JP2014040526A - FUNCTIONALIZED α-OLEFIN POLYMER, CURABLE COMPOSITION USING THE SAME AND CURED MATERIAL - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin material which is fluid at ordinary temperature and can undergo a curing reaction at ordinary temperature.SOLUTION: Provided is a functionalized α-olefin polymer having a carboxylic acid (anhydride) residue at a main chain terminal of the α-olefin polymer and satisfy the following (1) to (6): (1) weight average molecular weight (Mw) is 1,000 to 500,000; (2)molecular weight distribution (Mw/Mn) is 4.5 or less; (3) an amount of melt endotherm (ΔH-D) measured by a differential scanning calorimeter (DSC) is 50 J/g or less; (4) the 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) number of the carboxylic acid (anhydride) residue per molecule is 0.5 to 2.5; and (6) number of the terminal carboxylic acid (anhydride) residue-inner double bond per molecule is 0.5 to 2.5.

Description

  The present invention relates to a functionalized α-olefin polymer, a curable composition using the same, and a cured product.

In recent years, global environmental issues, workers' working environments, safety and health awareness are increasing. Under such circumstances, for example, in the field of hot-melt adhesives, conventional hot-melt adhesives have a melting point of 150 ° C. or higher and need to be heated, so a substance capable of low-temperature coating is required. .
For applications such as adhesives, materials with higher reactivity are desired, such as reactive adhesives (epoxy resin-based, polyurethane-based, polyamide-based), sealing materials, sealing materials, adhesives, plasticizers, etc. In applications, materials that are easy to handle and have high reactivity and materials that can control the reactivity are desired. In addition, there is an increasing need for olefin-based materials from the viewpoint of improving heat resistance and waterproofing.

As such an olefin-based material, Patent Document 1 discloses a propylene-based polymer as a radical initiator and maleic acid for the purpose of efficiently producing a high-adhesion, high-strength and soft modified propylene-based polymer. A method of reforming with a polar group-containing olefin compound such as is disclosed.
Patent Document 2 discloses that a monomer such as maleic acid is grafted in the presence of a radical initiator as a material useful as a polyolefin modifier, a dispersibility improver between different materials, a compatibilizer, and the like. A graft copolymer obtained by polymerization is disclosed.

JP2007-204700 WO08 / 066168

  In the field of adhesives and sealants, there is a demand for fluidity (good handleability) at room temperature. In the adhesive using a high melting point polypropylene, a temperature of 160 ° C. or more is required for the curing reaction, and there are problems such as poor handling and difficulty in construction.

In addition, in the case of copolymerization or addition polymerization using a radical initiator, it is difficult to control the amount of carboxylic acid residues, and the difference between a portion with a large amount of carboxylic acid residues and a portion with a small amount becomes large. As a result, molecules with strong polarity and molecules with weak polarity are mixed, and the function as a compatibilizer for polar and nonpolar materials is reduced, or there are many carboxylic acid residues in one molecular chain. By doing so, it may be difficult to control the crosslinking reaction by reaction with a compound such as polyamine or polyol.
The problem to be solved by the present invention is to provide a polyolefin material having fluidity at a relatively low temperature and capable of carrying out a curing reaction at a relatively low temperature.

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, an (anhydrous) carboxylic acid residue is added to an α-olefin polymer having an unsaturated group at the terminal, and the terminal (anhydrous) is obtained. It has been found that the above problems can be solved by a functionalized α-olefin polymer having a carboxylic acid residue.
That is, the present 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 an (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 endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
(4) The α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, propylene-1-butene copolymer, propylene-diene copolymer or 1-butene-diene copolymer.
(5) The number of (anhydrous) carboxylic acid residues per molecule is 0.5 to 2.5.
(6) The number of terminal (anhydrous) carboxylic acid residue-internal double bond structures per molecule is 0.5 to 2.5.
[2] The functionalized α-olefin polymer according to [1], wherein a melting endotherm ΔH-D measured by the differential scanning calorimeter (DSC) is 1 J / g or less.
[3] A curable composition comprising the functionalized α-olefin polymer according to [1] or [2] and a crosslinking agent.
[4] A cured product obtained by curing the curable composition according to [3].
[5] The functionalization according to [1] or [2], wherein an α-olefin polymer satisfying the following (1 ′) to (5 ′) is reacted with an unsaturated (anhydrous) carboxylic acid: A method for producing an α-olefin polymer.
(1 ′) The weight average molecular weight (Mw) is 1,000 to 500,000.
(2 ′) Molecular weight distribution (Mw / Mn) is 4.5 or less.
(3 ′) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
(4 ′) The α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, propylene-1-butene copolymer, propylene-diene copolymer or 1-butene-diene copolymer. .
(5 ′) The number of terminal unsaturated groups per molecule is 0.5 to 2.5.

  The functionalized α-olefin polymer of the present invention is a polyolefin material excellent in fluidity at a relatively low temperature, and is mixed with a crosslinking agent to form a curable composition, whereby a curing reaction at a relatively low temperature. Can be implemented.

[Functionalized α-olefin polymer]
The functionalized α-olefin polymer of the present invention has a (anhydrous) carboxylic acid residue at the terminal 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 endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
(4) The α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, propylene-1-butene copolymer, propylene-diene copolymer or 1-butene-diene copolymer.
(5) The number of (anhydrous) carboxylic acid residues per molecule is 0.5 to 2.5.
(6) The number of terminal (anhydrous) carboxylic acid residue-internal double bond structures per molecule is 0.5 to 2.5.

(A) (Anhydrous) Carboxylic Acid Residue As described above, the functionalized α-olefin polymer of the present invention has 0.5 to 2.5 terminal (anhydrous) carboxylic acid residues per molecule. When it is intended to be used as a compatibilizing agent, it is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, When used for an adhesive or a sealing material, the curing performance is important, and from the viewpoint of obtaining a crosslinked structure, it is preferably 1.2 to 2.5, and preferably 1.5 to 2.1. Further preferred. If the number of terminal (anhydrous) carboxylic acid residues per molecule is less than 0.5, no cross-linking curing reaction with the cross-linking agent occurs. The resulting cured product has a low molecular weight between crosslinks, and a cured product exhibiting rubber elasticity cannot be obtained.
The functionalized α-olefin polymer of the present invention is produced by an ene reaction between an α-olefin polymer having a carbon-carbon double bond at the end of the main chain and an unsaturated (anhydrous) carboxylic acid, as described later. can do. Since the functionalized α-olefin polymer of the present invention obtained by this reaction has (anhydrous) carboxylic acid residues at one or both ends of the main chain, the number of (anhydrous) carboxylic acid residues The control can be easily performed by controlling the number of terminal unsaturated groups of the raw α-olefin polymer.
The terminal (anhydrous) carboxylic acid residue is not particularly limited as long as it is a substituent formed by removing one hydrogen atom from carboxylic acid or carboxylic anhydride, but a (anhydrous) carboxylic acid residue having 1 to 20 carbon atoms. Are preferable, those having 1 to 10 carbon atoms are more preferable, those having 1 to 5 carbon atoms are more preferable, and specific examples include propionic acid residues, butyric acid residues, and (anhydrous) succinic acid residues.

The number of (anhydrous) carboxylic acid residues per molecule can be determined by the measurement method shown below.
A blend of an α-olefin polymer and an unsaturated (anhydrous) carboxylic acid before modification is pressed using a 0.1 mm spacer, infrared spectroscopy (IR) is performed, and a characteristic carbonyl (1700-1800 cm) is obtained. ^-1 ) and a calibration curve from the amount of unsaturated (anhydrous) carboxylic acid charged, then IR measurement of the press plate of the functionalized α-olefin polymer to be measured, The number of (anhydrous) carboxylic acid residues per molecule was determined.
Number of (anhydrous) carboxylic acid residues per molecule = [(anhydrous) carboxylic acid residue concentration] / 100 × Mn / monomer molecular weight (pieces)
Average molecular weight of monomer units (Mm) = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11
Number average molecular weight (Mn): Number average molecular weight determined from gel permeation chromatograph (GPC) (Anhydrous) Carboxylic acid residue concentration: IR measurement of press plate of functionalized α-olefin polymer to be measured The concentration of (anhydrous) carboxylic acid residue was calculated from the relationship between the calibration curve and the absorption amount of 1700 to 1800 cm ⁻¹ .
As a measuring instrument used for the IR measurement, for example, “FT / IR-5300” manufactured by JASCO Corporation can be used.

Further, in this specification, “having a (anhydrous) carboxylic acid residue at the terminal” means that the (anhydrous) carboxylic acid residue is a polymer main chain terminal (at least one terminal of the polymer main chain, preferably the polymer main chain). It is to show that it exists in both ends. Specifically, a peak of 1700 to 1750 cm ⁻¹ is observed by infrared absorption spectrum (IR), and it is derived from a terminal (anhydrous) carboxylic acid residue-internal double bond structure in ¹ H-NMR measurement. It shows having a peak of 85-5.50 ppm.
The functionalized α-olefin polymer of the present invention has an advantage that the curing efficiency in the curing reaction is improved by having a (anhydrous) carboxylic acid residue at the terminal. When (anhydrous) carboxylic acid residues are present in the polymer (side chain) other than the polymer ends, the number of (anhydrous) carboxylic acid residues per molecule exceeds 2.5, and as a result, The molecular weight between crosslinks (molecular weight between crosslink points) becomes small at the time of crosslink, the original performance of the original polymer is not maintained, and the cured product after crosslinkage is brittle. In addition, the presence of the (anhydrous) carboxylic acid residue at the terminal makes it possible to easily come into contact with the crosslinking agent during the crosslinking and curing reaction with the crosslinking agent, thereby improving the curing speed and curing efficiency. There is.

(B) melting endotherm ΔH-D
The functionalized α-olefin polymer used in the present invention has a melting endotherm ΔH-D measured by a differential scanning calorimeter (DSC) of 50 J / g or less, preferably 30 J / g or less, preferably 10 J / g. g or less is more preferable, and 1 J / g or less is particularly preferable. If the melting endotherm ΔH-D exceeds 50 J / g, the crystalline component increases, the fluidity at a relatively low temperature deteriorates, and problems arise in terms of energy saving during construction and the safety environment.
ΔH-D is obtained by DSC measurement. That is, 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 heated at 10 ° C./min. Let the melting endotherm be ΔH−D.
In order to control the melting endotherm to 50 J / g or less, it is necessary to control the mesopentad fraction [mmmm], which is an index of stereoregularity, to 80 mol% or less, depending on the structure of the main catalyst and the polymerization conditions. Can be controlled. For example, when controlling by the structure of a catalyst, it is necessary to design the space where a monomer coordinates to the central metal of a catalyst to an appropriate size. Depending on the size of the coordination space, the insertion of the monomer is difficult to occur, and the activity is reduced. If the structure is a racemic structure, a highly ordered polymer is obtained, and the melting endotherm exceeds 50 J / g. A meso-type structure is likely to give a polymer with low regularity and may have a melting endotherm of 50 J / g or less, but it is difficult to synthesize a polymer having a balance between the bond ratio and the melting endotherm. . For example, by using a double-crosslinking catalyst described later, it is possible to synthesize a polymer having a balance between a bonding ratio and a melting endotherm by controlling the coordination space of the monomer.

(C) Stereoregularity When the functionalized α-olefin polymer of the present invention has a (anhydrous) carboxylic acid residue at the propylene homopolymer main chain terminal or 1-butene homopolymer main chain terminal, the mesopentad moiety The rate [mmmm] is preferably less than 80 mol%, more preferably less than 60 mol%, still more preferably less than 40 mol%, and particularly preferably less than 20 mol%.
On the other hand, when the propylene-1-butene copolymer has a (anhydrous) carboxylic acid residue at the end of the main chain, the mesodyad fraction [m] is preferably 30 to 95 mol%, preferably 30 to 80 mol%. More preferably, it is more preferably 40 to 80 mol%.
The mesopentad fraction [mmmm] is controlled to be low, or the mesodiad fraction [m] is controlled to a moderate level to make it non-regular and completely amorphous so that it can be handled at room temperature. Can be cured. As a result, it can be used in the fields of sealing and reactive adhesion, which have been difficult to use in the past, especially in fields where adhesion to polyolefin-based substrates is required.
The control of the mesopentad fraction [mmmm] and the mesodyad fraction [m] is performed according to the structure of the main catalyst and the polymerization conditions. For example, when controlling by the catalyst structure, the space where the monomer coordinates to the central metal of the catalyst is controlled. It is necessary to design to a suitable size. Depending on the size of the coordination space, it is difficult to insert the monomer, and the activity is reduced. If the structure is a racemic structure, a highly regular polymer is obtained. If the structure is a meso structure, a polymer having a low regularity is obtained. It becomes easy to obtain.

The functionalized α-olefin polymer of the present invention preferably has a 2,1-bond fraction of less than 0.5 mol%, more preferably less than 0.4 mol%, and even more preferably 0.2 mol%. %.
The 2,1-bond fraction is controlled by controlling the 2,1-bond fraction in the α-olefin polymer used as a raw material by a method described later.

The functionalized α-olefin polymer of the present invention preferably has a total of 1,3-bond fraction and 1,4-bond fraction of less than 0.5 mol%, more preferably less than 0.4 mol%. More preferably, it is less than 0.1 mol%.
The above “total of 1,3-bond fraction and 1,4-bond fraction” means 1,3-3-when the functionalized α-olefin polymer of the present invention has a propylene homopolymer main chain. The bond fraction means 1,4-bond fraction when having a butene homopolymer main chain, and 1,3-bond content when having a propylene-1-butene copolymer main chain. It means the sum of the rate and 1,4-bond fraction.
The control of the 1,3-bond fraction and the 1,4-bond fraction is controlled by the method described later in the α-olefin polymer used as a raw material. It is done by doing.

In the present invention, the mesopentad fraction [mmmm] and the mesodiad fraction are reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al. Specifically, signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum, and mesopentad fraction [mmmm], racemic pentad fraction [rrrr], mesodyad fraction [m], racemic in the polymer chain. The dyad fraction [r], 1,3-bond fraction, 1,4-bond fraction, and 2,1-bond fraction were determined.
^{The 13} C-NMR spectrum was measured with the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Complete proton decoupling method Concentration: 230 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

(D) Weight average molecular weight / molecular weight distribution The functionalized α-olefin polymer of the present invention has a weight average molecular weight of 1,000 to 500,000 and 4,000 to 50,000 from the viewpoint of fluidity. It is preferably 5,000 to 40,000, more preferably 5,000 to 30,000. From the viewpoint of durability such as adhesive strength after curing and not easily peeled off, a higher molecular weight is preferable.

  The functionalized α-olefin polymer of the present invention preferably has a molecular weight distribution (Mw / Mn) of less than 4.5, from 1.4 to 3.0, from the viewpoint of reactivity and reaction curability. Is more preferable, and it is still more preferable that it is 1.6-2.5.

In addition, the said weight average molecular weight (Mw) and number average molecular weight (Mn) are things of polystyrene conversion measured with the following apparatus and conditions, The said molecular weight distribution (Mw / Mn) is these weight average molecular weights (Mw). ) And the number average molecular weight (Mn).
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(E) B viscosity From the viewpoints of reactivity, workability at room temperature, etc., the functionalized α-olefin polymer of the present invention preferably has a B viscosity (fluidity) at 30 ° C. of 5000 mPa · s or less, 2000 mPa · s. The following is more preferable.
Here, the said B viscosity shows what is measured according to ASTM-D 19860-91.

(F) Terminal (anhydrous) carboxylic acid residue-internal double bond structure As described later, the functionalized α-olefin polymer of the present invention has an α-olefin having a carbon-carbon double bond at the end of the main chain. Manufactured by an ene reaction between a polymer and an unsaturated (anhydrous) carboxylic acid. The functionalized α-olefin polymer of the present invention obtained by this reaction has a terminal (anhydrous) carboxylic acid residue-internal double bond structure. The number of internal double bonds is 0.5 to 2.5 per molecule, and when it is intended to be used as a compatibilizing agent, it is preferably 0.5 to 1.5. , 0.8 to 1.2, more preferably 1.2 to 2.5 when used for an adhesive or sealant. More preferably, it is one.

The number of internal double bonds per molecule can be determined by the measurement method shown below.
First, a hydrogen atom of an internal double bond in a terminal (anhydrous) carboxylic acid residue-internal double bond structure appearing at 4.85 to 5.50 ppm obtained from ¹ H-NMR measurement, 0.70 to 1.80 ppm The number of terminal (anhydrous) carboxylic acid residue-internal double bond structures can be calculated based on the hydrogen atom of the α-olefin main chain appearing in.
Terminal (anhydrous) carboxylic acid residue-internal double bond CH (i) in internal double bond structure: 4.85 to 5.50 ppm integrated value α-olefin main chain hydrogen atom (ii): 0.70 Integrated value of ˜1.80 ppm Average molecular weight of monomer units (Mm) = Propylene unit ratio × 42.08 + 1-Butene unit ratio × 56.11
Average number of hydrogen of monomer units (Hnum) = propylene unit ratio × 6 + 1-butene unit ratio × 8
Concentration of internal double bond = [(i) / ((ii) / (Hnum))
From the concentration (mol%) of the internal double bond calculated by the above method, the number average molecular weight (Mn) determined from the gel permeation chromatograph (GPC) and the average molecular weight (Mm) of the monomer unit, 1 The number of internal double bonds per molecule can be calculated.
Number of internal double bonds (pieces) = (Mn) / (Mm) × [concentration of internal double bonds]

[Method for producing functionalized α-olefin polymer]
The functionalized α-olefin polymer of the present invention is obtained by a production method in which an α-olefin polymer having a carbon-carbon double bond at the end of the main chain is reacted with an unsaturated (anhydrous) carboxylic acid. The α-olefin polymer used as a raw material is selected from a propylene homopolymer, a 1-butene polymer, and a diene copolymer. The 1-butene polymer is selected from 1-butene homopolymer and propylene-1-butene copolymer, and the diene copolymer is propylene-diene copolymer and 1-butene-diene copolymer. Selected from coalescence.

(Α-olefin polymer)
In the method for producing a functionalized α-olefin polymer of the present invention, the α-olefin polymer used as a raw material has the following characteristics (1 ′) to (5 ′), and the following characteristics (6 ′) to (8 It is preferable to have ').
(1 ′) The weight average molecular weight (Mw) is 1,000 to 500,000.
(2 ′) Molecular weight distribution (Mw / Mn) is 4.5 or less.
(3 ′) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
(4 ′) The α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, propylene-1-butene copolymer, propylene-diene copolymer or 1-butene-diene copolymer. .
(5 ′) The number of terminal unsaturated groups per molecule is 0.5 to 2.5.
(6 ') (6'-1) Mesopentad fraction [mmmm] is less than 80 mol%, or (6'-2) Mesodyad fraction [m] is 30 to 95 mol%.
(7 ′) The 2,1-bond fraction is less than 0.5 mol%.
(8 ′) The sum of 1,3-bond fraction and 1,4-bond fraction is less than 0.5 mol%.

(1 ′) Weight average molecular weight (Mw)
The α-olefin polymer used in the present invention preferably has a weight average molecular weight of 1,000 to 500,000, more preferably 2,000 to 50,000, from the viewpoint of fluidity. More preferably, it is 2,000-20,000.
The details of the weight average molecular weight (Mw) of the α-olefin polymer are the same as those in the functionalized α-olefin polymer.

(2 ′) Molecular weight distribution (Mw / Mn)
The α-olefin polymer used in the present invention preferably has a molecular weight distribution (Mw / Mn) of less than 4.5, from 1.4 to 2.2, from the viewpoint of reactivity and reaction curability. Is more preferable, and it is still more preferable that it is 1.6-2.1.
Details of the molecular weight distribution (Mw / Mn) of the α-olefin polymer are the same as those in the functionalized α-olefin polymer.

(3 ′) melting endotherm ΔH−D
The α-olefin polymer used in the present invention requires that the melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less, preferably 30 J / g or less, It is more preferably 10 J / g or less, and particularly preferably 1 J / g or less.
Details of the melting endotherm ΔH-D of the α-olefin polymer are the same as those of the functionalized α-olefin polymer.
(4 ′) α-olefin polymer The α-olefin polymer used in the present invention is a propylene homopolymer, 1-butene homopolymer, propylene-1-butene copolymer, propylene-diene copolymer or 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 preferably 20 mol% or more.
In the case of a propylene-diene copolymer, the structural unit derived from propylene is preferably 70 mol% or more, preferably 80 mol% or more, and 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, preferably 80 mol% or more, and preferably 90 mol% or more.
Among these, a propylene homopolymer and a 1-butene homopolymer are preferable from the viewpoint of compatibility when used as an adhesive composition and adhesive strength with a substrate.

(5 ′) Number of terminal unsaturated groups per molecule When the α-olefin polymer used in the present invention is a diene polymer, the number of terminal unsaturated groups per molecule is 0.5 to 0.5. 2.5 pieces. The α-olefin polymer may be any of propylene homopolymer, 1-butene polymer and diene copolymer, and the number of terminal unsaturated groups per molecule is 0.5 to 2. It is preferably 0, and when it is intended to be used as a compatibilizing agent, the number of silicon-containing groups per molecule is preferably 0.5 to 1.5, 0.8 to 1.2 is more preferable, and when used for an adhesive or a sealing material, it is preferably 1.2 or more, and more preferably 1.5 or more.
The number of terminal unsaturated groups per molecule is 2.0 at the maximum if only the main chain end, and when it is 2.0 or more, by copolymerizing dienes and the like, By introducing an unsaturated group, the number of terminal unsaturations per molecule can be controlled.

The number of terminal unsaturated groups per molecule is controlled by the structure of the main catalyst, the type of monomer and the polymerization conditions (polymerization temperature, hydrogen concentration, etc.).
The number of terminal unsaturated groups per molecule can be controlled by selecting the molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) in the presence of a catalyst.
For example, it can be obtained by performing a polymerization reaction in a molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) in the range of 0 to 5000. In order to increase the terminal unsaturated group selectivity and the catalytic activity, it is preferable to perform the polymerization reaction in the presence of a trace amount of hydrogen.
Usually, hydrogen functions as a chain transfer agent, and it is known that polymer chain ends have a saturated structure. It also has a function of reactivating the dormant to increase the catalytic activity. Although the influence of a trace amount of hydrogen on the catalyst performance is unknown, by using hydrogen within a specific range, the terminal unsaturated group selectivity is high and high activity can be achieved.
The molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) is preferably 200 to 4500, more preferably 300 to 4000, and most preferably 400 to 3000. When this molar ratio is 5,000 or less, production of an α-olefin polymer having an extremely low number of terminal unsaturated groups is suppressed, and an α-olefin polymer having the desired number of terminal unsaturated groups can be obtained. it can.

Examples of the terminal unsaturated group include a vinyl group, a vinylidene group, and a trans (vinylene) group. The terminal unsaturated group as defined in this specification means a vinyl group and a vinylidene group. Vinyl groups and vinylidene groups are radically polymerizable and have a wide range of applications for various reactions and can meet various requirements.
The terminal unsaturated group concentration and the number of terminal unsaturated groups in the α-olefin polymer used in the present invention mean the concentration and number of the total amount of vinyl groups and vinylidene groups. When only a vinyl group is present, it means the concentration and number of only the vinyl group, and when both vinyl group and vinylidene group are included, it means the concentration and number of both sums.

The above-mentioned terminal unsaturated group concentration and the number of terminal unsaturated groups per molecule can be determined by ¹ H-NMR measurement. Specifically, terminal vinylidene groups appearing in δ 4.8 to 4.6 (2H) obtained from ¹ H-NMR measurement, terminal vinyl groups appearing in δ 5.9 to 5.7 (1H), and δ 1.05 Based on the methyl group appearing at ˜0.60 (3H), the terminal unsaturated group concentration (C) (mol%) can be calculated.
CH _{2 of} vinylidene group (4.8 to 4.6 ppm) (i)
Vinyl group CH (5.9 to 5.7 ppm) (ii)
Side chain terminal CH ₃ (1.05 to 0.60 ppm) (iii)
Vinylidene group amount = [(i) / 2] / [(iii) / 3] × 100 mol%
Vinyl group amount = (ii) / [(iii) / 3] × 100 mol%
Terminal unsaturated group concentration = [vinylidene group amount] + [vinyl group amount]
From the terminal unsaturated group concentration (C, mol%) calculated by the above method, the number average molecular weight (Mn) and the monomer molecular weight (M) determined from the gel permeation chromatograph (GPC), per molecule The number of terminal unsaturated groups can be calculated.
Number of terminal unsaturated groups per molecule (number) = (Mn / M) × (C / 100)

(6′-1) Mesopentad fraction [mmmm]
When the α-olefin polymer used in the present invention is a propylene homopolymer or a 1-butene homopolymer, the mesopentad fraction [mmmm] is preferably less than 80 mol%, and less than 60 mol%. Is more preferable, it is still more preferable that it is less than 40 mol%, and it is especially preferable that it is less than 20 mol%.

(6'-2) Mesodyad fraction [m]
On the other hand, when the α-olefin polymer used in the present invention is a propylene-1-butene copolymer, the mesodyad fraction [m] is preferably 30 to 95 mol%, and preferably 30 to 80 mol%. It is more preferable, and it is still more preferable that it is 30-60 mol%.
The mesopentad fraction [mmmm] and the mesodyad fraction [m] can be controlled by the structure of the main catalyst and the polymerization conditions. For example, when controlling by the structure of a catalyst, it is necessary to design the space where a monomer coordinates to the central metal of a catalyst to an appropriate size. Depending on the size of the coordination space, it is difficult to insert the monomer, and the activity is reduced. If the structure is a racemic structure, a highly regular polymer is obtained. If the structure is a meso structure, a polymer having a low regularity is obtained. It becomes easy to obtain.

When the α-olefin polymer used in the present invention is a propylene homopolymer or a 1-butene homopolymer, the racemic pentad fraction [rrrr] is preferably less than 20 mol%, more preferably 1 More than 2 mol% and less than 20 mol%, more preferably more than 2 mol% and less than 15 mol%, particularly preferably more than 3 mol% and less than 10 mol%.
On the other hand, when the α-olefin polymer used in the present invention is a propylene-1-butene copolymer, the racemic dyad fraction [r] is preferably 1 to 50 mol%, and preferably 2 to 45 mol%. It is more preferable that it is 2-40 mol%.

(7 ′) 2,1-bond fraction The α-olefin polymer used in the present invention preferably has a 2,1-bond fraction of less than 0.5 mol%, more preferably 0.4 mol%. And more preferably less than 0.2 mol%. When the 2,1-bond fraction of the α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction and radical decomposition reaction described later is improved.
The 2,1-bond fraction is controlled depending on the structure of the main catalyst and the polymerization conditions. Specifically, the structure of the main catalyst has a large effect, and the 2,1-bond can be controlled by narrowing the insertion field of the monomer around the central metal of the main catalyst. The number of 2,1-bonds can be increased. For example, a catalyst called half-metallocene type has a wide insertion field around the central metal, so that structures such as 2,1-bonds and long-chain branches are likely to be generated. Although it can be expected to be suppressed, in the case of the racemic type, the stereoregularity becomes high, and it is difficult to obtain an amorphous polymer as shown in the present invention. For example, even a racemic type as described later introduces a substituent at the 3-position with a double-bridged metallocene catalyst and controls the insertion site of the central metal to obtain an amorphous polymer with very few 2,1-bonds. be able to.

(8 ′) 1,3-bond fraction and 1,4-bond fraction The α-olefin polymer used in the present invention preferably has a total of 1,3-bond fraction and 1,4-bond fraction. Is less than 0.5 mol%, more preferably less than 0.4 mol%, still more preferably less than 0.1 mol%. When the sum of the 1,3-bond fraction and 1,4-bond fraction of the α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction and radical decomposition reaction described later is improved.
The above “total of 1,3-bond fraction and 1,4-bond fraction” means 1,3-bond fraction when the α-olefin polymer used in the present invention is a propylene homopolymer. Means a 1,4-bond fraction in the case of a butene homopolymer, and a 1,3-bond fraction and 1,4-bond in the case of a propylene-1-butene copolymer. This means the sum of the combined fractions.
The control of the 1,3-bond fraction and the 1,4-bond fraction is performed according to the structure of the main catalyst and the polymerization conditions in the same manner as the control of the 2,1-bond fraction.

In the present invention, mesopentad fraction [mmmm], racemic pentad fraction [rrrr], mesodyad fraction [m], racemic diad fraction [r], 1,3-bond fraction, 1,4-bond fraction Rate and 2,1-bond fraction are reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al. Specifically, signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum, and mesopentad fraction [mmmm], racemic pentad fraction [rrrr], mesodyad fraction in poly (1-butene) chain were measured. [M], racemic dyad fraction [r], 1,3-bond fraction, 1,4-bond fraction, and 2,1-bond fraction were determined.
^{The 13} C-NMR spectrum was measured with the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / 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 Integration: 10,000 times

<In case of propylene homopolymer>
The 1,3-bond fraction, 1,4-bond fraction, and 2,1-bond fraction can be calculated from the above-mentioned ¹³ C-NMR spectrum measurement results according to the following formula.
1,3-bond fraction = (D / 2) / (A + B + C + D) × 100 (mol%)
2,1-bond fraction = {(A + B) / 2} / (A + B + C + D) × 100 (mol%)
A: integrated value of 15 to 15.5 ppm B: integrated value of 17 to 18 ppm C: integrated value of 19.5 to 22.5 ppm D: integrated value of 27.6 to 27.8 ppm

<Butene homopolymer>
The 1,4-bond fraction and the 2,1-bond fraction can be calculated by the following formula from the measurement result of the ¹³ C-NMR spectrum.
1,4-bond fraction = E / (A + B + C + D + E) × 100 (mol%)
2,1-bond fraction = {(A + B + D) / 3} / (A + B + C + D) × 100 (mol%)
A: Integration value of 29.0 to 28.2 ppm B: Integration value of 35.4 to 34.6 ppm C: Integration value of 38.3 to 36.5 ppm D: Integration value of 43.6 to 42.8 ppm E: 31.1 ppm integrated value

(Method for producing α-olefin polymer)
The α-olefin polymer used in the present invention uses, for example, a metallocene catalyst comprising a combination of the following components (Pa), (Pb) and (Pc), and hydrogen as a molecular weight regulator. Can be manufactured. Specifically, it can be produced by the method disclosed in WO2008 / 047860.
(Pa) Transition metal compound containing a metal element belonging to Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group (Pb) a transition metal Compound capable of reacting with compound to form ionic complex (Pc) Organoaluminum compound

<(P-a) component>
The transition metal compound containing a metal element belonging to Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group as the component (Pa) has the following general formula: The bibridged complex represented by (I) is mentioned.

In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table. Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. Metal etc. are mentioned. Among these, metal elements of Group 4 of the periodic table are preferable from the viewpoint of olefin polymerization activity, etc., and titanium, zirconium and hafnium are particularly preferable. From the viewpoint of yield of α-olefin polymer and catalytic activity, zirconium Is most preferred.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E ¹ and E ² is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
The substituent of the substituted cyclopentadienyl group, substituted indenyl group, or substituted heterocyclopentadienyl group has 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). A substituent such as a hydrocarbon group, a silicon-containing group or a heteroatom-containing group is shown.
X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of 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, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl 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 methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, cyclohexyl groups, octyl groups and other alkyl groups; vinyl groups, propenyl groups, cyclohexenyl groups, etc. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group. 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 amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, Tiger Se Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.

Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group and octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, Tiger Se Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like. Examples of the amine include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine. Alkylamines such as methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, phenylpropylamine; An arylamine such as naphthylamine can be mentioned.

  Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; anisole Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, and dioxane. Can be mentioned.

  Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specific examples include monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Monoalkenes such as phosphine, propenylphosphine, cyclohexenylphosphine, etc. Dialkenylphosphine in which two alkenyls are substituted for phosphine and phosphine hydrogen atoms; Trialkenylphosphine in which three alkenyls are substituted for phosphine hydrogens; Arylalkylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine having three hydrogen atoms substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, anthracenyl phosphine, phenanthenyl phosphine; phosphine water Atom alkyl aryl two substituted di (alkylaryl) phosphine; arylphosphine such as a hydrogen atom of phosphine alkylaryl three substituted with tri (alkylaryl) phosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein 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, May be different. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms or a silicon-containing group. Examples of such a cross-linking group include those represented by the following general formula (a).

(D is a group 14 element of the periodic table, and examples thereof include carbon, silicon, germanium and tin. R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other, and may be bonded to each other to form a ring structure.
Specific examples of the structure represented by the general formula (a) include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisylylene group, diphenyldisilylene group, and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

  Specific examples of the transition metal compound represented by the general formula (I) include specific examples described in WO2008 / 066168. Moreover, the analogous compound of the metal element of another group may be sufficient. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

Among the transition metal compounds represented by the general formula (I), compounds represented by the following general formula (II) are preferable.

In the above general formula (II), M represents a metal element belonging to Groups 3 to 10 of the periodic table, and A ^1a and A ^2a each represent a bridging 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 are preferred. A ^1a and A ^2a may be the same as 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 silicon-containing group, or a heteroatom-containing group. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the silicon-containing group are the same as those described in the 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, 3,5-bis ( (Trifluoro) phenyl group, fluorobutyl group and the like. Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups. Specifically, nitrogen-containing groups such as a dimethylamino group, a diethylamino group, and a diphenylamino group; a phenylsulfide group, a methylsulfide group, and the like Sulfur-containing groups of: phosphorus-containing groups such as dimethylphosphino groups and diphenylphosphino groups; oxygen-containing groups such as methoxy groups, ethoxy groups, and phenoxy groups. Among these, as R ⁴ and R ⁵ , a hydrogen atom, a halogen atom, a group containing a hetero atom such as oxygen or silicon, or a hydrocarbon group having 1 to 20 carbon atoms is preferable because of high polymerization activity. From the viewpoint of controlling the coordination space of the monomer and synthesizing a polymer having a balance between the bonding ratio and the melting endotherm, R ⁴ and R ⁵ are each a hydrogen atom, an ethyl group, an n-propyl group, an i-propyl group. Group, n-butyl group, trimethylsilylmethyl group and phenyl group are preferred. As R < ⁶ > -R < ¹³ >, a hydrogen atom or a C1-C20 hydrocarbon group is preferable. X and Y are the same as in general formula (I). q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

  Among the transition metal compounds represented by the above general formula (I), examples of the transition metal compounds of Group 4 of the periodic table include specific examples described in WO2008 / 066168. Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

On the other hand, among the transition metal compounds represented by the above general formula (II), when R ⁵ is a hydrogen atom and R ⁴ is not a hydrogen atom, transition metal compounds belonging to Group 4 of the periodic table are disclosed in WO2008 / 066168. Specific examples of the description are given. Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

<(Pb) component>
As the compound that can form an ionic complex by reacting with the (Pb) transition metal compound, a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained, and a catalyst having high activity. And borate compounds are preferred. Specific examples of the borate compound include those described in WO2008 / 066168. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.

<(Pc) component>
The catalyst used in the method for producing an α-olefin polymer used in the present invention may be a combination of the (Pa) component and the (Pb) component, and the (Pa) component and (Pb). In addition to the component, an organoaluminum compound may be used as the component (Pc).
As the organoaluminum compound of the component (Pc), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethyl Examples thereof include aluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.
Of these, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum is preferred, and triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum are more preferred. preferable.

The amount of component (Pa) used 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. L, more preferably 0.2 × 10 ^{−6 to} 1.2 × 10 ⁻⁵ mol / L, and particularly preferably 0.3 × 10 ^{−6 to} 1.0 × 10 ⁻⁵ mol / L. When the amount of the component (Pa) used is 0.1 × 10 ⁻⁶ mol / L or more, the catalytic activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the polymerization heat Can be easily removed.
The use ratio (Pa) / (Pb) of the component (Pa) and the component (Pb) is preferably 10/1 to 1/100, more preferably 2/1 to 1 in terms of molar ratio. 1/10. When (P−a) / (P−b) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed. Further, there is no fear that a large amount of boron is present in the target α-olefin polymer.
The use ratio (Pa) / (Pc) of the component (Pa) and the component (Pc) is preferably 1/1 to 1/10000, and more preferably 1/5 to 1/5 in terms of molar ratio. 1/2000, more preferably 1/10 to 1/1000. By using the component (Pc), the polymerization activity per transition metal can be improved. When (P−a) / (P−c) is in the range of 1/1 to 1/10000, the balance between the effect of adding the component (P−c) and the economy is good, and the target α -There is no fear that a large amount of aluminum is present in the olefin polymer.

  In the production method of the α-olefin polymer used in the present invention, the above-mentioned (Pa) component and (Pb) component, or (Pa) component, (Pb) component and (P-) It is also possible to perform preliminary contact using the component c). The preliminary contact can be performed by bringing the (P-a) component into contact with, for example, the (P-b) component, but the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing catalyst costs, such as improvement in catalyst activity and reduction in the proportion of the (Pb) component used as a promoter.

  The α-olefin polymer used in the present invention is a terminal unsaturated α-olefin polymer obtained from the α-olefin polymer obtained by the above production method as a raw material and further through a thermal decomposition reaction or a radical decomposition reaction. May be. The number of terminal unsaturated groups per molecule can be increased by thermal decomposition reaction or radical decomposition reaction.

The thermal decomposition reaction is performed by heat-treating the raw material α-olefin polymer obtained by the above production method.
The heating temperature can be adjusted by setting a target molecular weight and taking into consideration the results of experiments performed in advance, and is preferably 300 to 400 ° C, more preferably 310 to 390 ° C. If the heating temperature is less than 300 ° C, the thermal decomposition reaction may not proceed. On the other hand, when the heating temperature exceeds 400 ° C., the obtained terminal unsaturated α-olefin polymer may be deteriorated.
The thermal decomposition time (heat treatment time) is preferably 30 minutes to 10 hours, more preferably 60 to 240 minutes. When the thermal decomposition time is less than 30 minutes, the amount of the terminal unsaturated α-olefin polymer obtained may be small. On the other hand, when the thermal decomposition time exceeds 10 hours, the terminal unsaturated α-olefin polymer obtained may be deteriorated.

  For example, a stainless steel reaction vessel equipped with a stirrer is used as the pyrolysis reaction, and an inert gas such as nitrogen or argon is filled in the vessel, and the raw material α-olefin polymer is placed. The molten polymer phase is heated and melted, and the molten polymer phase is bubbled with an inert gas, and is heated at a predetermined temperature for a predetermined time while extracting a volatile product.

The radical decomposition reaction can be carried out at a temperature of 160 to 300 ° C. by adding 0.05 to 2.0% by mass of an organic peroxide with respect to the raw material α-olefin polymer.
The decomposition temperature is preferably 170 to 290 ° C, more preferably 180 to 280 ° C. When the decomposition temperature is less than 160 ° C., the decomposition reaction may not proceed. On the other hand, when the decomposition temperature is higher than 300 ° C., the decomposition proceeds vigorously, and the decomposition may be completed before the organic peroxide is sufficiently diffused uniformly into the molten polymer by stirring, which may reduce the yield.

  The organic peroxide to be added is preferably an organic peroxide having a 1 minute half-life temperature of 140 to 270 ° C., and specific examples of the organic peroxide include the following compounds: diisobutyryl peroxide, Cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecano Eight, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexyl Peroxypivalate, t-butyl peroxypivalate, di (3,5 5-trimethylhexanoyl) peroxide, dilauryl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethyl) Hexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) ) Peroxide, dibenzoyl 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 Sasan, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy- 3,5,5-trimethylhexanate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 3,5-di -Methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl4 , 4-Di- (t-butylperoxy) valate, di (2-t-butylperoxyisopropyl) Benzoate, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-Menthans hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Peroxide, cumene hydroperoxide, t-butyl hydroperoxide.

  The amount of organic peroxide added is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.8% by mass, and still more preferably based on the raw material α-olefin polymer. It is 0.2-1.7 mass%. When the addition amount 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 addition amount is 2.0% by mass or less, it is difficult to generate odor due to decomposition of the organic peroxide.

  The decomposition time of the decomposition reaction is, for example, 30 seconds to 10 hours, and preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, not only does the decomposition reaction not proceed sufficiently, but a large amount of undecomposed organic peroxide may remain. On the other hand, when the decomposition time is longer than 10 hours, there is a concern that the cross-linking reaction, which is a side reaction, may proceed, or the α-olefin polymer obtained may turn yellow.

  The radical decomposition reaction can be performed by using, for example, any one of decomposition by a batch method and decomposition by a continuous melt method.

When the radical decomposition reaction is carried out by the batch method, an inert gas such as nitrogen or argon is filled in a reaction vessel made of stainless steel or the like equipped with a stirrer, and the raw material α-olefin polymer is put and melted by heating and melting. A radical thermal decomposition reaction can be carried out by dropping an organic oxide and a raw material α-olefin polymer and heating the raw material α-olefin polymer for a predetermined time at a predetermined temperature.
The organic peroxide may be dropped within the range of the decomposition time, and the dropping may be either continuous dropping or divided dropping. Further, the reaction time from the dropping end time is preferably within the above reaction time range.

The organic peroxide may be dissolved in a solvent and dropped as a solution.
The solvent is preferably a hydrocarbon solvent, and specific examples include aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, hexadecane, and nanodecane; methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, And alicyclic hydrocarbons such as cyclododecane; and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. Among these solvents, a solvent having a boiling point of 100 ° C. or higher is preferable.

  In the decomposition, the raw material α-olefin polymer may be dissolved in a solvent. When the raw material α-olefin polymer is dissolved in a solvent for decomposition, the decomposition temperature is usually 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 as viewed from the average residence time is, for example, 20 seconds to 10 minutes. The melt continuous method can improve the mixing state and shorten the reaction time compared to the batch method.
The apparatus can use a single-screw or twin-screw melt extruder, preferably an extruder having an inlet in the middle of the barrel and capable of degassing under reduced pressure, and L / D = 10 or more. Machine.

  The radical decomposition reaction by the melt continuous method is a method in which the raw material α-olefin polymer is impregnated into the raw material α-olefin polymer, or the raw material α-olefin polymer and the organic peroxide are separately supplied and mixed using the above apparatus. Applicable methods are applicable.

Specifically, impregnation of the organic peroxide with the raw material α-olefin polymer is performed by adding a predetermined amount of organic peroxide to the raw material α-olefin polymer in the presence of an inert gas such as nitrogen, and By stirring in the range of ° C., the raw material pellets can be uniformly absorbed and impregnated. The raw material α-olefin polymer impregnated with the obtained organic peroxide (impregnated pellet) is decomposed by melt extrusion, or the impregnated pellet is added to the raw material α-olefin polymer as a master batch and decomposed. An unsaturated α-olefin polymer is obtained.
When the organic peroxide is solid or the organic peroxide has low solubility in the raw material α-olefin polymer, the raw material is prepared as a solution in which the organic peroxide is previously dissolved in a hydrocarbon solvent. The α-olefin polymer may be absorbed and impregnated.

  The raw material α-olefin polymer and the organic peroxide are separately mixed to supply the raw material α-olefin polymer and the organic peroxide at a constant flow rate to the extruder hopper, or the organic peroxide is supplied. This can be done by supplying a constant flow rate in the middle of the barrel.

[Method for producing functionalized α-olefin polymer]
The functionalized α-olefin polymer of the present invention can be produced by reacting the above α-olefin polymer with an unsaturated (anhydrous) carboxylic acid.

(Unsaturated (anhydrous) carboxylic acid)
The unsaturated (anhydrous) carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, specifically maleic acid, maleic anhydride, acrylic acid, acrylic ester, methacrylic acid. Acid ester etc. are mentioned.

In the reaction between the α-olefin polymer and the unsaturated (anhydrous) carboxylic acid, 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 reaction time can be shortened, which is preferable. On the other hand, a higher reaction temperature is preferable because the viscosity of the component polymer can be lowered, but if the reaction temperature is too high, the main chain of the component polymer may be cleaved. The reaction temperature is preferably 70 to 210 ° C, particularly preferably 80 to 200 ° C.
The reaction time in the above reaction is preferably about 0.5 to 12 hours, more preferably 2 to 8 hours.
Further, in the reaction between the α-olefin polymer and the unsaturated (anhydrous) carboxylic acid, it may be diluted with a hydrocarbon solvent or the like. By diluting, the viscosity at normal temperature can be further reduced, and the reaction can be made more efficient and the reaction time can be shortened. In the case of diluting with a solvent, the amount of the solvent with respect to the total amount of the α-olefin polymer and the unsaturated (anhydrous) carboxylic acid is preferably 50% by mass or less, more preferably 30% by mass or less from the viewpoint of measures against VOC and the like. More preferably, it is 10 mass% or less.

[Curable composition]
The curable composition of the present invention contains (A) the above functionalized α-olefin polymer and (B) a crosslinking agent, and (C) a polymerization accelerator, (D) a tackifier, and (E ) It may also contain a diluent.

(B) Crosslinking agent Any crosslinking agent may be used as long as it can react with the (anhydrous) carboxylic acid residue of the functionalized α-olefin polymer and can be crosslinked and cured. Examples thereof include polyamines and polyols.
Polyamines include methylenediamine, ethylenediamine, diaminopropane, diaminobutane, trimethylenediamine, trimethylhexamethylenediamine, hexamethylenediamine, octamethylenediamine, polyoxypropylenediamine and polyoxypropylenetriamine and other aliphatic polyamines, phenylenediamine, Aromatic polyamines such as 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether and 4,4′-diaminodiphenylsulfone, cyclopentane Diamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, bis-aminopropylpiperazine, thiourea, methyl ester Novis propylamine, and alicyclic diamines, such as norbornane diamine and isophorone diamine. Further, hydrazine such as hydrazine, carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and phthalic acid dihydrazide, melamine, spermine, spermidine, putrescine and the like can be mentioned.
Specific examples of the polyol include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentane. Diol, 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, hydrogenated bisphenol A and ethylene oxide of bisphenol A, or propylene oxide Adduct, trimethylol ethane, trimethylol propane, glycerine, erythritol, pentaerythritol, glucose, polytetrahydrofuran and the like.
Content of (B) crosslinking agent in the curable composition of this invention is 1-50 mass% normally with respect to 100 mass% of curable compositions of this invention, Preferably it is 10-30 mass%. .

(C) Polymerization accelerator As the polymerization accelerator, heteropolyacid, heteropolyacid salt, benzenesulfonic acid, toluenesulfonic acid, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate and the like are used.
The content of the (C) polymerization accelerator in the curable composition of the present invention is usually 0.1 to 5% by mass, preferably 0.5 to 100% by mass with respect to 100% by mass of the curable composition of the present invention. 3% by mass.

(D) Tackifiers Tackifiers (tackifier resins) include rosin and its derivatives, terpene resins and hydrogenated resins, styrene resins, coumarone-indene resins, dicyclopentadiene (DCPD) Resin and its hydrogenated resin, aliphatic (C5) petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and its hydrogenated resin, and copolymer of C5 and C9 From many commonly used tackifiers such as petroleum resins and hydrogenated resins thereof, those having good compatibility with the functionalized α-olefin polymer are selected. One of these tackifiers may be used alone, or two or more thereof may be used as a mixture.
Preferred tackifiers include terpene resins and their hydrogenated resins, styrene resins, and dicyclopentadiene (DCPD) resins from the viewpoint of the balance between removability and adhesion to curved and uneven surfaces. And its hydrogenated resin, aliphatic (C5) petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and its hydrogenated resin, and C5 -C9 copolymer petroleum resin It is preferable to use one kind of resin or a mixture of two or more kinds selected from the group of hydrogenated resins.
Content of (D) tackifier in the curable composition of this invention is 0-20 mass% normally with respect to 100 mass% of curable compositions of this invention, Preferably it is 0-10 mass%. It is.

(E) Diluent Examples of the diluent include oils such as naphthenic oils, paraffinic oils, and aroma oils, oils obtained by mixing them, and liquid rubbers such as liquid polybutene and liquid isopolybutylene. You may use these individually by 1 type or in mixture of 2 or more types.
Content of (E) diluent in the curable composition of this invention is 1-30 mass% normally with respect to 100 mass% of curable compositions of this invention, Preferably it is 1-20 mass%. .

(Other ingredients)
The curable composition of the present invention may contain additives such as fillers, pigments and antioxidants as long as the effects of the present invention are not impaired.

The filler includes an inorganic filler and an organic filler.
Examples of the inorganic filler include talc, white carbon, silica, mica, bentonite, aluminum compound, magnesium compound, barium compound, diatomaceous earth, glass beads or glass fibers, metal powder, or metal fibers.
Examples of the organic filler include starch (for example, powdered starch), fibrous leather (for example, natural organic fibers composed of cellulose such as cotton and hemp), and fibers composed of synthetic polymers such as nylon, polyester and polyolefin.

Examples of the pigment include inorganic pigments and organic pigments (for example, azo pigments and polycyclic pigments).
Inorganic pigments include oxides (titanium dioxide, zinc white (zinc oxide), iron oxide, chromium oxide, iron black, cobalt blue, etc., hydroxides: alumina white, iron oxide yellow, viridian, etc.), sulfides ( Zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, etc.), chromate (yellow lead, molybdate orange, zinc chromate, strontium chromate, etc.), silicate (white carbon, clay, talc, ultramarine blue, etc.), sulfate (Precipitated barium sulfate, barite powder, etc., as carbonates: calcium carbonate, lead white, etc.), ferrocyanide (bitumen), phosphate (manganese violet), carbon (carbon black), etc. are also used be able to.
Examples of azo pigments that are organic pigments include soluble azo (Kermin 6B, Lakelet C, etc.), insoluble azo (Disazo Yellow, Lakelet 4R, etc.), condensed azo (chromophthalo Yellow 3G, chromophthalscarlet RN, etc.), azo complex salts (nickel) Azo yellow, etc.) and pendidalone azo (permanent orange HL, etc.). Polycyclic pigments that are organic pigments include isoindolinone, isoindoline, quinophthalone, pyrazolone, flavatron, anthraquinone, diketo-pyrrolo-pyrrole, pyrrole, pyrazolone, pyranthrone, perinone, perylene, quinacridone, indigoid, oxazine, imidazolone Xanthene, carbonium, violanthrone, phthalocyanine, nitroso and the like.

When the filler and / or pigment content is (a) and the content of the functionalized α-olefin polymer of the present invention is (b), for example, (a) / (B) = 0.005 to 20, preferably 0.01 to 10.
When (a) / (b) is less than 0.005, improvement of the wettability and adhesiveness of the filler or pigment surface is insufficient, and in the curable composition, the dispersibility of the filler or pigment and the interfacial adhesiveness are insufficient. There is a fear. On the other hand, when (a) / (b) exceeds 20, component (b) not involved in the surface treatment exists, which is not preferable because the production cost increases.

  The curable composition of the present invention can be suitably used as an adhesive, a resin compatibilizer, a dispersion, or a coating agent.

The curable composition of the present invention can be used as a hot melt adhesive substrate. As other components of the hot melt adhesive, additives such as oils, tackifiers, antioxidants and the like are used within a normal range.
The curable composition of the present invention can be dissolved in a solvent and used as a solvent-type adhesive, and can be applied and sprayed to form a film on the surface of an adhesive substrate to adhere to an adherend. The curable composition of the present invention can also be used as an adhesive by dispersing it in a polar solvent such as water or making it into an emulsion. In addition, the curable composition of the present invention can be formed into a sheet or film, sandwiched between adhesive substrates, heated to a temperature higher than the temperature at which the adhesive flows, and bonded by cooling and solidification.

  The curable composition of the present invention can be used as a resin compatibilizer by adding, for example, 0.005 to 15% by mass to the resin composition containing polyolefin as an essential component.

The curable composition of the present invention can be made into a dispersion in which a functionalized α-olefin polymer is finely dispersed by dissolving in a solvent at room temperature or by heating. The concentration of the functionalized α-olefin polymer is in the range of 5-30% by weight.
Examples of the solvent include aliphatic hydrocarbon compounds such as hexane, heptane and decane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; alicyclic hydrocarbon compounds such as cyclohexane and methylcyclohexane; halogens such as chlorobenzene Hydrocarbons; ether compounds such as tetrahydrofuran and tetrahydropyran.
An emulsion can be obtained by using a polar solvent as the 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 for producing a dispersion, a solution in which a curable composition is dissolved in a solvent is added to the polar solvent while stirring to produce a solid fine particle component, and then the solvent is distilled off to produce a dispersion of the polar solvent. The example etc. to do can be illustrated.
Specifically, a method in which a 20 to 30% by mass solution of tetrahydrofuran is added to water at 20 to 50 ° C. little by little, then tetrahydrofuran is removed under reduced pressure, and the amount of water is adjusted to a desired concentration. Etc. can be illustrated. Other methods include known methods such as a method of directly dispersing in a polar solvent with high-speed stirring or a high shear field. If necessary, an anionic, cationic, nonionic surfactant or water-soluble polymer compound may be used as an additive.

  The dispersion can be coated or sprayed on a substrate to remove the solvent. A film or sheet can be placed on a substrate and coated by heating and cooling. In addition to these, a melted functionalized α-olefin polymer can be uniformly coated on a substrate and coated by a cooling and solidifying step.

  The functionalized α-olefin polymer of the present invention can be used as an adhesive, a resin compatibilizer, a dispersion, and a coating material in the same manner as described above, and also as a reactive hot melt adhesive, a sealing material, and a potting material. Can be used.

  The reactive hot melt adhesive is mainly composed of a functionalized α-olefin polymer containing alkoxysilicon and the α-olefin polymer of the present invention, and if necessary, an oil, a tackifier, an inorganic filler, and a silanol condensation catalyst. Including.

  Examples of the oil include oils such as naphthenic oils, paraffinic oils and aroma oils, oils obtained by mixing these oils, and liquid rubbers such as liquid polybutene and liquid isopolybutylene. You may use these individually by 1 type or in mixture of 2 or more types.

Examples of tackifiers (tackifier resins) include rosin and derivatives thereof, terpene resins and hydrogenated resins thereof, styrene resins, coumarone-indene resins, dicyclopentadiene (DCPD) resins and hydrogenated resins thereof. , Aliphatic (C5 series) petroleum resins and hydrogenated resins thereof, aromatic (C9 series) petroleum resins and hydrogenated resins thereof, and C5-C9 copolymerized petroleum resins and hydrogenated resins thereof From among many commonly used tackifiers, those having good compatibility with the functionalized α-olefin polymer are selected. One of these tackifier resins may be used alone, or two or more thereof may be used as a mixture.
Preferred tackifying resins include terpene resins and their hydrogenated resins, styrene resins, and dicyclopentadiene (DCPD) resins from the viewpoint of balance between removability and adhesion to curved surfaces and uneven surfaces. And its hydrogenated resin, aliphatic (C5) petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and its hydrogenated resin, and C5 -C9 copolymer petroleum resin It is preferable to use one kind of resin or a mixture of two or more kinds selected from the group of hydrogenated resins.

  Inorganic fillers include silica, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, Calcium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, serisalite, glass fiber, glass beads, silica balun , Aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, zinc borate, and various magnetic powders.

  An inorganic filler may be used in place of the inorganic filler, and surface treatment may be performed with various coupling agents such as silane and titanate. As this treatment method, a method of directly treating an inorganic filler with various coupling agents such as a dry method, a slurry method or a spray method, an integral blend method such as a direct method or a masterbatch method, or a dry concentrate method, etc. The method is mentioned.

The silanol condensation catalyst is preferably used in admixture. As the addition method, it is preferable to prepare a catalyst masterbatch having a high concentration of the silanol condensation catalyst in advance, blend the catalyst masterbatch with another reactive hot melt component, and knead or melt.
Examples of the silanol condensation catalyst include organic tin metal compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctate; organic bases, organic acids such as ethylamine acid, fatty acids, and the like, with dibutyltin dilaurate and dibutyltin being particularly preferable. Diacetate, dibutyltin dioctate. These addition amounts are 0.005-2.0 mass% with respect to alpha-olefin polymer modified material, Preferably it is 0.01-0.5 mass%.

As a method for curing the reactive hot melt adhesive, curing can be carried out by bringing it into contact with moisture or moisture in the presence or absence of a silanol condensation catalyst and curing it at room temperature or at room temperature.
In order to bring moisture or moisture into contact, for example, a reactive hot melt adhesive may be left in the air, or immersion or steam may be introduced into a water bath. The temperature may be room temperature, but a high temperature is preferable because crosslinking is performed in a short time.

The functionalized α-olefin polymer can be used for a sealing material and a potting material, and can be prepared in the same manner as the reactive hot melt adhesive when it requires a crosslinking performance.
When crosslinking performance is not required, a functionalized α-olefin polymer or a melt mainly composed of the α-olefin polymer of the present invention is used for sealing or potting, and is fixed by cooling and solidification.

[Cured product]
The present invention also provides a cured product obtained by curing the curable composition.
The curable composition of the present invention can carry out a curing reaction at a relatively low temperature. Specifically, a cured product can be obtained by curing reaction of the curable composition of the present invention at a relatively low temperature of 100 ° C. or lower. The curing reaction can be cured by mixing with a crosslinking agent to obtain the above-mentioned curable composition and curing under heat treatment or room temperature.

[Denatured body]
The present invention further provides a modified product obtained by modifying a terminal (anhydrous) carboxylic acid group of the functionalized α-olefin polymer.
Specific examples of the modified product include acid halides formed by halogenation, esters formed by reaction with alcohols, amides formed by reaction with amines, and the like.

  The curable composition of the present invention comprises a resin compatibilizer, a polyolefin emulsion, a reactive adhesive, a reactive hot melt adhesive, other adhesives, an adhesive, a sealing material, a sealing material, a potting material, and a reactivity. It can be used for applications such as plasticizers and modifiers.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these.

[ ¹³ C-NMR measurement]
The ¹³ C-NMR spectrum was measured with the following apparatus and conditions, and the mesopentad fraction [mmmm], racemic pentad fraction [rrrr], mesodyad fraction [m], racemic diad fraction [r], 1 , 3-bond fraction, 1,4-bond fraction and 2,1-bond fraction were determined.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / 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 Integration: 10,000 times

[DSC measurement]
Using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The amount of heat was determined as ΔH-D, glass transition temperature Tg and melting point Tm-D. For the melting point Tm-D, the peak top of the peak observed on the highest temperature side of the melting endothermic curve was defined as the melting point Tm-D.

[GPC measurement]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained.
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

[Terminal unsaturated group concentration]
Terminal vinylidene groups appearing in δ 4.8 to 4.6 (2H), terminal vinyl groups appearing in δ 5.9 to 5.7 (1H) and δ 1.05 to 0.60 (1H-NMR measurement obtained from ¹ H-NMR measurement) Based on the methyl group appearing in 3H), the terminal unsaturated group concentration (C) (mol%) was calculated.
CH _{2 of} vinylidene group (4.8 to 4.6 ppm) (i)
Vinyl group CH (5.9 to 5.7 ppm) (ii)
Side chain terminal CH ₃ (1.05 to 0.60 ppm) (iii)
Vinylidene group amount = [(i) / 2] / [(iii) / 3] × 100 mol%
Vinyl group amount = (ii) / [(iii) / 3] × 100 mol%
Terminal unsaturated group concentration (C) = [vinylidene group amount] + [vinyl group amount]

[Number of terminal unsaturated groups per molecule]
From the terminal unsaturated group concentration (C, mol%) calculated by the above method, the number average molecular weight (Mn) and the monomer molecular weight (M) determined from the gel permeation chromatograph (GPC), per molecule The number of terminal unsaturated groups was calculated.
Number of terminal unsaturated groups per molecule (number) = (Mn / M) × (C / 100)

[Number of (anhydrous) carboxylic acid residues per molecule]
<Denatured amount determination method>
A blend of an α-olefin polymer and an unsaturated (anhydrous) carboxylic acid before modification is pressed using a 0.1 mm spacer, infrared spectroscopy (IR) is performed, and a characteristic carbonyl (1700-1800 cm) is obtained. ^-1 ) and a calibration curve from the amount of unsaturated (anhydrous) carboxylic acid charged, then IR measurement of the press plate of the functionalized α-olefin polymer to be measured, The number of (anhydrous) carboxylic acid residues per molecule was determined.
Number of (anhydrous) carboxylic acid residues per molecule = [(anhydrous) carboxylic acid residue concentration] / 100 × Mn / monomer molecular weight (pieces)
Average molecular weight of monomer units (Mm) = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11
Number average molecular weight (Mn): Number average molecular weight determined from gel permeation chromatograph (GPC) (Anhydrous) Carboxylic acid residue concentration: IR measurement of press plate of functionalized α-olefin polymer to be measured The concentration of (anhydrous) carboxylic acid residue was calculated from the relationship between the calibration curve and the absorption amount of 1700 to 1800 cm ⁻¹ .
As a measuring instrument, an IR measuring instrument: “FT / IR-5300” manufactured by JASCO Corporation was used.

[Number of internal double bonds per molecule]
Terminal (anhydrous) carboxylic acid residue appearing at 4.85 to 5.50 ppm obtained from ¹ H-NMR measurement-hydrogen atom of internal double bond in internal double bond structure, appearing at 0.70 to 1.80 ppm Based on the hydrogen atoms of the α-olefin main chain, the number of terminal (anhydrous) carboxylic acid residue-internal double bonds was calculated as follows.
Terminal (anhydrous) carboxylic acid residue-CH (i) of internal double bond structure: 4.85 to 5.50 ppm integrated value α-olefin main chain hydrogen atom (ii): 0.70 to 1.80 ppm Integral value Average molecular weight of monomer units (Mm) = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11
Average number of hydrogen 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, the number average molecular weight (Mn) determined from the gel permeation chromatograph (GPC), and the monomer unit From the average molecular weight (Mm), the number of terminal (anhydrous) carboxylic acid-internal double bond structures per molecule was calculated according to the following formula.
Number of terminal (anhydrous) carboxylic acid-internal double bond structures per molecule = (Mn) / (Mm) x [terminal (anhydrous) carboxylic acid residue-internal double bond structure concentration]

[Liquidity]
The fluidity of the functionalized α-olefin polymer was visually confirmed and evaluated according to the following criteria.
A 5 g sample was collected in a 30 mL sample bottle, the lid was closed, and the sample was placed vertically in a constant temperature bath at 80 ° C. When visually confirmed after 10 minutes, the sample moved to the bottom (flowed), and when the surface was horizontal, it was evaluated as fluid.

Production Example 1
[Production of (1,1′-ethylene) (2,2′-tetramethyldisilylene) bisindenylzirconium dichloride (complex A)]
Magnesium (12 grams, 500 mmol) and tetrahydrofuran (30 ml) were charged into a 500 ml two-necked flask, and magnesium was activated by dropwise addition of 1,2-dibromoethane (0.2 ml). To this was added dropwise 2-bromoindene (20 grams, 103 mmol) dissolved in tetrahydrofuran (150 milliliters), and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldisilane (9.4 ml, 5.1 mmol) was added dropwise at 0 ° C. After stirring the reaction mixture at room temperature for 1 hour, the solvent was distilled off, the residue was extracted with hexane (150 ml × 2), and 1,2-di (1H-inden-2-yl) -1,1,2 was extracted. , 2-tetramethyldisilane was obtained as a white solid (15.4 grams, 44.4 mmol, 86% yield).
This was dissolved in diethyl ether (100 ml), n-butyllithium (2.6 mol / l, 38 ml, 98 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 1 hour to precipitate a white powder. The supernatant was removed and the solid was washed with hexane (80 ml) to give the lithium salt as a white powdery solid (14.6 grams, 33.8 mmol, 76%).
This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 ° C. The reaction mixture was stirred at room temperature for 1 hour and then evaporated to dryness, and the residue was extracted with hexane (150 milliliters) to give the bibridged ligand as a colorless oily liquid (14.2 grams, 37.9 millimoles). ).
This was dissolved in diethyl ether (120 ml), n-butyllithium (2.6 mol / liter, 32 ml, 84 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 1 hour to precipitate a white powder. The supernatant was removed, and the solid was washed with hexane (70 ml) to give a lithium salt of the bi-bridged ligand as a white powder (14.0 grams, 31 mmol, 81% yield).
To a suspension of the obtained lithium salt of the bi-bridged ligand (3.00 g, 6.54 mmol) in toluene (30 mL) at −78 ° C., zirconium tetrachloride (1.52 g, 6.54 mmol). ) In toluene (30 ml) was added dropwise with a cannula. After the reaction mixture was stirred at room temperature for 2 hours, the supernatant was separated, and the residue was further extracted with toluene.
Under reduced pressure, the solvent of the supernatant and the extract was distilled off to dryness to give (1,1′-ethylene) (2,2′-tetramethyldisilene) bis represented by the following formula (1) as a yellow solid. Indenyl zirconium dichloride (complex A) was obtained (2.5 grams, 4.7 mmol, 72% yield).

The measurement result of ¹ H-NMR is 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
[Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (complex B)]
In a Schlenk bottle, 3.0 g (6.97 mmol) of a lithium salt of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of tetrahydrofuran (THF) and brought to -78 ° C. Cooled down. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.
The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Obtained (yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 ml of ether. It cooled at -78 degreeC and the hexane solution (1.54 mol / L, 7.6 ml (11.7 mmol)) of n-butyltylium (n-BuLi) was dripped. After raising to room temperature and stirring for 12 hours, ether was distilled off. The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of the lithium salt as an ether adduct (yield 73%).
The result of the measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) is as follows.
δ: 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (Q, 4H, methylene), 6.2-7.7 (m, 8H, Ar-H)

Under a nitrogen stream, the lithium salt obtained above was dissolved in 50 ml of toluene. The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 ml) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. The obtained residue was recrystallized from dichloromethane to obtain 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H, Ar-H)

Production Example 3 (Production of 1-butene homopolymer)
In a heat-dried 2 liter autoclave, heptane (600 mL), triisobutylaluminum (2M, 0.3 mL, 0.6 mmol), complex A heptane slurry (10 μmol / mL, 0.6 mL, 0.4 μmol), manufactured by Albemarle A toluene solution of methylaluminoxane (2 mL, 3M, 6.0 mmol) was added, and hydrogen was further introduced at 0.05 MPa. The pressure was raised to 0.20 MPa by introducing 1-butene at the same time as bringing the temperature to 70 ° C. while stirring. Thereafter, 1-butene was continuously supplied so that the total pressure was maintained at 0.25 MPa, and polymerization was performed for 2 hours. After completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and after depressurization, the reaction product was taken out and dried under reduced pressure to obtain 210 g of 1-butene homopolymer (polymer A).

Production Example 4 (Production of propylene homopolymer)
In a heat-dried 2 liter autoclave, heptane (600 mL), triisobutylaluminum (2M, 0.3 mL, 0.6 mmol), heptane slurry of complex A (10 μmol / mL, 0.1 mL, 1.0 μmol), manufactured by Albemarle A toluene solution of methylaluminoxane (0.33 mL, 3M, 1.0 mmol) was added, and 0.04 MPa of hydrogen was further introduced. The pressure was increased to 0.70 MPa by introducing propylene at the same time as bringing the temperature to 70 ° C. while stirring. Thereafter, propylene was continuously supplied so that the total pressure was maintained at 0.70 MPa, and polymerization was performed for 1 hour. After completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and after depressurization, the reaction product was taken out and dried under reduced pressure to obtain 170 g of a propylene homopolymer (polymer B).

Production Example 5 (Production of 1-butene-propylene copolymer)
To a heat-dried 2 liter autoclave, heptane (180 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (180 mL), complex B heptane slurry (10 μmol / mL, 0.02 mL, 0.2 μmol), heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate (10 μmol / mL, 0.06 mL, 0.6 μmol) was added, and 0.05 MPa of hydrogen was further introduced. The total pressure was set to 0.6 MPa by introducing propylene at the same time as the temperature was 60 ° C. while stirring. Then, after superposing | polymerizing for 20 minutes, superposition | polymerization was stopped with 5 mL of ethanol, and 75g of 1-butene-propylene copolymers were obtained by drying a reaction material under reduced pressure (polymer C).

Production Example 6 (Production of 1-butene homopolymer)
To a heat-dried 1 liter autoclave, heptane (200 mL), triisobutylaluminum (2 M, 0.2 mL, 0.4 mmol), butene-1 (200 mL), heptane slurry of complex B (10 μmol / mL, 0.04 mL, 0 0.4 μmol), heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate (10 μmol / mL, 0.12 mL, 1.2 μmol) was added, and 0.1 MPa of hydrogen was further introduced. While stirring, the temperature was raised to 52 ° C. and polymerization was carried out for 30 minutes. After 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 polymers A to D obtained in Production Examples 3 to 6, melting endotherm ΔH-D, glass transition temperature Tg, mesopentad fraction [mmmm], mesodyad fraction [m], racemic pentad fraction [rrrr] , Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, 2,1-bond fraction, 1,3-bond fraction and 1,4-bond fraction Was measured. The results are shown in Table 1.

Production Example 7
[Production of 1-butene homopolymer]
70 g of the polymer A produced in Production Example 3 was charged into a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer. The mixture was stirred for 30 minutes under a nitrogen stream.
Stirring was started and the resin temperature was raised to 160 ° C. using a mantle heater. The mantle heater was controlled so that the resin temperature was constant at 280 ° C. To this, 0.4 ml of perhexa 25B was added dropwise over 4 minutes. After completion of the dropwise addition, the reaction was performed for 15 minutes, and then cooled to 110 ° C.
After completion of the reaction, drying under reduced pressure at 100 ° C. was carried out for 10 hours to radically decompose to obtain a 1-butene homopolymer (polymer A ′).

Production Examples 8 to 10
Propylene homopolymer, 1-butene-propylene copolymer or 1-butene homopolymer in Production Example 7 except that polymer B, polymer C, and polymer D were used in place of polymer A. (Polymers B ′ to D ′) were obtained.

  About the propylene homopolymer, 1-butene-propylene copolymer or 1-butene homopolymer obtained in Production Examples 7 to 10, the melting endotherm ΔH-D, glass transition temperature Tg, mesopentad fraction [mmmm], Mesodyad fraction [m], racemic pentad fraction [rrrr], weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, 2,1-bond fraction, 1,3-bond fraction and 1,4-bond fraction were measured. The results are shown in Table 2.

Example 1 (Production of functionalized polypropylene)
A 100 mL separable flask with a stirring blade was charged with 10 g of polymer A ′, 2.0 g of maleic anhydride, 0.012 g of oxalic acid, and 0.04 g of maleic acid, and then heated to 200 ° C. with a mantle heater in a nitrogen atmosphere. Stir for 5 hours. After the temperature was lowered to room temperature, the reaction product was washed four times with 20 mL of acetone and dried by heating to obtain a polymer having a terminal added with maleic acid (polymer A ″).

Examples 2-4
A polymer in which maleic acid was added to the terminal was obtained in the same manner as in Example 1 except that polymers B ′ to D ′ were used instead of polymer A ′ in Example 1 (polymers B ″ to D ″). .

  For the functionalized α-olefin polymers obtained in Examples 1 to 4, the weight average molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction [mmmm], the mesodyad fraction [m], the melting point Tm− D, melting endotherm ΔH-D, (anhydrous) carboxylic acid residue per molecule-number of internal double bond structures, 2,1-bond fraction, 1,3-bond fraction and 1,4-bond The total fraction was measured and the fluidity was evaluated. The results are shown in Table 3.

Comparative Example 1
[Synthesis of propylene polymer with conventional catalyst]
(1) Preparation of solid catalyst component After replacing a 0.5-liter stirrer three-necked flask with nitrogen gas, add 20 ml of dehydrated heptane, 4 g of diethoxymagnesium, and 1.6 g of dibutyl phthalate. The system was kept at 90 ° C., and 4 ml of titanium tetrachloride was added dropwise with stirring. Further, 111 ml of titanium tetrachloride was added dropwise, and the temperature was raised to 110 ° C. To the obtained solid phase part, 115 ml of titanium tetrachloride was added and reacted at 110 ° C. for another 2 hours. After completion of the reaction, the product was washed several times with 100 ml of purified heptane to obtain a solid catalyst component.

(2) Preparation of pre-polymerization catalyst component After replacing a 3-liter flask equipped with a stirrer with an internal volume of 0.5 liter with nitrogen gas, 300 ml of dehydrated heptane and 10 g of the solid catalyst component prepared in (1) above were added. added. After the system was brought to 15 ° C., 4.2 mmol of triethylaluminum and 1.1 mmol of cyclohexylmethyldimethoxysilane (CHMDS) were added, and propylene was introduced while stirring. After 2 hours, stirring was stopped, and as a result, a prepolymerized catalyst component in which 2 g of propylene was polymerized per 1 g of the solid catalyst component was obtained.

(3) Synthesis of propylene polymer A stainless steel autoclave with a stirrer with an internal volume of 10 liters was sufficiently dried and purged with nitrogen. The temperature was raised to 65 ° C. Next, 0.12 g of the prepolymerized catalyst component prepared in the above (2) was added and polymerized at 70 ° C. for 3 hours. As a result, 960 g of polymer powder of a propylene polymer was obtained. By repeating this polymerization reaction, a propylene polymer as a raw material for the maleic anhydride-modified propylene polymer was synthesized.

[Synthesis of maleic anhydride-modified propylene polymer]
To 100 parts by weight of the propylene polymer synthesized in (3), maleic anhydride: 0.3 part by weight and perhexine 25B / 40: 0.1 part by weight were added and thoroughly blended. This powder blend was melt kneaded at 180 ° C. using a 20 mm twin screw extruder. To 1 kg of the obtained pellet 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. This heating and stirring was performed in a pressure vessel. After the operation was completed, the pellets were collected and immersed in 1.5 kg of acetone for 15 hours. Thereafter, the pellets were collected, air-dried, and then vacuum-dried at 90 ° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer (polymer E).
Since polymer E is not a maleic anhydride addition reaction in an ene reaction, the number of (anhydrous) carboxylic acid residues per molecule was calculated by the following method.
<Denatured amount determination method>
The blend of polyolefin and organic acid before modification is pressed using a 0.1 mm spacer and IR is measured. From the characteristic absorption amount of carbonyl (1600 to 1900 cm ⁻¹ ) and the amount of organic acid charged, A calibration curve was prepared, and IR measurement of the acid-modified press plate was performed to determine the number of (anhydrous) carboxylic acid residues per molecule.
IR measuring instrument: “FT / IR-5300” manufactured by JASCO Corporation

  Moreover, about the maleic anhydride modified propylene polymer obtained in Comparative Example 1, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm], melting point Tm-D, melting endotherm ΔH− D The number of (anhydrous) carboxylic acid residue-internal double bond structures per molecule was measured. The results are shown in Table 4 together with the modification rate measured above.

Example 6 (Production of curable composition and cured product)
In a 30 mL sample bottle, polymer A ″ (3 g) obtained in Example 1 and Huntsman's triamine (Jefamine T403) (0.2 g) were mixed at room temperature to obtain a curable composition. .
Subsequently, when this curable composition was heated at 100 degreeC, the raise of the viscosity was observed within 30 minutes. When the obtained reaction product (1 g) was placed in a 20 mL sample bottle together with toluene (5 mL) and immersed in a water bath at 40 ° C. for 5 hours, it was insoluble in the solvent and exhibited rubber elasticity.

Comparative Example 2
In Example 6, a composition was produced in the same manner except that the polymer E (3 g) obtained in Comparative Example 1 was used in place of the polymer A, and then this was heated to 100 ° C., and 30 minutes passed. Even though the polymer E did not melt, the polymerization (crosslinking) reaction did not proceed.

  The functionalized α-olefin polymer of the present invention and the curable composition containing the same are used as a resin compatibilizing agent, polyolefin emulsion, reactive adhesive, reactive hot melt adhesive, other adhesives, pressure-sensitive adhesives, sealing agents. It can be widely used as a material and a raw material for stopping materials, sealing materials, potting materials, reactive plasticizers and the like.

Claims (5)

A functionalized α-olefin polymer having a (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 endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
(4) The α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, propylene-1-butene copolymer, propylene-diene copolymer or 1-butene-diene copolymer.
(5) The number of (anhydrous) carboxylic acid residues per molecule is 0.5 to 2.5.
(6) The number of terminal (anhydrous) carboxylic acid residue-internal double bond structures per molecule is 0.5 to 2.5.   The functionalized α-olefin polymer according to claim 1, wherein the melting endotherm ΔH-D measured by the differential scanning calorimeter (DSC) is 1 J / g or less.   A curable composition comprising the functionalized α-olefin polymer according to claim 1 or 2 and a crosslinking agent.   Hardened | cured material formed by hardening | curing the curable composition of Claim 3. The functionalized α-olefin polymer according to claim 1, wherein an α-olefin polymer satisfying the following (1 ′) to (5 ′) is reacted with an unsaturated (anhydrous) carboxylic acid. Manufacturing method.
(1 ′) The weight average molecular weight (Mw) is 1,000 to 500,000.
(2 ′) Molecular weight distribution (Mw / Mn) is 4.5 or less.
(3 ′) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
(4 ′) The α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, propylene-1-butene copolymer, propylene-diene copolymer or 1-butene-diene copolymer. .
(5 ′) The number of terminal unsaturated groups per molecule is 0.5 to 2.5.