WO2013118841A1 - End unsaturated α-olefin polymer and method for producing same - Google Patents

Abstract

The present invention provides: an end unsaturated α-olefin polymer which is a polymer of an α-olefin having at least 5 carbon atoms with a high degree of unsaturation; and a method for producing an end unsaturated α-olefin polymer which generates less by-products. The present invention is obtained by: an end unsaturated α-olefin polymer which is a homopolymer and/or a copolymer of an α-olefin having at least 5 carbon atoms, and which is characterized in that the end unsaturated group concentration is 2.0 to 30 mol%; a method for producing the end unsaturated α-olefin polymer by adding 0.05 to 5.0 mass% of an organic peroxide to a polyolefin which is the raw material and heat treating the mixture at a temperature of 200 to 380°C; and a method for producing the end unsaturated α-olefin polymer by heat treating the polyolefin which is the raw material at a temperature of 200 to 500°C with a residence time of an hour or less.

Description

Terminally unsaturated α-olefin polymer and process for producing the same

The present invention relates to a terminal unsaturated α-olefin polymer and a method for producing the same. More specifically, the present invention relates to a terminal unsaturated α-olefin polymer having a high concentration of terminal unsaturated groups, and an efficient method for producing a terminal unsaturated α-olefin polymer capable of reducing by-products.

High molecular weight polyolefin is widely used as an industrial component because it has high chemical stability, excellent mechanical properties, and is inexpensive. On the other hand, low molecular weight polyolefins are limited to use as waxes, but higher functionality is expected.

Although the functionalization of polyolefin has been performed for many years, there is no efficient production technology in the low molecular weight to medium molecular weight region, and additional technology such as polarity for polyolefin which is a hydrocarbon is also limited. In particular, attempts have been made in recent years to produce low to medium molecular weight polyolefins with metallocene catalysts, but there was a limit to the control and introduction of unsaturated functional groups required to give higher functions. .

Patent Documents 1 and 2 disclose thermal decomposition of high molecular weight polyolefins, particularly polypropylene, for the introduction of unsaturated groups (Patent Documents 1 and 2). Patent Document 1 discloses polypropylene obtained by pyrolyzing isotactic polypropylene at 370 ° C. (for example, the number of vinylidene groups per molecule is 1.8), and Patent Document 2 is pyrolysis obtained by pyrolyzing polybutene at 370 ° C. Polybutenes (for example, 1.53 to 1.75 vinylidene groups per molecule) are disclosed.

Patent Document 3 describes a method for producing a terminal unsaturated polyolefin using a homopolymer or copolymer of propylene or butene-1 as a raw material.
On the other hand, α-olefin polymers having a larger carbon number are used as the wax component and the lubricating oil component, but a large amount of unsaturated groups are efficiently produced particularly for α-olefin polymers having 5 or more carbon atoms. There is no specific disclosure about the method of introduction.

JP 2003-40921 A JP 2003-137927 A International Publication No. 2011/148586

In Patent Document 1 and Patent Document 2, the vinylidene number is increased by high-resolution decomposition of the high molecular weight product, but there are problems such as a decrease in yield of the target structure due to the generation of a large amount of by-products. I found out.
An object of the present invention is to provide a terminal unsaturated α-olefin polymer which is a polymer of an α-olefin having a high degree of unsaturation and having 5 or more carbon atoms.
Another object of the present invention is to provide a method for producing a terminal unsaturated α-olefin polymer with a small amount of by-products.

According to the present invention, the following inventions are provided.
[1] A terminal unsaturated α-olefin characterized in that it is a homopolymer and / or copolymer of an α-olefin having 5 or more carbon atoms and has a terminal unsaturated group concentration of 2.0 to 30 mol%. Olefin polymer.
[2] The terminal unsaturated α-olefin polymer according to [1], wherein the number of terminal unsaturated groups per molecule is more than 1.0 and 2.5 or less.
[3] The terminal unsaturated α-olefin polymer according to [1] or [2], containing 50 to 100% by mass of an α-olefin unit having 5 to 12 carbon atoms.
[4] The terminal unsaturated α-olefin polymer according to [1] or [2], containing 50 to 100% by mass of an α-olefin unit having 14 to 30 carbon atoms.
[5] The terminal unsaturated α according to any one of [1] to [4], wherein the kinematic viscosity at 100 ° C. is 3 to 2000 mm / s ² and the mesotriad fraction [mm] is 20 to 80 mol%. An olefin polymer.
[6] In melting behavior measurement using a differential scanning calorimeter, the melting point is 20 ° C. or more and 100 ° C. or less, only one peak temperature is observed, and the half width of the peak is 15 ° C. or less. [1] The terminally unsaturated α-olefin polymer according to any one of [5].
[7] Terminal unsaturation according to any one of [1] to [6], wherein the weight average molecular weight Mw is 500 to 100,000 and the molecular weight distribution Mw / Mn is 1.10 to 2.60. α-olefin polymer.
[8] The organic peroxide is added in an amount of 0.05 to 5.0% by mass with respect to the raw material polyolefin, and heat-treated at a temperature of 200 to 380 ° C. In any one of [1] to [7] A process for producing the terminal unsaturated α-olefin polymer as described.
[9] The production of a terminal unsaturated α-olefin polymer according to any one of [1] to [7], wherein the raw material polyolefin is heat-treated at a temperature of 200 to 500 ° C. for a residence time of 1 hour or less. Method.
[10] The method for producing a terminal unsaturated α-olefin polymer according to [8] or [9], wherein the heat treatment time is 30 seconds to 10 hours.

According to the present invention, a terminal unsaturated α-olefin polymer which is a polymer of α-olefin having a high degree of unsaturation and having 5 or more carbon atoms can be provided.
In addition, according to the present invention, it is possible to provide a method for producing a terminal unsaturated α-olefin polymer with a small amount of by-products.

[Terminal unsaturated α-olefin polymer]
The terminal unsaturated α-olefin polymer of the present invention is a homopolymer and / or copolymer of an α-olefin having 5 or more carbon atoms, and has a terminal unsaturated group concentration of 2.0 to 30 mol%. It is characterized by that.
The terminal unsaturated α-olefin polymer of the present invention has a high concentration of terminal unsaturated groups and is excellent in reactivity.

Examples of the α-olefin used in the production of the terminal unsaturated α-olefin polymer of the present invention include pentene-1, heptene-1, hexene-1, heptene-1, octene-1, decene-1, and 4-methylpentene. -1,3-methylbutene-1 and the like.
The terminal unsaturated α-olefin polymer of the present invention preferably contains 50 to 100% by mass of α-olefin units having 5 to 12 carbon atoms, and 50 to 100 α-olefin units having 14 to 30 carbon atoms. Even if it contains the mass%, it is preferable.

The terminal unsaturated α-olefin polymer of the present invention preferably has a mesotriad fraction [mm] of 20 to 80 mol%, more preferably 25 to 70 mol%, and more preferably 30 to 60 mol%. More preferably.
When the mesotriad fraction [mm] is less than 20 mol%, the handleability due to stickiness or the like is deteriorated, whereas when it exceeds 80 mol%, the crystallinity is increased, so that the low-temperature meltability is reduced, and the coating properties and the like are reduced. Workability becomes worse.

The terminal unsaturated α-olefin polymer of the present invention has a terminal unsaturated group concentration of 2.0 to 30 mol%, preferably 2.1 to 28 mol%, preferably 2.2 to 25 mol%. More preferably, it is 2.3 to 23 mol%, further preferably 2.5 to 20 mol%.
When the terminal unsaturated group concentration per molecule is less than 2.0 mol%, the reactivity is inferior and the adhesive performance is lowered. On the other hand, when the terminal unsaturated group concentration exceeds 30 mol%, the number of reaction points increases, and gel is generated to deteriorate the adhesion performance, and the melt fluidity deteriorates, and the workability such as coating property deteriorates.
In the terminal unsaturated α-olefin polymer of the present invention, the number of terminal unsaturated groups per molecule is preferably more than 1.0 and 2.5 or less, and 1.3 to 2.5 More preferably, it is more preferably 1.35 to 2.5, and particularly preferably 1.4 to 2.0.
When the number of terminal unsaturated groups per molecule exceeds 1.0, it is expected that heat resistance is imparted by a reaction starting from the terminal unsaturated group. On the other hand, when the number of terminal unsaturated groups per molecule is 2.5 or less, the branched structure of polyolefin decreases. Since the branched structure is different in linear structure and melt fluidity, the behavior such as coating may change.

Examples of the terminal unsaturated group include a vinyl group, a vinylidene group, and a trans (vinylene) group. The terminal unsaturated group 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 terminal unsaturated α-olefin polymer of 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 at δ4.8 to 4.6 (2H), terminal vinyl groups appearing at δ5.9 to 5.7 (1H) and δ1.05 obtained from ¹ H-NMR measurement. 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)
CH _{3 at the} end of the side chain (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)

The terminal unsaturated α-olefin polymer of the present invention preferably has a weight average molecular weight Mw of 500 to 100,000, more preferably 700 to 90,000, and more preferably 800 to 80,000. Further preferred.
When the weight average molecular weight is 500 or more, the flexibility of the polyolefin is improved when heat resistance is imparted to the polyolefin by a reaction based on the terminal vinylidene group. On the other hand, when the weight average molecular weight is 100,000 or less, the melt viscosity becomes small and workability such as coating property is improved.
The weight average molecular weight can be measured by gel permeation chromatography (GPC) method.

The terminal unsaturated α-olefin polymer of the present invention preferably has a molecular weight distribution Mw / Mn of 1.10 to 2.60, more preferably 1.10 to 2.55, and more preferably 1.10 to More preferably, it is 2.50.
When the molecular weight distribution is 1.10 or more, the production is facilitated. On the other hand, when the molecular weight distribution exceeds 2.60, the molecular weight distribution is wide and there is a concern about variation in the functional group concentration, and the performance such as curability deteriorates.

The molecular weight distribution Mw / Mn can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by the GPC method.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by the Universal Calibration method using the constants K and a of the Mark-Houwink-Sakurada formula in order to convert the polystyrene equivalent molecular weight into the molecular weight of the corresponding polymer. Can do.
Specifically, it can be determined by the method described in ““ Size Exclusion Chromatography ”, Sadao Mori, p. 67-69, 1992, Kyoritsu Publishing. K and α are described in “Polymer Handbook”, John Wiley & Sons, Inc. Moreover, it can also determine by a conventional method from the relationship of the intrinsic viscosity with respect to the newly calculated absolute molecular weight.

The measuring apparatus and measurement conditions of GPC are as follows, for example.
Detector: RI detector for liquid chromatography Waters 150C
Column: TOSO GMHHR-H (S) HT
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 mL / min Sample concentration: 0.3% by mass

The terminal unsaturated α-olefin polymer of the present invention has a melting point of 20 ° C. or more and 100 ° C. or less, only one peak temperature is observed in the melting behavior measurement using a differential scanning calorimeter, and the peak The full width at half maximum is preferably within 15 ° C.
The melting behavior was measured by using a differential scanning calorimeter (DSC). The sample was heated from room temperature to 190 ° C. at 100 ° C./min, held at 190 ° C. for 5 minutes, then −30 ° C. to 10 ° C. The temperature is lowered at / min, held at −30 ° C. for 5 minutes, and then heated to 190 ° C. at 10 ° C./min to obtain a melting curve showing an endothermic peak. Although it does not specifically limit as a differential scanning calorimeter, For example, DSC7 (brand name) by Perkin Elmer can be used. In the present invention, the temperature at the peak top in the obtained melting curve is defined as the melting point (Tm).
The melting point is preferably 30 to 90 ° C., more preferably 35 to 85 ° C., and still more preferably 40 to 80 ° C. from the viewpoint of low temperature melting property and storage property. The half-value width of the endothermic peak obtained when measuring the melting point is the peak width at 50% of the endothermic peak when the melting point (Tm) is measured by DSC, from the viewpoint of low-temperature melting component and sharp melt property. The temperature is preferably 1 to 9 ° C, more preferably 1 to 7 ° C, still more preferably 2 to 7 ° C. A small half-value width indicates that the endothermic peak is sharp, that is, the melting behavior is rapid. In this case, the occurrence of problems such as high-temperature storage stability and stickiness due to low-temperature melting components is suppressed.

The terminal unsaturated α-olefin polymer of the present invention preferably has a kinematic viscosity at 100 ° C. of 3 to 2000 mm / s ² .
The kinematic viscosity at 100 ° C. is a value measured in accordance with JIS K2283, preferably 10 to 1500 mm / s ² , more preferably 30 to 1000 mm / s ² , and still more preferably 50 to 500 mm / s ^2. s ² .
When the 100 ° C. kinematic viscosity is less than 3 mm / s ² , the performance in curing and the like is insufficient, and when the 100 ° C. kinematic viscosity exceeds 2000 mm / s ² , the viscosity is high and the fluidity at room temperature decreases. However, it is difficult to use in applications such as adhesives and sealing due to a decrease in performance such as coating properties.

[Method for producing terminally unsaturated α-olefin polymer]
The terminal unsaturated α-olefin polymer of the present invention uses a homopolymer and / or copolymer of an α-olefin having 5 or more carbon atoms as a raw material polyolefin, and an organic peroxide of 0.05 to 5.0% by mass is added, and heat treatment is performed at a temperature of 200 to 380 ° C.

The above method for producing a terminal unsaturated α-olefin polymer can reduce the amount of gaseous by-products, so that the purity can be improved. Further, the terminal unsaturated α-olefin polymer can be produced at low cost.
When the raw material polyolefin has a mesotriad fraction [mm] of 20 to 80 mol%, the raw material polyolefin can be easily melted at low temperatures or has good solubility in a solvent. It has a wide temperature range and can be decomposed at a relatively low temperature. Thereby, it has the merit which can control a side reaction. In addition, in the decomposition using the organic peroxide in combination, the decomposition can be efficiently performed with a milder and shorter reaction, and the above-mentioned merit of the raw material polyolefin can be increased. In particular, when the raw material polyolefin has a terminal unsaturated group in advance, the above merits can be maximized. In addition, since the mesotriad fraction of the decomposed product is derived from the raw material polyolefin, when [mm] is 20 to 80 mol%, it can be easily melted at a low temperature or has good solubility in a solvent. Spread.

The mesotriad fraction [mm] of the raw material polyolefin is the same as that of the terminal unsaturated α-olefin polymer.

The weight average molecular weight Mw of the raw material polyolefin is preferably 4,000 to 1,000,000, more preferably 5,000 to 900,000, and further preferably 6,000 to 800,000. preferable.
When the weight average molecular weight of the raw material polyolefin is 4,000 or more, the decomposition rate can be set high. On the other hand, when the weight average molecular weight of the raw material polyolefin is 1,000,000 or less, the viscosity at the time of decomposition becomes low, so that there are no restrictions on stirring power and stirring uniformity in the process.

The raw material polyolefin preferably has 0.40 to 1.00 terminal unsaturated groups per molecule, more preferably 0.45 to 1.00, still more preferably 0.50 to 1.00. And most preferably 0.55 to 1.00.
When the number of terminal unsaturated groups per molecule is 0.40 or more, the number of terminal unsaturated groups is sufficiently increased by decomposition, and the high molecular weight is decomposed to increase the number of terminal unsaturated groups. There is no need. On the other hand, when the number of terminal unsaturated groups per molecule is 1.00 or less, production by a technique using a polymerization catalyst described later becomes easy.

Raw material polyolefin can be manufactured by using a metallocene catalyst which consists of a combination of the following component (A), (B) and (C), for example, and using hydrogen as a molecular weight regulator. Specifically, it can be produced by the method disclosed in WO2008 / 047860.
(A) 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. (B) Reacts with a transition metal compound. (C) Organoaluminum compound that can form an ionic complex

As 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 (A), the following general formula (I ) Is represented.

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. Metal etc. are mentioned. Among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like, and zirconium is most preferable from the viewpoint of yield of terminal vinylidene group and catalytic activity.
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 5 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 Xs, the plurality of Xs 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, 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 alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group; vinyl group, propenyl group, cyclohexenyl group, 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 phenoxy group, methylphenoxy group, and dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, dicyclohexylamide group, methylethylamide group, and other alkylamide groups, divinylamide group, and 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, Cement racemase 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, 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, and specifically include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and 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; , Aromatic ether compounds such as phenetole, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane Is mentioned.

Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specifically, monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, 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 is an integer of 1 to 5 and represents [(valence of M) -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 bridging group include those represented by the following general formula (a), and specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, and a cyclohexylidene group. , 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldi A silylene group etc. can be mentioned. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

(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, and e represents an integer of 1 to 4.)

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 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 dimethylamino group, diethylamino group, and diphenylamino group; phenylsulfide group, 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 group containing a hetero atom such as a halogen atom, oxygen, or silicon is preferable because of high polymerization activity. R ⁶ to R ¹³ are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as in general formula (I). q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.

Of the transition metal compounds represented by the above general formula (II), when both indenyl groups are the same, examples of the transition metal compounds belonging to 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, the transition metal compound of Group 4 of the periodic table is 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.

As a compound capable of reacting with the transition metal compound (B) constituting the catalyst used in the present invention to form an ionic complex, a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained, and A borate compound is preferable in terms of high catalyst activity. 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 and 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.

The catalyst used in the production method of the present invention may be a combination of the component (A) and the component (B). In addition to the component (A) and the component (B), an organoaluminum compound is used as the component (C). Also good.
As the organoaluminum compound (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormal hexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride. Dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.
Among these, in the present invention, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum and trimethylaluminum Normal octyl aluminum is more preferred.

The amount of component (A) 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, More preferably, it is 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 component (A) 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 heat of polymerization is easy. Can be removed.
The use ratio (A) / (B) of the component (A) and the component (B) is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in terms of molar ratio. When (A) / (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 exists in the target terminal unsaturated α-olefin polymer.
The use ratio (A) / (C) of the component (A) to the component (C) is preferably 1/1 to 1/10000, more preferably 1/5 to 1/2000, still more preferably 1 in terms of molar ratio. / 10 to 1/1000. By using the component (C), the polymerization activity per transition metal can be improved. When (A) / (C) is in the range of 1/1 to 1/10000, the balance between the effect of addition of component (C) and economy is good, and the desired terminal unsaturated α-olefin weight There is no fear that a large amount of aluminum is present in the coalescence.
In the production method of the present invention, the preliminary contact may be performed using the above-described component (A) and component (B), or component (A), component (B) and component (C). The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the proportion of the (B) component used as the promoter.

In the production of the raw material polyolefin, when the hydrogen pressure in the polymerization reaction is 0.1 MPa or less, the terminal unsaturated group concentration of the terminal unsaturated α-olefin polymer obtained using the raw material polyolefin becomes 2.0 mol% or more. Cheap. The hydrogen pressure in the polymerization reaction of the raw material polyolefin is more preferably 0.005 to 0.100 MPa.
The polymerization temperature in the polymerization reaction is preferably 60 to 120 ° C., more preferably 70 to 100 ° C. When the polymerization temperature is 70 ° C. or higher, the terminal unsaturated group concentration of the terminal unsaturated α-olefin polymer obtained using the raw material polyolefin tends to be 2.0 mol% or higher.

In the production method of the present invention, the terminal unsaturated α-olefin polymer of the present invention is produced by decomposing the raw material polyolefin, preferably in an inert gas atmosphere. The decomposition is preferably a radical decomposition reaction, and the decomposition reaction proceeds under relatively mild conditions as compared with a thermal decomposition reaction that does not use an organic peroxide. On the other hand, in the case of a pyrolysis reaction, the reaction proceeds at a relatively high temperature at a temperature of 200 to 500 ° C. In the case of a thermal decomposition reaction at a high temperature, there are problems such as a decrease in the yield of the target structure due to the generation of a large amount of by-products. Is possible. Specifically, it is a method of shortening the residence time in the thermal decomposition reaction. The residence time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

The radical decomposition reaction can be carried out by adding 0.05 to 5.0% by mass of an organic peroxide to the raw material polyolefin and reacting at a temperature of 200 to 380 ° C.
By setting the amount of the organic peroxide added to the raw material polyolefin to be 0.05% by mass or more, the concentration of the terminal unsaturated group of the terminal unsaturated α-olefin polymer obtained can be increased.
The decomposition temperature is preferably 220 to 360, more preferably 250 to 350 ° C. When the decomposition temperature is less than 200 ° C., the decomposition reaction does not proceed, and the terminal unsaturated group concentration of the terminal unsaturated α-olefin polymer obtained may not be 2.0 mol% or more. On the other hand, when the decomposition temperature exceeds 380 ° C., the decomposition proceeds vigorously, and the decomposition may be completed before the organic peroxide is sufficiently uniformly diffused 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-trimethylhexanoyl) peroxide, dilauryl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2- Ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di (3-methyl Benzoyl) 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) cycl Hesasan, 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) Pyr) 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 the organic peroxide added is preferably 0.05 to 5.0% by mass, more preferably 1.0 to 4.0% by mass with respect to the raw material polyolefin. When the addition amount is less than 0.05% by mass, the decomposition reaction rate may be slowed and the production efficiency may be deteriorated. On the other hand, when the addition amount exceeds 5.0% by mass, the odor resulting from the decomposition of the organic peroxide may be a problem.

The decomposition time of the decomposition reaction is, for example, 30 seconds to 10 hours, preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, 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 exceeds 10 hours, there is a concern that the crosslinking reaction, which is a side reaction, may progress, and the resulting terminal unsaturated α-olefin polymer may turn yellow.

The radical decomposition reaction can be carried out by using, for example, either a batch method or a melt continuous method.

When the radical decomposition reaction is carried out by a batch method, for example, a reaction vessel made of stainless steel or the like equipped with a stirrer is filled with an inert gas such as nitrogen or argon, and the raw material polyolefin is put and melted by heating. In addition, a radical thermal decomposition reaction can be carried out by dropping an organic oxide and heating at a predetermined temperature for a predetermined time.
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.

Further, the raw material polyolefin may be dissolved in a solvent during decomposition.

When the radical decomposition reaction is carried out by a continuous melt process, 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.

For the radical decomposition reaction by the melt continuous method, a method of impregnating the raw material polyolefin with the organic peroxide using the above-mentioned apparatus, or a method of individually supplying and mixing the raw material polyolefin and the organic peroxide can be applied.

Specifically, the impregnation of the raw material polyolefin with the organic peroxide is performed by adding a predetermined amount of the organic peroxide to the raw material polyolefin in the presence of an inert gas such as nitrogen, and stirring the solution in the range of room temperature to 40 ° C. The raw material pellets can be uniformly absorbed and impregnated. The obtained raw material polyolefin impregnated with the organic peroxide (impregnated pellet) is decomposed by melt extrusion, or the impregnated pellet is added to the raw material polyolefin as a master batch and decomposed to obtain a terminal unsaturated polyolefin.
If the organic peroxide is solid or the organic peroxide has low solubility in the raw polyolefin, the raw polyolefin is absorbed and impregnated as a solution in which the organic peroxide is previously dissolved in a hydrocarbon solvent. It is good to let them.

Mixing by separately supplying the raw material polyolefin and the organic peroxide, the raw material polyolefin and the organic peroxide are supplied to the extruder hopper at a constant flow rate, or the organic peroxide is supplied at a constant flow rate in the middle of the barrel. Can be implemented.

By functionalizing the terminal unsaturated group using the terminal unsaturated α-olefin polymer of the present invention, 5 mol% or more (preferably 10 mol% or more) of the terminal unsaturated group was functionally modified. It can be a functionalized α-olefin polymer.
The functional group is preferably one or more functional groups selected from a hydroxyl group, an epoxy group, an alkoxysilicon group, an alkylsilicon group, a carboxyl group, an amino group, and an isocyanate group.
The terminal unsaturated α-olefin polymer of the present invention preferably has an acid anhydride structure. An acid anhydride structure is a structure in which one molecule of water is lost from two carboxyl groups of a carboxylic acid, and two acyl groups share one oxygen atom. Generally indicated by R ¹ COOCOR ² . For example, maleic anhydride, succinic anhydride, phthalic anhydride and the like can be mentioned.

Since the functionalized α-olefin polymer has a functional group, compatibility and dispersibility with a polar compound can be improved, and it becomes easy to obtain a composition with various polymers. Further, since the functionalized α-olefin polymer has a functional group, the solubility and dispersibility in a polar solvent such as water can be improved, and it can be used as an emulsion adhesive or a coating material. For application to polyolefin materials, adhesion and paintability can be imparted, and the surface condition of organic inorganic pigments can be improved, making it possible to produce polyolefin master batches. Can be granted.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical property measuring method and measuring device are shown below.

[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)
CH _{3 at the} end of the side chain (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)

[Kinematic viscosity]
Measured according to JIS K 2283.

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)]
The weight average molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC) method (polystyrene conversion).
GPC measuring 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 50
Sample concentration: 2.2 mg / milliliter Injection amount: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

[Melting point [Tm]]
Using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer, trade name: “DSC7”), the sample was heated from room temperature to 190 ° C. at 100 ° C./min, held at 190 ° C. for 5 minutes, − The temperature was lowered to 30 ° C. at 10 ° C./min, held at −30 ° C. for 5 minutes, and then heated to 190 ° C. at 10 ° C./min to obtain a melting curve showing an endothermic peak. The peak top temperature in the obtained melting curve was defined as the melting point (Tm).

[Half-width [° C]]
The peak width at 50% height of the endothermic peak when the melting point (Tm) was measured by DSC was measured.

[Mesotriad fraction [mm]]
It was determined using ¹³ C-NMR by the method described in Macromolecules, 24, 2334 (1991) and Polymer, 30, 1350 (1989).

[Reactivity evaluation]
Evaluation was made according to the following criteria.
A: The concentration of terminal unsaturated groups is 2.0 to 30 mol%, and the number of terminal unsaturated groups per molecule is 1.7 to 2.0. ○: The concentration of terminal unsaturated groups is 2.0. ˜30 mol%, and the number of terminal unsaturated groups per molecule is more than 1.0 and less than 2.5 ×: the concentration of terminal unsaturated groups is less than 2.0 mol% or more than 30 mol%

[Room temperature fluidity]
Evaluation was made according to the following criteria.
Existence: It confirmed that it had fluidity by visual observation at room temperature.
None: It was confirmed by visual observation at room temperature that there was no fluidity.

Production Example 1
[Manufacture of raw material polyolefin]
In a heat-dried 1 liter autoclave, 400 ml of 1-hexene, 1 mmol of triisobutylaluminum, 2 μmol of (1,1′-ethylene) (2,2′-tetramethyldisylylene) -bis (indenyl) zirconium dichloride, Tetrakis pentafluorophenyl borate (8 μmol) was added, and hydrogen (0.05 MPa) was further introduced. Polymerization was conducted for 1 hour at a temperature of 80 ° C. with stirring. After completion of the polymerization reaction, the reaction solution was transferred into acetone. The precipitate was filtered and then heated and dried under reduced pressure to obtain 200 g of terminal unsaturated low stereoregular poly 1-hexene as a raw material polyolefin.
About the obtained raw material polyolefin, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule, terminal unsaturated group concentration, and yield It was measured. The results are shown in Table 1.

Production Example 2
[Manufacture of raw material polyolefin]
In a heat-dried 1 liter autoclave, 400 ml of 1-decene, 1 mmol of triisobutylaluminum, 2 μmol of (1,1′-ethylene) (2,2′-tetramethyldisylylene) -bis (indenyl) zirconium dichloride, Tetrakis pentafluorophenyl borate (8 μmol) was added, and hydrogen (0.05 MPa) was further introduced. Polymerization was carried out at 90 ° C. for 1 hour with stirring. After completion of the polymerization reaction, the reaction solution was transferred into acetone. The precipitate was filtered and then heated and dried under reduced pressure to obtain 230 g of terminal unsaturated low stereoregular poly 1-decene as a raw material polyolefin.
About the obtained raw material polyolefin, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule, terminal unsaturated group concentration, and yield It was measured. The results are shown in Table 1.

Production Example 3
[Manufacture of raw material polyolefin]
In a heat-dried 1 liter autoclave, 1-dodecene 400 ml, triisobutylaluminum 1 mmol, (1,1′-ethylene) (2,2′-tetramethyldisylylene) -bis (indenyl) zirconium dichloride 2 μmol, Tetrakis pentafluorophenyl borate (8 μmol) was added, and hydrogen (0.05 MPa) was further introduced. Polymerization was carried out at 90 ° C. for 1 hour with stirring. After completion of the polymerization reaction, the reaction solution was transferred into acetone. The precipitate was filtered and then heated and dried under reduced pressure to obtain 220 g of terminal unsaturated low stereoregular poly 1-dodecene as a raw material polyolefin.
About the obtained raw material polyolefin, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule, terminal unsaturated group concentration, and yield It was measured. The results are shown in Table 1.

Production Example 4
[Manufacture of raw material polyolefin]
In a heat-dried 1 liter autoclave, 400 ml of 1-octadecene, 1 mmol of triisobutylaluminum, 2 μmol of (1,1′-ethylene) (2,2′-tetramethyldisylylene) -bis (indenyl) zirconium dichloride, Tetrakis pentafluorophenyl borate (8 μmol) was added, and hydrogen (0.05 MPa) was further introduced. Polymerization was carried out at 90 ° C. for 1 hour with stirring. After completion of the polymerization reaction, the reaction solution was transferred into acetone. The precipitate was filtered and then heated and dried under reduced pressure to obtain 190 g of a terminal unsaturated low stereoregular poly 1-octadecene as a raw material polyolefin.
About the obtained raw material polyolefin, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule, terminal unsaturated group concentration, and yield It was measured. The results are shown in Table 1.

Production Example 5
[Manufacture of raw material polyolefin]
In a heat-dried 1 liter autoclave, 400 ml of an α-olefin mixture having 26 to 28 carbon atoms, 1 mmol of triisobutylaluminum, (1,1′-ethylene) (2,2′-tetramethyldisilene) -bis (indenyl) 2 micromoles of zirconium dichloride and 8 micromoles of tetrakispentafluorophenylborate were added, and 0.05 MPa of hydrogen was further introduced. Polymerization was conducted for 1 hour at 110 ° C. with stirring. After completion of the polymerization reaction, the reaction solution was transferred into acetone. The precipitate was filtered and then heated and dried under reduced pressure to obtain 175 g of a terminal unsaturated low stereoregular C26-28 copolymer as a raw material polyolefin.
About the obtained raw material polyolefin, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule, terminal unsaturated group concentration, and yield It was measured. The results are shown in Table 1.

Production Example 6
[Preparation of catalyst mixture]
In a 10 ml glass Schlenk bottle under a nitrogen atmosphere, 0.20 mmol of triisobutylaluminum (0.5 mmol / ml of toluene solution; 0.4 ml), (1,1′-dimethylsilylene) (2,2 ′ -Dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride 4 micromolar (5 micromole / milliliter toluene solution; 0.8 milliliter) and N, N'-dimethylanilinium tetrakis (pentafluorophenyl) in powder form 0.08 mmol (64 milligrams) of borate was added and stirred for about 1 minute at room temperature. Then, 1 milliliter of 1-dodecene was added and further stirred for 1 hour at room temperature to prepare a catalyst mixture.
[Manufacture of raw material polyolefin]
In a 1 liter autoclave that had been dried by heating, 234 ml of 1-dodecene, 166 ml of 1-octene, and 0.3 mmol of triisobutylaluminum were added, and the temperature was raised to 90 ° C. After adding 1.6 ml of the catalyst mixture obtained by the above preparation step, 0.05 MPaG of hydrogen was introduced to initiate polymerization. After 120 minutes, the remaining 1.6 ml of the catalyst mixture was added, and further reacted at 90 ° C. for 120 minutes, and then 10 ml of methanol was added to stop the polymerization. The contents were taken out and added to 200 ml of 1% by weight NaOH aqueous solution and stirred. This solution was transferred to a separatory funnel, the organic layer was separated, the organic layer was washed with water, and the organic layer was removed with Toyo filter paper 2C filter paper. Toluene, raw materials, methanol and the like were distilled off from the obtained solution with a rotary evaporator (oil bath 100 ° C. under reduced pressure of about 1.0 × 10 ⁻⁴ MPaG) to obtain 235 g of a colorless transparent liquid. Further, using a thin-film distillation device (molecular distillation device MS-300 special model manufactured by Shibata Kagaku, high vacuum evacuation device DS-212Z), distillation is performed at 180 ° C. under reduced pressure of 5 × 10 ⁻⁶ MPa, and the number of carbon atoms is 24 or less. By removing the above component, 205 g of a terminal unsaturated low stereoregular 1-octene / 1-dodecene copolymer, which is a raw material polyolefin, was obtained.
About the obtained raw material polyolefin, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule, terminal unsaturated group concentration, and yield It was measured. The results are shown in Table 1.

Example 1
[Production of terminal unsaturated α-olefin polymer]
40 g of the raw material polyolefin produced in Production Example 1 was introduced into a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer, and stirred for 30 minutes under a nitrogen stream.
Stirring was stopped, and the resin temperature was raised to 160 ° C. using a mantle heater. After confirming that it was in a molten state, stirring was resumed. The mantle heater was controlled so that the resin temperature was constant at 270 ° C. To this, 0.4 ml of cumene hydroperoxide was added dropwise over 4 minutes. After completion of the dropwise addition, the reaction was performed for 4 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 obtain radically decomposed amorphous poly-1-hexene which is a terminal unsaturated α-olefin polymer.
The yield of the obtained terminal unsaturated α-olefin polymer was 99.1% by mass with respect to the raw material polyolefin, and the amount of by-products was very small. The weight average molecular weight (Mw) of the terminal unsaturated α-olefin polymer was 8800, and the molecular weight distribution (Mw / Mn) was 1.64. The number of terminal unsaturated groups per molecule was 1.9.

Example 2
[Production of terminal unsaturated α-olefin polymer]
40 g of the raw material polyolefin produced in Production Example 2 was introduced into a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer, and stirred for 30 minutes under a nitrogen stream.
Stirring was stopped, and the resin temperature was raised to 160 ° C. using a mantle heater. After confirming that it was in a molten state, stirring was resumed. The mantle heater was controlled so that the resin temperature was constant at 270 ° C. To this, 0.4 ml of cumene hydroperoxide was added dropwise over 4 minutes. After completion of the dropwise addition, the reaction was performed for 4 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 obtain radically decomposed poly 1-decene as a terminal unsaturated α-olefin polymer.
The yield of the obtained terminal unsaturated α-olefin polymer was 99.2% by mass based on the raw material polyolefin, and the amount of by-products was very small. The terminal unsaturated α-olefin polymer had a weight average molecular weight (Mw) of 9100 and a molecular weight distribution (Mw / Mn) of 1.72. The number of terminal unsaturated groups per molecule was 1.8.

Example 3
[Production of terminal unsaturated α-olefin polymer]
40 g of the raw material polyolefin produced in Production Example 3 was placed in a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer and stirred for 30 minutes under a nitrogen stream.
Stirring was stopped, and the resin temperature was raised to 160 ° C. using a mantle heater. After confirming that it was in a molten state, stirring was resumed. The mantle heater was controlled so that the resin temperature was constant at 270 ° C. To this, 0.4 ml of cumene hydroperoxide was added dropwise over 4 minutes. After completion of the dropwise addition, the reaction was performed for 4 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 obtain radically decomposed poly 1-dodecene as a terminal unsaturated α-olefin polymer.
The yield of the obtained decomposed poly 1-dodecene was 99.9% by mass based on the raw material polyolefin, and the amount of by-products was very small. The terminal unsaturated α-olefin polymer had a weight average molecular weight (Mw) of 8500 and a molecular weight distribution (Mw / Mn) of 1.81. The number of terminal unsaturated groups per molecule was 1.7.

Example 4
[Production of terminal unsaturated α-olefin polymer]
40 g of the raw material polyolefin produced in Production Example 4 was placed in a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer, and stirred for 30 minutes under a nitrogen stream.
Stirring was stopped, and the resin temperature was raised to 160 ° C. using a mantle heater. After confirming that it was in a molten state, stirring was resumed. The mantle heater was controlled so that the resin temperature was constant at 270 ° C. To this, 0.4 ml of cumene hydroperoxide was added dropwise over 4 minutes. After completion of the dropwise addition, the reaction was performed for 4 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 obtain radically decomposed poly 1-octadecene as a terminal unsaturated α-olefin polymer.
The yield of the obtained terminal unsaturated α-olefin polymer was 99.9% by mass based on the raw material polyolefin, and the amount of by-products was very small. The terminal unsaturated α-olefin polymer had a weight average molecular weight (Mw) of 8500 and a molecular weight distribution (Mw / Mn) of 1.81. The number of terminal unsaturated groups per molecule was 1.5.

Example 5
[Production of terminal unsaturated α-olefin polymer]
40 g of the raw material polyolefin produced in Production Example 5 was charged into a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer, and stirred for 30 minutes under a nitrogen stream.
Stirring was stopped, and the resin temperature was raised to 160 ° C. using a mantle heater. After confirming that it was in a molten state, stirring was resumed. The mantle heater was controlled so that the resin temperature was constant at 270 ° C. To this, 0.4 ml of cumene hydroperoxide was added dropwise over 4 minutes. After completion of the dropwise addition, the reaction was performed for 4 minutes, and then cooled to 110 ° C.
After completion of the reaction, drying under reduced pressure at 100 ° C. was performed for 10 hours to obtain a radically decomposed C26-28 copolymer which is a terminal unsaturated α-olefin polymer.
The yield of the obtained terminal unsaturated α-olefin polymer was 98.9% by mass based on the raw material polyolefin, and the amount of by-products was very small. The terminal unsaturated α-olefin polymer had a weight average molecular weight (Mw) of 6500 and a molecular weight distribution (Mw / Mn) of 1.79. The number of terminal unsaturated groups per molecule was 1.5.

Example 6
[Production of terminal unsaturated α-olefin polymer]
Glass beads were filled in a tubular reactor having an inner diameter of 10 mm and a length of 50 cm, and heated to 400 ° C. with a mantle heater. The raw material polyolefin obtained in Production Example 6 was continuously decomposed with a pump at a flow rate of 40 ml / hour to obtain a terminal unsaturated 1-octene / 1-dodecene copolymer. The residence time at this time was 27 minutes.
About the obtained terminal unsaturated 1-octene / 1-dodecene copolymer, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule The terminal unsaturated group concentration and the yield were measured. The results are shown in Table 2.

Comparative Example 1
[Production of terminal unsaturated propylene polymer]
In a stainless steel reactor with an internal volume of 20 L with a stirrer, n-heptane was 24 L / h, triisobutylaluminum was 15 mmol / h, and dimethylanilinium tetrakispentafluorophenylborate and (1,2'-dimethylsilylene) ( The catalyst component obtained by contacting 2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, triisobutylaluminum and propylene in a mass ratio of 1: 2: 20 was converted to 6 μmol in terms of zirconium. / H was continuously fed.
The polymerization temperature was set to 83 ° C., and propylene and hydrogen were continuously supplied so that the hydrogen concentration in the gas phase of the reactor was 0.86 mol% and the total pressure in the reactor was maintained at 0.7 MPa · G. A polymerization reaction was performed.
Irganox 1010 (manufactured by Ciba Specialty Chemicals), which is a stabilizer, is added to the resulting polymerization solution so that the content is 500 ppm by mass, and n-heptane, which is a solvent, is removed to obtain a raw material. A low crystalline polypropylene which is polypropylene was obtained. This raw material polypropylene was made into resin pellets by underwater cutting.
The resulting raw material polypropylene had a stereoregularity [mmmm] of 45 mol%, a weight average molecular weight (Mw) of 45,600, and a terminal unsaturated group number of 0.95 / molecule.

Using the raw material polypropylene, radical decomposition was performed under the following conditions to produce a terminal unsaturated propylene polymer.
Specifically, 70 g of raw material polypropylene was put 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 stopped and the resin temperature was raised to 120 ° C. using a mantle heater. Stirring was resumed after confirming that it was in a molten state, and the mantle heater was controlled so that the resin temperature was constant at 320 ° C. To this molten resin, 1.2 g of cumene hydroperoxide (trade name: Park Mill P, manufactured by NOF Corporation) was dropped over 4 minutes. After completion of dropping, the reaction was allowed to proceed for 4 minutes, followed by air cooling and cooling to 110 ° C. While maintaining the temperature at 110 ° C., 200 ml of toluene was added to prepare a uniform solution.
The toluene solution was recovered in a Teflon (registered trademark) vat, the toluene was removed, and the residue was dried under reduced pressure at 100 ° C. for 8 hours to obtain radically decomposed polypropylene.
About the obtained terminal unsaturated propylene polymer, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], number of terminal unsaturated groups per molecule, terminal unsaturated group concentration, And the yield was measured. The results are shown in Table 2.

Comparative Example 2
The raw material polyolefin produced in Production Example 2 was used for evaluation as it was.
About the obtained terminal unsaturated α-olefin polymer, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesotriad fraction [mm], kinematic viscosity at 100 ° C., melting point (Tm), terminal unsaturated group The concentration and the number of terminal unsaturated groups per molecule were measured. The results are shown in Table 2.

The terminal unsaturated α-olefin polymers of Examples 1 to 6 have high terminal unsaturated group concentrations of 2.0 mol% or more, and can be said to be highly reactive polymers. Therefore, it can be said that it can be suitably used as a use or raw material for reactive adhesives, reactive hot melt adhesives, other adhesives, pressure-sensitive adhesives, sealing materials, sealing materials, reactive plasticizers, and the like. Moreover, since it is an olefin polymer having 5 or more carbon atoms, it can be said that there are effects such as improvement of material heat resistance and improvement of waterproofness.
In contrast, since Comparative Example 1 is a terminal unsaturated olefin polymer having 3 carbon atoms, the terminal unsaturated concentration per molecular weight was less than 2.0 mol%. Moreover, since the decomposition reaction was not performed in the comparative example 2, the terminal unsaturated concentration per molecular weight was less than 2.0 mol%. Furthermore, since the terminal unsaturated group concentration is low, the reactivity of the obtained polymer is low, and it is difficult to use it in applications such as reactive adhesives, sealing materials, sealing materials, adhesives, and plasticizers. It was.

The terminal unsaturated α-olefin polymer of the present invention uses a terminal unsaturated group as a reaction point, thereby imparting adhesiveness, paintability, and coating properties to a chemically inert polyolefin material. It can be used in fields such as the production of alloy materials with resins and compositions with inorganic and organic fillers. Furthermore, by using as a reactive raw material, it can be widely used as a raw material for reactive adhesives, reactive hot melt adhesives, other adhesives, pressure-sensitive adhesives, sealing materials, sealing materials, potting materials, reactive plasticizers, etc. Available.

Claims (10)

1. A terminal unsaturated α-olefin polymer, which is a homopolymer and / or copolymer of an α-olefin having 5 or more carbon atoms, and has a terminal unsaturated group concentration of 2.0 to 30 mol% .
2. The terminal unsaturated α-olefin polymer according to claim 1, wherein the number of terminal unsaturated groups per molecule is more than 1.0 and 2.5 or less.
3. The terminal unsaturated α-olefin polymer according to claim 1 or 2, comprising 50 to 100% by mass of an α-olefin unit having 5 to 12 carbon atoms.
4. The terminal unsaturated α-olefin polymer according to claim 1 or 2, comprising 50 to 100% by mass of an α-olefin unit having 14 to 30 carbon atoms.
5. The terminal unsaturated α-olefin polymer according to any one of claims 1 to 4, having a kinematic viscosity at 100 ° C of 3 to 2000 mm / s ² and a mesotriad fraction [mm] of 20 to 80 mol%.
6. In the melting behavior measurement using a differential scanning calorimeter, the melting point is 20 ° C. or more and 100 ° C. or less, only one peak temperature is observed, and the half width of the peak is within 15 ° C. 6. The terminal unsaturated α-olefin polymer according to any one of 5 above.
7. 7. The terminal unsaturated α-olefin polymer according to claim 1, having a weight average molecular weight Mw of 500 to 100,000 and a molecular weight distribution Mw / Mn of 1.10 to 2.60. .
8. The terminal unsaturation according to any one of claims 1 to 7, wherein the organic peroxide is added in an amount of 0.05 to 5.0 mass% with respect to the raw material polyolefin, and is heated at a temperature of 200 to 380 ° C. A method for producing an α-olefin polymer.
9. The method for producing a terminal unsaturated α-olefin polymer according to any one of claims 1 to 7, wherein the raw material polyolefin is heat-treated at a temperature of 200 to 500 ° C within a residence time of 1 hour.
10. The method for producing a terminal unsaturated α-olefin polymer according to claim 8 or 9, wherein the heat treatment time is 30 seconds to 10 hours.