JPH05320280A - Styrene block copolymer and its production - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a styrene-based copolymer suitable as a high-performance heat-resistant elastomer or as a material such as a polymer alloy and a high-impact-resistant material, and a method for efficiently producing the same. [Structure] A styrene-based block copolymer comprising a styrene-based polymer segment having a high syndiotactic structure and a polymer segment of an anionically-polymerizable monomer; Block copolymer formed by adding, and in the presence of an anionic polymerization initiator, an anionic polymerizable monomer is polymerized to form a polymer, which is then contact-reacted with a transition metal compound, and then an aluminoxane or the transition metal compound. By reacting with a styrene-based monomer in the presence of a compound capable of forming an ionic complex, a block copolymer is obtained.
The styrene block copolymer is manufactured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene block copolymer and a method for producing the same, and more specifically, it is a syndiotactic styrene suitable as a high performance heat resistant elastomer or as a material for polymer alloys, high impact resistance materials and the like. -Based block copolymer and method for efficiently producing the same, and further hydrogenation of the syndiotactic styrene-based block copolymer to obtain highly improved hydrogenation of solvent resistance, weather resistance and heat resistance. It relates to a block copolymer.

[0002]

2. Description of the Related Art Styrene-based polymers conventionally produced by radical polymerization or the like are molded into various shapes by various molding methods, and are used for household appliances, office equipment, household products, packaging containers, toys, It is widely used as furniture, synthetic paper, and other industrial materials, but its three-dimensional structure has an atactic structure, which has the drawback of poor heat resistance and chemical resistance. The present inventors' group has succeeded in developing a styrene-based polymer having a high degree of syndiotactic structure, as a solution to the drawbacks of the styrene-based polymer having an atactic structure, and further developed the styrene-based polymer having a high syndiotactic structure. We have also developed a styrenic copolymer, which is a copolymer of a base monomer and other components. For example, a syndiotactic block copolymer of olefin and styrene, which is useful as an elastomer and as a compatibilizing agent for polyolefin resins (Japanese Patent Application No. 2-251360), and a syndyne of styrene with olefin or diene. Otatic graft copolymer (Japanese Patent Application No. 2-407148)
Found. However, the former syndiotactic block copolymer of olefin and styrene is a relatively low molecular weight polymer, and when developed as an elastomer, the molecular weight of the olefin polymer site cannot be increased, and therefore, However, there is a problem that the characteristics of the elastomer cannot be fully brought out. On the other hand, in the latter graft copolymer of olefin or diene and styrene, it is necessary to highly control the copolymerization factors such as the graft starting point concentration and the graft efficiency, and a more convenient method for production has been desired. ..

[0003]

Under these circumstances, the present invention provides a styrenic block copolymer suitable as a high-performance heat-resistant elastomer or as a raw material for polymer alloys, high-impact materials, etc. The purpose is to develop a method for efficiently producing

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a polymer of a styrene-based polymer segment having a high syndiotactic structure and an anion-polymerizable monomer is used. As a block copolymer consisting of a segment is useful as a material such as a polymer alloy or an impact resistant material because it is given an compatibilizing ability as an elastomer, and by hydrogenating this block copolymer, It has been found that a solvent having highly improved solvent resistance, weather resistance and heat resistance can be obtained. Further, the block copolymer is obtained by polymerizing an anion-polymerizable monomer in the presence of an anionic polymerization initiator, then treating with a transition metal compound, and further block-copolymerizing a styrene-based monomer in the presence of a specific catalyst. Therefore, it was found that it can be easily obtained. The present invention has been completed based on such findings. That is,
The present invention has the general formula (I)

[0005]

[Chemical 3]

[In the formula, R ¹ represents a hydrogen atom, a halogen atom or a substituent containing at least one of a carbon atom, a tin atom and a silicon atom, and m is an integer of 1 to 5,
When m is plural, each R ¹ may be the same or different, and R ¹ may form a condensed ring with the benzene ring. ] The repeating unit represented by
A styrene-based block copolymer containing a repeating unit derived from an anion-polymerizable monomer and having a syndiotactic structure (A) having a high stereoregularity of the repeating unit, and the styrene-based block copolymer The present invention provides a hydrogenated block copolymer obtained by partial hydrogenation or complete hydrogenation. Further, the styrene-based block copolymer is prepared by polymerizing an anion-polymerizable monomer in the presence of a monofunctional or polyfunctional anionic polymerization initiator to substantially produce a polymer, and then (a) a transition metal. In the presence of a compound capable of reacting with a compound, and then reacting with (b) an aluminoxane or (c) the transition metal compound to form an ionic complex, the compound of the general formula (II)

[0007]

[Chemical 4]

[In the formula, R ¹ and m are the same as described above. ] It can manufacture by block-copolymerizing with the styrene-type monomer represented by these. The anionic polymerizable monomer used as one of the raw materials for the styrene block copolymer of the present invention is not particularly limited, but is described in "Polymer Handbook" (published by John Willy & Sons), Chapter 2 Among the monomers described, a conjugated monomer having a Q (resonance factor) value of 0.2 or more and an e (polarity factor) value of -1.50 or more is preferable. Examples of such a conjugated monomer include olefins such as diphenylethylene and indene, isoprene; 1,3-butadiene; 2-fluoro-1,3.
-Butadiene; 2,3-dichloro-1,3-butadiene; dienes such as 1,3-cyclohexadiene, α-
Methyl styrene; alkyl styrene such as 2,4,6-trimethylstyrene, halogen, haloalkyl-substituted styrene,
Aromatic vinyl compounds such as 1-vinylnaphthalene, 2-isopropenylnaphthalene and 4-chloro-1-vinylnaphthalene, and non-conjugated substances such as ethylene, vinyl acetate, vinyl chloride and vinylidene chloride in addition to the conjugated monomer. Monomers can also be used. These anion-polymerizable monomers may be used alone or in combination of two or more, and of these, olefins and dienes are particularly preferable.

To produce the styrenic block copolymer of the present invention, first, the anionic polymerizable monomer is polymerized in the presence of an anionic polymerization initiator. Among the anionic polymerization initiators used at this time, examples of monofunctional initiators include alkali metals such as cesium, rubidium, potassium, sodium and lithium; alkali metal alkyls such as n-butyl lithium, octyl potassium and benzyl barium; Alkaline earth metal alkyls, alkali metal aromatic compound complexes such as sodium-naphthalene, alkali metal amides such as potassium amide and diethyl lithium amide, magnesium compounds such as phenyl magnesium bromide and diethyl magnesium, (C _{6
^{H 5) 2 C-O -}} Na + alkali metal ketyl such as lithium aluminum hydride (LiAlH _4), dimethoxyethoxy sodium aluminum hydride (NaAlH
₂ (OCH ₂ CH ₂ OCH ₃ ) ₂ ) and other ate complexes, n-butoxy potassium and other alkoxides, and p-vinylbenzyl magnesium chloride and other functional group-containing metal compounds, depending on the type of monomer used. It is selected appropriately. For example, when ethylene is used as the monomer, a combination of an alkyl metal compound and a tertiary diamine compound is effective. Examples of polyfunctional initiators include equimolar reaction products of carbon-carbon double bonds with divinylbenzene, trivinylbenzene or α, ω non-conjugated diolefins, alkyl lithium and the like.

The anionic polymerizable monomer is subjected to anionic polymerization using these anionic polymerization initiators. At this time, a solvent may or may not be used. When a solvent is used, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane,
Aliphatic hydrocarbons such as cyclopentane and non-polar solvents such as aromatic hydrocarbons such as benzene and toluene are preferably used. These solvents may be used alone or in combination of two or more. The temperature of anionic polymerization is usually selected in the range of −78 to 200 ° C. according to the kind of the monomer used. For example, when using ethylene, 3
In the range of 0 to 70 ° C, 0 to 60 when a diene is used.
When using an unsaturated carboxylic acid derivative in the range of ° C,
It is advantageous to choose in the range of 78 to -20 ° C. further,
The aurone-polymerizable monomer is usually used in a ratio of 2 mol times or more with respect to the anionic polymerization initiator. When ethylene is used as the anionically polymerizable monomer,
From the viewpoint of improving the catalytic activity, it is desirable to add the tertiary diamine compound in a ratio of 1.5 to 2.5 mols per mol of the polymerization initiator.

In this manner, after substantially producing the polymer, the unreacted anionically polymerizable monomer is removed by a usual method, for example, a method such as flash distillation, and then the catalyst ( A transition metal compound is added as the component a), and a catalytic reaction is performed. However, when the unreacted anionically polymerizable monomer forms a block chain by copolymerizing with a styrene-based monomer that continues to react,
It is not necessary to remove the unreacted anionically polymerizable monomer. There are various transition metal compounds of the above-mentioned component (a), preferably the general formula M ¹ R ² ... R ^k (III) [wherein M ¹ is Ti, Zr, Cr, V, Nb, Ta or Hf is shown, and R ^{2 to} R ^k are each a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms; 20 aryl groups; alkylaryl groups or arylalkyl groups;
C1-C20 acyloxy group, allyl group, substituted allyl group, acetylacetonato group, substituted acetylacetonato group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen molecule, Lewis base, chain unsaturated Ligands such as hydrocarbons or cyclic unsaturated hydrocarbons, cyclopentadienyl groups, substituted cyclopentadienyl groups, indenyl groups, substituted indenyl groups, tetrahydroindenyl groups,
A substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. Further, k represents a valence of a metal and usually represents an integer of 2 to 5].

Examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group Examples thereof include an enyl group and a trimethylsilylcyclopentadienyl group. In addition, the ligands of R ^{2 to} R ^k may form a crosslinked body by a covalent bond between the ligands. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom,
Iodine atom; As the alkyl group having 1 to 20 carbon atoms, a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, octyl group, 2-ethylhexyl group, etc. The alkoxy group is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group or the like, and the aryl group having 6 to 20 carbon atoms, the alkylaryl group or the arylalkyl group is a phenyl group, a tolyl group, a xylyl group, or benzyl. Examples of the acyloxy group having 1 to 20 carbon atoms such as a group include a heptadecylcarbonyloxy group, a substituent including a silicon atom such as a trimethylsilyl group and a (trimethylsilyl) methyl group, and a Lewis base including dimethyl ether, diethyl ether, Ethers such as tetrahydrofuran,
Thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as benzonitrile, trimethylamine, triethylamine, tributylamine; N, N-dimethylaniline, pyridine; amines such as 2,2′-bipyridine, phenanthroline, As chain unsaturated hydrocarbons such as phosphines such as triethylphosphine and triphenylphosphine, as cyclic unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives, Examples thereof include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the crosslink by a covalent bond include methylene crosslink, dimethylmethylene crosslink, ethylene crosslink, dimethylsilylene crosslink, and dimethylstannylene crosslink.

Specific examples of the titanium compound include tetramethoxy titanium, tetraethoxy titanium and tetra-n.
-Butoxy titanium, tetraisopropoxy titanium, titanium tetrachloride, titanium trichloride, titanium dichloride, titanium hydride, cyclopentadienyltrimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl tripropyl titanium, cyclopentadi Phenyltributyltitanium, methylcyclopentadienyltrimethyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyl Titanium, pentamethylcyclopentadienyltributyltitanium, cyclopentadienylmethyltitanium dichloride, cyclopentadienylethyltitanium dichloride, pentamethylcyclopen Dienyl methyl titanium dichloride, pentamethyl click cyclopentadienyl ethyl titanium dichloride, cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl diethyl titanium monochloride, cyclopentadienyltitanium trimethoxide,
Cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethyl Cyclopentadienyl titanium tripropoxide, pentamethylcyclopentadienyl titanium tributoxide, pentamethylcyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadi Phenyl methoxy titanium dichloride, cyclopentadienyl dimethoxy titanium chloride, pentamethyl cyclopentadienyl methoxy titanium dichloride, cyclopentadienyl Revenge Le titanium, pentamethylcyclopentadienyl methyl diethoxy titanium, indenyl titanium trichloride, indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl trimethyl titanium, etc. indenyl tribenzylamine titanium and the like.

Among the transition metal compounds represented by the general formula (111), specific examples of the zirconium compound in which M ¹ is zirconium include dicyclopentadienyl zirconium dichloride, tetrabutoxy zirconium, zirconium tetrachloride and tetra. Phenylzirconium, cyclopentadienylzirconium trimethoxide, pentamethylcyclopentadienylzirconium trimethoxide, cyclopentadienyltribenzylzirconium,
Pentamethylcyclopentadienyltribenzylzirconium, bisindenylzirconium dichloride, zirconium dibenzyldichloride, zirconium tetrabenzyl, tributoxyzirconium chloride, triisopropoxyzirconium chloride, (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethyl Cyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) trichlorozirconium, (Cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethylzyl , (Methylcyclopentadienyl) triphenylzirconium, (Methylcyclopentadienyl) tribenzylzirconium, (Methylcyclopentadienyl) trichlorozirconium, (Methylcyclopentadienyl) dimethyl (methoxy) zirconium, (Dimethylcyclopentadienyl) Pentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, bis (cyclopentadienyl) dimethylzirconium, bis ( Cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzyl Zirconium,
Bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) ) Dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium , Bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclo) N-dienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium, ethylenebis (indenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium , Dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9- Fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethyldi Koniumu,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutyl (9-fluorenyl) (cyclo Pentadienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,3)
5-trimethylcyclopentadienyl) dimethyl zirconium and the like can be mentioned.

Specific examples of the hafnium compound include cyclopentadienyl hafnium trimethoxyside, pentamethylcyclopentadienyl hafnium trimethoside, cyclopentadienyl tribenzyl hafnium, pentamethyl cyclopentadienyl tribenzyl hafnium, bis. Examples include indenyl hafnium dichloride, hafnium dibenzyl dichloride, hafnium tetrabenzyl, tributoxy hafnium chloride, triisopropoxy hafnium chloride, hafnium tetrachloride, dicyclopentadienyl hafnium dichloride and tetraethoxy hafnium. As a specific example of vanadium,
Vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclo Examples include pentadienyl vanadium dichloride, cyclopentadienyl vanadium dichloride, dicyclopentadienylmethyl vanadium, and the like. Specific examples of niobium compounds include:
Examples thereof include niobium pentachloride, tetrachloromethyl niobium, dichlorotrimethyl niobium, dicyclopentadienyl niobium dichloride, dicyclopentadienyl niobium trihydride, pentabtoxniobium and the like. Specific examples of the tantalum compound include tantalum pentachloride, dichlorotrimethyltantalum, dicyclopentadienyltantalum trihydride, pentabtoxniobium, and the like, and specific examples of the chromium compound include chromium trichloride, tetrabutoxychromium,
Tetramethyl chrome, dicyclopentadienyl chrome,
Examples include dibenzene chrome.

Further, as other transition metal compounds,
The transition metal compound supported on a carrier such as a magnesium compound or a silicon compound can be used, and the transition compound modified with an electron donating compound can also be used. Particularly preferable among these transition metal compounds are titanium compounds and zirconium compounds. The amount of these transition metal compounds used is usually 0.5 to 10 with respect to 1 mol of the anionic polymerization initiator.
0 mol, preferably 0.5 to 30 mol, more preferably 0.5.
It is selected in the range of 8 to 2 mol. In addition, the temperature for the catalytic reaction with the transition metal compound is usually -78 to 100.
℃, preferably selected in the range of -78 ~ 80 ℃,
The contact time is usually 0.1 to 10 hours, preferably 0.5 to 1 hour. In the present invention, after the transition metal compound is added and the catalytic reaction is carried out in this manner, the catalyst (b) aluminoxane (c) reacts with the transition metal compound in the presence of a compound capable of forming an ionic complex. Then, the styrene-based monomer represented by the general formula (II) is block-copolymerized.

Examples of the styrenic monomer represented by the general formula (II) include styrene; p-methylstyrene; o-methylstyrene; m-methylstyrene; 2,4
-Dimethylstyrene; 2,5-dimethylstyrene; 3,
4-dimethylstyrene; 3,5-dimethylstyrene; p
-Alkyl styrenes such as tertiary butyl styrene, p-chlorostyrene; m-chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene; o-bromostyrene; p-fluorostyrene; m-
Fluorostyrene; o-fluorostyrene; halogenated styrene such as o-methyl-p-fluorostyrene, 4
-Vinyl biphenyl; 3-vinyl biphenyl; vinyl biphenyls such as 2-vinyl biphenyl, 1- (4-vinylphenyl) -naphthalene; 2- (4-vinylphenyl) -naphthalene; 1- (3-vinylphenyl)- Naphthalene; 2- (3-vinylphenyl) -naphthalene; 1
-(2-vinylphenyl) -naphthalene; vinylphenylnaphthalenes such as 2- (2-vinylphenyl) naphthalene, 1- (4-vinylphenyl) -anthracene;
2- (4-vinylphenyl) -anthracene; 9- (4
-Vinylphenyl) -anthracene; 1- (3-vinylphenyl) -anthracene; 2- (3-vinylphenyl) -anthracene; 9- (3-vinylphenyl) -anthracene; 1- (2-vinylphenyl) -anthracene. 2- (2-vinylphenyl) -anthracene; 9-
Vinylphenyl anthracenes such as (2-vinylphenyl) -anthracene, 1- (4-vinylphenyl)-
Phenanthrene; 2- (4-vinylphenyl) -phenanthrene; 3- (4-vinylphenyl) -phenanthrene; 4- (4-vinylphenyl) -phenanthrene; 9
-(4-vinylphenyl) -phenanthrene; 1- (3
-Vinylphenyl) -phenanthrene; 2- (3-vinylphenyl) -phenanthrene; 3- (3-vinylphenyl) -phenanthrene; 4- (3-vinylphenyl)
-Phenanthrene; 9- (3-vinylphenyl) -phenanthrene; 1- (2-vinylphenyl) -phenanthrene; 2- (2-vinylphenyl) -phenanthrene;
3- (2-vinylphenyl) -phenanthrene; 4-
(2-Vinylphenyl) -phenanthrene; 9- (2-
Vinylphenyl) -phenanthrene and other vinylphenylphenanthrenes, 1- (4-vinylphenyl) -pyrene; 2- (4-vinylphenyl) -pyrene; 1- (3
-Vinylphenyl) -pyrene; 2- (3-vinylphenyl) -pyrene; 1- (2-vinylphenyl) -pyrene;
Vinylphenylpyrenes such as 2- (2-vinylphenyl) -pyrene, 4-vinyl-p-terphenyl; 4-vinyl-m-terphenyl; 4-vinyl-o-terphenyl; 3-vinyl-p- Terphenyl; 3-vinyl-m-
Terphenyl; 3-vinyl-o-terphenyl; 2-vinyl-p-terphenyl; 2-vinyl-m-terphenyl; vinylterphenyls such as 2-vinyl-o-terphenyl, 4- (4- Vinylphenyl terphenyls such as vinylphenyl) -p-terphenyl, 4-vinyl-4′-methylbiphenyl; 4-vinyl-3′-methylbiphenyl; 4-vinyl-2′-methylbiphenyl; 2
-Methyl-4-vinylbiphenyl; vinylalkylbiphenyls such as 3-methyl-4-vinylbiphenyl, 4
-Vinyl-4'-fluorobiphenyl; 4-vinyl-
3'-fluorobiphenyl;4-vinyl-2'-fluorobiphenyl;4-vinyl-2-fluorobiphenyl;
4-vinyl-3-fluorobiphenyl; 4-vinyl-
4'-chlorobiphenyl;4-vinyl-3'-chlorobiphenyl;4-vinyl-2'-chlorobiphenyl; 4-
Vinyl-2-chlorobiphenyl; 4-vinyl-3-chlorobiphenyl; 4-vinyl-4'-bromobiphenyl;
4-vinyl-3'-bromobiphenyl; 4-vinyl-
2′-bromobiphenyl; 4-vinyl-2-bromobiphenyl; halogenated vinylbiphenyls such as 4-vinyl-3-bromobiphenyl, trialkylsilylvinylbiphenyls such as 4-vinyl-4′-trimethylsilylbiphenyl, 4 -Vinyl-4'-trimethylstannylbiphenyl; trialkylstannylvinylbiphenyls such as 4-vinyl-4'-tributylstannylbiphenyl, trialkylsilylmethylvinylbiphenyl such as 4-vinyl-4'-trimethylsilylmethylbiphenyl , 4-vinyl-4'-trimethylstannylmethylbiphenyl; trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-tributylstannylmethylbiphenyl, p-chloroethylstyrene;
m-chloroethylstyrene; halogen-substituted alkylstyrene such as o-chloroethylstyrene, p-trimethylsilylstyrene; m-trimethylsilylstyrene; o-
Trimethylsilylstyrene; p-triethylsilylstyrene; m-triethylsilylstyrene; o-triethylsilylstyrene; alkylsilylstyrenes such as p-dimethyltert-butylsilylstyrene, p-dimethylphenylsilylstyrene; p-methyldiphenylsilylstyrene Phenyl group-containing silylstyrenes such as p-triphenylsilylstyrene, p-dimethylchlorosilylstyrene; p-methyldichlorosilylstyrene;
Examples thereof include halogen-containing silylstyrenes such as p-trichlorosilylstyrene; p-dimethylbromosilylstyrene; p-dimethyliodosilylstyrene, and silyl group-containing silylstyrenes such as p- (p-trimethylsilyl) dimethylsilylstyrene. These styrenic monomers may be used alone or in combination of two or more. The aluminoxane used as the catalyst component (b) is obtained by contacting an organoaluminum compound with a condensing agent, and has the general formula (IV)

[0018]

[Chemical 5]

[In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, and p represents a number of 0 to 50, preferably 5 to 30. ] And a chain aluminoxane represented by the general formula (V)

[0020]

[Chemical 6]

[Wherein R ³ is the same as above and q is 2
-50, preferably 5-30. ] Cyclic aluminoxane represented by Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, etc. Among them, trimethylaluminum is preferable. Also,
As the condensing agent, water can be mentioned as a typical one, but in addition to this, various substances such as trialkylaluminum that undergoes a condensation reaction, such as copper sulfate pentahydrate, water adsorbed to an inorganic substance or an organic substance, can be used. Can be mentioned.

In general, the contact product of an organoaluminum compound such as trialkylaluminum and water, together with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, is a mixture of unreacted trialkylaluminum and various condensation products, and Is a molecule in which these are intricately associated, and these are various products depending on the contact conditions between the trialkylaluminum and water as the condensing agent. At this time, the method of contacting the alkylaluminum compound and water is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and water is added later, and a metal salt is contained There is a method of reacting water of crystallization, water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound. The water may contain up to about 20% of ammonia, amine such as ethylamine, sulfur compound such as hydrogen sulfide, phosphorus compound such as phosphite. Although this reaction proceeds in the absence of a solvent, it is preferably carried out in a solvent, and preferable solvents include hexane, heptane,
Examples thereof include aliphatic hydrocarbons such as decane and aromatic hydrocarbons such as benzene, toluene and xylene.

In the case of using the hydrous compound after the above-mentioned catalytic reaction, the solid residue of this aluminoxane (for example, an alkylaluminoxane) is filtered off, and the filtrate is heated under normal pressure or reduced pressure at a temperature of 30 to 200 ° C. Preferably 40
At a temperature of up to 150 ° C. for 20 minutes to 8 hours, preferably 30
What was heat-treated while distilling off the solvent in the range of 5 minutes to 5 hours is preferable. In this heat treatment, the temperature may be appropriately determined depending on various situations, but it is usually performed in the above range. Generally, at a temperature of less than 30 ° C., the effect does not appear,
Further, when the temperature exceeds 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, which is not preferable. Then, depending on the treatment conditions of the heat treatment, the reaction product is obtained in the form of a colorless solid or solution. The product thus obtained can be used as a catalyst solution by dissolving or diluting it with a hydrocarbon solvent, if necessary.

A suitable example of an aluminoxane which is a contact product of an organoaluminum compound used as such a catalyst component and a condensing agent, particularly an alkylaluminoxane, is an aluminum-methyl group (Al- The high magnetic field component in the methyl proton signal region based on CH ₃ ) bond is 50% or less. That is, when the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum of the above contact product is observed in a toluene solvent at room temperature, the methyl proton signal based on “Al—CH ₃ ” is a tetramethylsilane (TMS) standard. In the range of 1.0 to -0.5 ppm. TMS
Of the proton signal (0 ppm) in the methyl proton observation region based on “Al—CH ₃ ”,
Methyl proton signal based on -CH ₃ ", TMS
Toluene's methyl proton signal 2.35 in reference
High magnetic field component (i.e., -0.1 to -0.
5 ppm) and other magnetic field components (ie 1.0 to -0.1 pp)
When it is divided into m), the high magnetic field component of 50% or less, preferably 45 to 5%, can be suitably used as the catalyst component.

Further, (c) the catalyst used as a catalyst component
Capable of reacting with transition metal compounds to form ionic complexes
There is no particular limitation on the compound, but a cation and multiple groups
A compound consisting of an anion bound to an element, ie
Compound (c) is a group IIIB, IVB, VB or VIB of the periodic table
Tribe, VIIB, VIII, IA, IB, IIA, IIB, IV
Cations containing elements selected from Group A and VIIA and multiple
Is based on the periodic table of groups VB, VIB, VIIB, VIII, IB
Group II, IIIB, IIIA, IVA and VA elements
A compound consisting of an anion bound to, especially a cation
Coordination complexation consisting of aonine with multiple groups bound to an element
Compounds can be preferably used. For example, general formula (VI)
Is (VII) ([L¹-R^Four]^{U +})_V (M²Z¹Z²... Z^e]^(ef)-)_W ... (VI) or ([L²]^{U +})_V (M³Z¹Z²... Z^e]^(ef)-)_W ... (VII) (However, L²Is M^Four, R^FiveR⁶M^Five, R⁷ ₃C or R⁸M
^Five[Wherein L¹Is Lewis base, M²And M³Is
VB group, VIB group, VIIB group, VIII group of the periodic table,
Selected from IB, IIB, IIIA, IVA, and V groups
Element, M^FourAnd M^FiveAre IIIB and IV of the periodic table, respectively
Group, V, VIB, VIIB, VIII, I, IB, II
An element selected from Group A, Group IIB and Group VIIA, Z¹~ Z^e
Are hydrogen atom, dialkylamino group and alcohol
Si group, C1-C20 alkoxy group, C6-C20
Aryloxy group, C1-C20 alkyl group, charcoal
Aryl groups, alkylaryl groups, and ants having a prime number of 6 to 20
Alkyl group, halogen-substituted hydrocarbon having 1 to 20 carbon atoms
Elementary group, C1-C20 acyloxy group, organic metalloy
Z group or halogen atom, Z¹~ Z^eHaha 2 and above
The above may be bonded to each other to form a ring. R^FourIs water
Elementary atom, C1-C20 alkyl group, C6-C20
Aryl group, alkylaryl group or arylalkyl of
R group, R^FiveAnd R⁶Are each cyclopentadiene
Nyl group, substituted cyclopentadienyl group, indenyl group or
Is a fluorenyl group, R⁷Is alkyl having 1 to 20 carbons
Group, aryl group, alkylaryl group or arylal
Indicates a kill group. R⁸Is tetraphenylporphyrin,
A macrocyclic ligand such as tarocyanine is shown. f is M ², M
³Is an integer of 1 to 7, e is an integer of 2 to 8, and u is
[L¹-R^Four], [L²] With an ionic valence of 1 to 7
Number, v is an integer of 1 or more, and w = (v × u) / (ef)
is there. ] It is a compound represented by these.

Specific examples of the Lewis base represented by L ¹ are ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, N. , N-dimethylaniline, methyldiphenylamine, pyridine; 2,
Amines such as 2′-bipyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phenanthroline, triethylphosphine,
Phosphines such as triphenylphosphine and diphenylphosphine; ethers such as dimethyl ether, diethyl ether and tetrahydrofuran dioxane; thioethers such as diethylthioether and tetrahydrothiophene; esters such as ethylbenzoate; nitriles such as acetonitrile and benzonitrile. And so on.

Also, M²And M³As a concrete example of
B, Al, Si, P, As, Sb, M, etc.^FourWith a concrete example of
Then, Li, Na, Ag, Cu, Br, I, I₃Na
Th, M^FiveAs specific examples of Mn, Fe, Co, Ni,
Zn etc. are mentioned. Z¹~ Z ^eAs a concrete example of
For example, a dimethylamino group as the dialkylamino group,
Diethylamino group; as an alkoxy group having 1 to 20 carbon atoms
Methoxy group, ethoxy group, n-butoxy group, carbon number 6
A phenoxy group as the aryloxy group of -20, 2,6
-Dimethylphenoxy group, naphthyloxy group, carbon number 1
~ 20 alkyl groups as methyl, ethyl, n-type
Ropyl group, iso-propyl group, n-butyl group, n-o
Octyl group, 2-ethylhexyl group, C6-20
Reel group, alkylaryl group or arylalk
Group as a phenyl group, p-tolyl group, benzyl group,
Interfluorophenyl group, 3,5-di (trifluoromethine)
Tyl) phenyl group, 4-tert-butylphenyl
Group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group
Phenyl group, 2,4-dimethylphenyl group, 2,3-dimethyl
Cylphenyl group, 1,2-dimethylphenyl group, carbon number
1-20 halogen-substituted hydrocarbon groups as p-fluoro
Phenyl group, 3,5-difluorophenyl group, pentac
Lolophenyl group, 3,4,5-trifluorophenyl
Group, pentafluorophenyl group, 3,5-di (triflu
Oromethyl) phenyl group, F, C as halogen atom
l, Br, I, pentamethylanti as an organic metalloid group
Mon group, trimethylsilyl group, trimethylgermyl group,
Diphenylarsine group, dicyclohexyl antimony
Group, a diphenylboron group. R^Four, R⁷Concrete
Examples include those similar to those listed above.
R^FiveAnd R⁶Specific examples of the substituted cyclopentadienyl group of
Is a methylcyclopentadienyl group, butylcyclo
Pentadienyl group, pentamethylcyclopentadienyl
Examples thereof include those substituted with an alkyl group such as a group. This
Here, the alkyl group usually has 1 to 6 carbon atoms and is not substituted.
The number of alkyl groups can be selected from an integer of 1 to 4
It

Of the compounds represented by the above general formulas (VI) and (VII), those in which M ² and M ³ are boron are preferable. Among the compounds of the general formulas (VI) and (VII), the following compounds can be used particularly preferably. For example, as the compound of the general formula (VI), triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl tetraphenylborate) are used. Ammonium, benzyltri (n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, benzyl tetraphenylborate Rumethylsulfonium, triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate , Tetra (pentafluorophenyl)
Tetraethylammonium borate, tetra (pentafluorophenyl) borate [methyltri (n-butyl) ammonium], tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], tetra (pentafluorophenyl) borate methyldiphenylammonium, tetra Methyltriphenylammonium (pentafluorophenyl) borate, Dimethyldiphenylammonium tetra (pentafluorophenyl) borate, Anilinium tetra (pentafluorophenyl) borate, Methylanilinium tetra (pentafluorophenyl) borate, Dimethyl tetra (pentafluorophenyl) borate Anilinium, trimethylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate (m-ni Roanilinium), dimethyl (p-bromoanilinium) tetra (pentafluorophenylmethyl) borate, pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N-benzylpyridinium), tetra (pentafluorophenyl) borate (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetrafelphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-
Examples thereof include dimethylanilinium ditrifluoromethylphenyl) borate and triethylammonium tow hexafluoroarsenate.

On the other hand, examples of the compound of the general formula (VII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetra (pentafluorophenyl) borate, tetra Decamethylferrocenium (pentafluorophenyl) borate, Acetylferrocenium tetra (pentafluorophenyl) borate, Formylferrocenium tetra (pentafluorophenyl) borate, Cyanoferrocenium tetra (pentafluorophenyl) borate, Tetra ( Silver pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Sodium borate, tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate , Silver hexafluoroarsenate, silver hexafluoroantimonate, and the like. And as compounds other than the general formulas (VI) and (VII), for example, tri (pentafluorophenyl) boric acid, tri [3,5-di (trifluoromethyl) phenyl] boric acid, triphenylboric acid, etc. are also used. be able to.

In the present invention, an organometallic compound can be used as the component (d) together with the catalyst component (b) or the catalyst component (c), if desired. As the (d) organometallic compound which is optionally used in combination, a compound represented by the general formula M ⁶ (R ⁹ ) _r (VIII) is used. This general formula (VIII)
In the formula, R ⁹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl having 7 to 20 carbon atoms. Indicates a group. Specifically, for example,
Examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, hexyl group, 2-ethylhexyl group and phenyl group. M ⁶ represents lithium, sodium, potassium, magnesium, zinc, cadmium, aluminum, boron, gallium, silicon or tin. Further, r represents the valence of M ⁶ . There are various compounds represented by the general formula (VIII). Specifically, alkyllithium compounds such as methyllithium, ethyllithium, propyllithium and butyllithium, alkylmagnesium compounds such as diethylmagnesium, ethylbutylmagnesium and dinormalbutylmagnesium, dimethylzinc, diethylzinc, dipropylzinc and dibutylzinc. Such as dialkylzinc compounds, alkylgallium compounds such as trimethylgallium, triethylgallium and tripropylgallium, alkylboron compounds such as triethylboron, tripropylboron and tributylboron, alkyltin compounds such as tetraethyltin, tetrapropyltin and tetraphenyltin And so on. In addition, there are various compounds when M ⁶ is aluminum. Specific examples thereof include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trioctylaluminum.

The proportion of each component used in the catalyst is not particularly limited, but when the component (b) is used as a catalyst, the molar ratio of the component (a) to the component (b) is 1: 2.
0 to 1: 10000, preferably 1: 100 to 1:20
It is preferable to use the component (b) so that it becomes 00. on the other hand,
When the component (c) is used, the molar ratio of the component (a) to the component (c) is 1: 0.01 to 1: 100, preferably 1 :.
It is preferable to use the component (c) so that the ratio is 1 to 1:10. The amount of the component (d) used as desired is usually selected in the range of 0 to 100 mol with respect to 1 mol of the component (a). By using this component (d), the polymerization activity can be improved, but even if it is used in too large an amount, the effect equivalent to the amount added is not exhibited. The component (d) may be used in contact with the contact-treated product of the component (a), the component (c) or the component (a) and the component (c). This contact may be carried out in advance, or may be sequentially added into the polymerization system for contact. The ratio of the styrene-based monomer to the catalyst used is not particularly limited, but the styrene-based monomer / transition metal compound molar ratio is usually in the range of 10 to 10 ⁹ , preferably 10 ² to 10 ^7. To be selected.

The polymerization temperature, the polymerization time, the polymerization method and the like may be appropriately selected, but usually 0 to 120.
℃, preferably 10 ~ 80 ℃, the polymerization time is 1 second ~
It may be selected within the range of 10 hours. The polymerization method may be bulk, solution or suspension polymerization. In the solution polymerization, usable solvents include aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene. Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferable. in this case,
The monomer / solvent (volume ratio) can be arbitrarily selected. In this way, (A) represented by the general formula (I)
A styrene-based block copolymer having a styrene-based polymer segment having a highly syndiotactic structure composed of a repeating unit and a polymer segment composed of a repeating unit derived from (B) an anion-polymerizable monomer is obtained. The syndiotactic structure here is
The stereochemical structure is a syndiotactic structure, that is, it has a stereostructure in which a phenyl group or a substituted phenyl group, which is a side chain, is alternately located in the opposite direction with respect to the main chain formed from carbon-carbon bonds. Tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method is the proportion of a plurality of continuous constitutional units, for example, diad in the case of 2 and triad in the case of 3.
Individual cases can be indicated by a pentad. The styrenic polymer having a high syndiotactic structure referred to in the present invention is, in the chain of styrenic repeating units, preferably 75% or more by racemic dyad, more preferably 85% or more, or preferably racemic pentad. Indicates those having a syndiotacticity of 30% or more, more preferably 50% or more. However, the degree of syndiotacticity varies slightly depending on the type of substituent.

The styrenic block copolymer contains the repeating unit (A) in a proportion of 0.05 to 99.5 mol% and has a molecular weight of 135 ° C. in 1,2,4-trichlorobenzene. The reduced viscosity at a concentration of 0.05 g / deciliter measured at a temperature of 0.01 to 20 deciliter / g
It is desirable to be in the range of. If the reduced viscosity is less than 0.01 deciliter / g, the physical properties of the polymer are not sufficiently exhibited, and if it exceeds 20 deciliter / g, the moldability becomes poor. In this styrene block copolymer, the arrangement of the repeating unit (A) and the repeating unit (B) is usually a diblock polymer of (A)-(B) or (A)-(B)-(A). It is a triblock polymer or a mixture thereof. The present invention also provides a hydrogenated block copolymer obtained by partially or completely hydrogenating the above-mentioned styrene block copolymer. The method of partial hydrogenation or complete hydrogenation is not particularly limited, and a method conventionally used in the hydrogenation of aromatic rings can be used. Specifically, the styrene block copolymer is dissolved in a suitable solvent, preferably an alicyclic hydrocarbon solvent, and Raney nickel or a hydrogenation catalyst such as palladium, ruthenium or platinum supported on carbon is dissolved in this solution. In addition, a method of heating this slurry under the pressure of hydrogen can be used. Hydrogenation temperature is usually 50-300
℃, hydrogen pressure is usually atmospheric pressure to 200kg / cm ² G
It is selected in the range of. The hydrogenated block copolymer thus obtained has a syndiotactic structure having a high stereoregularity of the partially or completely hydrogenated repeating unit (A). Further, the content of the repeating unit is 0.05
~ 99.5 mol% and measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C of 0.05 g /
It is desirable that the reduced viscosity at a concentration of deciliter is in the range of 0.01 to 20 deciliter / g. This hydrogenated block copolymer has remarkably improved solvent resistance, weather resistance, heat resistance, etc. as compared with the unhydrogenated styrene block copolymer.

[0034]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 (1) Preparation of methylaluminoxane 200 ml of toluene, 17.7 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) and trimethylaluminum were placed in a glass container having an inner volume of 500 ml and purged with argon. Twenty-four milliliters (250 mmol) were added and the reaction was carried out at 40 ° C. for 8 hours. afterwards,
From the solution obtained by removing the solid components, toluene was further distilled off under reduced pressure to obtain a contact-treated product (methylaluminoxane) 6.
7 g was obtained. The molecular weight of this product measured by the freezing point depression method was 610. Also, JP-A-62-32539
High magnetic field component by ¹ H-NMR measurement based on Japanese Patent No. ¹ ,
That is, observing the proton nuclear magnetic resonance spectrum at room temperature the toluene solution (Al-CH ₃₎ methyl proton signal based on the binding seen in the range of 1.0 to-0.5 ppm in tetramethylsilane standard. The proton signal of tetramethylsilane (0 ppm) is Al-
Because of the observation area based on the methyl proton based on the CH ₃ bond, it is measured based on the methyl proton signal 2.35ppm toluene methyl proton signal based on the Al-CH ₃ bonds in tetramethylsilane standard, high magnetic field component When divided into (ie, -0.1 to -0.5 ppm) and other magnetic field components (ie, 1.0 to -0.1 ppm), the high magnetic field component was 43% of the whole.

(2) Block precursor (polybutadiene)
Manufacture of a sufficiently dried 200 ml flask was replaced with dry nitrogen, then charged with 50 ml of toluene and 2.0 mmol of n-butyllithium, heated to 30 ° C., and then divinylbenzene (m-form 39.0 wt%). , P body 11.0
(1.0 wt%) of the m- and p-forms was diluted with toluene to 20 ml, and the solution was added dropwise over 20 minutes. After the dropping was completed, the reaction was performed for 15 minutes. Then, to this, 1,3 thoroughly dried with molecular sieve (4A)
-Introducing butadiene into the above reaction system under atmospheric pressure,
At 4 hours and 30 minutes. Thereafter, 2.0 mmol of pentamethylcyclopentadienyltrimethoxytitanium [Cp ^* Ti (OMe) ₃ ] was added thereto and reacted for 50 minutes. During this time, the introduction of 1,3-butadiene was stopped, and nitrogen was introduced instead, and unreacted 1,3
-Butadiene was released out of the system.

(3) Production of Block Copolymer 10 ml of this polymer was added to a solution of 20 ml of styrene containing 20 mmol of aluminoxane prepared in advance, and a contact reaction was carried out at 70 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into a large amount of methanol and thoroughly deashed and washed to obtain 2.80 g of a white powdery polymer. It is proved below that the obtained polymer is a block copolymer. First, in order to separate a copolymer that does not contain at least a homopolymer of 1,3-butadiene, extraction is performed using carbon tetrachloride that completely dissolves the block precursor (1,3-butadiene homopolymer). I separated. The solvent-insoluble portion thus obtained was 82 wt%, and the content of 1,3-butadiene unit was 18.7 wt as a result of ¹ H-NMR analysis.
%Met. The melting point of this product was 256.5 ° C. The melting point is DSC-200 manufactured by Seiko Denshi KK and is used in a nitrogen atmosphere according to the following profile (4)
It was determined by measuring the value observed in. (1) 30 to 305 ° C 20 ° C / min (temperature increase) (2) 305 ° C 5 minutes hold (3) 305 to 30 ° C 7 ° C / min (temperature decrease) (4) 30 to 300 ° C 20 ° C / min (rise) Temperature) Further, under the following conditions, measurement was carried out by mounting a differential refractometer as a detector on gel permeation chromatography (GPC). Apparatus: Waters ALC / GPC 150C Column: TSK HM + GMH6 × 2 Solvent: TCB (1,2,4-trichlorobenzene) Temperature: 135 ° C. As a result, a monodisperse distribution pattern having sensitivity only on the styrene side was shown. The styrene-equivalent weight average molecular weight Mw was 89500, and Mw / Mn was 2.6. In addition, by ¹³ C-NMR, phenyl C1 of styrene chain was obtained.
Has an absorption position of 145.2 ppm, which shows extremely good syndiotacticity. From the above analysis results,
It was found to be a triblock copolymer in which 1,3-butadiene chains and styrene chains having a high syndiotactic structure are chemically bonded.

Example 2 In Example 1 (2), 80 ml of toluene was added.
N-butyllithium with and without divinylbenzene
In place of 1.0 mmol of um and 1,3-butadiene
Reaction with 20 ml of Ren for 140 minutes at 20 ℃
Let Then, to this, cyclopentadienyl titanium
Mutrichloride (CpTiCl ₃) Add 1.0 mmol
And reacted for 15 minutes. After that, prepared toluene
30 ml, styrene 30 ml, aluminum
12.5 of the above polymer was added to a solution containing 20 mmol of noxane.
Add milliliter and copolymerize at 50 ℃ for 7 minutes
It was The amount of the obtained copolymer was 2.8 g. This copolymer
Was analyzed in the same manner as in Example 1 (3).
It was

Extraction fractionation was performed sufficiently with an acetone / chloroform (80/20 volume ratio) mixed solvent that completely dissolves the block precursor (polystyrene). The solvent-insoluble portion was 72 wt%. The melting point of this product is 25
9.3 ° C., weight average molecular weight determined by GPC of 54
The value of 900 and Mw / Mn was 2.07. Furthermore, ¹³ C-
According to NMR, phenyl C1 in the styrene chain was found to be 145.2
Absorption observed in atactic polystyrene was present on the near magnetic field side, which was observed at ppm. On the other hand, ¹ H-
By NMR, it was confirmed that both syndiotactic polystyrene and atactic polystyrene were present in the region corresponding to the methine and methylene protons of the main chain of polystyrene. The atactic polystyrene content of this product was 12 wt%.

Example 3 (1) Tri-n-tetra (pentafluorophenyl) borate
Preparation of butylammonium Pentafluorophenyllithium prepared from promopentafluorobenzene (152 mmol) and butyllithium (152 mmol) was reacted with 45 mmol of boron trichloride in hexane to give tri (pentafluorophenyl) boron as white. Obtained as a solid. 41 mmol of this tri (pentafluorophenyl) boron was reacted with 41 mmol of pentafluorophenyllithium to obtain lithium tetra (pentafluorophenyl) boric acid as a white solid. Then, 16 mmol of lithium tetra (pentafluorophenyl) borate and 16 mmol of tri-n-butylammonium hydrochloride are reacted in water to give tri-n-butylammonium tetra (pentafluorophenyl) borate as a white solid (12.8 mmol). I was able to get (2) Production of block copolymer with 1,3-butadiene In Example 1- (2), 10 ml of a polymer obtained by adding Cp ^* Ti (OMe) ₃ and reacting for 20 minutes was previously prepared. Prepared 100 ml of styrene, 1 mmol of triisobutylaluminum (TIBA), tetra (pentafluorophenyl) prepared in (1) above.
The solution was added to a solution containing 0.1 mmol of tri-n-butylammonium borate and copolymerized at 70 ° C. for 4 hours. The yield of the block copolymer was 3.2 g.

Example 4 The block copolymer obtained in Example 1 was placed in a decahydronaphthalene solvent at a temperature of 140 ° C. and the polymer concentration was 2 wt.
%, Hydrogen partial pressure 30 kg / cm ² G, carbon-supported ruthenium catalyst (Ru content 5 wt%) concentration 4 wt%, and reaction time 6 hours. Then, the obtained polymer was isolated from the reaction solution. No absorption based on benzene ring or butadiene was observed in the NMR spectrum and IR spectrum of this product.

[0041]

The styrenic block copolymer of the present invention comprises a styrenic polymer segment having a high syndiotactic structure and a polymer segment of an anionically polymerizable monomer. It is preferably used as an elastomer or a material such as a polymer alloy or a high impact resistance material. In addition, according to the method of the present invention, the styrenic block copolymer, particularly a high-performance triblock copolymer having a styrene-based polymer segment having a highly syndiotactic structure at both ends, can be easily produced. be able to. Furthermore, the partially or completely hydrogenated product of the styrene block copolymer of the present invention is remarkably excellent in solvent resistance, weather resistance, heat resistance and the like.

Claims (6)

[Claims] 1. (A) General formula: [In the formula, R ¹ represents a substituent containing at least ^one of a hydrogen atom, a halogen atom or a carbon atom, a tin atom and a silicon atom, m is an integer of 1 to 5, and when m is plural, R ^{1 s} may be the same or different, and R ^{1 s} may form a condensed ring with the benzene ring. ] And a repeating unit derived from an anion-polymerizable monomer (B),
Further, (A) a styrene block copolymer having a syndiotactic structure having a high stereoregularity of repeating units. 2. The content of (A) repeating units is from 0.05 to
It is in the range of 99.5 mol% and has a reduced viscosity of 0.01 to 20 deciliter / g at a concentration of 0.05 g / deciliter measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C. The styrene block copolymer according to claim 1. 3. The arrangement of (A) repeating units and (B) repeating units is (A)-(B) or (A)-(B)-
The styrenic block copolymer according to claim 1, which is (A) or a mixture of both. 4. A block copolymer obtained by partially hydrogenating or completely hydrogenating the styrene block copolymer according to claim 1, 2. 5. The partially or completely hydrogenated repeating unit (A) has a syndiotactic structure with high stereoregularity, and its content is in the range of 0.05 to 99.5 mol%. And in 1,2,4-trichlorobenzene,
The block copolymer according to claim 4, wherein the reduced viscosity at a concentration of 0.05 g / deciliter measured at a temperature of 135 ° C is 0.01 to 20 deciliter / g. 6. An anion-polymerizable monomer is polymerized in the presence of a monofunctional or polyfunctional anionic polymerization initiator to substantially form a polymer, and then the (a) transition metal compound is subjected to a catalytic reaction. Then, in the presence of a compound capable of reacting with (b) an aluminoxane or (c) the transition metal compound to form an ionic complex, the compound represented by the general formula: [In the formula, R ¹ represents a substituent containing at least ^one of a hydrogen atom, a halogen atom or a carbon atom, a tin atom and a silicon atom, m is an integer of 1 to 5, and when m is plural, R ^{1 s} may be the same or different, and R ^{1 s} may form a condensed ring with the benzene ring. ] The block copolymerization with the styrene-type monomer represented by these is carried out, The manufacturing method of the styrene-type block copolymer of Claim 1, 2 or 3 characterized by the above-mentioned.