyl group and methine group was measured by ¹³ C nuclear magnetic resonance spectroscopy, and the meso-penta-unit (mmmm) fraction and the outer-rotor five-unit [rrrr] in the poly(1-butene) linkage were determined. Fraction, meso-diad fraction [m], racemo-diad fraction [r], 1,3-binding fraction, 1,4-binding fraction And 2,1-binding fraction.

The measurement of the ¹³ C-NMR spectrum was carried out under the following apparatus and conditions.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

<The case of propylene homopolymer>

The 1,3-binding fraction and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,3-binding fraction = (D/2) / (A + B + C + D) × 100 (% by mole)

2,1-binding fraction = {(A+B)/2}/(A+B+C+D)×100 (mole%)

A: integral value of 15~15.5ppm

B: integral value of 17~18ppm

C: integral value of 19.5~22.5ppm

D: integral value of 27.6~27.8ppm

<The case of butene homopolymer>

The 1,4-binding fraction and the 2,1-binding fraction can be calculated from the measurement results of the above ¹³ C-NMR spectrum by the following formula.

1,4-binding fraction = E / (A + B + C + D + E) × 100 (% by mole)

2,1-binding fraction = {(A+B+D)/3}/(A+B+C+D)×100 (mole%)

A: integral value of 29.0~28.2ppm

B: integral value of 35.4~34.6ppm

C: integral value of 38.3~36.5ppm

D: integral value of 43.6~42.8ppm

E: integral value of 31.1 ppm

(d1') weight average molecular weight (Mw)

The two-end unsaturated α-olefin polymer used in the fifth invention is preferably from 1,000 to 500,000 in terms of fluidity, preferably from 2,000 to 50,000, and from 3,000 to 20,000 in terms of fluidity. More preferably, it is particularly good for 5,000 to 20,000, preferably 6000 to 450,000, preferably 8,000 to 300,000, and preferably 10,000 to 70,000.

The details of the weight average molecular weight (Mw) of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(d2') molecular weight distribution (Mw/Mn)

The two-end unsaturated α-olefin polymer used in the fifth invention has a molecular weight distribution (Mw/Mn) of less than 4.5, and is 1.4 to 3.0, 1.5 to 2.6, from the viewpoint of reactivity and reaction hardenability. The order of 1.1~2.5, 1.4~2.2, 1.6~2.1, 1.6~2.0 is better.

The details of the molecular weight distribution (Mw/Mn) of the α-olefin polymer are the same as those of the above-described functionalized α-olefin polymer.

(Method for producing two-terminal unsaturated α-olefin polymer)

In the α-olefin polymer used in the fifth invention, for example, a metallocene catalyst formed by a combination of the following components (Pa), (Pb) and (Pc) can be used, and hydrogen can be used as a molecular weight modifier. The terminally unsaturated α-olefin polymer is further produced by a thermal decomposition reaction or a radical decomposition reaction. Specifically, it can be manufactured according to the method disclosed in WO2008/047860.

(P-a) a transition metal compound containing a metal element of Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group, or a substituted fluorenyl group

(P-b) a compound obtained by reacting with a transition metal compound to form an ionic dislocation

(P-c) organoaluminum compound

<(P-a) component>

The transition metal compound containing a metal element of Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group or a substituted fluorenyl group as the component (Pa) includes the following general A two-crosslinked complex represented by formula (I).

In the above general formula (I), M represents the 3~10 of the periodic table. Specific examples of the metal element of the group include titanium, zirconium, hafnium, tantalum, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid metals. Among them, titanium, zirconium and hafnium are preferred from the viewpoint of olefin polymerization activity and the like, and zirconium is preferred from the viewpoints of the yield of α-olefin polymer and catalyst activity.

E ¹ and E ² each represent a substituent selected from a substituted cyclopentadienyl group, a fluorenyl group, a substituted fluorenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, a decylamino group (-N<), a phosphino group ( -P<), a hydrocarbon group [>CR-, >C<] and a ruthenium-containing group [>SiR-, >Si<] (however, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group) The ligand in the form can form a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As the E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, a fluorenyl group and a substituted fluorenyl group are preferred, and at least one of E ¹ and E ² is a cyclopentadienyl group or a substituted cyclopentane group. Alkenyl, fluorenyl or substituted fluorenyl.

The substituent of the above-mentioned substituted cyclopentadienyl group, substituted fluorenyl group or substituted heterocyclopentadienyl group means a carbon number of 1 to 20 (preferably, a carbon number of 1 to 10, more preferably a carbon number of 1 to 6). A substituent such as a hydrocarbon group, a ruthenium-containing group or a hetero atom-containing group.

X represents a ligand for σ-binding, and when X is a complex number, the complex X may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of the X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a decylamine having 1 to 20 carbon atoms. The base, the ruthenium-containing group having 1 to 20 carbon atoms, the phosphide group having 1 to 20 carbon atoms, the sulfide group having 1 to 20 carbon atoms, and the fluorenyl group having 1 to 20 carbon atoms.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group and an ethyl group. An alkyl group such as a propyl group, a butyl group, a hexyl group, a cyclohexyl group or an octyl group; an alkenyl group such as a vinyl group, a propenyl group or a cyclohexenyl group; an arylalkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group; An aryl group such as a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthracenyl group or a phenanthryl group. Among them, an alkyl group such as a methyl group, an ethyl group or a propyl group or an aryl group such as a phenyl group is preferred.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group. An alkoxy group such as an ethoxy group, a propoxy group or a butoxy group, a phenylmethoxy group, a phenylethoxy group or the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the decylamino group having 1 to 20 carbon atoms include dimethyl decylamino group, diethyl decylamino group, dipropyl decylamino group, dibutyl decylamino group, dicyclohexyl decylamino group, and Alkenylamino group such as alkyl guanylamino group or alkyl sulfonylamino group or divinyl decylamino group, dipropylene decylamino group, dicyclohexenyl amide group; diphenylmethyl guanylamino group, benzene An arylalkylguanamine group such as a benzylaminoamine group or a phenylpropylguanamine group; an arylguanamine group such as a diphenylguanamine group or a dinaphthylguanamine group.

Examples of the fluorene-containing group having 1 to 20 carbon atoms include a monohydrocarbon-substituted fluorenyl group such as a methyl decyl group or a phenyl fluorenyl group; a dihydrocarbon-substituted decyl group such as a dimethyl decyl group or a diphenyl fluorenyl group; Methyl decyl, triethyl decyl, tripropyl decyl, tricyclohexyl decyl, triphenyl decyl, dimethylphenyl decyl, methyl diphenyl decyl, trimethyl decyl, a trihydrocarbon-substituted decyl group such as a trinaphthyl fluorenyl group; a hydrocarbon-substituted decyl ether group such as a trimethyl decyl alkyl ether group; a hydrazine-substituted alkyl group such as a trimethyl decylalkyl group; Aryl and the like. Among them, trimethyldecylmethyl, phenyl Dimethyl decyl ethyl or the like is preferred.

As a phosphide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; An alkenyl sulfide group such as a propylene-based sulfide group or a cyclohexene sulfide group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; Phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide An aryl sulfide group such as a benzyl group, a naphthyl sulfide group, a methylnaphthyl sulfide group, an anthracene sulfide group, or a phenanthrene sulfide group.

As a sulfide group having 1 to 20 carbon atoms, methyl sulfur is exemplified. An alkyl sulfide group such as a compound group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, or an octyl sulfide group; a vinyl sulfide group; An alkenyl sulfide group such as a propylene-based sulfide group or a cyclohexene sulfide group; an arylalkyl sulfide group such as a benzyl sulfide group, a phenylethyl sulfide group or a phenylpropyl sulfide group; Phenyl sulfide group, toluene sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide An aryl sulfide group such as a benzyl group, a naphthyl sulfide group, a methylnaphthyl sulfide group, an anthracene sulfide group, or a phenanthrene sulfide group.

Examples of the fluorenyl group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a palmitoyl group, a stearyl group, and an oil group. Formyl, toluene, salicyl, cinnamyl, An arylsulfonyl group such as a naphthylmethyl group or an o-phthalic acid group; a dinonyl oxalate group, a propylenediamine group, an amber fluorenyl group or the like derived from each of a dicarboxylic acid such as oxalic acid, malonic acid or succinic acid.

On the other hand, Y represents a Lewis base, and Y represents a complex number, and the plural Ys may be the same or different, and may be crosslinked with other X, E ¹ , E ² or Y. Specific examples of the Lewis base of Y include amines, ethers, phosphines, and thioethers. The amine may, for example, be an amine having 1 to 20 carbon atoms, and specific examples thereof include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine and An alkylamine such as ethylamine, dipropylamine, dibutylamine, dicyclohexylamine or methylethylamine; vinylamine, propenylamine, cyclohexenamine, divinylamine, dipropylene An alkenylamine such as an amine or a dicyclohexenamine; an arylalkylamine such as a phenylamine, a phenylethylamine or a phenylpropylamine; or an arylamine such as a diphenylamine or a dinaphthylamine.

Examples of the ethers include methyl ether, ethyl ether, and propyl group. An aliphatic single ether compound such as ether, isopropyl ether, butyl ether, isobutyl ether, n-pentyl ether or isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl Ether, methyl-n-pentyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-pentyl An aliphatic mixed ether compound such as an ether or ethyl isoamyl ether; an aliphatic such as a vinyl ether, an allyl ether, a methyl vinyl ether, a methyl allyl ether, an ethyl vinyl ether or an ethyl allyl ether An unsaturated ether compound; an aromatic ether compound such as anisole, phenethyl ether, phenyl ether, benzyl ether, phenylbenzyl ether, α-naphthyl ether or β-naphthyl ether, ethylene oxide, A cyclic ether compound such as propylene oxide, epoxytrimethane, tetrahydrofuran, tetrahydropyran or dioxane.

Examples of the phosphine include a phosphine having 1 to 20 carbon atoms. Specific Illustrative of monohydrocarbon substituted phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, butyl phosphine, hexyl phosphine, cyclohexyl phosphine, octyl phosphine; dimethyl phosphine, diethyl phosphine, dipropyl phosphine, Dihydrocarbon substituted phosphines such as butylphosphine, dihexylphosphine, dicyclohexylphosphine, dioctylphosphine; trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexyl An alkyl phosphine such as a phosphine or a trioctylphosphine substituted phosphine, or a monoalkenylphosphine such as a vinyl phosphine, a propenylphosphine or a cyclohexene phosphine or a dienyl group in which a hydrogen atom of a phosphine is substituted by two alkenyl groups. a phosphine; a trialkylene phosphine in which a hydrogen atom of a phosphine is substituted by three alkenyl groups; an arylalkylphosphine such as benzylphosphine, phenylethylphosphine or phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine substituted by a base or alkenyl group; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propyl a phenylphosphine, a biphenylphosphine, a naphthylphosphine, a methylnaphthylphosphine, a phosphonium phosphine, a phenanthroline; a bis(alkylaryl)phosphine in which a hydrogen atom of a phosphine is substituted by two alkylaryl groups; a hydrogen atom substituted by three alkyl aryl groups (alkyl) Yl) phosphine arylphosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent cross-linking groups which combine two ligands, and represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group, and a ruthenium-containing group. , tin-containing groups, -O-, -CO-, -S-, -SO ₂ -, -Se-, -NR ¹ -, -PR ¹ -, -P(O)R ¹ -, -BR ¹ - Or -AlR ¹ -, R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

In such a crosslinking group, at least one of the crosslinking groups is composed of a hydrocarbon group having 1 or more carbon atoms. The cross-linking group or the base containing bismuth is preferred. Examples of such a crosslinking group include those shown in the following general formula (a).

(D is a group 14 element of the periodic table, and examples thereof include carbon, ruthenium, osmium, and tin. R ² and R ^{3 are} each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different and each other Binding can form a ring structure. e represents an integer from 1 to 4).

Specific examples of the structure represented by DR ² R ³ include a methyl group, an ethyl group, an ethylene group, a propylene group, an isopropylidene group, a cyclohexylene group, a 1,2-cyclodimethylene group, and a sub Vinyl (CH ₂ = C=), dimethyl decyl, diphenyl decyl, methyl phenyl decyl, dimethyl nonenyl, dimethyl titanium alkenyl, tetramethyl dinonyl, Diphenyldidecyl and the like. Among them, an ethyl group, an isopropylidene group, a tetramethyldidecyl group, and a dimethylalkyl group are preferred.

As a transition metal compound of the general formula (I) Specific examples of WO2008/066168 can be mentioned as examples. Further, it may be a similar compound of a metal element of another group. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

Among the transition metal compounds represented by the above general formula (I), a compound represented by the following general formula (II) is preferred.

In the above general formula (II), M represents a metal element of Groups 3 to 10 of the periodic table, and each of A ^1a and A ^2a represents a crosslinking group represented by the general formula (a) in the above general formula (I), and CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C(CH ₃ ) ₂ C, (CH ₃ ) ₂ Si, (CH ₃ ) ₂ Si(CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si is preferred. A ^1a and A ^2a may be the same or different from each other. R ⁴ to R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a ruthenium-containing group or a hetero atom-containing group. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the ruthenium-containing group are the same as those described in the above general formula (I). Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, and 3,5-. Bis(trifluoro)phenyl, fluorobutyl, and the like. Examples of the hetero atom-containing group include a hetero atom-containing group having 1 to 20 carbon atoms, and specific examples thereof include a nitrogen group such as a dimethylamino group, a diethylamino group or a diphenylamino group; and a phenyl group; a sulfur-containing group such as a sulfide group or a methyl sulfide group; a phosphorus-containing group such as a dimethylphosphino group or a diphenylphosphino group; or an oxygen-containing group such as a methoxy group, an ethoxy group or a phenoxy group. Among them, R ⁴ and R ^{5 have a} high polymerization activity of a hydrocarbon group having a halogen atom, a hetero atom such as oxygen or hydrazine, and a hydrocarbon having 1 to 20 carbon atoms. Further, from the viewpoint of synthesizing a polymer having a balance between a binding ratio and a melting endothermic amount, it is preferred that R ⁴ and R ^{5 have} a different structure such as an isopropyl group or an isopentyl group.

R ⁶ to R ^{13 are} preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as the general formula (I). q represents an integer of 1 to 5 [(a valence of M)-2], and r represents an integer of 0 to 3.

Among the transition metal compounds represented by the above formula (I), specific examples of the transition metal compound of Group 4 of the periodic table include those described in WO2008/066168. Further, it may be a similar compound of a metal element of a group other than Group 4. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

On the other hand, in the transition metal compound represented by the above formula (II), when R ⁵ is a hydrogen atom and R ^{4 is a} non-hydrogen atom, the transition metal compound of Group 4 of the periodic table may be as described in WO2008/066168. Specific examples. Further, it may be a similar compound of a metal element of a group other than Group 4. Preferred are transition metal compounds of Group 4 of the periodic table, of which zirconium compounds are also preferred.

<(P-b) component>

The compound obtained by reacting the above (Pb) with a transition metal compound to form an ionic dislocation is obtained from the viewpoint of obtaining a relatively low molecular weight high-purity terminally unsaturated olefin polymer and high catalyst activity. A borate compound is preferred. Specific examples of the boric acid ester compound described in WO2008/066168 are mentioned. These may be used alone or in combination of two or more. When the molar ratio of hydrogen to the transition metal compound (hydrogen/transition metal compound) is 0, iridium (pentafluorophenyl) is used. Preferably, dimethylaniline borate, triphenylcarbenium quinone (pentafluorophenyl)borate, and methyl anilide of fluorene (perfluorophenyl)borate are preferred.

<(P-c) component>

The catalyst for using the method for producing a single-end unsaturated α-olefin polymer used in the fifth invention may be combined with the above (Pa) component and (Pb) component, in addition to the above (Pa) component and (Pb) component. An organoaluminum compound can be used as the (Pc) component.

Examples of the organoaluminum compound as the component (Pc) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and dimethyl aluminum. Chloride, diethylaluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum Semi-chloride, etc. These organoaluminum compounds may be used alone or in combination of two or more.

Among them, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum is preferred, and triisobutyl aluminum is used. It is preferred that tri-n-hexyl aluminum and tri-n-octyl aluminum.

The amount of the component (Pa) is usually 0.1 × 10 ^-6 to 1.5 × 10 ^-5 mol / L, preferably 0.15 × 10 ^-6 to 1.3 × 10 ^-5 mol / L, more preferably 0.2 × 10 ^{- 6} ~ 1.2 × 10 ^-5 mol / L, particularly preferably 0.3 × 10 ^-6 ~ 1.0 × 10 ^-5 mol / L. When the amount of the component (Pa) is 0.1 × 10 ^-6 mol/L or more, the catalyst activity can be sufficiently exhibited, and when it is 1.5 × 10 ^-5 mol/L or less, the heat of polymerization can be easily removed.

Use ratio of (P-a) component to (P-b) component (P-a)/(P- b) When expressed in terms of molar ratio, it is preferably from 10/1 to 1/100, more preferably from 2/1 to 1/10. When (P-a)/(P-b) is in the range of 10/1 to 1/100, the effect as a catalyst can be obtained, and the catalyst cost per unit mass of the polymer can be suppressed. Further, there is a concern that a large amount of boron is present in the target α-olefin polymer.

When the ratio (Pa)/(Pc) of the (Pa) component to the (Pc) component is expressed by the molar ratio, it is preferably 1/1 to 1/10000, preferably 1/5 to 1/2000, more preferably It is 1/10~1/1000. By using the (P-c) component, the polymerization activity per transition metal can be improved. If (Pa)/(Pc) is in the range of 1/1 to 1/10000, the balance between the addition effect of the (Pc) component and the economy will be good, and the amount of aluminum present in the target-free α-olefin polymer will be present. Concerns.

In the method for producing a single-end unsaturated α-olefin polymer used in the fifth invention, the (Pa) component and the (Pb) component or the (Pa) component, the (Pb) component, and the (Pc) component may be used. Make preliminary contact. The preliminary contact can be carried out by bringing the (P-a) component into contact with the component (P-b), for example, and the method is not particularly limited, and a known method can be used. By such preparatory contact, it is effective in reducing the activity of the catalyst or reducing the catalyst cost such as a decrease in the use ratio of the (P-b) component of the catalyst.

(thermal decomposition reaction)

The thermal decomposition reaction can be carried out by heat-treating a single-end unsaturated α-olefin polymer.

The heating temperature can be pre-implemented according to the molecular weight of the target set. The experimental results are adjusted, preferably from 300 to 400 ° C, more preferably from 310 to 390 ° C. When the heating temperature is less than 300 ° C, there is a concern that the thermal decomposition reaction cannot be carried out. On the other hand, when the heating temperature exceeds 400 ° C, there is a concern that the obtained both terminal unsaturated α-olefin polymer is deteriorated.

Further, the thermal decomposition time (heat treatment time) is preferably from 30 minutes to 10 hours, more preferably from 60 to 240 minutes. If the thermal decomposition time is less than 30 minutes, the amount of the resulting unsaturated α-olefin polymer produced at the both ends may be too small. On the other hand, when the thermal decomposition time exceeds 10 hours, the obtained both terminal unsaturated α-olefin polymer may be deteriorated.

The above thermal decomposition reaction, for example, is used as a thermal decomposition device a reaction vessel such as stainless steel equipped with a stirring device, filled with an inert gas such as nitrogen or argon, placed in a single-end unsaturated α-olefin polymer, and then heated and melted to foam the molten polymer phase with an inert gas. Thereafter, the volatile product is removed and heated at a predetermined temperature for a predetermined period of time.

(radical decomposition reaction)

The radical decomposition reaction can be carried out at a temperature of 160 to 300 ° C, and the organic peroxide can be added in an amount of 0.05 to 2.0% by mass based on the single-end unsaturated α-olefin polymer.

The above decomposition temperature is preferably from 170 to 290 ° C, more preferably from 180 to 280 ° C. If the decomposition temperature is less than 160 ° C, there is a concern that the decomposition reaction cannot proceed. On the other hand, if the decomposition temperature exceeds 300 ° C, the decomposition will be intense, and the organic peroxide will be sufficiently stirred in the molten polymer. The decomposition before the diffusion has ended, and there is a concern that the yield is lowered.

Among the organic peroxides to be added, an organic peroxide having a one-minute half-life temperature of 140 to 270 ° C is preferable, and specific examples of the organic peroxide include the following compounds: diisobutylphosphonium peroxide; Propyl phenyl neodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3 , 3-tetramethylbutyl peroxy neodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, t-hexyl Oxidized neodecanoate, t-butyl peroxy neoheptanoate, t-hexyl peroxy valerate, t-butyl peroxy valerate, bis(3,5,5-trimethylhexyl) Peroxide, dilaurate peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2) -ethylhexyl peroxy)hexane, t-hexylperoxy-2-ethylhexanoate, bis(4-methylbenzylidene) peroxide, t-butylperoxy 2-ethylhexanoate, bis(3-methylbenzylidene) peroxide, benzhydryl peroxide, 1,1-di(t-butylperoxy)-2- A Cyclohexane, 1,1-di(t-hexylpropylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane 1,1-di(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexyl peroxidation Isopropyl monocarbonate, t-butyl peroxy maleate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t -butylperoxyisopropyl monocarbonate, t-butylperoxide 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 3,5-di-methyl-2,5- Bis(benzimidylperoxy)hexane, t-butylperoxyacetate, 2,2-di-(t-butylperoxy) Butane, t-butyl peroxybenzoate, n-butyl 4,4-di-(t-butylperoxy)valerate, bis(2-t-butylperoxy) Propyl)benzoate, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t -butyl cumene peroxide, di-t-butyl peroxide, p-Menthans hydrogen peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy) Alkyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide.

The amount of the organic peroxide added is preferably not to the single end The saturated α-olefin polymer is 0.1 to 1.8% by mass, more preferably 0.2 to 1.7% by mass. When the amount added is less than 0.05% by mass, the decomposition reaction rate becomes slow, and there is a concern that the production efficiency is deteriorated. On the other hand, when the amount added exceeds 2.0% by mass, there is a concern that the odor caused by the decomposition of the organic peroxide becomes a problem.

The decomposition time of the decomposition reaction, for example, 30 seconds to 10 hours, It is preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, the decomposition reaction is not sufficiently carried out, and there is a concern that a large amount of undecomposed organic peroxide remains. On the other hand, when the decomposition time exceeds 10 hours, the progress of the crosslinking reaction of the side reaction may become a problem, or the obtained both terminal unsaturated α-olefin polymer may become yellow.

The radical decomposition reaction can be carried out, for example, by any method which is decomposed by a batch method and decomposed by a melt continuous method.

When the radical decomposition reaction is carried out by a batch method, a reaction vessel such as stainless steel equipped with a stirring device is filled with an inert gas such as nitrogen or argon. The body is placed in a single-end unsaturated α-olefin polymer to be heated and melted, and an organic oxide is dropped into the molten single-end unsaturated α-olefin polymer, and heated at a predetermined temperature for a predetermined period of time. Base thermal decomposition reaction.

The dropping of the above organic peroxide may be carried out by dropping in the range of the above decomposition time, and the dropping may be either continuous dropping or batch dropping. Further, it is preferred that the reaction time from the end of the dropping time be set within the range of the above reaction time.

The organic peroxide can be dripped as a solution dissolved in a solvent.

The solvent is preferably a hydrocarbon solvent, and specific examples thereof include aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, hexadecane, and nonadecane; methylcyclopentane; An alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, cyclooctane or cyclododecane; and an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene or trimethylbenzene. Among these solvents, a solvent having a boiling point of 100 ° C or higher is also preferred.

Further, the single-end unsaturated α-olefin polymer can be dissolved in a solvent at the time of decomposition. The decomposition temperature at which the single-end unsaturated α-olefin polymer is dissolved in a solvent to be decomposed is generally in the range of 100 to 250 ° C, preferably in the range of 120 to 200 ° C.

When the radical decomposition reaction is carried out by the melt continuous method, the reaction time in the average residence time is, for example, 20 seconds to 10 minutes. The melt continuous method is compared with the batch method to make the mixed state good and the reaction time can be shortened.

The apparatus may use a single-axis or two-axis melt extruder, preferably an extruder having an injection port during the barreling process and capable of degassing under reduced pressure, which is an extruder having an L/D=10 or more.

Free radical decomposition reaction by melt continuous method The apparatus may be a method in which an organic peroxide is impregnated into a single-end unsaturated α-olefin polymer, or a method in which a single-end unsaturated α-olefin polymer and an organic peroxide are separately supplied and mixed.

Organic peroxide to mono-terminal unsaturated α-olefin polymer The impregnation is specifically carried out by adding a predetermined amount of the organic peroxide to the mono-terminal unsaturated α-olefin polymer in the presence of an inert gas such as nitrogen, and stirring the mixture at room temperature to 40 ° C to uniformly coat the raw material particles. Absorbed and impregnated. The obtained single-end unsaturated α-olefin polymer impregnated with an organic peroxide (hereinafter referred to as "dip particles") is decomposed by melt extrusion or the impregnated particles are added as a masterbatch to the mono-terminal unsaturated α- The olefin polymer is decomposed to obtain a two-end unsaturated α-olefin polymer.

Further, when the organic peroxide is a solid or organic peroxide having low solubility to the mono-terminal unsaturated α-olefin polymer, the solution of the organic peroxide in the hydrocarbon solvent may be absorbed and impregnated at the single end. Saturated alpha-olefin polymer.

Single-end unsaturated α-olefin polymer and organic peroxidation The mixture of the individual supplies is supplied to the raw material α-olefin polymer and the organic peroxide at a constant flow rate in the hopper portion of the extruder, or may be supplied at a constant flow rate during the barreling of the organic peroxide.

[sclerosing composition]

The curable composition of the fifth invention is prepared by blending (A) the functionalized α-olefin polymer and (B) a polyisocyanate compound, and further adding (C) a diluent, (D) adhesion imparting It is also preferable that one or more types of the agent and (E) hardening-promoting catalyst are used.

(B) Polyisocyanate compound

The (B) polyisocyanate compound used in the fifth invention is an organic compound having two or more isocyanate groups in one molecule, and a reactive isocyanate group having a hydroxyl group to the functionalized α-olefin polymer. Examples of the (B) polyisocyanate compound include aromatic, aliphatic, and alicyclic compounds.

Specific examples thereof include 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'- and 2,2'-diphenylmethane diisocyanate. Mixture (all above MDI), toluene diisocyanate (TDI), carbodiimide modified diphenylmethane diisocyanate, polymethyl polyphenyl isocyanate, phenyl diisocyanate, naphthalene-1,5- Aromatic polyisocyanates such as diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate, cis (isocyanate phenyl) phosphorothioate, cumene-2,4-diisocyanate; benzodimethyl di An aliphatic-aromatic polyisocyanate such as isocyanate (XDI) or tetramethyl dimethyl diisocyanate (TMXDI) (isocyanate group is an isocyanate group which does not have an aliphatic hydrocarbon and directly bonds to an aromatic ring, that is, a molecule a polyisocyanate having no isocyanate group directly bonded to an aromatic ring; Further, it may be exemplified by hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4 - an aliphatic polyisocyanate such as isocyanate methyl octane, 1,3,6-hexamethyl-triisocyanate or trimethylhexamethyl-diisocyanate; and trans-cyclohexane-1,4-di Isocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated toluene diisocyanate, hydrogenated dimethyl diisocyanate, hydrogenated tetramethyl benzene dimethyl An alicyclic polyisocyanate such as a diisocyanate; a cyclized trimer (isocyanurate modified product), a biuret modified product or an ethylene glycol or a 1,4-butyl group of the above polyisocyanate compound; Alkanediol, propylene glycol, dipropylene glycol, trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene glycol glycol, polyester polyol, acrylic polyol, hydrogenated dimer acid diisocyanate , hydrogenation of polyalkadiene polyols, polyalkadiene polyols Part jian ethylene - vinyl acetate copolymer addition, castor oil-based polyol compound and the polyol polyisocyanate compound and the like react.

These polyisocyanate compounds may be used in combination of two or more kinds, and the isocyanate groups of these polyisocyanate compounds may further be phenols, anthracenes, sulfoxides, mercaptans, alcohols, ε-caprolactam, ethyleneimine. A so-called blocked isocyanate compound which is blocked by a blocking agent such as α-pyrrolidone, diethyl malonate, sodium hydrogen sulfite or boric acid may also be used.

The aforementioned (A) functional group in the curable composition of the fifth invention The compounding ratio of the α-olefin polymer to the (B) polyisocyanate compound is not particularly limited, but (A) the isocyanate group (NCO) of the hydroxyl (OH) (B) polyisocyanate compound of the functionalized α-olefin polymer The final ratio (NCO/OH) is preferably 0.3 to 5 in terms of molar ratio, and preferably 0.5 to 4.

Here, the term "final ratio" is used to produce the actual hardened body, and the following methods are used.

A single method; first, at least a component obtained by removing a polyisocyanate compound from a total blending component is added and mixed to obtain a mixture. A polyisocyanate compound and a component which has not been previously used for mixing are added to the mixture and mixed to obtain a liquid polymer composition. The preferred CO/OH ratio at this time is 0.5 to 2.5 in terms of molar ratio.

Prepolymer method (1); in the presence of a certain equivalent ratio NCO / OH of 1.7 ~ 25, the functionalized α-olefin polymer and polyisocyanate compound, in the presence or absence of part or all of other additives In the presence of the reaction, a prepolymer is obtained after the reaction. The residual component is mixed with the prepolymer to obtain a liquid polymer composition. The preferred NCO/OH ratio at this time is 0.5 to 2.5 in terms of molar ratio. At this time, when the prepolymer is obtained, the Mohr ratio NCO/OH ratio of the functional group related to the reaction is substantially 1.0, so that the final NCO/OH ratio is in the range of 0.5 to 2.5.

The prepolymer method (2); in the range of the specified equivalent ratio NCO/OH of 1.7 to 5, the entire component is added and reacted to obtain a prepolymer. The prepolymer is reacted with moisture (water) in the air.

(C) thinner

Examples of the diluent include oils such as naphthenic oils, paraffinic oils, and aromatic oils, and oils thereof, and liquid rubbers such as liquid polybutene and liquid isopolybutene. These may be used alone or in combination of two or more.

The content of the (C) diluent in the curable composition of the fifth invention is generally from 1 to 50% by mass, preferably from 2 to 40% by mass, based on 100% by mass of the curable composition of the fifth invention.

(D) Adhesive imparting agent

As the adhesion imparting agent (adhesive imparting resin), rosin and its derivatives, terpene resin and hydrogenated resin thereof, styrene resin, coumarone-indene resin, and dicyclopentadiene (DCPD) system can be used. Resin and its hydrogenated resin, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated resin thereof, and C5-C9 copolymerized petroleum resin and Among the tackifiers which are generally used, such as a hydrogenated resin, those having good compatibility with the functionalized α-olefin polymer are selected. Alternatively, one of these adhesiveness-imparting agents may be used alone or two or more of them may be used as a mixture.

The preferred adhesion imparting agent is selected from the group consisting of terpene resins and hydrogenated resins, styrene resins, and dicyclopentane from the viewpoint of balance between removability and adhesion to curved surfaces and irregularities. Alkene (DCPD) resin and hydrogenated resin thereof, aliphatic (C5) petroleum resin and hydrogenated resin thereof, aromatic (C9) petroleum resin and hydrogenated tree thereof One type of resin or a mixture of two or more types of a group of a copolymerized petroleum resin of a C5-based-C9 type and a hydrogenated resin thereof is preferred.

The content of the (D) adhesiveness-imparting agent in the curable composition of the fifth invention is generally 1 to 50% by mass, preferably 2 to 45% by mass based on 100% by mass of the curable composition of the fifth invention. %.

(E) hardening promoting catalyst

Specific examples of the (E) curing-promoting catalyst include tri-ethylenediamine, tetramethylguanidine, N,N,N'N'-tetramethylhexane-1,6-diamine, and N. ,N,N'N"N"-pentamethyldiethylideneamine, bis(2-dimethylaminoethyl)ether, 1,2-dimethylimidazole, N-methyl-N' a tertiary amine such as -(2-dimethylamino)ethylpiperazine or diazabicycloundecene; stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptan, Organometallic compounds such as dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiol, dioctyltin thiocarboxylate, phenyl mercury propionate, lead octenoate; A carboxylate of a tertiary amine or the like.

(E) Addition amount of the hardening-promoting catalyst When the functionalized α-olefin polymer is at least 10 parts by mass, the hardening promoting effect is not excessive and the risk of local abnormal reaction (gelation) is excessive. Sex will decrease.

(other ingredients)

The curable composition of the fifth invention may contain an additive such as a filler, a pigment or an antioxidant in a range that does not impair the effects of the fifth invention.

The filler contains an inorganic filler and an organic filler.

Examples of the inorganic filler include cerium oxide, aluminum oxide, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, cerium oxide, ferrite, calcium hydroxide, magnesium hydroxide, and hydrogen. Alumina, basic magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium citrate, talc, clay, mica, montmorillonite, bentonite, sepiolite, Igne vermiculite, sericite, glass fiber, glass beads, cerium oxide system, barium, aluminum nitride, boron nitride, tantalum nitride, carbon black, graphite, carbon fiber, carbon bar, zinc borate, various magnetic powders Wait.

An inorganic filler may be used instead of the inorganic filler, or a surface treatment may be carried out by various coupling agents such as a decane-based or titanate-based compound. Examples of the treatment method include a method in which an inorganic filler is directly treated with various coupling agents such as a dry method, a slurry method, or a spray method, or a collective mixing method such as a direct method or a master batch method, or a dry concentration method. And other methods.

Examples of the organic filler include starch (for example, powdered starch), fibrous leather, natural organic fiber (for example, cellulose such as cotton or hemp), and synthetic polymers such as nylon, polyester, and polyolefin. Synthetic fibers and the like.

Among the above pigments, there are inorganic pigments and organic pigments (for example, azo-based pigments and polycyclic pigments).

Examples of the inorganic pigment include oxides (titanium dioxide, zinc oxide (zinc oxide), iron oxide, chromium oxide, iron black, cobalt blue, etc., as hydroxides: hydrated alumina, iron oxide yellow, chrome green, etc.). Sulfide (zinc sulfide, zinc antimony white, cadmium yellow, vermilion, cadmium red, etc.), chromate (yellow lead, molybdenum) Orange, zinc chromate, strontium chromate, etc., citrate (white carbon, clay, talc, ultramarine, etc.), sulfate (precipitated barium sulfate, barite powder, etc., as carbonate: calcium carbonate, lead white, etc. In addition to these, ferricyanide (iron blue), phosphate (manganese violet), carbon (carbon black), and the like can be used.

Examples of the azo-based pigment of the organic pigment include soluble azo (carmine 6B, lake red C, etc.), insoluble azo (disazo yellow, lake red 4R, etc.), and condensed azo (dyeing yellow 3G, Dyeing magenta RN, etc.), azo wrong salt (nickel azo yellow, etc.), benzimidazolone azo (permanent orange HL, etc.). Examples of the polycyclic type pigment which is an organic pigment include isoindolinone, isoporphyrin, quinophthalone, pyrazolone, anthraquinone yellow, anthracene, diketone-pyrrolo-pyrrole, and pyrrole. , pyrazolone, anthrone, purple ring ketone, hydrazine, quinacridone, anthracene, oxazine, imidazolinone, xanthene, normal carbon, purpurin, phthalocyanine, nitroso and the like.

The curable composition of the fifth invention can be produced by mixing the above components by any method.

(E) The hardening promoting catalyst can be used after mixing. (E) The method of adding the hardening-promoting catalyst is to pre-modulate the catalyst masterbatch with a high concentration (E) hardening-promoting catalyst, blending the catalyst masterbatch with other components, and then kneading or melting. .

Further, the curable composition of the fifth invention can be produced using a solvent.

In the curable composition of the fifth aspect of the invention, when it is used as a solvent-based adhesive dissolved in a solvent, it can be applied and sprayed, and then a film is formed on the surface of the substrate to be adhered to the object.

Further, the polymerizable composition of the fifth invention is subjected to a polar solvent such as water. It can also be used as an adhesive when dispersing or emulsifying. Further, the curable composition of the fifth invention is formed into a sheet shape or a film shape, sandwiched between the substrates, heated to a temperature at which the curable composition can flow, and then cured by cooling and solidification.

[hardened matter]

The fifth invention further provides a cured product which hardens the above hardenable composition.

The curable composition of the fifth invention can be subjected to a hardening reaction at a low temperature. Specifically, when the curable composition of the fifth invention is subjected to a curing reaction at 100 ° C or lower, a cured product can be obtained. The hardening reaction is a method of preparing a curable composition of the fifth invention, directly reacting the functionalized α-olefin polymer with a polyisocyanate compound, or prepolymerizing by the prepolymer method (2) described above. A method in which a substance is contacted with moisture or moisture, and then cured by heat treatment or aging at room temperature. When moisture or moisture is brought into contact, for example, the curable adhesive composition of the fifth invention may be placed in the air, immersed in a water tank, and steam may be introduced. Further, the temperature may be room temperature (25 ° C), but if it is set to a high temperature, crosslinking may be carried out in a short time.

The curable composition of the fifth invention can be used for a resin compatibilizing agent, an emulsification of a polyolefin, a reactive adhesive, a reactive hot-melt adhesive, other adhesives, an adhesive, a sealing material, a sealing material, and a potting. Materials, reactive plasticizers, modifiers, etc.

The cured product of the fifth invention can be used for a reactive adhesive, a reactive hot melt adhesive, other adhesives, an adhesive, a sealing material, a sealing material, and a potting Materials, reactive plasticizers, modifiers, etc. Further, since the cured product obtained by the above curing method has heat resistance, it can be used even in a high temperature environment.

[Examples]

The invention is further illustrated by the examples, but the invention is not limited by the examples.

<First invention> Synthesis Example 1-1 [(1,2'-Dimethylhydrazinyl)(2,1'-dimethylarylene)-bis(3-phenylindole)zirconium dichloride (wrong A) Synthesis〕

Under a nitrogen stream, 76.5 ml (229.5 mmol) of a diethyl ether solution of phenylmagnesium bromide was placed in a 1000 ml flask and cooled in an ice bath. Here, 30 g (227.2 mmol) of 1-nonanone was dissolved in 300 ml of diethyl ether, and the mixture was gradually added dropwise. After stirring at room temperature for one hour, it was cooled in an ice bath, and 6 mol/l of hydrochloric acid was added dropwise. After stirring at room temperature, the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After the aqueous phase was separated, the organic phase was dried and solvent was evaporated to give &lt;3&gt;

Next, 16.7 g (87.1 mmol) of 1-phenylindole obtained was placed in a 300 ml flask and dissolved in 70 ml of dimethyl hydrazine. 4 ml of water was placed and cooled in an ice bath. Here, 15.6 g (87.1 mmol) of N-bromosuccinimide was gradually added, and the mixture was stirred at room temperature for 10 hours. Put this in the ice bath After cooling, 60 ml of water was added, and the organic layer was extracted with diethyl ether. After the aqueous phase was separated, the organic phase was dried and then evaporated to ethylamine.

Crude product of 2-bromo-1-indan-1-ol obtained above 24.0 g (83.3 mmol) was placed in a 300 ml flask, dissolved in 200 ml of toluene, and 0.48 g (2.5 mmol) of p-toluenesulfonic acid was added. A Dean-Stark tube was attached to the flask and refluxed for 2 hours. The solvent was distilled off, and the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After separating the aqueous phase, the organic phase was dried and the solvent was removed to give a crude product of 2-bromo-1-phenylindole. This was purified by column to give 2-bromo-1-phenylindole 17.9 g (66.4 mmol) (yield 80%).

Next, the resulting 2-bromo-1-phenylindole was obtained under a nitrogen stream. 2.7 g (10.0 mmol) was placed in a 200 ml Schlenk bottle, dissolved in 50 ml of diethyl ether, and cooled at 0 ° C, and a solution of n-butyllithium (n-BuLi) in hexane (concentration 2.6 mol/ l) 3.8 ml (10.0 mmol), stirred at room temperature for 3 hours. This was again cooled at 0 ° C, and 30 ml of diethyl ether and 12.5 ml (20.0 mmol) of a solution of t-butyllithium (t-BuLi) in pentane (concentration: 1.6 mol/l) were added, and stirred at room temperature for 3 hours. .

After stirring, the mixture was cooled to -78 ° C, and dichloromethane (dichloromethanehexane) This was again cooled to -78 ° C, and 0.6 ml (5.0 mmol) of dichloromethane was added dropwise, and stirred at room temperature overnight. Thereafter, after adding water and stopping the reaction, (1,2'-dimethylarylene) (2,1'-dimethylhydrazinyl) bis(3-phenylindole) 1.1 g (precipitated) 2.2 mmol), this was taken (yield: 44%).

Secondly, in the Schlenk bottle, the above-mentioned (1, 2’- Dimethylhydrazinyl)(2,1'-dimethylhydrazinyl)bis(3-phenylindole) 1.6g (3.2mmol) was dissolved in 12.6ml of diethyl ether, cooled at 0 ° C, added n 2.6 ml (6.6 mmol) of a butyllithium (n-BuLi) hexane solution (concentration: 2.6 mol/l) was again returned to room temperature and stirred for 1 hour.

The solvent was distilled off from the obtained solution, and the residual solid was washed with 20 ml of hexane, and then dried under reduced pressure to obtain quantitative (1,2'-dimethyl sulfenyl) (2,1'- A white solid of an ether adduct of a lithium salt of dimethyl sulfinyl) bis(3-phenylhydrazine).

The ether addition of the lithium salt obtained above was suspended under a nitrogen stream The mixture was suspended in 18 ml of dichloromethane, cooled to -78 ° C, and a suspension of 0.74 g (3.2 mmol) of methylene chloride (8 ml) previously cooled to -78 ° C was added dropwise to the suspension, and then returned to the chamber. After the temperature, the mixture was stirred for 4 hours.

The resulting solution was filtered, and the filtrate was concentrated to give a yellow solid. This was washed with 10 ml of hexane to obtain (1,2'-dimethyl sulfenyl) (2,1'-dimethyl sulfenyl) bis(3-phenylindole) zirconium dichloride ( Yellow microcrystals of the wrong form A) 1.3 g (2.0 mmol). (yield 62%)

The ¹ H-NMR spectrum of the yellow microcrystal was obtained, and the following results were obtained.

^{1 H-NMR (500MHz, CDCl3} ): δ0.31 (s, -Me 2 Si-, 6H), 1.21 (s, -Me 2 Si-, 6H), 7.18-7.69 (m, Ar-H, 18H)

Example 1-1 [Manufacture of terminally unsaturated liquid polypropylene]

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, 0.2 micromolar of the wrong body, 0.8 micromoles of quinone pentafluorophenyl borate, and then hydrogen were introduced. 0.05MPa. Propylene was added while stirring, the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 60 ° C for 30 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 100 g of terminally unsaturated liquid polypropylene.

For the obtained terminally unsaturated liquid polypropylene, the 2,1-binding fraction, the 1,3-binding fraction, the melting heat absorption ΔHD, the glass transition temperature Tg, and the meso-penta unit [mmmm] were measured by the following measurement methods. 〕 fraction, external pentad fraction [rrrr] fraction, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of unsaturation groups per molecule, and evaluation of decomposition efficiency, reactivity and fluidity. The results are shown in Table 1-1.

[ ¹³ C-NMR measurement]

The ¹³ C-NMR spectrum was measured under the following apparatus and conditions to obtain a 2,1-binding fraction, a 1,3-binding fraction, a meso-penta-unit [mmmm] fraction, and an external-rotating pentad. [rrrr] fraction.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: mixed solvent of 1,2,4-trichlorobenzene and heavy benzene of 90:10 (capacity ratio)

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

[DSC measurement]

Using a differential scanning calorimeter (DSC-7 manufactured by Perkin-Elmer Co., Ltd.), 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the heat of fusion obtained by heating at 10 ° C /min was taken as Δ. HD and the glass transition temperature Tg were obtained, and the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve at this time was obtained as the melting point Tm-D.

[GPC measurement]

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were determined by a gel permeation chromatography (GPC) method. The following apparatus and conditions were used for the measurement, and the weight average molecular weight in terms of polystyrene was obtained.

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0ml/min

Sample concentration: 2.2 mg/ml

Injection volume: 160μl

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

[terminal unsaturated group concentration]

The terminal vinylidene at δ4.8~4.6(2H) obtained by ¹ H-NMR, the terminal vinyl group at δ5.9~5.7 (1H) and the δ1.05~0.60 (3H) Based on the methyl group present, the terminal unsaturated group concentration (C) (% by mole) was calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturated group concentration (C) = [vinylidene amount] + [vinyl amount]

[Number of unsaturation groups per molecule)

The terminal unsaturated group concentration (C, mol%) calculated by the above method and the number average molecular weight (Mn) and monomer molecular weight (M) obtained by gel permeation chromatography (GPC), The number of terminal unsaturated groups per molecule was calculated by the following formula.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

[decomposition efficiency]

The decomposition efficiency was calculated by the following formula and evaluated based on the following.

Decomposition efficiency (%) = [(weight average molecular weight (Mw) before decomposition - weight average molecular weight (Mw) after decomposition) / weight average molecular weight (Mw) before decomposition] × 100%

○: Decomposition efficiency ≧ 40%

×: decomposition efficiency <40%

[reactivity]

The polymethylhydroquinone was mixed and hardened at 110 ° C for 2 hours. The hardening condition was visually confirmed and the reactivity was evaluated.

◎: It is completely hardened.

○: Although it is not completely cured, it exhibits a hardened state to the extent that fluidity disappears.

×: There is no hardening at all, and the state of fluidity is maintained.

〔fluidity〕

The fluidity was visually confirmed at room temperature, and evaluation was performed on the following basis.

○: shows the fluidity of the high viscosity oil level.

△: shows the fluidity of the degree of honey.

×: Completely no fluidity.

Example 1-2 [Production of terminally unsaturated liquid polypropylene]

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, 0.2 micromolar of the wrong body, 0.8 micromoles of quinone pentafluorophenyl borate, and then hydrogen were introduced. 0.05MPa. Propylene was added while stirring, the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 70 ° C for 30 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 100 g of terminally unsaturated liquid polypropylene.

For the obtained terminally unsaturated liquid polypropylene, 2,1-binding fraction, 1,3-binding fraction, melting heat absorption ΔHD, glass transition temperature Tg, meso-penta-unit [mmmm] fraction were measured. The external rotation pentad fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of terminal unsaturated groups per molecule, and the decomposition efficiency, reactivity, and fluidity were evaluated. The results are shown in Table 1-1.

Example 1-3 [Production of terminally unsaturated liquid polypropylene]

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, 0.2 micromolar of the wrong body, 0.8 micromoles of quinone pentafluorophenyl borate, and then hydrogen were introduced. 0.05MPa. Propylene was placed while stirring, the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 80 ° C for 30 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 100 g of terminally unsaturated liquid polypropylene.

For the obtained terminally unsaturated liquid polypropylene, 2,1-binding fraction, 1,3-binding fraction, melting heat absorption ΔH-D, glass transition temperature were measured. Tg, meso-penta-unit [mmmm] fraction, external-rotating penta-unit [rrrr] fraction, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, Also, the decomposition efficiency, reactivity, and fluidity were evaluated. The results are shown in Table 1-1.

Example 1-4 [Production of High Terminal Unsaturated Liquid Polypropylene]

70 g of terminally unsaturated liquid PP produced in Example 1-1 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. Stirring was carried out for 30 minutes under a nitrogen stream.

Stirring was started, and the temperature of the resin was raised to 160 ° C using a mantle heater. The mantle heater was controlled to a temperature at which the resin temperature was 230 °C. Here, 0.4 ml of PERHEXA25B was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After the completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours to carry out radical decomposition to obtain a highly terminally unsaturated liquid polypropylene.

For the obtained high-end unsaturated liquid polypropylene, the 2,1-binding fraction, the 1,3-binding fraction, the melting heat absorption ΔHD, the glass transition temperature Tg, and the meso-penta-unit [mmmm] fraction were measured. The external rotatory unit rrrr fraction, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), and the number of terminal unsaturated groups per molecule. Also, the decomposition efficiency, reactivity, and fluidity were evaluated. The results are shown in Table 1-1.

Further, the yield of the obtained highly terminally unsaturated liquid polypropylene was 99.3% by mass in terms of the terminally unsaturated liquid polypropylene to be charged, and the by-product amount was a trace amount.

Example 1-5 [Production of High End Unsaturated Liquid Polypropylene]

70 g of the terminally unsaturated liquid polypropylene produced in Example 1-1 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. Stirring was carried out for 30 minutes under a nitrogen stream.

After the stirring was started, the resin temperature was raised to 160 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 230 °C. Here, PERHEXA25B 0.4 ml was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours to carry out radical decomposition to obtain a highly terminally unsaturated liquid polypropylene.

For the obtained high-end unsaturated liquid polypropylene, the 2,1-binding fraction, the 1,3-binding fraction, the melting heat absorption ΔHD, the glass transition temperature Tg, and the meso-penta-unit [mmmm] fraction were measured. The excimer pentad fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the number of terminal unsaturated groups per molecule were evaluated for decomposition efficiency, reactivity, and fluidity. The results are shown in Table 1-1.

Further, the yield of the obtained highly terminally unsaturated liquid polypropylene was 99.3% by mass in terms of the terminally unsaturated liquid polypropylene to be charged, and the by-product amount was a trace amount.

Synthesis Example 1-2 [Synthesis of (1,1'-Extended Ethyl) (2,2'-Tetramethyldialkylene) Bismuth Zirconium Dichloride (Limited B)

Magnesium (12g, 500 millimolar) in a 500 ml 2-neck flask Tetrahydrofuran (30 ml) was added to 1,2-dibromoethane (0.2 ml) to activate magnesium. 2 -Bromoindole (20 g, 103 mmol) dissolved in tetrahydrofuran (150 ml) was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldioxane (9.4 ml, 5.1 mmol) was added dropwise at 0 °C. After the reaction mixture was stirred at room temperature for 1 hour, the solvent was evaporated, and the residue was evaporated to ethyl ether (150 ml, 2) to give 1,2-di(1H-indol-2-yl)-1,1, 2,2-Tetramethyldioxane as a white solid (15.4 g, 44.4 mmol, yield 86%).

This was dissolved in diethyl ether (100 ml), and n-butyllithium (2.6 mol/liter, 38 ml, 98 mmol) was added dropwise at 0 ° C, and after stirring at room temperature for 1 hour, precipitated white. powder. The clear liquid was removed and the solid was washed with EtOAc (EtOAc) (EtOAc)

This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 °C. After the reaction mixture was stirred at room temperature for 1 hour, it was dried and solidified, and the residue was extracted with hexane (150 ml) to obtain a colorless oily liquid (14.2 g, 37.9 mmol). ear).

This was dissolved in diethyl ether (120 ml), and n-butyllithium (2.6 mol/liter, 32 ml, 84 mmol) was added dropwise at 0 ° C, and a white powder was precipitated after stirring at room temperature for 1 hour. . The clear liquid was removed, and the solid was washed with hexane (70 ml) to give a white powder (14.0 g, 31 mmol, yield 81%) of the lithium salt of the cross-linking ligand.

Lithium salt of the obtained cross-linked ligand (3.00 g, 6.54 mmol) To a suspension of toluene (30 ml) of the ear, a suspension of zirconium tetrachloride (1.52 g, 6.54 mmol) in toluene (30 ml) was dropped at -78 °C in a transfer tube. After the reaction mixture was stirred at room temperature for 2 hours, the clear liquid was separated, and the residue was extracted with toluene.

The solvent of the clear liquid and the extract was distilled off under reduced pressure, and dried and solidified to obtain (1,1'-extended ethyl group) (2,2'- represented by the following formula (1) as a yellow solid. Tetramethyldialkylene)bisindole zirconium dichloride (wrong B) (2.5 g, 4.7 mmol, yield 72%).

The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ): δ 0.617 (s, 6H, -SiMe ₂ -), 0.623 (s, 6H, -SiMe ₂ -), 3.65-3.74, 4.05 - 4.15 (m, 4H, CH ₂ CH ₂ ), 6.79 (s, 2H, CpH), 7.0-7.5 (m, 8H, Aromatic-H)

Example 1-6 [Production of terminally unsaturated liquid polybutene]

In a heated and dried 1 liter pressure sterilizer, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (200 mL), and B (10 μmol/mL, 0.20mL, 2.0μmol), MAO (2000μmol) made by Tosoh Fine Chemical Co., Ltd., and then introduced into hydrogen 0.1 MPa. The temperature was set to 70 ° C while stirring, and polymerization was carried out for 30 minutes. After the completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to give 82 g of 1-butene homopolymer.

For the obtained terminally unsaturated liquid polybutene, the 2,1-binding fraction, the 1,3-binding fraction, the melting heat absorption ΔHD, the glass transition temperature Tg, and the meso-penta-unit [mmmm] fraction were measured. The external rotation pentad fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of terminal unsaturated groups per molecule, and the decomposition efficiency, reactivity, and fluidity were evaluated. The results are shown in Table 1-1.

Example 1-7 [Production of High Terminal Unsaturated Liquid Polybutene]

70 g of the terminally unsaturated liquid polybutene produced in Example 1-6 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. Stirring was carried out for 30 minutes under a nitrogen stream.

After the stirring was started, the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 230 °C. Here, PERHEXA25B 0.4 ml was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours to carry out radical decomposition to obtain a highly terminally unsaturated liquid polybutene.

For the obtained high-end unsaturated liquid polybutene, the 2,1-binding fraction, the 1,3-binding fraction, the melting heat absorption ΔHD, the glass transition temperature Tg, and the meso-equivalent unit (mmmm) were measured. Rate, outer rotation five units [rrrr The fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the number of unsaturation groups per molecule, and the decomposition efficiency, reactivity, and fluidity were evaluated. The results are shown in Table 1-1.

Further, the yield of the highly terminally unsaturated liquid polybutene obtained was 99.3 mass% with respect to the terminal unsaturated liquid polybutene charged, and the amount of by-product was a trace amount.

Comparative Example 1-1

Referring to Organometallics 2000, 19, 1870-1878, a synthetic C [dimethyl sulfenyl (η ¹ -tert-butyl decylamine) (η ⁵ -tetramethylcyclopentadiene) titanium dichloride] was synthesized.

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mM of triisobutylaluminum, 0.2 mM of malformed pentad, and 0.8 micromole of quinone pentafluorophenyl borate were added. Hydrogen 0.05 MPa. Propylene was placed while stirring, and the pressure was raised to a total pressure of 0.5 MPa, and polymerization was carried out at a temperature of 90 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 50 g of terminally unsaturated liquid propylene.

For the obtained terminally unsaturated liquid polypropylene, 2,1-binding fraction, 1,3-binding fraction, melting heat absorption ΔHD, glass transition temperature Tg, meso-penta-unit [mmmm] fraction, The excimer pentad fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the number of terminal unsaturated groups per molecule were evaluated for decomposition efficiency, reactivity, and fluidity. The results are shown in Table 1-1.

Comparative Example 1-2

70 g of the terminally unsaturated liquid polypropylene produced in Comparative Example 1-1 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device, and stirred under a nitrogen stream for 30 minutes.

After the stirring was started, the resin temperature was raised to 160 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 230 °C. Here, PERHEXA25B 0.4 ml was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours to carry out radical decomposition to obtain a highly terminally unsaturated liquid polypropylene.

For the obtained high-end unsaturated liquid polypropylene, the 2,1-binding fraction, the 1,3-binding fraction, the melting heat absorption ΔHD, the glass transition temperature Tg, and the meso-penta-unit [mmmm] fraction were measured. The excimer pentad fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the number of terminal unsaturated groups per molecule were evaluated for decomposition efficiency, reactivity, and fluidity. The results are shown in Table 1-1.

The yield of the obtained highly terminally unsaturated liquid polypropylene was 99.3 mass% with respect to the terminal unsaturated liquid polypropylene charged, and the amount of by-products was a trace amount.

Comparative Example 1-3

Reference to JP-A-11-193309, Synthesis of sterilant D [dimethyl decyl (2,3,4,5-tetramethylcyclopentadiene) (3-tert-butyl-5-methyl-2-benzene) oxygen Base) titanium dichloride].

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mM of triisobutylaluminum, D 2 micromolar of dysentery, and 8 micromoles of quinol pentafluorophenyl borate were further introduced. Hydrogen 0.05 MPa. Propylene was placed while stirring, and the pressure was raised to a total pressure of 0.65 MPa, and polymerization was carried out at a temperature of 70 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 30 g of terminally unsaturated liquid polypropylene.

For the obtained terminally unsaturated liquid polypropylene, 2,1-binding fraction, 1,3-binding fraction, melting heat absorption ΔHD, glass transition temperature Tg, meso-penta-unit [mmmm] fraction, The excimer pentad fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the number of terminal unsaturated groups per molecule were evaluated for decomposition efficiency, reactivity, and fluidity. The results are shown in Table 1-1.

Comparative Example 1-4

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, and malformed E[(1,2'-dimethylarylene) (2,1'- Dimethylhydrazinyl)-biguanide zirconium dichloride] 0.2 micromolar, quinone pentafluorophenyl borate 0.8 micromolar, further introduced with hydrogen 0.05 MPa. Propylene was placed while stirring, and the pressure was raised to a total pressure of 0.65 MPa, and polymerization was carried out at a temperature of 70 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 20 g of terminally unsaturated liquid polypropylene.

For the obtained high-end unsaturated liquid polypropylene, the 2,1-binding fraction, the 1,3-binding fraction, the melting heat absorption ΔHD, the glass transition temperature Tg, and the meso-penta-unit [mmmm] fraction were measured. The excimer pentad fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the number of terminal unsaturated groups per molecule were evaluated for decomposition efficiency, reactivity, and fluidity. The results are shown in Table 1-1.

<Second invention> [DSC measurement]

Using a differential scanning calorimeter (DSC-7 manufactured by Perkin-Elmer Co., Ltd.), 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the heat of fusion obtained by heating at 10 ° C /min was taken as Δ. HD and the glass transition temperature Tg.

[GPC measurement]

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were determined by a gel permeation chromatography (GPC) method. The following apparatus and conditions were used for the measurement, and the weight average molecular weight in terms of polystyrene was obtained.

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0ml/min

Sample concentration: 2.2 mg/ml

Injection volume: 160μl

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

[Number of unsaturation groups per molecule)

The terminal unsaturated group concentration (C, mol %) calculated by the following method and the number average molecular weight (Mn) and the monomer molecular weight (M) obtained by the above gel permeation chromatography (GPC) are as follows The formula calculates the number of terminal unsaturated groups per molecule.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

(end unsaturated group concentration)

The terminal vinylidene at δ4.8~4.6(2H) obtained by ¹ H-NMR, the terminal vinyl group at δ5.9~5.7 (1H) and the δ1.05~0.60 (3H) Based on the methyl group present, the terminal unsaturated group concentration (C) (% by mole) was calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturated group concentration (C) = [vinylidene amount] + [vinyl amount]

[ ¹³ C-NMR measurement]

The ¹³ C-NMR spectrum was measured under the following apparatus and conditions to obtain a meso pentad fraction (mmmm) fraction and an external pentad fraction [rrrr] fraction.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

Further, from the measurement results of the above ¹³ C-NMR spectrum, the 1,3-binding fraction, the 1,4-binding fraction, and the 2,1-binding fraction were calculated by the following formula.

<The case of propylene-based polymer>

1,3-binding fraction = (D/2) / (A + B + C + D) × 100 (% by mole)

2,1-binding fraction = {(A+B)/2}/(A+B+C+D)×100 (mole%)

A: integral value of 15~15.5ppm

B: integral value of 17~18ppm

C: integral value of 19.5~22.5ppm

D: integral value of 27.6~27.8ppm

<1-butene-based polymer>

1,4-binding fraction = E / (A + B + C + D + E) × 100 (% by mole)

2,1-binding fraction = {(A+B+D)/3}/(A+B+C+D)×100 (mole%)

A: integral value of 29.0~28.2ppm

B: integral value of 35.4~34.6ppm

C: integral value of 38.3~36.5ppm

D: integral value of 43.6~42.8ppm

E: integral value of 31.1 ppm

[assessment] (1) Hardening reactivity of the composition at low temperature

The polymethylhydroquinone and the hydroquinone alkylation catalyst were mixed in air in polypropylene or polybutene to produce a curable adhesive composition, which was directly cured at room temperature (25 ° C) for 2 hours. This hardening condition was visually confirmed and the reactivity was evaluated.

○: It is completely cured.

△: The hardening reaction progressed and the viscosity increased.

×: No hardening at all.

(2) The composition is rational at normal temperature

For the composition, the presence or absence of fluidity at 25 ° C was visually confirmed.

○: There is fluidity.

×: No fluidity.

(3) Heat resistance of hardened material

The cured product was heated in a glass oven at 180 ° C for 10 minutes, and the cured form before and after heating was visually observed while hardening by tactile measurement. The rubber elasticity of the object.

○: The shape was maintained and the rubber elasticity was exhibited.

△: The shape changed in heating for 10 minutes, and the state changed to a state in which no rubber elasticity was exhibited.

×: The shape cannot be maintained and the rubber elasticity is not displayed.

Manufacturing Example 2-1 [(1,2'-Dimethylhydrazinyl)(2,1'-dimethylarylene)-bis(3-phenylindole)zirconium dichloride (former A)

Under a nitrogen stream, 76.5 ml (229.5 mmol) of a diethyl ether solution of phenylmagnesium bromide was placed in a 1000 ml flask and cooled in an ice bath. Here, 30 g (227.2 mmol) of 1-nonanone was dissolved in 300 ml of diethyl ether, and the mixture was gradually added dropwise. After stirring at room temperature for one hour, it was cooled in an ice bath, and 6 mol/l of hydrochloric acid was added dropwise. After stirring at room temperature, the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After the aqueous phase was separated, the organic phase was dried and solvent was evaporated to give &lt;3&gt;

Next, we will get the 1-phenyl hydrazine 16.7g (87.1mmol). It was placed in a 300 ml flask and dissolved in 70 ml of dimethyl hydrazine. 4 ml of water was placed and cooled in an ice bath. Here, 15.6 g (87.1 mmol) of N-bromosuccinimide was gradually added, and the mixture was stirred at room temperature for 10 hours. This was cooled in an ice bath, 60 ml of water was added, and the organic layer was extracted with diethyl ether. After the aqueous phase was separated, the organic phase was dried and then evaporated to ethylamine.

Crude product of 2-bromo-1-indan-1-ol obtained above 24.0 g (83.3 mmol) was placed in a 300 ml flask, dissolved in 200 ml of toluene, and 0.48 g (2.5 mmol) of p-toluenesulfonic acid was added. A Dean-Stark tube was attached to the flask and refluxed for 2 hours. The solvent was distilled off, and the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After separating the aqueous phase, the organic phase was dried and the solvent was removed to give a crude product of 2-bromo-1-phenylindole. This was purified by column to give 2-bromo-1-phenylindole 17.9 g (66.4 mmol) (yield 80%).

Next, the resulting 2-bromo-1-phenylindole was obtained under a nitrogen stream. 2.7 g (10.0 mmol) was placed in a 200 ml Schlenk bottle, dissolved in 50 ml of diethyl ether, and cooled at 0 ° C, and a solution of n-butyllithium (n-BuLi) in hexane (concentration 2.6 mol/ l) 3.8 ml (10.0 mmol), stirred at room temperature for 3 hours. This was again cooled at 0 ° C, and 30 ml of diethyl ether and 12.5 ml (20.0 mmol) of a solution of t-butyllithium (t-BuLi) in pentane (concentration: 1.6 mol/l) were added, and stirred at room temperature for 3 hours. .

After stirring, the mixture was cooled to -78 ° C, and dichloromethane (dichloromethanehexane) This was again cooled to -78 ° C, and 0.6 ml (5.0 mmol) of dichloromethane was added dropwise, and stirred at room temperature overnight. Thereafter, after adding water and stopping the reaction, (1,2'-dimethylarylene) (2,1'-dimethylhydrazinyl) bis(3-phenylindole) 1.1 g (precipitated) 2.2 mmol), this was taken (yield: 44%).

Secondly, in the Schlenk bottle, the above-mentioned (1, 2’- Dimethylhydrazinyl)(2,1'-dimethylhydrazinyl)bis(3-phenylindole) 1.6g (3.2mmol) was dissolved in 12.6ml of diethyl ether and cooled at 0 ° C. However, 2.6 ml (6.6 mmol) of a hexane solution (concentration: 2.6 mol/l) of n-butyllithium (n-BuLi) was added, and the mixture was again returned to room temperature and stirred for 1 hour.

The solvent was distilled off from the obtained solution, and the residual solid was washed with 20 ml of hexane, and then dried under reduced pressure to obtain quantitative (1,2'-dimethyl sulfenyl) (2,1'- A white solid of an ether adduct of a lithium salt of dimethyl sulfinyl) bis(3-phenylhydrazine).

The ether addition of the lithium salt obtained above was suspended under a nitrogen stream The mixture was suspended in 18 ml of dichloromethane, cooled to -78 ° C, and a suspension of 0.74 g (3.2 mmol) of methylene chloride (8 ml) previously cooled to -78 ° C was added dropwise to the suspension, and then returned to the chamber. After the temperature, the mixture was stirred for 4 hours.

The resulting solution was filtered, and the filtrate was concentrated to give a yellow solid. This was washed with 10 ml of hexane to obtain (1,2'-dimethyl sulfenyl) (2,1'-dimethyl sulfenyl) bis(3-phenylindole) zirconium dichloride ( Yellow microcrystals of the wrong form A) 1.3 g (2.0 mmol) (yield 62%).

The ¹ H-NMR spectrum of the yellow microcrystal was obtained, and the following results were obtained.

^{1 H-NMR (500MHz, CDCl3} ): δ0.31 (s, -Me 2 Si-, 6H), 1.21 (s, -Me 2 Si-, 6H), 7.18-7.69 (m, Ar-H, 18H)

Manufacturing Example 2-2 [Manufacture of (1,1'-extended ethyl)(2,2'-tetramethyldialkylene)biguanide zirconium dichloride (wrong B)

Magnesium (12g, 500 millimolar) in a 500 ml 2-neck flask Tetrahydrofuran (30 ml) was added to 1,2-dibromoethane (0.2 ml) to activate magnesium. 2 -Bromoindole (20 g, 103 mmol) dissolved in tetrahydrofuran (150 ml) was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldioxane (9.4 ml, 5.1 mmol) was added dropwise at 0 °C. After the reaction mixture was stirred at room temperature for 1 hour, the solvent was evaporated, and the residue was evaporated to ethyl ether (150 ml, 2) to give 1,2-di(1H-indol-2-yl)-1,1, 2,2-Tetramethyldioxane as a white solid (15.4 g, 44.4 mmol, yield 86%).

This was dissolved in diethyl ether (100 ml), and n-butyllithium (2.6 mol/liter, 38 ml, 98 mmol) was added dropwise at 0 ° C, and after stirring at room temperature for 1 hour, precipitated white. powder. The clear liquid was removed and the solid was washed with EtOAc (EtOAc) (EtOAc)

This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 °C. After the reaction mixture was stirred at room temperature for 1 hour, it was dried and solidified, and the residue was extracted with hexane (150 ml) to obtain a colorless oily liquid (14.2 g, 37.9 mmol). ear).

This was dissolved in diethyl ether (120 ml), and n-butyllithium (2.6 mol/liter, 32 ml, 84 mmol) was added dropwise at 0 ° C, and a white powder was precipitated after stirring at room temperature for 1 hour. . The clear liquid was removed, and the solid was washed with hexane (70 ml) to give a white powder (14.0 g, 31 mmol, yield 81%) of the lithium salt of the cross-linking ligand.

Lithium salt of the obtained cross-linked ligand (3.00 g, 6.54 mmol) To a suspension of toluene (30 ml) of the ear, a suspension of zirconium tetrachloride (1.52 g, 6.54 mmol) in toluene (30 ml) was dropped at -78 °C in a transfer tube. After the reaction mixture was stirred at room temperature for 2 hours, the clear liquid was separated, and the residue was extracted with toluene.

The solvent of the clear liquid and the extract was distilled off under reduced pressure, and dried and solidified to obtain (1,1'-extended ethyl group) (2,2'- represented by the following formula (1) as a yellow solid. Tetramethyldialkylene)bisindole zirconium dichloride (wrong B) (2.5 g, 4.7 mmol, yield 72%).

The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ): δ 0.617 (s, 6H, -SiMe ₂ -), 0.623 (s, 6H, -SiMe ₂ -), 3.65-3.74, 4.05 - 4.15 (m, 4H, CH ₂ CH ₂ ), 6.79 (s, 2H, CpH), 7.0-7.5 (m, 8H, Aromatic-H)

Production Example 2-3 [Manufacture of Polymer (A)]

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mM of triisobutylaluminum, 0.2 A of micromolar, and 肆5 Fluorophenyl borate 0.8 micromolar, further introduced hydrogen 0.05 MPa. Propylene was placed while stirring, the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 60 ° C for 30 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 100 g of polypropylene (polymer (A)).

With respect to the obtained polymer (A), the heat of fusion ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of unsaturation groups per molecule, and meso five units (mmmm) were measured. Fraction, external pentad fraction [rrrr] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 2-1.

Manufacturing Example 2-4 [Manufacture of Polymer (B)]

70 g of the polymer (A) obtained in Production Example 2-3 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. Stirring was carried out for 30 minutes under a nitrogen stream.

After the stirring was started, the resin temperature was raised to 160 ° C using a mantle heater. The sheathed electric resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours, and subjected to radical decomposition to obtain polypropylene (polymer (B)).

For the obtained polymer (B), the melting heat absorption ΔH-D was measured, Weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, meso five unit [mmmm] fraction, external pentad fraction [rrrr] fraction, 2, 1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 2-1.

Further, the yield of the polymer (B) obtained was 99.3% by mass based on the terminally unsaturated liquid polypropylene (polymer (A)) charged, and the amount of the by-product was a trace amount.

Manufacturing Example 2-5 [Manufacture of Polymer (C)]

In a heated and dried 1 liter pressure sterilizer, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (200 mL), and B (10 μmol/mL, 0.20 mL, 2.0 μmol), MAO (2000 μmol) manufactured by Tosoh Fine Chemical Co., Ltd., and then introduced with hydrogen 0.1 MPa. The temperature was set to 70 ° C while stirring, and polymerization was carried out for 30 minutes. After the completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 82 g of a 1-butene homopolymer (polymer (C)).

With respect to the obtained polymer (C), the heat of fusion ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of unsaturation groups per molecule, and meso five units (mmmm) were measured. Fraction, external pentad fraction [rrrr] fraction, 2,1-binding fraction, 1,4-binding fraction, and glass transition temperature Tg. The results are shown in Table 2-1.

Manufacturing Example 2-6 [Manufacture of Polymer (D)]

70 g of the polymer (C) obtained in Production Example 5 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. Stirring was carried out for 30 minutes under a nitrogen stream.

After the stirring was started, the resin temperature was raised to 200 ° C using a mantle heater. The sheathed electric resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours to carry out radical decomposition to obtain a 1-butene homopolymer (polymer (D)).

With respect to the obtained polymer (D), the heat of fusion ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of unsaturation groups per molecule, and meso five units (mmmm) were measured. Fraction, external pentad fraction [rrrr] fraction, 2,1-binding fraction, 1,4-binding fraction, and glass transition temperature Tg. The results are shown in Table 2-1.

Further, the yield of the polymer (D) obtained was 99.3% by mass based on the terminally unsaturated liquid polybutene (polymer (C)) charged, and the amount of the by-product was a trace amount.

Further, the same decomposition efficiency, reactivity, and fluidity evaluation as in Example 1-1 were carried out, and the glass transition temperature Tg was further measured. The results are shown below.

Decomposition efficiency: ○

Reactivity: ◎

Liquidity: ○

Glass transfer temperature Tg (°C): ◎ (-30 ° C)

Manufacturing Example 2-7 [Manufacture of Polymer (E)]

In a heated and dried 1 liter pressure sterilizer, heptane (400 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), skeletal B (10 μmol/mL, 0.20 mL, 2.0 μmol), East MAO (2000 μmol) manufactured by Cao Fine Chemical Co., Ltd., further introducing hydrogen 0.1 MPa. Propylene was placed while stirring, and the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 50 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 105 g of a polypropylene (polymer (E)).

With respect to the obtained polymer (E), the heat of fusion ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of unsaturation groups per molecule, and meso five units (mmmm) were measured. Fraction, external pentad fraction [rrrr] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 2-1.

Manufacturing Example 2-8 [Manufacture of Polymer (F)]

A stainless steel reactor (content: 500 ml) equipped with a stirring device was placed in 70 g of the polymer (E) obtained in Production Example 2-7. Nitrogen Stir for 30 minutes under running.

Stirring was started and the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a propylene homopolymer (polymer (F)).

With respect to the obtained polymer (F), the heat of fusion ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of unsaturation groups per molecule, and meso pentads (mmmm) were measured. Fraction, external pentad fraction [rrrr] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 2-1.

Further, the yield of the polymer (F) obtained was 99.5% by mass based on the terminally unsaturated liquid polypropylene (polymer (E)) charged, and the amount of the by-product was a trace amount.

Further, in the same manner as in Example 1-1, the decomposition efficiency, the reactivity, and the fluidity were evaluated, and the glass transition temperature Tg was further measured. The results are shown below.

Decomposition efficiency: ◎

Reactivity: ◎

Liquidity: ○

Glass transfer temperature Tg (°C): ◎ (0 ° C)

Manufacturing Example 2-9 [Manufacture of Polymer (G)]

Synthetic phantom C [dimethyl ¹ -tert-butyl decylamine (η ⁵ -tetramethylcyclopentadiene) titanium dichloride as described in Organometallics 2000, 19, 1870-1878 ].

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mM of triisobutylaluminum, 0.2 mM of malformed pentadyl, and 0.8 micromolar of quinone pentafluorophenyl borate were further introduced. Hydrogen 0.05 MPa. Propylene was placed while stirring, and the pressure was raised to a total pressure of 0.5 MPa, and polymerization was carried out at a temperature of 90 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 50 g of polypropylene (polymer (G)).

The obtained polymer (G) was measured for melting heat absorption ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, and meso five units (mmmm). Fraction, external pentad fraction [rrrr] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 2-1.

Example 2-1 [Manufacture of hardenable adhesive composition]

20 g of the polymer (A) obtained in Production Example 2-3 was dissolved in 10 ml of heptane, and then 0.7 g of polymethylhydroquinone (product name: HMS-991, manufactured by AZmax Co., Ltd.) was added, and stirred at room temperature. Until it is fully uniform. After being homogeneous, a platinum-divinyltetramethyldioxane malformation xylene solution (manufactured by AZmax Co., Ltd., trade name: SIP6831.2, only at the end) was added at room temperature (25 ° C) while stirring. 130 ppm of a polyoxyalkylene having a Si-H bond other than that, and a curable adhesive composition was produced to directly perform a hardening reaction. After the numbering, the viscosity was increased, and the reaction was confirmed, and it was poured into a container of 10 cm × 10 cm × 0.5 cm, dried under reduced pressure, and the solvent was distilled off to obtain a cured product.

The obtained cured product was subjected to measurement of an infrared absorption spectrum to consume an unsaturated bond, and it was confirmed that the hydroquinone alkylation proceeded. Further, the cured product was heated in a glass oven at 180 ° C for 10 minutes to observe a change in shape. It was confirmed that the shape was maintained even in a heated state, which was a cured product showing rubber elasticity.

Example 2-2 [Manufacture of hardenable adhesive composition]

A curable adhesive composition was produced in the same manner as in Example 2-1 except that the polymer (A) in Example 2-1 was changed to the polymer (B) obtained in Production Example 2-4, and the curing reaction was directly carried out. After that, a hardened material is obtained.

The obtained cured product was subjected to measurement of an infrared absorption spectrum to consume an unsaturated bond, and it was confirmed that the hydroquinone alkylation proceeded. Further, the cured product was heated in a glass oven at 180 ° C for 10 minutes to observe a change in shape. It was confirmed that the shape was maintained even in a heated state, which was a cured product showing rubber elasticity.

Example 2-3 [Manufacture of hardenable adhesive composition]

20 g of the polymer (B) obtained in Production Example 2-4 was heated at 60 ° C, and after low viscosity, polymethylhydroquinone (AZmax) was used, trade name: HMS-991, only 0.7 g of a polyoxyalkylene having a Si-H bond other than the terminal was stirred at room temperature until it was sufficiently homogeneous. After being uniformly obtained, a xylene solution (manufactured by AZmax Co., Ltd., trade name: SIP6831.2) of 130 ppm was added at room temperature (25 ° C) while stirring at room temperature (25 ° C). The sclerosing adhesive adheres to the composition and directly causes it to undergo a hardening reaction. After the numbering, the viscosity was increased, and the reaction was confirmed, and it was poured into a container of 10 cm × 10 cm × 0.5 cm, dried under reduced pressure, and the solvent was distilled off to obtain a cured product.

The obtained cured product was subjected to measurement of an infrared absorption spectrum to consume an unsaturated bond, and it was confirmed that the hydroquinone alkylation proceeded. Further, the cured product was heated in a glass oven at 180 ° C for 10 minutes to observe a change in shape. It was confirmed that the shape was maintained even in a heated state, which was a cured product showing rubber elasticity.

Example 2-4 [Manufacture of hardenable adhesive composition]

A curable adhesive composition was produced in the same manner as in Example 2-1 except that the polymer (A) in Example 2-1 was changed to the polymer (D) obtained in Production Example 2-6, and the curing reaction was directly carried out. After that, a hardened material is obtained.

The obtained cured product was subjected to measurement of an infrared absorption spectrum to consume an unsaturated bond, and it was confirmed that the hydroquinone alkylation proceeded. Further, the cured product was heated in a glass oven at 180 ° C for 10 minutes to observe a change in shape. It was confirmed that the shape was maintained even in a heated state, which was a cured product showing rubber elasticity.

Example 2-5 [Manufacture of hardenable adhesive composition]

A curable adhesive composition was produced in the same manner as in Example 2-1 except that the polymer (A) in Example 2-1 was changed to the polymer (F) obtained in Production Example 2-8, and the curing reaction was directly carried out. After that, a hardened material is obtained.

The obtained cured product was subjected to measurement of an infrared absorption spectrum to consume an unsaturated bond, and it was confirmed that the hydroquinone alkylation proceeded. Further, the cured product was heated in a glass oven at 180 ° C for 10 minutes to observe a change in shape. It was confirmed that the shape was maintained even in a heated state, which was a cured product showing rubber elasticity.

Comparative Example 2-1

The polymer (A) in Example 2-1 was changed to the production example 2-9. A binder composition was produced in the same manner as in Example 2-1 except for the obtained polymer (G). When the curing reaction was attempted directly, no increase in viscosity was observed even when the reaction was carried out for several hours. Further, the reaction liquid was poured into a container of 10 cm × 10 cm × 0.5 cm, and the solvent was distilled off under reduced pressure, but the cured product was still not obtained and maintained in a liquid state.

Comparative Example 2-2

The polymer (A) in Example 2-1 was changed to the polymer (C) obtained in Production Example 2-5 (the number of terminal unsaturation groups per molecule was 0.3), and Example 2-1 Similarly, the adhesive composition was produced, and although the hardening reaction was attempted directly, no increase in viscosity was observed even after the reaction for several hours. Further, the reaction liquid was poured into a container of 10 cm × 10 cm × 0.5 cm, and the solvent was distilled off under reduced pressure, but the cured product was still not obtained and maintained in a liquid state.

Comparative Example 2-3

According to (Organometallics 1994, 13, 954), the complex D [dimethyl sulfenyl bis(2-methylbenzoindole) zirconium dichloride] was synthesized.

Instead of the wrong form A 0.2 micromolar in Production Example 2-3, the wrong body D (10 μmol/mL, 0.30 mL, 0.6 μmol) was used, and heptane of dimethylanilinium quinone (pentafluorophenyl) borate was used. In the same manner as in Production Example 2-3, 68 g of a polypropylene (polymer (H)) was obtained in the same manner as in Production Example 2-3 except that the slurry was changed to a temperature of 70 ° C in a slurry of 1.8 μmol (10 μmol/mL, 0.18 mL). [mmmm] = 90.4 mol%.

The obtained polymer (H) was dissolved in 10 ml of heptane at room temperature, but was not completely dissolved, and could not be reacted with polymethylhydroquinone.

Reference example 2-1

20 g of the polymer (B) obtained in Production Example 2-4 was dissolved in 10 ml of heptane, and then both ends of Si-H polymethylhydroquinone (AZmax (manufactured by AZ), trade name: DMS-H03, only two ends were added. 0.7 g of a polyoxyalkylene having a Si-H bond was stirred at room temperature until it was sufficiently homogeneous. After the mixture was uniformly added, a xylene solution (manufactured by AZmax Co., Ltd., trade name: SIP6831.2) of platinum-divinyltetramethyldioxane was added to a solution of 130 ppm at room temperature to obtain a binder composition. The substance is directly subjected to a hardening reaction. After the numbering, the viscosity was increased, and the reaction was confirmed, and it was poured into a container of 10 cm × 10 cm × 0.5 cm, dried under reduced pressure, and the solvent was distilled off to obtain a cured product.

The obtained cured product was subjected to measurement of an infrared absorption spectrum to consume an unsaturated bond, and it was confirmed that the hydroquinone alkylation proceeded. The obtained cured product is weaker in material strength than the cured product of the embodiment, and is easily torn by the hand.

<Third invention> [ ¹³ C-NMR measurement]

Using a ¹³ C-NMR spectrum measurement under the following apparatus and conditions, 2,1-binding fraction, 1,3-binding fraction, 1,4-binding fraction, meso-penta[mmmm] Fraction, and the outer rotatory five-element [rrrr] fraction.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

[DSC measurement]

Using a differential scanning calorimeter (DSC-7 manufactured by Perkin-Elmer Co., Ltd.), 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the heat of fusion obtained by heating at 10 ° C /min was taken as Δ. HD and the glass transition temperature Tg.

[GPC measurement]

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were determined by a gel permeation chromatography (GPC) method. The following equipment is used in the measurement. The conditions were set to obtain a weight average molecular weight in terms of polystyrene.

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0ml/min

Sample concentration: 2.2 mg/ml

Injection volume: 160μl

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

[terminal unsaturated group concentration]

The terminal vinylidene at δ4.8~4.6(2H) obtained by ¹ H-NMR, the terminal vinyl group at δ5.9~5.7 (1H) and the δ1.05~0.60 (3H) Based on the methyl group present, the terminal unsaturated group concentration (C) (% by mole) was calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturated group concentration (C) = [vinylidene amount] + [vinyl amount]

[Number of unsaturation groups per molecule)

The terminal unsaturated group concentration (C, mol%) calculated by the above method and the number average molecular weight (Mn) and monomer molecular weight (M) obtained by gel permeation chromatography (GPC), The number of terminal unsaturated groups per molecule was calculated by the following formula.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

[Number of bases containing ruthenium per molecule)

(A) Base concentration of ruthenium containing terminal enthalpy by ¹³ C-NMR (% by mole)

(B) Number average molecular weight (Mn) of the functionalized α-olefin polymer as determined by gel permeation chromatography (GPC)

(C) Average molecular weight (Mm) of monomer units = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11

From the above formula, the number of groups containing ruthenium per molecule can be calculated.

Number of groups containing ruthenium at the end of each molecule = (Mn/M) × [base concentration of ruthenium containing terminal] / 100

As a method for calculating the base concentration of the terminal ruthenium, the terminal unsaturated concentration may be reduced by the side reaction. Therefore, as shown below, ¹³ C-NMR is used to calculate the appearance of Si-CH _{2 in the} vicinity of 20 to 22 ppm. The peak concentration of CH ₂ .

CH ₂ (i) of Si-CH ₂ : integral value of 20-22 ppm

CH ₂ (ii) of propylene units: integral value of peaks appearing at 46.4 ppm

CH ₂ (iii) butene units: a peak integration value on the occurrence of the 40.4ppm

Base concentration of cerium at the end = [(i) / ((ii) + (iii))] × 100 (% by mole)

[B viscosity]

The measurement was carried out in accordance with ASTM-D19860-91.

[rational at normal temperature]

The fluidity at a relatively low temperature was visually confirmed and evaluated on the following basis.

◎: Fluidity at 60 ° C.

○: Fluidity at 100 °C.

△: It has a relatively high viscosity at 100 ° C, but it is barely fluid.

×: No fluidity at 100 ° C.

[hardening reactivity at lower temperatures]

In the examples and the comparative examples, the cured product obtained by curing the curable composition was evaluated on the basis of the following criteria.

◎: Completely hardened at 60 °C.

○: Completely cured at 100 °C.

△: Partially hardened at 100 °C.

×: Even at 100 ° C, there was no hardening at all.

[heat resistance of hardened material]

The cured product was heated in a glass oven at 120 ° C for 10 minutes, and the form of the cured product after heating was visually observed, and the rubber elasticity of the cured product was evaluated by the following evaluation criteria.

○: The shape was maintained and the rubber elasticity was exhibited.

×: The shape was not maintained, and rubber elasticity was not exhibited.

Manufacturing Example 3-1 [(1,2'-Dimethylhydrazinyl)(2,1'-dimethylarylene)-bis(3-phenylindole)zirconium dichloride (former A)

Under a nitrogen stream, 76.5 ml (229.5 mmol) of a diethyl ether solution of phenylmagnesium bromide was placed in a 1000 ml flask and cooled in an ice bath. Here, 30 g (227.2 mmol) of 1-nonanone was dissolved in 300 ml of diethyl ether, and the mixture was gradually added dropwise. After stirring at room temperature for one hour, it was cooled in an ice bath, and 6 mol/l of hydrochloric acid was added dropwise. After stirring at room temperature, the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After the aqueous phase was separated, the organic phase was dried and solvent was evaporated to give &lt;3&gt;

Next, we will get the 1-phenyl hydrazine 16.7g (87.1mmol). It was placed in a 300 ml flask and dissolved in 70 ml of dimethyl hydrazine. 4 ml of water was placed and cooled in an ice bath. Here, 15.6 g (87.1 mmol) of N-bromosuccinimide was gradually added, and the mixture was stirred at room temperature for 10 hours. This was cooled in an ice bath, 60 ml of water was added, and the organic layer was extracted with diethyl ether. After the aqueous phase is separated, the organic phase is dried and the solvent is removed to give 2-bromo-1-indan- The crude product of 1-ol was 24.0 g (83.3 mmol) (yield: 96%).

24.0 g (83.3 mmol) of the crude product of 2-bromo-1-indan-1-ol obtained above was placed in a 300 ml flask, dissolved in 200 ml of toluene, and 0.48 g (2.5 mmol) of p-toluenesulfonic acid was added. A Dean-Stark tube was attached to the flask and refluxed for 2 hours. The solvent was distilled off, and the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After separating the aqueous phase, the organic phase was dried and the solvent was removed to give a crude product of 2-bromo-1-phenylindole. This was purified by column to give 2-bromo-1-phenylindole 17.9 g (66.4 mmol) (yield 80%).

Next, 2.7 g (10.0 mmol) of the obtained 2-bromo-1-phenylindole was placed in a 200 ml Schlenk bottle under a nitrogen stream, dissolved in 50 ml of diethyl ether, and cooled at 0 ° C to add n. 3.8 ml (10.0 mmol) of a butyllithium (n-BuLi) hexane solution (concentration: 2.6 mol/l) was stirred at room temperature for 3 hours. This was again cooled at 0 ° C, and 30 ml of diethyl ether and 12.5 ml (20.0 mmol) of a solution of t-butyllithium (t-BuLi) in pentane (concentration: 1.6 mol/l) were added, and stirred at room temperature for 3 hours. .

After stirring, the mixture was cooled to -78 ° C, and dichloromethane (dichloromethanehexane) This was again cooled to -78 ° C, and 0.6 ml (5.0 mmol) of dichloromethane was added dropwise, and stirred at room temperature overnight. Thereafter, after adding water and stopping the reaction, (1,2'-dimethylarylene) (2,1'-dimethylhydrazinyl) bis(3-phenylindole) 1.1 g (precipitated) 2.2 mmol), this was taken (yield: 44%).

Next, in the Schlenk bottle, the above-mentioned (1,2'-dimethylhydrazinyl)(2,1'-dimethylhydrazinyl)bis(3-phenyl group) was obtained. 茚) 1.6 g (3.2 mmol) was dissolved in 12.6 ml of diethyl ether, cooled at 0 ° C, and hexane solution (concentration 2.6 mol/l) of n-butyllithium (n-BuLi) was added (2.6 ml (6.6 mmol)). , return to room temperature again and stir for 1 hour.

The solvent was distilled off from the obtained solution, and the residual solid was washed with 20 ml of hexane, and then dried under reduced pressure to obtain quantitative (1,2'-dimethyl sulfenyl) (2,1'- A white solid of an ether adduct of a lithium salt of dimethyl sulfinyl) bis(3-phenylhydrazine).

The ether addition of the lithium salt obtained above was suspended under a nitrogen stream The mixture was suspended in 18 ml of dichloromethane, cooled to -78 ° C, and a suspension of 0.74 g (3.2 mmol) of methylene chloride (8 ml) previously cooled to -78 ° C was added dropwise to the suspension, and then returned to the chamber. After the temperature, the mixture was stirred for 4 hours.

The resulting solution was filtered, and the filtrate was concentrated to give a yellow solid. This was washed with 10 ml of hexane to obtain (1,2'-dimethyl sulfenyl) (2,1'-dimethyl sulfenyl) bis(3-phenylindole) zirconium dichloride ( Yellow microcrystals of the wrong form A) 1.3 g (2.0 mmol). (yield 62%)

The ¹ H-NMR spectrum of the yellow microcrystal was obtained, and the following results were obtained.

^{1 H-NMR (500MHz, CDCl3} ): δ0.31 (s, -Me 2 Si-, 6H), 1.21 (s, -Me 2 Si-, 6H), 7.18-7.69 (m, Ar-H, 18H)

Manufacturing Example 3-2 [Manufacture of (1,1'-extended ethyl)(2,2'-tetramethyldialkylene)biguanide zirconium dichloride (wrong B)

Magnesium (12 g, 500 mmol) and tetrahydrofuran (30 ml) were placed in a 500 ml 2-neck flask, and magnesium was activated by dropwise addition of 1,2-dibromoethane (0.2 ml). 2 -Bromoindole (20 g, 103 mmol) dissolved in tetrahydrofuran (150 ml) was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldioxane (9.4 ml, 5.1 mmol) was added dropwise at 0 °C. After the reaction mixture was stirred at room temperature for 1 hour, the solvent was evaporated, and the residue was evaporated to ethyl ether (150 ml, 2) to give 1,2-di(1H-indol-2-yl)-1,1, 2,2-Tetramethyldioxane as a white solid (15.4 g, 44.4 mmol, yield 86%).

This was dissolved in diethyl ether (100 ml), and n-butyllithium (2.6 mol/liter, 38 ml, 98 mmol) was added dropwise at 0 ° C, and after stirring at room temperature for 1 hour, precipitated white. powder. The clear liquid was removed and the solid was washed with EtOAc (EtOAc) (EtOAc)

This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 °C. After the reaction mixture was stirred at room temperature for 1 hour, it was dried and solidified, and the residue was extracted with hexane (150 ml) to obtain a colorless oily liquid (14.2 g, 37.9 mmol) of 2 cross-linking ligands. ).

This was dissolved in diethyl ether (120 ml), and n-butyllithium (2.6 mol/liter, 32 ml, 84 mmol) was added dropwise at 0 ° C, and a white powder was precipitated after stirring at room temperature for 1 hour. . The clear liquid was removed, and the solid was washed with hexane (70 ml) to give a white powder (14.0 g, 31 mmol, yield 81%) of the lithium salt of the cross-linking ligand.

Zirconium tetrachloride (1.52 g, 6.54 mmol) at -78 ° C in a suspension of the obtained lithium salt of the cross-linking ligand (3.00 g, 6.54 mmol) in toluene (30 ml). A suspension of toluene (30 ml) was dropped through a transfer tube. After the reaction mixture was stirred at room temperature for 2 hours, the clear liquid was separated, and the residue was extracted with toluene.

The solvent of the clear liquid and the extract was distilled off under reduced pressure, and dried and solidified to obtain (1,1'-extended ethyl group) (2,2'- represented by the following formula (1) as a yellow solid. Tetramethyldialkylene)bisindole zirconium dichloride (wrong B) (2.5 g, 4.7 mmol, yield 72%).

The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ): δ 0.617 (s, 6H, -SiMe ₂ -), 0.623 (s, 6H, -SiMe ₂ -), 3.65-3.74, 4.05 - 4.15 (m, 4H, CH ₂ CH ₂ ), 6.79 (s, 2H, CpH), 7.0-7.5 (m, 8H, Aromatic-H)

Manufacturing Example 3-3 [Manufacture of Raw Material α-Olefin Polymer (A)]

Adding heptane to a 1 liter pressure sterilizer heated and dried 400 ml, triisobutylaluminum 0.5 mmol, malformed A 0.2 micromolar, quinone pentafluorophenyl borate 0.8 micromolar, further introduced with hydrogen 0.05 MPa. Propylene was placed while stirring, the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 60 ° C for 30 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 100 g of a raw material α-olefin polymer (A).

For the obtained raw material α-olefin polymer (A), the melting heat absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, the external-rotating penta-unit [rrrr] fraction, and the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction, and 1,3-binding fraction. The results are shown in Table 3-1.

Manufacturing Example 3-4 [Manufacture of Raw Material α-Olefin Polymer (B)]

A stainless steel reactor (content: 500 ml) equipped with a stirring device was placed in 70 g of the raw material α-olefin polymer (A) produced in Production Example 3-3. Stirring was carried out for 30 minutes under a nitrogen stream.

Stirring was started, and the temperature of the resin was raised to 160 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After the completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and self-contained. After the decomposition of the base, the raw material α-olefin polymer (B) is obtained.

For the obtained raw material α-olefin polymer (B), the melting heat absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, the external-rotating penta-unit [rrrr] fraction, and the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction, 1,3-binding fraction, and 1,4-binding fraction. The results are shown in Table 3-1.

Further, the yield of the obtained raw material α-olefin polymer (B) was 99.3% by mass based on the raw material α-olefin polymer (A) charged, and the amount of by-products was a trace amount.

Manufacturing Example 3-5 [Manufacture of Raw Material α-Olefin Polymer (C)]

In a heated and dried 1 liter pressure sterilizer, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), 1-butene (200 mL), and B (10 μmol/mL, 0.20 mL, 2.0 μmol), MAO (2000 μmol) manufactured by Tosoh Fine Chemical Co., Ltd., and further introduced with hydrogen 0.1 MPa. The polymerization was carried out for 30 minutes while the temperature was changed to 70 ° C while stirring. After the completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to give 82 g of 1-butene homopolymer.

For the obtained raw material α-olefin polymer (C), the melting heat absorption ΔH-D, the glass transition temperature Tg, the meso five unit [mmmm] fraction, the external rotation five unit [rrrr] fraction, and the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction, 1,3-binding fraction, and 1,4-binding fraction. The results are shown in Table 3-1.

Manufacturing Example 3-6 [Manufacture of Raw Material α-Olefin Polymer (D)]

A stainless steel reactor (content: 500 ml) equipped with a stirring device was charged with 70 g of a raw material α-olefin polymer (C) produced in Production Example 3-5. Stirring was carried out for 30 minutes under a nitrogen stream.

Stirring was started and the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a raw material α-olefin polymer (D).

For the obtained raw material α-olefin polymer (D), the melting heat absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, the external-rotating penta-unit [rrrr] fraction, and the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction, 1,3-binding fraction, and 1,4-binding fraction. The results are shown in Table 3-1.

Further, the yield of the obtained raw material α-olefin polymer (D) was 99.3% by mass based on the raw material α-olefin polymer (C) charged, and by-product The amount is a small amount.

Further, in the same manner as in Example 1-1, the decomposition efficiency, the reactivity, and the fluidity were evaluated, and the glass transition temperature Tg was further measured. The results are shown below.

Decomposition efficiency: ○

Reactivity: ◎

Liquidity: ○

Glass transfer temperature Tg (°C): ◎ (-30 ° C)

Manufacturing Example 3-7 [Manufacture of Raw Material α-Olefin Polymer (E)]

Synthetic phantom C [dimethyl ¹ -tert-butyl decylamine (η ⁵ -tetramethylcyclopentadiene) titanium dichloride as described in Organometallics 2000, 19, 1870-1878 ].

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mM of triisobutylaluminum, 0.2 mM of malformed pentadyl, and 0.8 micromolar of quinone pentafluorophenyl borate were further introduced. Hydrogen 0.05 MPa. Propylene was placed while stirring, and the pressure was raised to a total pressure of 0.5 MPa, and polymerization was carried out at a temperature of 90 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 50 g of a raw material α-olefin polymer (E).

For the obtained raw material α-olefin polymer (E), the melting heat absorption ΔHD, the glass transition temperature Tg, the meso five unit [mmmm] fraction, the external rotation pentad fraction, the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), not sufficient at the end of each molecule And the number of the base, the 2,1-binding fraction, the 1,3-binding fraction, and the 1,4-binding fraction. The results are shown in Table 3-1.

Manufacturing Example 3-8 [Manufacture of Raw Material α-Olefin Polymer (F)]

70 g of the raw material α-olefin polymer (E) produced in Production Example 7 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. The mixture was stirred for 30 minutes under a nitrogen stream.

Stirring was started and the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a raw material α-olefin polymer (F).

For the obtained raw material α-olefin polymer (F), the melting heat absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, the external-rotating penta-unit [rrrr] fraction, and the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction, 1,3-binding fraction, and 1,4-binding fraction. The results are shown in Table 3-1.

Manufacturing Example 3-9 [Manufacture of Raw Material α-Olefin Polymer (G)]

The mod (D) was synthesized according to WO2003/070788.

In a heating and drying 1 liter pressure sterilizer, 200 ml of heptane, 200 ml of 1-butene, and 0.5 mmol of triisobutylaluminum were added, and hydrogen was further introduced into 0.2 MPa.

After stirring to a temperature of 65 ° C, triphenylcarbonium pentafluorophenyl borate 0.8 micromolar, (1,2'-dimethylarylene) (2,1'-dimethyl The hydrazinyl)-bis(3-trimethyldecylmethylhydrazine) zirconium dichloride 0.2 micromolar was polymerized for 30 minutes. After the completion of the polymerization reaction, the reaction product was dried under reduced pressure to give 80 g of 1-butene polymer.

For the obtained raw material α-olefin polymer (G), the melting heat absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, the external-rotating penta-unit [rrrr] fraction, and the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction, 1,3-binding fraction, and 1,4-binding fraction. The results are shown in Table 3-1.

Manufacturing Example 3-10 [Manufacture of Raw Material α-Olefin Polymer (H)]

A stainless steel reactor (content: 500 ml) equipped with a stirring device was placed in 70 g of a raw material α-olefin polymer (G) produced in Production Example 3-9. The mixture was stirred for 30 minutes under a nitrogen stream.

Stirring was started and the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 ° C temperature. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a raw material α-olefin polymer (H).

For the obtained raw material α-olefin polymer (H), the melting heat absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, the external-rotating penta-unit [rrrr] fraction, and the weight average molecular weight were measured. (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction, 1,3-binding fraction, and 1,4-binding fraction. The results are shown in Table 3-1.

Example 3-1 (manufacturing of functionalized polypropylene)

20 g of the raw material α-olefin polymer (B) produced in Production Example 3-4 and 0.7 g of diethoxymethyl decane were added as a catalyst for platinum-divinyltetramethyldioxane (Azumax). 130 ppm of SIP6831.0) manufactured by Co., Ltd., and reacted at 100 ° C for 5 hours.

With respect to the obtained functionalized polypropylene, the unsaturated bond in the vicinity of 1640 cm ^-1 was observed by the infrared absorption spectrum, and it was confirmed that the hydroquinone addition was carried out, and it was confirmed that the hydroquinone alkylated polypropylene was produced. Similarly, as a result of ¹³ C-NMR measurement, it was confirmed that the peak of Si-C from the end of the main chain was observed at 20 to 22 ppm, and the peak of Si-C derived from the side chain was not observed at 13 to 15 ppm.

For the obtained functionalized polypropylene, the number of ruthenium groups per one molecule of the main chain, the heat of absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, and the external-rotating five-element [rrrr The fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the B viscosity were evaluated for fluidity. The results are shown in Table 3-2.

Example 3-2 (Production of Functionalized Poly-1-butene)

Addition of 20 g of the raw material α-olefin polymer (D) and 0.7 g of diethoxymethyl decane manufactured in Preparation Example 3-6 to add platinum-divinyltetramethyldioxane as a catalyst (Azumax) 130 ppm of SIP6831.0) manufactured by Co., Ltd., and reacted at 100 ° C for 5 hours.

With respect to the obtained functionalized poly-1-butene, the disappearance of the unsaturated bond in the vicinity of 1640 cm ^{-1 was} confirmed by the measurement of the infrared absorption spectrum, and it was confirmed that the hydroquinone addition was carried out, and the hydroquinone alkylation poly 1 was confirmed. Butene is produced. Similarly, as a result of ¹³ C-NMR measurement, it was confirmed that the peak of Si-C from the end of the main chain was observed at 20 to 22 ppm, and the peak of Si-C from the side chain was not observed at 13 to 15 ppm.

For the obtained functionalized poly 1-butene, the number of ruthenium groups per one molecule of the main chain, the heat of absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit (mmmm) fraction, and the outer-shell five were measured. The unit [rrrr] fraction, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), and B viscosity were evaluated for fluidity. The results are shown in Table 3-2.

Example 3-3 (Production of Functionalized Poly-1-butene)

20 g of the raw material α-olefin polymer (H) and 0.7 g of diethoxymethyl decane manufactured by the production of Examples 3-10, and a platinum-divinyltetramethyldioxane complex (as a catalyst) was added ( 130 mg of SIP6831.0 manufactured by Azumax Co., Ltd., and reacted at 100 ° C for 5 hours.

With respect to the obtained functionalized poly-1-butene, the disappearance of the unsaturated bond in the vicinity of 1640 cm ^{-1 was} confirmed by the measurement of the infrared absorption spectrum, and it was confirmed that the hydroquinone addition was carried out, and the hydroquinone alkylation poly 1 was confirmed. Butene is produced. Similarly, as a result of ¹³ C-NMR measurement, it was confirmed that the peak of Si-C from the end of the main chain was observed at 20 to 22 ppm, and the peak of Si-C from the side chain was not observed at 13 to 15 ppm.

For the obtained functionalized poly 1-butene, the number of ruthenium groups per one molecule of the main chain, the heat of fusion ΔH-D, the glass transition temperature Tg, and the inside were measured. The racemic five-unit [mmmm] fraction, the outer-rotating five-unit [rrrr] fraction, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the B-viscosity were evaluated for fluidity. The results are shown in Table 3-2.

Example 3-4 (Manufacture of hardenable composition and cured product)

To 10 g of the hydroquinone-alkylated polypropylene of Example 3-1, 15 mg of dibutyltin dilaurate was added at room temperature, and the mixture was stirred until uniform to obtain a curable composition, which was poured into a container of 10 × 10 cm × 0.5 cm. In the middle and stand still. This was dried under reduced pressure at 60 ° C for 8 hours, and then formed into a sheet. The sheet was allowed to stand in an environment of 23 ° C and a humidity of 50% for 16 hours to produce a cured product.

The obtained cured product was heated on a hot plate controlled at 120 ° C for 10 minutes, and the shape change was observed. As a result, it was confirmed that the shape was maintained in a heated state, and it was a cured product showing rubber elasticity.

Example 3-5 (Manufacture of hardenable composition and cured product)

10 g of hydroquinone-alkylated polybutene-butene of Example 3-2 was added with 15 mg of dibutyltin dilaurate at room temperature, and the mixture was stirred until uniform to obtain a hardenable composition, which was injected at 10 × 10 cm × 0.5 cm. In the container and stand still. This was dried under reduced pressure at 60 ° C for 8 hours, and then formed into a sheet. The sheet was allowed to stand in an environment of 23 ° C and a humidity of 50% for 16 hours to produce a cured product.

The obtained cured product was heated on a hot plate controlled at 120 ° C for 10 minutes, and the shape change was observed. As a result, it was confirmed that the shape was maintained in a heated state, and it was a cured product showing rubber elasticity.

Example 3-6 (Manufacture of hardenable composition and cured product)

10 g of hydroquinone-alkylated polybutene-butene of Example 3-3 was added at a temperature of 100 ° C to 15 mg of dibutyltin dilaurate, and the mixture was stirred until uniform to obtain a hardenable composition, which was poured into 10 × 10 cm × 0.5 cm. Leave it in the container. This was dried under reduced pressure at 100 ° C for 8 hours, and then formed into a sheet. The sheet was allowed to stand in an environment of 23 ° C and a humidity of 50% for 16 hours to produce a cured product.

The obtained cured product was heated on a hot plate controlled at 120 ° C for 10 minutes, and the shape change was observed. As a result, it was confirmed that the shape was maintained in a heated state, and it was a cured product showing rubber elasticity.

Comparative Example 3-1

20 g of the raw material α-olefin polymer (F) and 0.7 g of diethoxymethyl decane manufactured by the production of Examples 3-8, and a platinum-divinyltetramethyldioxane complex as a catalyst was added ( 130 mg of SIP6831.0 manufactured by Azumax Co., Ltd., and reacted at 100 ° C for 5 hours. As a result of measurement by ¹³ C-NMR, it was confirmed that the peak of Si-C at the end of the autonomous chain was not observed at 20 to 21 ppm, so that no alkoxydecane was added at the end of the main chain, and polymerization of the raw material α-olefin was carried out. No terminal unsaturated group which undergoes hydroquinone alkylation was observed for the substance (F).

To 10 g of the above-mentioned polypropylene and alkoxydecane mixture, 15 mg of dibutyltin dilaurate was added at room temperature, and the mixture was stirred until homogeneous, and this was poured into a container of 10 × 10 × 0.5 cm and allowed to stand. This was dried at 60 ° C for 8 hours under reduced pressure, and then formed into a sheet. The sheet was allowed to stand in an environment of 23 ° C and a humidity of 50% for 16 hours to produce a cured product, but the resulting composition was obtained. The material did not harden.

The liquid composition thus obtained was heated on a hot plate controlled at 120 ° C for 10 minutes, and the shape change was observed. As a result, it was found that fluidity was obtained before heating, and it was difficult to maintain the shape at normal temperature, so that the hardened composition could not be obtained.

Comparative Example 3-2 (Alkoxydecane modification of LMPP)

According to Example 3-1 of JP-A-2006-348153, a decane modified product of a propylene polymer was synthesized. As a result of measurement by ¹³ C-NMR, the peak of Si-C from the end of the main chain was not observed at 20 to 22 ppm. Further, the peak of Si-C derived from the side chain was observed at 13 to 15 ppm, and it was confirmed that it was not the main chain, but the addition of the alkoxydecane was carried out at the end of the side chain.

The composition of the cured composition was attempted in the same manner as in Example 3-4. However, although the melting point of the decane modified product of the propylene polymer was 74.4 ° C, the viscosity was high even at 100 ° C, and only a part of it was hardened.

Comparative Example 3-3 (decane-modified propylene polymer, "Linkron XPM800HM" manufactured by Mitsubishi Chemical Corporation)

The results of measurement at ¹³ C-NMR, a peak derived from the main chain terminal Si-C in 20 ~ 22ppm not observed. Further, the peak of Si-C derived from the side chain was observed at 13 to 15 ppm, and the non-back main chain was determined, and the alkoxy decane was added to the end of the side chain. The composition of the cured composition was attempted in the same manner as in Example 3-4, but it was not melted at 100 ° C or lower, and a hardened composition could not be obtained.

<Fourth invention> [ ¹³ C-NMR measurement]

The ¹³ C-NMR spectrum was measured by the following apparatus and conditions, and the meso-penta-unit [mmmm] fraction, the external-rotating five-element [rrrr] fraction, and the meso-diad fraction were determined. [m], racemo-diad fraction [r], 1,3-binding fraction, 1,4-binding fraction, and 2,1-binding fraction.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

[DSC measurement]

Using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), 10 mg of the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the heat of melting obtained by heating at 10 ° C /min was used as the heat of absorption. ΔHD, the glass transition temperature Tg or the melting point Tm-D was determined. The melting point Tm-D is the peak of the peak observed on the highest temperature side of the melting endothermic curve as the melting point Tm-D.

[GPC measurement]

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were determined by a gel permeation chromatography (GPC) method. The following apparatus and conditions were used for the measurement, and the weight average molecular weight in terms of polystyrene was obtained.

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0ml/min

Sample concentration: 2.2 mg/ml

Injection volume: 160μl

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

[terminal unsaturated group concentration]

The terminal vinylidene at δ4.8~4.6(2H) obtained by ¹ H-NMR, the terminal vinyl group at δ5.9~5.7 (1H) and the δ1.05~0.60 (3H) Based on the methyl group present, the terminal unsaturated group concentration (C) (% by mole) was calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturated group concentration (C) = [vinylidene amount] + [vinyl amount]

[Number of unsaturation groups per molecule)

The terminal unsaturated group concentration (C, mol%) calculated by the above method and the number average molecular weight (Mn) and monomer molecular weight (M) obtained by gel permeation chromatography (GPC), Calculate each molecule by the following formula The number of unsaturation groups at the end.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

[Number of (anhydrous) carboxylic acid residues per molecule] <Modified quantitative method>

The blend of the α-olefin polymer and the unsaturated (anhydrous) carboxylic acid before the modification is applied at a time interval of 0.1 mm, and then subjected to infrared spectrometry (IR), which is characterized by a carbonyl group (1700 to 1800 cm ^-1 ). The amount of absorption is compared with the amount of the unsaturated (anhydrous) carboxylic acid, and the IR measurement of the pressure-sensitive plate of the functionalized α-olefin polymer to be measured is performed, and each molecule is determined by the following formula. The number of (anhydrous) carboxylic acid residues.

Number of (anhydrous) carboxylic acid residues per molecule = [(anhydrous carboxylic acid residue concentration] / 100 × Mn / molecular weight of the monomer (unit)

Average molecular weight (Mm) of monomer units = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11

Number average molecular weight (Mn): number average molecular weight obtained by gel permeation chromatography (GPC)

(anhydrous) carboxylic acid residue concentration: IR measurement of a pressure plate for performing a functionalized α-olefin polymer to be measured, and calculating (anhydrous) carboxylic acid residue from the relationship between the calibration curve and the absorption amount of 1700 to 1800 cm ^-1 The concentration of the base.

The measuring instrument used was an IR measuring machine: "FT/IR-5300" manufactured by JASCO Corporation.

[Number of internal double bonds per molecule]

The terminal (anhydrous) carboxylic acid residue which appears in the range of 4.85 to 5.50 ppm by the ¹ H-NMR measurement, the hydrogen atom of the internal double bond in the internal double bond structure, and the α-olefin backbone present in the range of 0.70 to 1.80 ppm The number of the terminal (anhydrous) carboxylic acid residue-internal double bond was calculated as shown below.

Terminal (anhydrous) carboxylic acid residue - CH(i) of internal double bond structure: integral value of 4.85~5.50ppm

Hydrogen atom of the α-olefin main chain (ii): integral value of 0.70 to 1.80 ppm

Average molecular weight (Mm) of monomer units = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11

Average hydrogen number of monomer units (Hnum) = propylene unit ratio × 6 + 1 - butene unit ratio × 8

Terminal (anhydrous) carboxylic acid residue - internal double bond structure concentration = [(i) / ((ii) / (Hnum))]

The terminal (anhydrous) carboxylic acid residue-internal double bond structure concentration (C, mol %) calculated by the above method and the number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) And the average molecular weight (Mm) of the monomer unit, and the number of the terminal (anhydrous) carboxylic acid-internal double bond structure per molecule was calculated by the following formula.

Number of carboxylic acid-internal double bond structures per one molecule (anhydrous) = (Mn) / (Mm) × [terminal (anhydrous) carboxylic acid residue - internal double bond structure concentration]

〔fluidity〕

The fluidity of the functionalized α-olefin polymer was visually confirmed and evaluated on the following basis.

A 5 g sample was placed in a 30 mL sample vial, and the lid was closed and placed in a longitudinal direction in a thermostat at 80 °C. After visual confirmation after 10 minutes, the sample moved to the bottom (flow), and when the surface became horizontal, it was evaluated as fluidity.

Manufacturing Example 4-1 [Manufacture of (1,1'-extended ethyl)(2,2'-tetramethyldialkylene)biguanide zirconium dichloride (wrong A)

Magnesium (12 g, 500 mmol) and tetrahydrofuran (30 ml) were placed in a 500 ml 2-neck flask, and magnesium was activated by dropwise addition of 1,2-dibromoethane (0.2 ml). 2 -Bromoindole (20 g, 103 mmol) dissolved in tetrahydrofuran (150 ml) was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldioxane (9.4 ml, 5.1 mmol) was added dropwise at 0 °C. After the reaction mixture was stirred at room temperature for 1 hour, the solvent was evaporated, and the residue was evaporated to ethyl ether (150 ml, 2) to give 1,2-di(1H-indol-2-yl)-1,1, 2,2-Tetramethyldioxane as a white solid (15.4 g, 44.4 mmol, yield 86%).

This was dissolved in diethyl ether (100 ml), and n-butyllithium (2.6 mol/liter, 38 ml, 98 mmol) was added dropwise at 0 ° C, and after stirring at room temperature for 1 hour, precipitated white. powder. The clear liquid was removed and the solid was washed with EtOAc (EtOAc) (EtOAc)

This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 °C. After the reaction mixture was stirred at room temperature for 1 hour, it was dried and solidified, and the residue was extracted with hexane (150 ml) to obtain a colorless oily liquid (14.2 g, 37.9 mmol) of 2 cross-linking ligands. ).

This was dissolved in diethyl ether (120 ml), and n-butyllithium (2.6 mol/liter, 32 ml, 84 mmol) was added dropwise at 0 ° C, and a white powder was precipitated after stirring at room temperature for 1 hour. . The clear liquid was removed, and the solid was washed with hexane (70 ml) to give a white powder (14.0 g, 31 mmol, yield 81%) of the lithium salt of the cross-linking ligand.

Zirconium tetrachloride (1.52 g, 6.54 mmol) at -78 ° C in a suspension of the obtained lithium salt of the cross-linking ligand (3.00 g, 6.54 mmol) in toluene (30 ml). A suspension of toluene (30 ml) was dropped through a transfer tube. After the reaction mixture was stirred at room temperature for 2 hours, the clear liquid was separated, and the residue was extracted with toluene.

The solvent of the clear liquid and the extract was distilled off under reduced pressure, and dried and solidified to obtain (1,1'-extended ethyl group) (2,2'- represented by the following formula (1) as a yellow solid. Tetramethyldialkylene)bisindole zirconium dichloride (wrong A) (2.5 g, 4.7 mmol, yield 72%).

The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ): δ 0.617 (s, 6H, -SiMe ₂ -), 0.623 (s, 6H, -SiMe ₂ -), 3.65-3.74, 4.05 - 4.15 (m, 4H, CH ₂ CH ₂ ), 6.79 (s, 2H, CpH), 7.0-7.5 (m, 8H, Aromatic-H)

Manufacturing Example 4-2 [(1,2'-Dimethylhydrazinyl)(2,1'-dimethylhydrazinyl)-bis(3-trimethyldecylmethylmethyl)zirconium dichloride (wrong B) Manufacturing]

To the Schlenk bottle, a lithium salt of (1,2'-dimethylarylene) (2,1'-dimethylhydrazinyl)-bis(indole) 3.0 g (6.97 mmol) was dissolved in tetrahydrofuran. 50 ml of THF) was cooled at -78 °C. 2.1 ml (14.2 mmol) of iodomethyltrimethyl decane was slowly added dropwise and stirred at room temperature for 12 hours.

The solvent was distilled off, and 50 ml of ether was added and washed with a saturated ammonium chloride solution. After liquid separation, the organic phase is dried and the solvent is removed to give (1,2'-dimethyl sulfenyl) (2,1 '-dimethyl sulfenyl)-bis(3-trimethyldecyl) Methyl hydrazine) 3.04 g (5.88 mmol) (yield 84%).

Next, under the nitrogen flow, put the above-mentioned (1, 2'- in the Schlenk bottle. Dimethylsulfanylalkyl) (2,1'-dimethylhydrazinyl)-bis(3-trimethyldecylmethylhydrazine) 3.04 g (5.88 mmol) and 50 ml of ether. After cooling to -78 ° C, a solution of n-butyllithium (n-BuLi) in hexane (1.54 mol/L, 7.6 ml (11.7 mmol)) was added dropwise. After returning to room temperature and stirring for 12 hours, the ether was distilled off. The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of the ether salt of the lithium salt (yield: 73%).

The results measured by ¹ H-NMR (90 MHz, THF-d ₈ ) are shown below.

δ: 0.04 (s, 18H, trimethyldecyl), 0.48 (s, 12H, dimethyl sulfenyl), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methyl). 3.38 (q, 4H, methyl group), 6.2-7.7 (m, 8H, Ar-H)

The lithium salt obtained above was dissolved in 50 ml of toluene under a nitrogen stream. The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of toluene (20 ml) of zirconium tetrachloride previously cooled to -78 ° C was added dropwise thereto. After dripping, stirring was carried out for 6 hours at room temperature. The solvent of the reaction solution was distilled off. The obtained residue was recrystallized from methylene chloride to give (1,2'-dimethyl sulfenyl) (2,1'-dimethyl sulfenyl)-bis(3-trimethyldecane). Methyl hydrazine) zirconium dichloride 0.9 g (1.33 mmol) (yield 26%).

The measurement results by ¹ H-NMR (90 MHz, CDCl ₃ ) are shown below.

δ: 0.0 (s, 18H, trimethyldecyl), 1.02, 1.12 (s, 12H, dimethyl sulfenyl), 2.51 (dd, 4H, methyl), 7.1-7.6 (m, 8H, Ar-H)

Production Example 4-3 (Production of 1-butene homopolymer)

In a heated and dried 2 liter pressure sterilizer, heptane (600 mL), triisobutylaluminum (2M, 0.3 mL, 0.6 mmol), and a solution of heptane mud (10 μmol/mL, 0.6 mL, 0.4) were added. Μmol), a toluene solution of methylaluminoxane manufactured by Albemarle Co., Ltd. (2 mL, 3 M, 6.0 mmol), and further introduced into 0.05 MPa of hydrogen. The temperature was raised to 70 ° C while stirring, and 1-butene was introduced to raise the pressure to 0.20 MPa. Thereafter, it was intended to continuously supply 1-butene at a total pressure of 0.25 MPa, and polymerization was carried out for 2 hours. After the completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was taken out after depressurization, and dried under reduced pressure to obtain 210 g of 1-butene homopolymer (Polymer A).

Production Example 4-4 (Manufacture of propylene homopolymer)

In a 2 liter autoclave sterilizer heated and dried, heptane (600 mL), triisobutylaluminum (2M, 0.3 mL, 0.6 mmol), and a solution of heptane a heptane slurry (10 μmol/mL, 0.1 mL, 1.0) were added. Μmol), a toluene solution of methylaluminoxane manufactured by Albemarle Co., Ltd. (0.33 mL, 3 M, 1.0 mmol), and further introduced into a hydrogen gas of 0.04 MPa. While setting the temperature to 70 ° C while stirring, the propylene was introduced and the pressure was raised to 0.70 MPa. Thereafter, propylene was continuously supplied at a total pressure maintained at 0.70 MPa, and polymerization was carried out for 1 hour. After the completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and after depressurization, the reactant was taken out, and after drying under reduced pressure, 170 g of a propylene homopolymer (Polymer B) was obtained.

Production Example 4-5 (Production of 1-butene-propylene copolymer)

Add heptane (180 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (180 mL), and a solution B of heptane slurry (10 μmol/) to a heated, dry 2 liter pressure sterilizer. mL, 0.02 mL, 0.2 μmol), heptane slurry of dimethylanilide (pentafluorophenyl) borate (10 μmol/mL, 0.06 mL, 0.6 μmol) was further introduced into hydrogen 0.05 MPa. After introducing propylene while setting the temperature to 60 ° C while stirring, the total pressure was set to 0.6 MPa. Thereafter, after polymerization for 20 minutes, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 75 g (polymer C) of a 1-butene-propylene copolymer.

The decomposition efficiency, reactivity, and fluidity were evaluated in the same manner as in Example 1-1, and the glass transition temperature Tg was measured. The results are shown below.

Decomposition efficiency:-

Reactivity: ○

Liquidity: ○

Glass transfer temperature Tg (°C): ◎ (-22 ° C)

Production Example 4-6 (Production of 1-butene homopolymer)

In a heated and dried 1 liter pressure sterilizer, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (200 mL), and a solution B heptane slurry were added ( 10 μmol/mL, 0.04 mL, 0.4 μmol), heptane slurry of dimethylanilide (pentafluorophenyl) borate (10 μmol/mL, 0.12 mL, 1.2 μmol), and then introduced into hydrogen 0.1 MPa. The temperature was set to 52 ° C while stirring, and polymerization was carried out for 30 minutes. After the completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 80 g of 1-butene homopolymer (Polymer D).

For the polymers A to D obtained in Production Examples 4-3 to 4-6, the melting heat absorption ΔHD, the glass transition temperature Tg, the meso-penta-unit [mmmm] fraction, and the inner-rotational unit (meso-diad) were measured. ) fraction [m], external pentad fraction [rrrr] fraction, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, 2,1-binding fraction Rate, 1,3-binding fraction and 1,4-binding fraction. The results are shown in Table 4-1.

Manufacturing Example 4-7 [Manufacture of 1-butene homopolymer]

Stainless steel reactor with stirring device (content 500ml) In the above, 70 g of the polymer A produced in Production Example 4-3 was charged. The mixture was stirred for 30 minutes under a nitrogen stream.

Stirring was started, and the temperature of the resin was raised to 160 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, PERHEXA25B 0.4 ml was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a 1-butene homopolymer (polymer A').

The decomposition efficiency, reactivity, and fluidity were evaluated in the same manner as in Example 1-1, and the glass transition temperature Tg was measured. The results are shown below.

Decomposition efficiency: ○

Reactivity: ◎

Liquidity: ○

Glass transfer temperature Tg (°C): ◎ (-30 ° C)

Manufacturing Example 4-8~4-10

In the production example 4-7, a polymer propylene, a polymer C, and a polymer D were used instead of the polymer A, and a propylene homopolymer, a 1-butene-propylene copolymer or a 1-butene homopolymer was obtained in the same manner ( Polymer B'~D').

For the propylene homopolymer obtained in Production Examples 4-7 to 4-10, 1- Butene-propylene copolymer or 1-butene homopolymer, determination of melting heat absorption △HD, glass transition temperature Tg, meso-penta-unit [mmmm] fraction, meso-diad fraction [m], external rotation five units [rrrr] fraction, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), the number of terminal unsaturated groups per molecule, 2,1-binding fraction, 1,3-binding fraction, and 1,4-binding fraction. The results are shown in Table 4-2.

Example 4-1 (manufacturing of functionalized polypropylene)

After adding 10 g of polymer A', 2.0 g of maleic anhydride, 0.012 g of oxalic acid, and 0.04 g of maleic acid to a 100 mL separable flask equipped with a stirring blade, the mixture was heated to a blanket heater in a nitrogen atmosphere. Stirring was carried out for 5 hours at 200 °C. After cooling to room temperature, the reactant was washed four times with 20 mL of acetone, and dried by heating to obtain a polymer (polymer A") having a maleic acid added to the terminal.

Example 4-2~4-4

For Example 4-1, the polymer B'~D' was used in place of the polymer A'. In the same manner as in the examples, a polymer (polymer B" to D") in which maleic acid was added to the terminal was obtained.

For the functionalized α-olefin polymers obtained in Examples 4-1 to 4-4, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), meso-penta-unit (mmmm) fraction, and internal rotation were measured. Meso-diad fraction [m], melting point Tm-D, melting heat absorption ΔHD, number of (anhydrous) carboxylic acid residues per molecule (internal double bond structure number, 2,1-binding fraction) The total of the 1,3-binding fraction and the 1,4-binding fraction was evaluated for fluidity. The results are shown in Table 4-3.

Comparative Example 4-1 [Synthesis of propylene polymer by conventional catalyst] (1) Modulation of solid catalyst components

The 0.5 liter inner flask was equipped with a stirrer and replaced with nitrogen. Then, 20 ml of dehydrated heptane, 4 g of diethoxymagnesium, and 1.6 g of dibutyl phthalate were added to maintain 90 in the system. At ° C, 4 ml of titanium tetrachloride was added dropwise with stirring. Further, 111 ml of titanium tetrachloride was added dropwise thereto, and the temperature was raised to 110 °C. 115 ml of titanium tetrachloride was added to the obtained solid phase portion, and further reacted at 110 ° C for 2 hours. After the completion of the reaction, the product was washed with 100 ml of purified heptane several times to obtain a solid catalyst component.

(2) Modulation of preliminary polymerization catalyst components

A three-neck flask equipped with a stirrer having an inner volume of 0.5 liter was replaced with nitrogen, and then 300 ml of dehydrated heptane and 10 g of the solid catalyst component prepared by the above (1) were added. After setting the inside of the system to 15 ° C, triethylaluminum 4.2 mmol and cyclohexylmethyldimethoxydecane (CHMDS) 1.1 mmol were added, and propylene was introduced while stirring. After 2 hours, the stirring was stopped, and as a result, 1 g of a prepolymerized catalyst component of propylene was polymerized per 1 g of the solid catalyst component.

(3) Synthesis of propylene polymer

A stainless steel autoclave with a mixer of 10 liters was thoroughly dried and replaced with nitrogen. 2 kg of propylene, 6 mmol of triethylaluminum, and 2 cyclopentyldimethoxydecane (DCPDS) 3.0 were added. Millions, warmed to 65 ° C. Secondly, the preliminary aggregated touch modulated by the above (2) is input. The medium component was 0.12 g, and polymerization was carried out at 70 ° C for 3 hours. As a result, 960 g of a polymer powder of a propylene polymer was obtained. By repeating the polymerization reaction, a propylene polymer which is a raw material of a maleic anhydride-modified propylene polymer is synthesized.

[Synthesis of Maleic Anhydride Modified Propylene Polymer]

Maleic anhydride was added to 100 parts by weight of the propylene polymer synthesized in (3): 0.3 parts by weight, PERHEXYNE 25B/40: 0.1 parts by weight, and sufficiently blended. This powder blend was melt-kneaded at 180 ° C using a 20 mm two-axis extruder. To 1 kg of the obtained granular sample, 0.5 kg of acetone and 0.7 kg of heptane were added, and the mixture was heated and stirred at 85 ° C for 2 hours. Moreover, the heating and stirring is carried out in a pressure resistant container. After the end of the operation, the granules were recovered, and this was immersed in 1.5 kg of acetone for 15 hours. Thereafter, the pellet was recovered and air-dried, and vacuum-dried at 90 ° C for 6 hours to obtain a maleic anhydride-modified propylene polymer (Polymer E).

Further, since the polymer E was not subjected to the maleic anhydride addition reaction of the olefin reaction, the number of (anhydrous) carboxylic acid residues per molecule was calculated by the following method.

<Modified quantitative method>

The blend of the polyolefin before the modification and the organic acid was pressed at intervals of 0.1 mm, and the IR was measured, and the absorption amount of the characteristic carbonyl group (1600 to 1900 cm ^-1 ) and the loading amount of the organic acid were used as a calibration curve. The IR measurement of the pressure plate of the acid-modified body was carried out to determine the number of (anhydrous) carboxylic acid residues per molecule.

IR measuring machine: "FT/IR-5300" manufactured by JASCO Corporation

Further, with respect to the maleic anhydride-modified propylene polymer obtained in Comparative Example 4-1, a weight average molecular weight (Mw), a molecular weight distribution (Mw/Mn), a meso five unit [mmmm] fraction, and a melting point Tm-D were measured. The melting heat ΔHD, the number of (anhydrous) carboxylic acid residues per one molecule - the internal double bond structure. The modification rate and the result measured by the above were also shown in Table 4-4.

Example 4-6 (Manufacture of hardenable composition and cured product)

In a 30 mL sample vial, the polymer A" (3 g) obtained in Example 1 and the triamine (Jeffamine T403) (0.2 g) manufactured by Huntsman Co., Ltd. were mixed at room temperature to obtain a curable composition.

Next, after the curable composition was heated to 100 ° C, the viscosity within 30 minutes was observed to rise. The obtained reactant (1 g) and toluene (5 mL) were simultaneously placed in a 20 mL sample vial and immersed in a water bath of 40 ° C for 5 hours, which was insoluble in a solvent and showed rubber elasticity.

Comparative Example 4-2

In the same manner as in Example 4-6, except that the polymer E (3 g) obtained in Comparative Example 4-1 was used as the substituted polymer A, the composition was produced in the same manner, and after heating to 100 ° C, the polymer E was further after 30 minutes. It does not melt and does not undergo a polymerization (crosslinking) reaction.

<Fifth invention> [ ¹³ C-NMR measurement]

The ¹³ C-NMR spectrum was measured under the following apparatus and conditions to obtain a 2,1-binding fraction, a 1,3-binding fraction, a 1,4-binding fraction, and a meso five unit (mmmm). Fraction, and the outer rotatory five-element [rrrr] fraction.

Device: JNM-EX400 type ¹³ C-NMR device manufactured by JEOL Ltd.

Method: Proton completely decoupled

Concentration: 230mg/ml

Solvent: 1,2,4-trichlorobenzene/heavy benzene (volume ratio 90/10) mixed solvent

Temperature: 130 ° C

Pulse width: 45°

Pulse repetition time: 4 seconds

Cumulative number: 10,000 times

[DSC measurement]

Using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), 10 mg of the sample was held at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the heat of melting was obtained after raising the temperature at 10 ° C /min. The ΔHD and the glass transition temperature Tg were determined.

[GPC measurement]

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were determined by a gel permeation chromatography (GPC) method. The following apparatus and conditions were used for the measurement, and the weight average molecular weight in terms of polystyrene was obtained.

<GPC measuring device>

Column: TOSO GMHHR-H(S)HT

Detector: RI detector for liquid spectrum WATERS 150C

<Measurement conditions>

Solvent: 1,2,4-trichlorobenzene

Measuring temperature: 145 ° C

Flow rate: 1.0ml/min

Sample concentration: 2.2 mg/ml

Injection volume: 160μl

Proofreading curve: Universal Calibration

Parsing program: HT-GPC (Ver.1.0)

[terminal unsaturated group concentration]

The terminal vinylidene at δ4.8~4.6(2H) obtained by ¹ H-NMR, the terminal vinyl group at δ5.9~5.7 (1H) and the δ1.05~0.60 (3H) Based on the methyl group present, the terminal unsaturated group concentration (C) (% by mole) was calculated.

Vinylidene CH ₂ (4.8 ~ 4.6ppm). . . (i)

Vinyl CH (5.9~5.7ppm). . . (ii)

CH ₃ at the end of the side chain (1.05~0.60ppm). . . (iii)

The amount of vinylidene = [(i)/2] / [(iii) / 3] × 100 mol%

Vinyl amount = (ii) / [(iii) / 3] × 100 mol%

Terminal unsaturated group concentration (C) = [vinylidene amount] + [vinyl amount]

[Number of unsaturation groups per molecule)

The terminal unsaturated group concentration (C, mol%) calculated by the above method and the number average molecular weight (Mn) and monomer molecular weight (M) obtained by gel permeation chromatography (GPC), The number of terminal unsaturated groups per molecule was calculated by the following formula.

Number of unsaturation groups per 1 molecule = (Mn/M) × (C/100)

[Number of terminal hydroxyl groups per molecule]

(A) The terminal hydroxyl group concentration (% by mole) obtained by ¹³ C-NMR

(B) Number average molecular weight (Mn) of the functionalized α-olefin polymer as determined by gel permeation chromatography (GPC)

(C) Average molecular weight (Mm) of monomer units = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11

From the above formula, the number of terminal hydroxyl groups per molecule can be calculated.

Number of terminal hydroxyl groups per molecule = (Mn/M) × [terminal hydroxyl concentration] / 100

As a method for calculating the terminal hydroxyl group concentration, there is a possibility that the terminal unsaturated concentration is reduced by a side reaction, and as shown below, ¹³ C-NMR is used to calculate OH-CH ₂ from 68 to 70 ppm. The concentration of the peaks.

CH ₂ (i) of OH-CH ₂ : integral value of 68-70 ppm

CH ₂ (ii) of propylene units: integral value of peaks appearing at 46.4 ppm

CH ₂ (iii) of butene units: integral value of the peak appearing at 40.4 ppm

Terminal hydroxyl concentration = [(i) / ((ii) + (iii))] × 100 (% by mole)

[B viscosity]

The measurement was carried out in accordance with ASTM-D19860-91.

[rational at normal temperature]

The fluidity at a lower temperature was visually confirmed and evaluated on the following basis.

◎: fluidity at 60 °C.

○: fluidity at 100 °C.

△: Since it has a relatively high viscosity at 100 ° C, it is barely fluid.

×: No fluidity at 100 ° C.

[hardening reactivity at lower temperatures]

In the examples and the comparative examples, the cured product obtained by curing the curable composition was evaluated based on the following criteria.

◎: Completely hardened at 60 °C.

○: Completely cured at 100 °C.

△: Hardened partially at 100 °C.

×: There is almost no hardening at 100 °C.

[heat resistance of hardened material]

The cured product was heated in a glass oven at 120 ° C for 10 minutes, and the form of the cured product after heating was visually observed, and the rubber elasticity of the cured product was measured and evaluated by the following evaluation criteria.

○: The shape was maintained and the rubber elasticity was exhibited.

×: The shape was not maintained, and rubber elasticity was not shown.

Manufacturing Example 5-1 [(1,2'-Dimethylhydrazinyl)(2,1'-dimethylarylene)-bis(3-phenylindole)zirconium dichloride (former A)

Under a nitrogen stream, 76.5 ml (229.5 mmol) of a diethyl ether solution of phenylmagnesium bromide was placed in a 1000 ml flask and cooled in an ice bath. Here, 30 g (227.2 mmol) of 1-nonanone was dissolved in 300 ml of diethyl ether, and the mixture was gradually added dropwise. After stirring at room temperature for one hour, it was cooled in an ice bath, and 6 mol/l of hydrochloric acid was added dropwise. After stirring at room temperature, the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After the aqueous phase is separated, the organic phase is dried and the solvent is removed to give 1-phenylindole. 37.2 g (193.4 mmol) (yield 85%).

Next, we will get the 1-phenyl hydrazine 16.7g (87.1mmol). It was placed in a 300 ml flask and dissolved in 70 ml of dimethyl hydrazine. 4 ml of water was placed and cooled in an ice bath. Here, 15.6 g (87.1 mmol) of N-bromosuccinimide was gradually added, and the mixture was stirred at room temperature for 10 hours. This was cooled in an ice bath, 60 ml of water was added, and the organic layer was extracted with diethyl ether. After the aqueous phase was separated, the organic phase was dried and then evaporated to ethylamine.

Crude product of 2-bromo-1-indan-1-ol obtained above 24.0 g (83.3 mmol) was placed in a 300 ml flask, dissolved in 200 ml of toluene, and 0.48 g (2.5 mmol) of p-toluenesulfonic acid was added. A Dean-Stark tube was attached to the flask and refluxed for 2 hours. The solvent was distilled off, and the organic layer was extracted with diethyl ether and washed with saturated aqueous sodium hydrogen carbonate. After separating the aqueous phase, the organic phase was dried and the solvent was removed to give a crude product of 2-bromo-1-phenylindole. This was purified by column to give 2-bromo-1-phenylindole 17.9 g (66.4 mmol) (yield 80%).

Next, the resulting 2-bromo-1-phenylindole was obtained under a nitrogen stream. 2.7 g (10.0 mmol) was placed in a 200 ml Schlenk bottle, dissolved in 50 ml of diethyl ether, and cooled at 0 ° C, and a solution of n-butyllithium (n-BuLi) in hexane (concentration 2.6 mol/ l) 3.8 ml (10.0 mmol), stirred at room temperature for 3 hours. This was again cooled at 0 ° C, and 30 ml of diethyl ether and 12.5 ml (20.0 mmol) of a solution of t-butyllithium (t-BuLi) in pentane (concentration: 1.6 mol/l) were added, and stirred at room temperature for 3 hours. .

After stirring, it was cooled to -78 ° C and dichlorodimethyl decane was added dropwise. 0.6 ml (5.0 mmol) was stirred at room temperature overnight. This was again cooled to -78 ° C, and 0.6 ml (5.0 mmol) of dichloromethane was added dropwise, and stirred at room temperature overnight. Thereafter, after adding water and stopping the reaction, (1,2'-dimethylarylene) (2,1'-dimethylhydrazinyl) bis(3-phenylindole) 1.1 g (precipitated) 2.2 mmol), this was taken (yield: 44%).

Secondly, in the Schlenk bottle, the above-mentioned (1, 2’- Dimethylhydrazinyl)(2,1'-dimethylhydrazinyl)bis(3-phenylindole) 1.6g (3.2mmol) was dissolved in 12.6ml of diethyl ether, cooled at 0 ° C, added n 2.6 ml (6.6 mmol) of a butyllithium (n-BuLi) hexane solution (concentration: 2.6 mol/l) was again returned to room temperature and stirred for 1 hour.

The solvent was distilled off from the obtained solution, and the residual solid was washed with 20 ml of hexane, and then dried under reduced pressure to obtain quantitative (1,2'-dimethyl sulfenyl) (2,1'- A white solid of an ether adduct of a lithium salt of dimethyl sulfinyl) bis(3-phenylhydrazine).

The ether addition of the lithium salt obtained above was suspended under a nitrogen stream The mixture was suspended in 18 ml of dichloromethane, cooled to -78 ° C, and a suspension of 0.74 g (3.2 mmol) of methylene chloride (8 ml) previously cooled to -78 ° C was added dropwise to the suspension, and then returned to the chamber. After the temperature, the mixture was stirred for 4 hours.

The resulting solution was filtered, and the filtrate was concentrated to give a yellow solid. This was washed with 10 ml of hexane to obtain (1,2'-dimethyl sulfenyl) (2,1'-dimethyl sulfenyl) bis(3-phenylindole) zirconium dichloride ( Yellow microcrystals of the wrong form A) 1.3 g (2.0 mmol). (yield 62%)

The ¹ H-NMR spectrum of the yellow microcrystal was obtained, and the following results were obtained.

^{1 H-NMR (500MHz, CDCl3} ): δ0.31 (s, -Me 2 Si-, 6H), 1.21 (s, -Me 2 Si-, 6H), 7.18-7.69 (m, Ar-H, 18H)

Manufacturing Example 5-2 [Manufacture of (1,1'-extended ethyl)(2,2'-tetramethyldialkylene)biguanide zirconium dichloride (wrong B)]

Magnesium (12 g, 500 mmol) and tetrahydrofuran (30 ml) were placed in a 500 ml 2-neck flask, and magnesium was activated by dropwise addition of 1,2-dibromoethane (0.2 ml). 2 -Bromoindole (20 g, 103 mmol) dissolved in tetrahydrofuran (150 ml) was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldioxane (9.4 ml, 5.1 mmol) was added dropwise at 0 °C. After the reaction mixture was stirred at room temperature for 1 hour, the solvent was evaporated, and the residue was evaporated to ethyl ether (150 ml, 2) to give 1,2-di(1H-indol-2-yl)-1,1, 2,2-Tetramethyldioxane as a white solid (15.4 g, 44.4 mmol, yield 86%).

This was dissolved in diethyl ether (100 ml), and n-butyllithium (2.6 mol/liter, 38 ml, 98 mmol) was added dropwise at 0 ° C, and after stirring at room temperature for 1 hour, precipitated white. powder. The clear liquid was removed and the solid was washed with EtOAc (EtOAc) (EtOAc)

This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 °C. After the reaction mixture was stirred at room temperature for 1 hour, it was dried and solidified, and the residue was taken up in hexane. After extraction (150 ml), a colorless oily liquid (14.2 g, 37.9 mmol) of 2 cross-linking ligands was obtained.

This was dissolved in diethyl ether (120 ml), and n-butyllithium (2.6 mol/liter, 32 ml, 84 mmol) was added dropwise at 0 ° C, and a white powder was precipitated after stirring at room temperature for 1 hour. . The clear liquid was removed, and the solid was washed with hexane (70 ml) to give a white powder (14.0 g, 31 mmol, yield 81%) of the lithium salt of the cross-linking ligand.

Zirconium tetrachloride (1.52 g, 6.54 mmol) at -78 ° C in a suspension of the obtained lithium salt of the cross-linking ligand (3.00 g, 6.54 mmol) in toluene (30 ml). A suspension of toluene (30 ml) was dropped through a transfer tube. After the reaction mixture was stirred at room temperature for 2 hours, the clear liquid was separated, and the residue was extracted with toluene.

The solvent of the clear liquid and the extract was distilled off under reduced pressure, and dried and solidified to obtain (1,1'-extended ethyl group) (2,2'- represented by the following formula (1) as a yellow solid. Tetramethyldialkylene)bisindole zirconium dichloride (wrong B) (2.5 g, 4.7 mmol, yield 72%).

The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ): δ 0.617 (s, 6H, -SiMe ₂ -), 0.623 ( s, 6H, -SiMe ₂ -), 3.65-3.74, 4.05 - 4.15 (m, 4H, CH ₂ CH ₂ ), 6.79 (s, 2H, CpH), 7.0-7.5 (m, 8H, Aromatic-H)

Manufacturing Example 5-3 [Manufacture of Raw Material α-Olefin Polymer (A)]

In a heated and dried 1 liter pressure sterilizer, 400 ml of heptane, 0.5 mM of triisobutylaluminum, 0.2 micromolar of malformed body, 0.8 micromolar of quinone pentafluorophenyl borate, further introduced Hydrogen 0.05 MPa. Propylene was placed while stirring, the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 60 ° C for 30 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 100 g of a raw material α-olefin polymer (A).

With respect to the obtained raw material α-olefin polymer (A), the melting heat absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of terminal unsaturated groups per molecule, and meso-five were measured. Unit [mmmm] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 5-1.

Manufacturing Example 5-4 [Manufacture of Raw Material α-Olefin Polymer (B)]

70 g of the raw material α-olefin polymer (A) produced in Production Example 5-3 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. Stirring was carried out for 30 minutes under a nitrogen stream.

Start stirring and use a mantle heater to raise the resin temperature to 160 ° C. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a raw material α-olefin polymer (B).

The obtained raw material α-olefin polymer (B) was measured for melting heat absorption ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, and meso- 5 Unit [mmmm] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 5-1.

Further, the yield of the obtained raw material α-olefin polymer (B) was 99.3% by mass based on the raw material α-olefin polymer (A) charged, and the amount of by-products was a trace amount.

Manufacturing Example 5-5 [Manufacture of Raw Material α-Olefin Polymer (C)]

In a heated and dried 1 liter pressure sterilizer, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), 1-butene (200 mL), and B (10 μmol/mL, 0.20 mL, 2.0 μmol), MAO (2000 μmol) manufactured by Tosoh Fine Chemical Co., Ltd., and further introduced with hydrogen 0.1 MPa. The polymerization was carried out for 30 minutes while the temperature was changed to 70 ° C while stirring. After the end of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 1-butene homopolymerization. 82g

With respect to the obtained raw material α-olefin polymer (C), the melting heat absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of terminal unsaturated groups per molecule, and meso-five were measured. Unit [mmmm] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 5-1.

Manufacturing Example 5-6 [Manufacture of Raw Material α-Olefin Polymer (D)]

70 g of the raw material α-olefin polymer (C) produced in Production Example 5-5 was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. The mixture was stirred for 30 minutes under a nitrogen stream.

Stirring was started and the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a raw material α-olefin polymer (D).

The obtained raw material α-olefin polymer (D) was measured for melting heat absorption ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, and meso- 5 Unit [mmmm] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 5-1.

Further, the yield of the obtained raw material α-olefin polymer (D) was 99.3% by mass based on the raw material α-olefin polymer (C) charged, and the amount of by-products was a trace amount.

Manufacturing Example 5-7 [Manufacture of Raw Material α-Olefin Polymer (E)]

In a heated and dried 1 liter pressure sterilizer, heptane (400 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), skeletal B (10 μmol/mL, 0.20 mL, 2.0 μmol), East MAO (2000 μmol) manufactured by Cao Fine Chemical Co., Ltd., further introducing hydrogen 0.1 MPa. Propylene was placed while stirring, and the total pressure was raised to 0.7 MPa, and polymerization was carried out at a temperature of 50 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 105 g of a raw material α-olefin polymer (E).

Manufacturing Example 5-8 [Manufacture of Raw Material α-Olefin Polymer (F)]

Next, 70 g of the obtained raw material α-olefin polymer (E) was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. The mixture was stirred for 30 minutes under a nitrogen stream.

Stirring was started and the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.4 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the end of the drip, after 15 minutes of reaction, Cool to 110 ° C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a raw material α-olefin polymer (F).

The obtained raw material α-olefin polymer (F) was measured for melting heat absorption ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, and meso-five Unit [mmmm] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 5-1.

Further, the yield of the obtained raw material α-olefin polymer (F) was 99.5% by mass based on the raw material α-olefin polymer (E) charged, and the amount of by-products was a trace amount.

Manufacturing Example 5-9 [Manufacture of Raw Material α-Olefin Polymer (G)]

Synthetic phantom C [dimethyl ¹ -tert-butyl decylamine (η ⁵ -tetramethylcyclopentadiene) titanium dichloride as described in Organometallics 2000, 19, 1870-1878 ].

In a 1 liter autoclave sterilizer which was heated and dried, 400 ml of heptane, 0.5 mM of triisobutylaluminum, 0.2 micromolar of malformed body, and 0.8 micromolar of quinone pentafluorophenyl borate were added. Further, hydrogen was introduced into 0.05 MPa. Propylene was placed while stirring, and the pressure was raised to a total pressure of 0.5 MPa, and polymerization was carried out at a temperature of 90 ° C for 60 minutes. After the completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization liquid was heated, and dried under reduced pressure to obtain 50 g of a raw material α-olefin polymer (G).

The obtained raw material α-olefin polymer (G) was measured for melting heat absorption ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), number of terminal unsaturated groups per molecule, and meso-five Unit [mmmm] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 5-1.

Manufacturing Example 5-10 [Manufacture of dimethyl sulfinyl (2-anthracene) (1-(2-methyl-4,5-benzofluorenyl)) zirconium dichloride (wrong D)] Synthesis of (2-methyl-4,5-benzo-1-indanone)

Dichloromethane (100 mL), naphthalene (5 g, 0.039 mol), and 2-bromoisobutylphosphonium bromide (9 g, 0.039 mol) were placed in a 300 mL three-neck flask equipped with a nitrogen introduction tube. Aluminum chloride (6 g, 0.047 mol) was slowly introduced under a nitrogen stream. After 1 hour, the reaction solution was poured into cold water (200 mL), and the organic phase was separated using a separating funnel. The organic phase was dried over magnesium sulfate, filtered, and evaporated.

Synthesis of (2-methyl-4,5-benzopyrene)

2-Methyl-4,5-benzo-1-indanone (6.4 g) was dissolved in methanol (100 mL). Sodium borohydride (1 g, 0.026 mol) was slowly added to the solution. After 30 minutes, water (100 mL) and ether (100 mL) were poured and extracted. The organic phase was separated using a separatory funnel. The organic phase was dried over magnesium sulfate, filtered, and the solvent was evaporated to give 2-A. Base-4,5-benzoxanol (5.7 g). The obtained 2-methyl-4,5-benzoxanol (5.7 g) was dissolved in toluene (100 mL), p-toluidinesulfonate (0.5 g) was added, and the Dean-Stark apparatus was used. A minute of reflux and a dehydration reaction. After the completion of the reaction, the solvent was evaporated to dryness, and the residue was purified (yield: hexane) to give the objective compound (3 g) (yield: 48%).

(Synthesis of 2-茚-dimethylchlorodecane)

Magnesium powder (1.3 g) and iodine (0.01 g) and dehydrated THF (20 mL) were placed in a Dimroth tube and a 200 mL three-necked flask equipped with a titration funnel. 2-bromoindole (synthesized according to J. Org. Chem. 47, (4), 705 (1982)) (5.4 g, 27.2 mmol) and dehydrated THF (40 mL) were placed in a titration funnel and slowly dried under nitrogen. The drip is gently refluxed. After the end of the dropping, stirring was carried out at room temperature for 30 minutes. Thereafter, trimethylsulfonyl chloride (3.1 g, 28.5 mmol) and dehydrated THF (20 mL) were placed in a titration funnel, and the solution was added dropwise at -78 °C. After the completion of the dropwise addition, stirring was carried out for 8 hours at room temperature. The solvent was distilled off under reduced pressure and extracted with anhydrous hexane (100 mL). The solvent was distilled off under reduced pressure to give 5.3 g (yield: 91%) of desired compound.

Synthesis of ((2-茚)(1-(2-methyl-4,5-benzofluorenyl)) dimethyl decane)

2-Methyl-4,5-benzopyrene (1.26 g, 7 mmol) and dehydrated hexane (50 mL) were placed in a nitrogen-substituted 200 mL Schlenk tube. In the solution A solution of n-butyllithium in hexane (1.50 M, 4.7 mL, 7 mmol) was added dropwise at -78 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours, and then 2-methyl-4,5-benzoindole lithium was precipitated. After the suspension was allowed to stand, the clear liquid was removed by decantation. Dehydrated THF (25 mL) was added thereto, cooled to -78.degree. C., and then a mixture of the previously synthesized 2-indole dimethyl chloro decane (1.46 g, 7 mmol) in dehydrated THF (25 mL). After the completion of the dropwise addition, stirring was carried out for 4 hours at room temperature. After the end of the reaction, water (50 mL) was added and the mixture was evaporated. After the extracting solution was separated by a sep. funnel, the obtained organic phase was dried over magnesium sulfate and filtered, and the solvent was evaporated to give the objective compound (2.2 g) (yield: 89%).

(Synthesis of dimethyl sulfinyl (2-anthracene) (1-(2-methyl-4,5-benzofluorenyl)) zirconium dichloride)

The previously synthesized (2-茚)(1-(2-methyl-4,5-benzofluorene)) dimethyl decane (1.0 g, 2.8 mmol) was placed in a nitrogen-substituted 200 mL Schlenk tube. Dehydrated hexane (40 mL). A solution of n-butyllithium in hexane (1.50 M, 3.7 mL, 5.6 mmol) was dropped from this solution at -78 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours to precipitate (2-(2-methyl-4,5-benzofluorene)) dimethyl decane dilithium. After the suspension was allowed to stand, the clear liquid was removed by decantation. Dehydrated toluene (25 mL) was added thereto, cooled to -78 ° C, and a suspension of zirconium tetrachloride (0.9 g, 2.8 mmol) in dehydrated toluene (25 mL) was added dropwise. After the completion of the dropwise addition, stirring was carried out for 6 hours at room temperature. After the reaction was completed, it was filtered through a cannula, and the filtrate was concentrated and then dehydrated hexane was added. Filter the resulting precipitate and dry it To the target compound 0.2g (yield 12%)

The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (δppm/CDCl ₃ ): 8.0-7.0 (m, 8H), 6.50 (s, 1H), 6.08 (d, 1H), 5.93 (d, 1H), 2.45 (s, 3H), 1.12 ( s, 3H), 0.99 (s, 3H)

Manufacturing Example 5-11 [Manufacture of Raw Material α-Olefin Polymer (H)] (Micron polymerization of propylene)

A 1 liter stainless steel pressure autoclave equipped with a stirring device was heated to 80 ° C, dried under sufficient reduced pressure, and then returned to atmospheric pressure under dry nitrogen and cooled to room temperature. Under a dry nitrogen stream, 400 ml of dry deoxidized toluene and a heptane solution (2.0 M) of triisobutylaluminum were placed in 0.5 ml (1.0 mmol), and the mixture was temporarily stirred at 350 rpm. Thereafter, a toluene solution of MAO (2.03 M, 0.5 ml, 1.0 mmol) and a heptane slurry (10 μmol/liter, 2.0 ml, 20.0 μmol) of the wrong body D obtained in the above (Production Example 5-10) were autoclaved. Quickly invest in the device. Thereafter, stirring was started at 400 rpm. Next, hydrogen was set to 0.01 MPa, and then propylene was pressurized at a total pressure of 0.75 MPa for 3 minutes, while the temperature was raised to 50 ° C, and polymerization was carried out for 1 hour. After the completion of the reaction, 20 ml of methanol was placed in an autoclave, and unreacted propylene was removed by pressure reduction. The reaction mixture was poured into 2 liters of methanol, and the charged polypropylene was precipitated, and dried by filtration to obtain 54 g of a raw material α-olefin polymer (H).

Manufacturing Example 5-12 [Manufacture of Raw Material α-Olefin Polymer (I)]

20 g of the obtained raw material α-olefin polymer (H) was placed in a stainless steel reactor (content: 500 ml) equipped with a stirring device. Stirring was carried out for 30 minutes under a nitrogen stream.

Stirring was started and the resin temperature was raised to 200 ° C using a mantle heater. The sheathed resistance heater controls the resin temperature to a certain temperature of 280 °C. Here, 0.11 ml of Percumyl P (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise over 4 minutes. After the completion of the dropwise addition, the reaction was carried out for 15 minutes, and then cooled to 110 °C.

After completion of the reaction, the mixture was dried under reduced pressure at 100 ° C for 10 hours and subjected to radical decomposition to obtain a raw material α-olefin polymer (I).

With respect to the obtained raw material α-olefin polymer (I), the melting heat absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the number of terminal unsaturated groups per molecule, and meso-five were measured. Unit [mmmm] fraction, 2,1-binding fraction, 1,3-binding fraction, and glass transition temperature Tg. The results are shown in Table 5-1.

Further, the yield of the obtained raw material α-olefin polymer (I) was 99.5% by mass based on the raw material α-olefin polymer (H) charged, and the amount of by-products was a trace amount.

Example 5-1 [Production of Functionalized α-Olefin Polymer] (borohydride reaction)

In a 500 ml flask, 10 g of the raw material α-olefin polymer (B) synthesized in Production Example 5-4 was dissolved in 50 ml of tetrahydrofuran, and then 50 ml of a 1.2 N borane tetrahydrofuran solution was added dropwise under a nitrogen atmosphere at room temperature. Reacted for one night.

(acidification (hydroxyl imparting) reaction)

To the reaction product, 7.5 ml of distilled water was slowly added dropwise, and 20 ml of a 3N-NaOH aqueous solution was added thereto, and then 20 ml of 30% hydrogen peroxide water was slowly dropped. The reaction solution was stirred overnight at room temperature. 200 ml of distilled water was added to the reaction liquid, and the mixture was extracted with 200 ml of toluene, and washed with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to give 8 g of the functionalized α-olefin polymer (A) as a viscous liquid.

For the obtained functionalized α-olefin polymer (A), the number of terminal hydroxyl groups per molecule, the heat of absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the meso-penta unit were measured. Mmmmm] fraction, B viscosity, glass transition temperature Tg, and fluidity were evaluated. The results are shown in Table 5-2.

[Manufacture of hardenable composition and cured product]

4.0 g of the functionalized α-olefin polymer (A) produced as described above Under a normal temperature nitrogen flow, 0.4 g of isophorone diisocyanate and 0.04 g of n-butyltin dilaurate (curing catalyst) were added while stirring in a separable flask to obtain a curable composition. The obtained curable composition was poured into a container of 2.5 × 2.5 cm, and allowed to stand at room temperature for 1 hour to prepare a cured product.

The obtained cured product was heated on a hot plate controlled at 120 ° C for 10 minutes, and the shape change was observed. As a result, it was confirmed that the shape was maintained in a heated state, and it was a cured product showing rubber elasticity.

Example 5-2 [Production of Functionalized α-Olefin Polymer]

A functionalized α-olefin polymer was produced in the same manner as in Example 5-1, except that the raw material α-olefin polymer (B) was used, except that the raw material α-olefin polymer (D) synthesized in Production Example 5-6 was used. (B).

For the obtained functionalized α-olefin polymer (B), the number of terminal hydroxyl groups per molecule, the heat of absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the meso-penta unit were measured. Mmmmm] fraction, B viscosity, glass transition temperature Tg, and fluidity were evaluated. The results are shown in Table 5-2.

[Manufacture of hardenable composition and cured product]

A curable composition and a cured product were produced in the same manner as in Example 5-1 except that the functionalized α-olefin polymer (A) was used instead of the functionalized α-olefin polymer (B).

The resulting hardened material was subjected to 10 minutes on a hot plate controlled at 120 ° C. The bell was heated and the shape change was observed. As a result, it was confirmed that the shape was maintained in a heated state, and it was a cured product showing rubber elasticity.

Example 5-3 [Production of Functionalized α-Olefin Polymer]

A functionalized α-olefin polymer was produced in the same manner as in Example 5-1 except that the raw material α-olefin polymer (B) was used instead of the raw material α-olefin polymer (F) synthesized in Production Example 5-8. (C).

For the obtained functionalized α-olefin polymer (C), the number of terminal hydroxyl groups per molecule, the heat of absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the meso-penta unit were measured. Mmmmm] fraction, B viscosity, glass transition temperature Tg, and fluidity were evaluated. The results are shown in Table 5-2.

[Manufacture of hardenable composition and cured product]

A curable composition and a cured product were produced in the same manner as in Example 5-1 except that the functionalized α-olefin polymer (A) was used instead of the functionalized α-olefin polymer (C).

The obtained cured product was heated on a hot plate controlled at 120 ° C for 10 minutes, and the shape change was observed. As a result, it was confirmed that the shape was maintained in a heated state, and it was a cured product showing rubber elasticity.

Example 5-4 [Production of Functionalized α-Olefin Polymer]

Into a 100 mL separable flask equipped with a stirring blade, 40 g of the α-olefin polymer (F) produced in Production Example 5-8, 4.0 g of maleic anhydride, and 0.024 g of oxalic acid were placed in a nitrogen atmosphere. The mantle heater was heated to 200 ° C and stirred for 5 hours. After cooling to room temperature, the reactant was washed four times with acetone (80 mL), and dried by heating to obtain a polymer obtained by adding maleic acid to the terminal.

For the polymer obtained by terminal addition of maleic acid, the number of terminal hydroxyl groups per molecule, the heat of absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), and the meso-penta unit were measured. Mmmmm] fraction, B viscosity, glass transition temperature Tg, and fluidity were evaluated. The results are shown in Table 5-2.

500mL of 3 with Dimroth tube and titration funnel Into the flask, 0.4 g of lithium aluminum hydride and 100 mL of dehydrated tetrahydrofuran (THF) were charged. 40 g of the above-mentioned maleic acid-added polymer was dissolved in 100 mL of dehydrated THF, and the mixture was placed in a titration funnel, and the THF slurry of the lithium aluminum hydride was added dropwise thereto over 30 minutes while stirring. After the completion of the dropwise addition, stirring was carried out for 2 hours at room temperature. After the completion of the reaction, 50 mL of water was slowly added, and 100 mL of hexane was placed, and the organic layer was separated by a separating funnel. The organic layer was dried over magnesium sulfate, and after filtration, the solvent was evaporated under reduced pressure to give a functionalized α-olefin polymer having a hydroxyl group.

[Manufacture of hardenable composition and cured product]

Substituting the functionalized α-olefin polymer (A), using the functionalized α-olefin polymer having a hydroxyl group obtained as described above, and Example 5-1 The curable composition and the cured product are produced in the same manner.

The obtained cured product was heated on a hot plate controlled at 120 ° C for 10 minutes, and the shape change was observed. As a result, it was confirmed that the shape was maintained in a heated state, and it was a cured product showing rubber elasticity.

Comparative Example 5-1

The functionalized α-olefin polymer was produced in the same manner as in Example 5-1 except that the raw material α-olefin polymer (B) was used, and the raw material α-olefin polymer (G) synthesized in Production Example 5-9 was used. Since there is no terminal unsaturated group, the hydroxyl group cannot be imparted.

For the polymer, the number of terminal hydroxyl groups per molecule, the heat of absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the meso-penta-unit (mmmm) fraction, the B-viscosity, and the glass were measured. The temperature Tg is transferred and the fluidity is evaluated. The results are shown in Table 5-2.

Although no hydroxyl group was added, 4.0 g of the obtained polymer was added to a separable flask under a normal temperature nitrogen stream, and 0.4 g of isophorone diisocyanate and 0.04 g of n-butyltin dilaurate (curing catalyst) were added thereto. Composition. The obtained composition was poured into a container of 2.5 × 2.5 cm, and left at room temperature for 1 hour, and the curing reaction was not performed, and a cured product could not be obtained. Therefore, the composition after standing could not maintain the shape on the hot plate controlled at 120 ° C, and showed no rubber elasticity.

For the polymer, the number of terminal hydroxyl groups per molecule, the heat of absorption ΔH-D, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the meso-penta-unit (mmmm) fraction, the B-viscosity, and the glass were measured. The glass transfer temperature Tg, which in turn evaluates the fluidity. The results are shown in Table 5-2.

Comparative Example 5-2

The functionalized α-olefin polymer was produced in the same manner as in Example 5-1 except that the raw material α-olefin polymer (B) was used, except that the raw material α-olefin polymer (H) synthesized in Production Example 5-11 was used. The solubility in the THF solvent is poor, and the hydroxyl group cannot be imparted.

For the polymer, the number of terminal hydroxyl groups per molecule, the heat of absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the meso-penta-unit (mmmm) fraction, the B-viscosity, and the glass were measured. The temperature Tg is transferred and the fluidity is evaluated. The results are shown in Table 5-2.

Although the hydroxyl group was not provided, 4.0 g of the obtained polymer was stirred under a normal temperature nitrogen stream, and 0.4 g of isophorone diisocyanate and 0.04 g of n-butyltin dilaurate (curing catalyst) were added while stirring. The composition was obtained. The obtained composition was poured into a container of 2.5 × 2.5 cm, and allowed to stand at room temperature for 1 hour, but no hardening reaction proceeded, and the shape was not maintained on a hot plate controlled to 120 ° C, and rubber elasticity was not exhibited.

Comparative Example 5-3

The functionalized α-olefin polymer was produced in the same manner as in Example 5-1 except that the raw material α-olefin polymer (B) was used, and the raw material α-olefin polymer (I) synthesized in Production Example 5-12 was used. The solubility of the THF solvent is poor, and the hydroxyl group cannot be imparted.

For the polymer, the number of terminal hydroxyl groups per molecule was measured, and the melting was measured. The heat ΔH-D, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the meso-penta-unit (mmmm) fraction, the B-viscosity, and the glass transition temperature Tg were evaluated for fluidity. The results are shown in Table 5-2.

Although it was not possible to provide a hydroxyl group, 4.0 g of the obtained polymer was added to a separable flask under a normal temperature nitrogen stream, and 0.4 g of isophorone diisocyanate and 0.04 g of n-butyltin dilaurate (curing catalyst) were added thereto. Composition. The obtained composition was poured into a container of 2.5 × 2.5 cm, and allowed to stand at normal temperature for 1 hour, but no hardening reaction was carried out, and the shape was not maintained on a hot plate controlled at 120 ° C, and rubber elasticity was not exhibited.

Comparative Example 5-4

The functionalized α-olefin polymer was produced in the same manner as in Example 5-1 except that the raw material α-olefin polymer (B) was used to produce the raw material α-olefin polymer (A) synthesized in Example 5-3. For the polymer, the number of terminal hydroxyl groups per molecule, the heat of absorption ΔHD, the weight average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the meso-penta-unit (mmmm) fraction, the B-viscosity, and the glass were measured. The temperature Tg is transferred and the fluidity is evaluated. The results are shown in Table 5-2.

4.0 g of the obtained polymer was added to a separable flask under a normal temperature nitrogen stream, and 0.4 g of isophorone diisocyanate and 0.04 g of n-butyltin dilaurate (curing catalyst) were added to obtain a composition. The obtained composition was poured into a 2.5×2.5 cm container and left at room temperature for 1 hour. The hardening reaction was very slow, and the obtained cured product was not sufficiently cross-linked, so it could not be controlled on a hot plate controlled at 120 ° C. The shape is maintained without showing rubber elasticity.

[Industrial availability]

Since the α-olefin polymer of the present invention is used for a reaction point at the terminal unsaturated group, it can be used for imparting adhesion to a chemically inert polyolefin material, coating property, coating property, and resin other than polyolefin. The manufacture of alloy materials, and inorganic. In the field of organic filler composition and the like. Moreover, when it is used as a reactive raw material, it can be used as a reactive adhesive, a reactive hot melt adhesive, other adhesives, an adhesive, a sealing material, a sealing material, a potting material, a reactive plasticizer, or the like. It is widely used.

Claims (44)

An α-olefin polymer characterized by satisfying the following (1) to (4), (1) 2, 1-binding fraction is less than 0.5 mol%, and (2) 1,3-binding fraction And the total of the 1,4-binding fraction is less than 0.5 mol%, and (3) the melting heat absorption ΔHD measured by differential scanning calorimetry (DSC) is less than 1.0 J/g, (4) A propylene polymer or a butylene polymer. The α-olefin polymer of claim 1 which is in the following (5) to (8), wherein (5) the meso-penta-unit [mmmm] fraction is less than 20 mol%, (6) The Racemic pentad fraction [rrrr] is less than 20 mol%, (7) the weight average molecular weight (Mw) is 100 to 500,000, and (8) the molecular weight distribution (Mw/Mn) is 2.0 or less. The α-olefin polymer of claim 1 or 2, wherein the following (9) is further satisfied, and (9) the number of terminal unsaturation groups per molecule is from 0.5 to 2.5. The α-olefin polymer according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) is from 300 to 50,000. The α-olefin polymer according to any one of claims 1 to 4, wherein the number of terminal unsaturation groups per molecule is from 1.0 to 2.5. A functionalized alpha-olefin polymer characterized by the functionalization of an alpha-olefin polymer according to any one of claims 1 to 5. An adhesive composition characterized by containing a functionalized alpha-olefin polymer as claimed in claim 6. A sealant composition characterized by containing a functionalized alpha-olefin polymer as claimed in claim 6. A potting compound composition characterized by containing a functionalized alpha-olefin polymer as claimed in claim 6. A curable adhesive composition comprising (A) a propylene-based polymer or a 1-butene-based polymer having the following properties (a1) and (a2), and (B) having two or more hydrogen- a polyoxane of hydrazine bond, and (C) a hydrogenation catalyst of (C); (a1) a melting heat absorption ΔHD measured by a differential scanning calorimeter (DSC) of less than 50 J/g; (a2) per molecule The number of terminal unsaturation groups is 0.5 to 2.5. The sclerosing adhesive composition of claim 10, wherein the aforementioned melting heat absorption ΔH-D is less than 10 J/g. The sclerosing adhesive composition according to claim 10 or 11, wherein the polyoxyalkylene (B) is a polyoxyalkylene having a Si-H bond at a portion other than the terminal. The sclerosing adhesive composition according to any one of claims 10 to 12, wherein the propylene-based polymer and the 1-butene-based polymer (A) further have the following characteristics (a3) and (a4); (a3) The weight average molecular weight Mw is 1,000 to 500,000; (a4) the molecular weight distribution Mw/Mn is 1.1 to 2.5. The sclerosing adhesive composition of claim 13, wherein the propylene-based polymer and the 1-butene-based polymer (A) further have the following characteristics (a3'); (a3') the weight average molecular weight Mw is 5,000 to 20,000 . The sclerosing adhesive composition according to any one of claims 10 to 14, wherein the propylene-based polymer and the 1-butene-based polymer (A) further have the following characteristics (a5) and (a6); (a5) The 2,1-binding fraction is less than 0.5 mol%; the sum of the (a6) 1,3-binding fraction and the 1,4-binding fraction is less than 0.5 mol%. The sclerosing adhesive composition according to any one of claims 10 to 15, which further comprises (D) an adhesion-imparting agent or a subsequent imparting agent, and (E) a diluent. A cured product characterized in that the hardenable adhesive composition according to any one of claims 10 to 16 is hardened at a temperature of 100 ° C or lower. An adhesive comprising a sclerosing adhesive composition according to any one of claims 10 to 16 or a hardened material according to claim 17. A sealant comprising the hardenable adhesive composition of any one of claims 10 to 16 or the hardened material of claim 17. A functionalized α-olefin polymer characterized in that it has a ruthenium-containing group at the end of the α-olefin polymer main chain and satisfies the following (1) to (4); (1) the aforementioned terminal per molecule The number of bases of bismuth is 0.5~2.0, and (2) the melting endotherm measured by differential scanning calorimeter (DSC) The amount ΔHD is 50 J/g or less, (3) the weight average molecular weight (Mw) is 3,000 to 500,000, and (4) the α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, or a propylene-1. - Butene copolymer. The functionalized α-olefin polymer of claim 20, wherein the melting heat absorption ΔH-D measured by a differential scanning calorimeter (DSC) is 10 J/g or less, and the molecular weight distribution (Mw/Mn) is less than 4.5. A process for producing a functionalized α-olefin polymer according to claim 20 or 21, characterized in that the number of terminally unsaturated groups per molecule is from 0.5 to 2.0, and has hydrogen-oxime The compound of the bond is reacted. A curable composition characterized by comprising (A) a functionalized α-olefin polymer as claimed in claim 20 or 21 and (B) a hardening promoting catalyst. The curable composition of claim 23, which further comprises (C) an adhesion-imparting agent and (D) a diluent. A cured product characterized by hardening a hardenable composition as claimed in claim 23 or 24. A method of producing a cured product according to claim 25, characterized in that the hardenable composition according to claim 23 or 24 is cured at a temperature of 100 ° C or lower. A functionalized alpha-olefin polymer of claim 20 or 21 which is for use in an adhesive, sealant, adhesive, or modifier. A cured product of claim 25 which is for use in an adhesive, a sealant, an adhesive, or a modifier. A functionalized α-olefin polymer characterized by having (anhydrous) a carboxylic acid residue at the end of the α-olefin polymer and satisfying the following (1) to (6); (1) a weight average molecular weight (Mw) It is 1,000 to 500,000; (2) the molecular weight distribution (Mw/Mn) is 4.5 or less; (3) the melting heat absorption ΔHD measured by differential scanning calorimetry (DSC) is 50 J/g or less; (4) the aforementioned α - the olefin polymer is a propylene homopolymer, a 1-butene homopolymer, a propylene-1-butene copolymer, a propylene-diene copolymer or a 1-butene-diene copolymer; (5) per molecule The number of (anhydrous) carboxylic acid residues is from 0.5 to 2.5; (6) the number of terminal (anhydrous) carboxylic acid residues per molecule - the internal double bond structure is from 0.5 to 2.5. The functionalized α-olefin polymer of claim 29, wherein the heat of fusion ΔH-D measured by the aforementioned differential scanning calorimeter (DSC) is 1 J/g or less. A hardenable composition characterized by containing a functionalized alpha-olefin polymer as claimed in claim 29 or 30 and a crosslinking agent. A cured product characterized by hardening a hardenable composition as claimed in claim 31. A process for producing a functionalized α-olefin polymer according to claim 30 or 31, which is characterized in that an α-olefin polymer satisfying the following (1') to (5') and an unsaturated (anhydrous) carboxylic acid are obtained. Reacting (1') weight average molecular weight (Mw) is 1,000 to 500,000; (2') molecular weight distribution (Mw/Mn) is 4.5 or less; (3') melting heat absorption measured by differential scanning calorimeter (DSC) HD is 50 J/g or less; (4') The aforementioned α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, a propylene-1-butene copolymer, a propylene-diene copolymer or a 1-butene The ene-diene copolymer; (5') the number of terminal unsaturated groups per molecule is from 0.5 to 2.5. A functionalized alpha-olefin polymer characterized in that the alpha-olefin polymer has a hydroxyl group, and the alpha-olefin polymer is a propylene homopolymer, a 1-butene homopolymer, or a propylene-1-butene copolymer. And satisfying the following (1) to (4); (1) the weight average molecular weight (Mw) is 1,000 to 500,000: (2) the molecular weight distribution (Mw/Mn) is 1.1 to 2.5; (3) per 1 molecule The number of the hydroxyl groups is 1.1 to 4.5; and (4) the melting heat absorption ΔHD measured by a differential scanning calorimeter (DSC) is 50 J/g or less. The functionalized α-olefin polymer of claim 34, wherein the heat of fusion ΔH-D measured by a differential scanning calorimeter (DSC) is 1 J/g or less. The functionalized α-olefin polymer of claim 34 or 35, wherein the number of the aforementioned hydroxyl groups per molecule is from 1.1 to 4.0. The functionalized α-olefin polymer according to any one of claims 34 to 36, wherein the aforementioned α-olefin polymer is a Mesopotent (mmmm) fraction. It is a propylene homopolymer or a 1-butene homopolymer of 20 mol% or less. The functionalized α-olefin polymer according to any one of claims 34 to 36, wherein the α-olefin polymer has a Mesodaiaddo fraction [m] of 70 mol% or less of propylene-1-butene. Copolymer. The functionalized alpha-olefin polymer of any one of claims 34 to 38, which is used in an adhesive, a sealant, an adhesive, or a modifier. A curable composition characterized by adding (A) the functionalized α-olefin polymer according to any one of claims 34 to 39 and (B) a polyisocyanate compound. The sclerosing composition of claim 40, which further comprises (C) a hardening promoting catalyst. A cured product characterized by hardening a hardenable composition as claimed in claim 40 or 41. A cured product of claim 42, which is for use in an adhesive, a sealant, an adhesive, or a modifier. A method for producing a functionalized α-olefin polymer according to any one of claims 34 to 39, which is characterized in that the raw material α-olefin polymer having a number of terminal unsaturated groups per molecule is 1.1 to 2.0 Hydroxylated.