JPH05320251A - Styrene polymer, production thereof, and multilayer material comprising the same - Google Patents

Abstract

PURPOSE:To produce a styrene polymer having a compatibility and an adhesive power by polymerizing a styrene monomer in the presence of a specific catalyst and introducing functional groups into molecular ends of the resulting polymer. CONSTITUTION:A styrene monomer of formula I (wherein R<1> is H, halogen, or a group having at least one kind of atom selected from the group consisting of C, Sn, and Si; and m is 1-5 provided that if m is plural, R<1> may form a condensed ring with the benzene ring) is polymerized in the presence of a catalyst mainly comprising a transition metal compd. and aluminoxane or a catalyst mainly comprising a transition metal compd. and a compd. which reacts with the transition metal compd. to form an ionic complex. The resulting polymer is reacted with a compd. having a halogen or active hydrogen atom and at least one kind of group selected from the group consisting of O, N, S, P and halogen, and CO2 or H2S to give a styrene polymer which has a reduced viscosity (in 1,2,4-trichlorobenzene, at 135 deg.C, in a concn. of 0.05g/dl) of 0.01-20dl/g and a syndiotactic structure comprising repeating units of formula II and terminated with functional groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel styrene polymer, a method for producing the same, and a multilayer material using the styrene polymer. More specifically, the present invention provides
An end-functionalized styrenic polymer having a high syndiotactic structure, which retains the crystallinity characteristic of syndiotactic polystyrene, and is provided with compatibilizing ability and adhesive ability, and a method for efficiently producing the same, and The present invention relates to a multilayer material using the styrene polymer.

[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 research group of the present inventors has succeeded in developing a styrene-based polymer having a high syndiotactic structure so far by solving such drawbacks of the styrene-based polymer having an atactic structure. A styrene-based copolymer in which a styrene-based monomer and another monomer are copolymerized has also been developed (JP-A-62-104).
No. 818, No. 62-187708, No. 63-
No. 241009). These polymers are excellent in heat resistance, chemical resistance and electrical properties, and are expected to be applied in various fields. However, syndiotactic polystyrene has drawbacks such as poor compatibility with other resins and almost no adhesion to metals and the like. By the way, a copolymer of unsaturated carboxylic acid ester and the like and syndiotactic polystyrene is known (JP-A-3-7705, Japanese Patent Application Nos. 2-314327 and 3-89509). .. However, these copolymers have high crystallinity when the content of comonomer is low. However, when the content of comonomer is increased, an amorphous polymer is formed and syndiotactic polystyrene Mechanical properties, thermal properties, and chemical properties cannot be fully utilized. Therefore, in order to maintain a high degree of syndiotacticity, there is a limit to the amount of comonomer that can be copolymerized, and materials that utilize the characteristics of syndiotactic polystyrene by combining with other thermoplastic resins and fillers can be used. It has the drawback that it cannot be obtained over a wide area. It is also possible to use a resin compatibilizer as the third component, but the molding temperature of syndiotactic polystyrene is high, and there is no suitable one, and the addition of the third component may lead to a decrease in performance. Not preferable.

[0003]

Under the above circumstances, the present invention maintains the crystallinity inherent in the styrene resin having a syndiotactic structure, and at the same time, has a high degree of compatibility and adhesion. It was made for the purpose of developing a styrene polymer having a syndiotactic structure.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a highly syndiotactic compound having a terminal functional group and having a reduced viscosity in a specific range is used. It has been found that a styrenic polymer having a structure can meet the purpose. The present invention has been completed based on such findings. That is, the 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. ] A styrene-based polymer having a functional group at the terminating end of the structural unit represented by
0.0 measured at a temperature of 135 ° C. in trichlorobenzene
Reduced viscosity of 0.01 to 20 at a concentration of 5 g / deciliter
Provided is a styrene-based polymer having a syndiotactic structure which has a high degree of stereoregularity of the chain of the structural units while having a deciliter / g, and provides a multilayer material having at least one layer of the styrene-based polymer. To do. Furthermore, the present invention provides the compound of general formula (II)

[0007]

[Chemical 4]

[R ¹ and m in the formula are the same as above]
And (b) a catalyst containing (a) a transition metal compound and (b) an aluminoxane as a main component, or (b) (a) a transition metal compound and (c) the transition metal compound. Polymerization is performed in the presence of a catalyst containing a compound capable of reacting to form an ionic complex as a main component, and a polymer is substantially formed. Then, the polymer has a halogen atom or active hydrogen, and has an oxygen atom and a nitrogen atom. A method for producing the styrene-based polymer by reacting a compound having a substituent containing at least one selected from an atom, a sulfur atom, a phosphorus atom and a halogen atom, or carbon dioxide or carbon disulfide Is provided.

Examples of the styrene-based monomer represented by the general formula (II) used as a raw material for the styrene-based polymer of the present invention include styrene; p-methylstyrene;
-Methyl styrene; m-methyl styrene; 2,4-dimethyl styrene; 2,5-dimethyl styrene; 3,4-dimethyl styrene; 3,5-dimethyl styrene; alkyl styrene such as p-tert-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-vinylbiphenyl; 3-vinylbiphenyl; vinylbiphenyl such as 2-vinylbiphenyl 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; vinylphenylanthracenes such as 9- (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; vinylphenylphenanthrenes such as 9- (2-vinylphenyl) -phenanthrene, 1- (4-vinylphenyl) -pyrene;
2- (4-vinylphenyl) -pyrene; 1- (3-vinylphenyl) -pyrene; 2- (3-vinylphenyl)-
Pyrene; 1- (2-vinylphenyl) -pyrene; 2-
Vinylphenylpyrenes such as (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;
Vinyl terphenyls such as 2-vinyl-o-terphenyl, vinyl phenyl terphenyls such as 4- (4-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'-
4-vinyl-3'-chlorobiphenyl;4-vinyl-2'-chlorobiphenyl;4-vinyl-2-chlorobiphenyl;4-vinyl-3-chlorobiphenyl;4-vinyl-4'-bromobiphenyl4-vinyl-3'-bromobiphenyl;4-vinyl-2'-bromobiphenyl;4-vinyl-2-bromobiphenyl;
Halogenated vinyl biphenyls such as 4-vinyl-3-bromobiphenyl, trialkylsilyl vinyl biphenyls such as 4-vinyl-4′-trimethylsilyl biphenyl, 4-vinyl-4′-trimethylstannyl biphenyl; 4-vinyl- Trialkylstannylvinylbiphenyls such as 4′-tributylstannylbiphenyl, trialkylsilylmethylvinylbiphenyls such as 4-vinyl-4′-trimethylsilylmethylbiphenyl, 4-vinyl-4′-trimethylstannylmethylbiphenyl; Trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4′-tributylstannylmethylbiphenyl, p-chloroethylstyrene; m-chloroethylstyrene; halogen-substituted alkylstyrenes such as o-chloroethylstyrene , P- trimethylsilylstyrene; m-trimethylsilyl styrene; o-trimethylsilyl styrene; p-triethylsilyl styrene;
m-triethylsilylstyrene; o-triethylsilylstyrene; alkylsilylstyrenes such as p-dimethyltertiary-butylsilylstyrene; p-dimethylphenylsilylstyrene; p-methyldiphenylsilylstyrene; p-triphenylsilylstyrene Phenyl group-containing silylstyrenes, p-dimethylchlorosilylstyrene; p-methyldichlorosilylstyrene; p-trichlorosilylstyrene; p-dimethylbromosilylstyrene; p-dimethyliodosilylstyrene and other halogen-containing silylstyrenes, p- Examples include silyl group-containing silylstyrenes such as (p-trimethylsilyl) dimethylsilylstyrene. These styrene-based monomers may be used alone or in combination of two or more.

In order to produce the styrenic polymer of the present invention, a catalyst containing (a) a transition metal compound (a) and (b) an aluminoxane as main components, or (b)
A compound containing, as a main component, a compound capable of reacting with (a) a transition metal compound and (c) a transition metal compound to form an ionic complex is used. There are various transition metal compounds of the above-mentioned component (a), but the general formula (III) M ¹ R ² ... R ^k ... (III) [wherein, M ¹ is Ti , Zr, Cr, V, Nb, Ta or Hf, 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; An aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group;
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;
Examples of chain unsaturated hydrocarbons include amines such as 2,2′-bipyridine and phenanthroline, and phosphines such as triethylphosphine and triphenylphosphine.
Examples of cyclic unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene and cyclooctatetraene. Examples thereof include ene and derivatives thereof. Examples of the covalent bond include methylene bridge, dimethylmethylene bridge,
Examples include ethylene crosslinks, dimethylsilylene crosslinks, and dimethylstannylene crosslinks.

Specific examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium 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 (III), specific examples of zirconium compounds 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,
It is possible to use the transition metal compound supported on a carrier such as a magnesium compound or a silicon compound,
A compound obtained by modifying the above transition compound with an electron donating compound can also be used. Particularly preferable among these transition metal compounds are titanium compounds and zirconium compounds. For the (a) catalyst, (b) aluminoxane is used together with the (a) transition metal compound. This aluminoxane is obtained by contacting an organoaluminum compound with a condensing agent, and has the general formula (IV)

[0016]

[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)

[0018]

[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 with water is a mixture of unreacted trialkylaluminum and various condensation products, together with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane. 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 this aluminoxane (for example, alkylaluminoxane), when a hydrous compound or the like is used after the above-mentioned catalytic reaction, the solid residue 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.

The (b) catalyst includes the above-mentioned (a) transition metallization
Together with the compound, reacts with the transition metal compound (c) to form an ion
A compound capable of forming a sex complex is used. To this compound
There is no particular limitation, but the cation and multiple groups are elements.
A compound consisting of an anion bound to
(C) is IIIB group, VB group, VIB group, VIIB group, VI of the periodic table
Group II, IA, IB, IIA, IIB, IVA and VIIA
A cation containing an element selected from
VB, VIB, VIIB, VIII, IB, IIB, IIIA
Anio bonded to an element selected from Group A, Group IVA and Group VA
Compounds consisting of cations, especially cations and multiple groups
A coordination complex compound composed of bound aonine is preferably used
You can For example, general formula (VI) or (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 alkoxy
Group, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, C1-C20 alkyl group, carbon
Number 6 to 20 aryl group, alkylaryl group, aryl
Alkyl group, halogen-substituted hydrocarbon having 1 to 20 carbon atoms
Group, acyloxy group having 1 to 20 carbon atoms, organic metalloid
A group or a halogen atom, Z¹~ Z^eHaha 2 or more
May combine with each other to form a ring. R^FourIs hydrogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or arylalkyl
Group, R^FiveAnd R⁶Are each cyclopentadiene
Group, substituted cyclopentadienyl group, indenyl group or
Fluorenyl group, R⁷Is an alkyl group having 1 to 20 carbon atoms,
Aryl group, alkylaryl group or arylalkyl
Indicates a group. R⁸Is tetraphenylporphyrin, phthalo
A macrocyclic ligand such as cyanine is shown. f is M², M³of
The valence is an integer of 1 to 7, e is an integer of 2 to 8, and u is [L¹
-R^Four], [L ²] Is an integer of 1 to 7 in the valence number, and v is
An integer of 1 or more, w = (v × u) / (ef). ]
Is a compound represented by.

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

Among the compounds represented by the general formulas (VI) and (VII), those in which M ² and M ³ are boron are preferable. Among the compounds represented by 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 can be used. Ammonium, benzyltri (n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), tetraphenylborate trimethylsulfonium, tetraphenylborate benzene 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 as the component (d) can be used in combination with the catalyst (a) or the catalyst (b) if desired. As the (d) organometallic compound optionally used in combination, a compound represented by the general formula M ⁶ (R ⁹ ) _r ... (VIII) is used. In this general formula (VIII), 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 a carbon atom. Number 7
~ 20 aralkyl groups are shown. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group,
Examples thereof include n-butyl group, i-butyl group, hexyl group, 2-ethylhexyl group and phenyl group. And M
⁶ is lithium, sodium, potassium, magnesium,
Zinc, cadmium, aluminum, boron, gallium,
Indicates 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. Also, M ⁶ is
There are various compounds in the case of aluminum. Specific examples thereof include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trioctylaluminum.

Regarding the use ratio of each component in the catalyst,
Is not particularly limited, but in the (a) catalyst,
The molar ratio of the component (a) and the component (b) is 1:20 to 1: 1.
0000, preferably 1: 100 to 1: 2000
It is better to use both components. On the other hand, for (b) catalyst
Then, the molar ratio of the component (a) and the component (c) is 1: 0.0.
1 to 1: 100, preferably 1: 1 to 1:10
It is better to use both components of sea urchin. In this case, with (a) component
Component (c) is contacted in advance, and the contact-treated product is separated and washed.
It may be used as a polymer or may be contacted in the polymerization system. Also,
Used in (a) catalyst or (b) catalyst as desired
The amount of the component (d) used is relative to 1 mol of the component (a).
Then, it is usually selected in the range of 0 to 100 mol. this
By using the component (d), the polymerization activity is improved.
Can be used, but it is equivalent to the amount added if too much is used
The effect does not appear. The component (d) is composed of (a)
Min, the contact between the (c) component or the (a) component and the (c) component
You may use it by making it contact with a touch-treated product. This contact is
It may be contacted, or added sequentially to the polymerization system to make contact.
May be. Also, the usage ratio of styrene monomer and catalyst
There is no particular limitation about, but usually styrene monomer /
The molar ratio of the transition metal compound is 10 to 10⁹, Preferably 1
0 ²-10⁷Chosen to be in the range.

To produce the styrenic polymer of the present invention, the styrenic monomer is first polymerized in the presence of any of the above catalysts. At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent and the like may be appropriately selected. Usually -50 to 200 ° C, preferably 30 to 100
At a temperature of ° C, 1 second to 10 hours, preferably 1 minute to
Polymerization is performed for about 6 hours. Further, as the polymerization method,
Any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane, etc., may be used alone or in combination. Can be used in combination. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like.

In the present invention, after the polymer is substantially produced in this manner, the functionalization treatment of the polymerization end is performed. In this functionalization treatment, the resulting polymer has a substituent having a halogen atom or active hydrogen and containing at least one selected from oxygen atom, nitrogen atom, sulfur atom, phosphorus atom and halogen atom. It is carried out by reacting a compound or carbon dioxide or carbon disulfide. Examples of the compound having the above-mentioned substituent include 4-bromophenethyl alcohol, 4-bromophenol, 3-bromo-1-propanol, 2-bromobenzyl alcohol, 4-bromo-2,6-dimethylphenol, 2-bromo. Halogen-substituted alcohols and phenols such as ethanol and 4-bromo-2-naphthol,
α-bromo-p-toluic acid, o-bromobenzoic acid, m
-Bromobenzoic acid, p-bromobenzoic acid, succinic anhydride, 2-bromo-n-butyric acid, 6-bromohexanoic acid, α
Carboxylic acids such as -bromoisobutyric acid, 2-bromoisobutyric acid, 2-bromopropionic acid, 3-bromopropionic acid, 11-bromoundecanoic acid, 5-bromovaleric acid, chloroacetic acid and bromoacetic acid, and ester compounds thereof, o
-Bromobenzonitrile, m-bromobenzonitrile,
p-bromobenzonitrile, α-bromotolunitrile,
Nitriles such as 3-bromopropionitrile and 4-bromobutyronitrile, bromoacetone, α-bromoacetophenone, 1-bromo-2-butanone, 2′-bromoacetophenone, 3′-bromoacetophenone, 4-bromoacetophenone Such as ketones, ethers such as o-bromoanisole, epichlorohydrin, 4-bromodiphenyl ether, epibromohydrin, 2-bromoethylethyl ether, bromomethyl ether, o-
Amines such as bromoaniline, m-bromoaniline, p-bromoaniline, 4-bromo-N, N-dimethylaniline, 2-bromo-4-methylaniline, 3-bromophenylhydrazine hydrochloride and 3-bromopropylamine , Nitro compounds such as o-bromonitrobenzene, 2
-Sodium bromosulfonate, sulfonic acids such as 2-bromosulfonic acid, 4-bromo-1-butene, 2-bromo-2-butene, 5-bromo-1-pentene, 3-bromo-1-propene, 3- Chloro-1-propene, 3-
Examples thereof include olefins such as bromo-1-propene and chloromethylstyrene, acetylenes, halogen compounds such as bromodichloromethane, acid chlorides such as bromoacetyl chloride and m-bromobenzoyl chloride, and further isocyanate compounds. These compounds are
One kind may be used, or two or more kinds may be used in combination.

There are no particular restrictions on the conditions for the functionalization of the polymerization ends, but it is usually -80 to 100 ° C., preferably −
The reaction may be performed at a temperature of 30 to 80 ° C. for about 0.1 second to 3 hours, preferably about 1 second to 1 hour. The amount of the terminal functionalizing agent used is usually 1 mol of the transition metal compound.
It is selected in the range of 0.1 to 10 ⁶ mol, preferably 1 to 10 ⁴ mol. In this way, end-functionalized styrenic polymers with a high degree of syndiotactic structure are obtained.
The syndiotactic structure here means that the stereochemical structure is a syndiotactic structure, that is, a phenyl group or a substituted phenyl group, which is a side chain with respect to the main chain formed from a carbon-carbon bond, is alternately located in opposite directions. The tacticity is determined by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ¹³ C
The tacticity measured by the NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2, triad in the case of 3 and pentad in the case of 5. The styrene-based polymer having a high syndiotactic structure referred to in the present invention means, in the chain of styrene-based repeating units, preferably 75% or more, more preferably 85% as a racemic dyad.
Or more, or racemic pentads having a syndiotacticity of preferably 30% or more, more preferably 50% or more. However, the degree of syndiotacticity varies slightly depending on the type of substituent.

The molecular weight of the styrenic polymer of the present invention is such that the reduced viscosity at a concentration of 0.05 g / deciliter measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C. is 0.01 to 20 deciliter. It is necessary to be in the range of / g. If this reduced viscosity is less than 0.01 deciliter / g, the physical properties of the polymer will not be sufficiently exhibited. On the other hand, when it exceeds 20 deciliter / g, the moldability becomes poor. The multilayer material of the present invention has at least one layer composed of the terminally functionalized styrenic polymer having the above-mentioned highly syndiotactic structure, and there are no particular restrictions on the material of the other layers, and for example, thermal Any of a plastic resin, a thermosetting resin, a metal and other materials can be used. Various types of thermoplastic resins,
For example, a polyolefin resin, a polystyrene resin, a condensation polymer, an addition polymerization polymer, etc. may be mentioned. Specific examples of the polyolefin resin include high-density polyolefin, low-density polyethylene, poly-3-methyl-butene-1; poly-4-methyl-pentene-1, or butene-1 as a comonomer component; hexene-1; Linear low-density polyethylene obtained by using octene-1; 4-methylpentene-1; 3-methylbutene-1 and the like, chemically modified products thereof, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer Examples thereof include saponified products, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ethylene-based ionomer polypropylenes, and chemically modified products thereof. Specific examples of the polystyrene resin include general-purpose polystyrene, isotactic polystyrene and other syndiotactic polystyrene, and high-impact polystyrene (rubber modified). Specific examples of the condensation type polymer include polyacetal resin, polycarbonate resin, polyamide resin such as nylon 6, nylon 6.6, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resin, polyimide resin, polysulfone resin. , Polyethersulfone resin, polyphenylene sulfide resin and the like. Examples of the addition polymerization type high molecular weight polymer include, for example, a polymer obtained from a polar vinyl monomer or a polymer obtained from a diene type monomer, specifically, polymethylmethacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, Examples thereof include an acrylonitrile-butadiene-styrene copolymer, a diene polymer in which a diene chain is hydrogenated, and a thermoplastic elastomer.

As the thermosetting resin, for example, phenol resin, epoxy resin, unsaturated polyester resin,
Alternatively, these fiber-reinforced materials may be used. on the other hand,
Examples of the metal material include aluminum, copper, iron, nickel, tin, chromium, silver, stainless steel, duralumin, brass, and the like. Other materials include, for example, ceramics, glass, paper, fiber, cloth, wood. And so on. These materials may be used alone or in combination of two or more depending on the purpose of use. The shape and state of each layer or part constituting the multilayer material of the present invention are various, and examples include film-shaped, sheet-shaped, fiber (woven fabric, non-woven fabric) -shaped, various molded bodies, sintered bodies, simple bodies, and the like. There are crystals, foams, and porous materials. Further, there is no particular limitation on the method of forming each material into multiple layers, and various conventional methods may be used. For example, when the other material is a thermoplastic resin, a coextrusion method, a lamination method, a pressing method or the like is used, and when the other material is a metal, particularly when the metal to be laminated is a relatively thin one. For this, a lamination method, a metal vapor deposition method, an electrostatic coating method or the like is used. Further, in the case of laminating on a molded body or a thick material, a method of coating the surface by heat fusion, impregnation, coating or the like of a film or sheet can be used.
The multilayer material of the present invention may have various shapes and modes, for example, a film, a sheet, a fiber, a cloth, a molded body, a sintered body, a single crystal, a foam or a porous body. Layers made of the styrene-based polymer, which are laminated, impregnated or coated by coating, or a composite thereof. Further, the multilayer material of the present invention is widely used in various fields such as films, sheets (particularly stampable sheets), containers and packaging materials, automobile parts, electric / electronic parts and the like.

[0035]

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) Polymerization of p-methylstyrene In a three-necked flask having an internal volume of 1 liter, under a nitrogen atmosphere,
150 ml of toluene, prepared by the above (1)
Cylaluminoxane 40 mmol, p-methylstyrene
20 ml was added and the temperature was raised to 80 ° C. 80 ° C
After holding for 5 minutes, cyclopentadienyl titanium
Mutrimethoxide [CpTi (OMe) ₃] 100 My
Cromol was added to initiate the polymerization. Polymerize for 8 minutes
After that, 1 into the terminator (terminal functionalizing agent) shown in Table 1
/ 4 each, react for 1 minute, then add methanol
Deactivated. The results are shown in Table 1.

[0037]

[Table 1]

Note) Solvent toluene 30 ml, temperature 40-50 ° C. Reduced viscosity is 135 in 1,2,4-trichlorobenzene
Measured at a concentration of 0.05 g / deciliter measured at a temperature of ° C.

As shown in Table 1, absorption due to carboxylic acid was observed in the infrared absorption spectrum. ¹³ C-
As a result of NMR analysis, the C ₁ carbon signal was 142.1 pp.
m was confirmed, and it was confirmed to have a syndiotactic structure.

Examples 2-4 Under the conditions shown in Table 2, end-functionalized syndiotactic polystyrene was produced.

[0041]

[Table 2]

[0042]

[Table 3]

Note) Toluene: 50 ml, styrene: 8 ml, methylaluminoxane: 3.75 mmol, CpTiCl ₃ (cyclopentadienyltitanium trichloride): 10 μmol, temperature: 70 ° C.

A small amount of each polymer was dissolved in toluene, and the mixture was developed by thin layer chromatography using hexane / chloroform (50/50 volume ratio) as a developing solution. In each case, the R _f value was smaller than that of the syndiotactic polystyrene that was not used. Therefore, Example 2
The polymer obtained in 4 was found to have a higher polarity than normal syndiotactic polystyrene and is believed to be end-functionalized.

Examples 5-7 High molecular weight end-functionalized syndiotactic polystyrene was prepared under the conditions shown in Table 3. Although the solvent resistance was high and the terminals could not be confirmed as shown in Examples 2 to 4, it can be presumed that the terminals were similarly functionalized.

[0046]

[Table 4]

Note) Toluene: 50 ml, Styrene: 10 ml, Methylaluminoxane: 3
Mmol Cp ^* Ti (OMe) ₃ (pentamethylcyclopentadienyltrimethoxide): 5 μmol Temperature: 70 ° C.

[0048]

[Table 5]

Example 8 (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 epichlorohydrin-terminated syndiotactic polystyrene 150 ml of toluene and 200 ml of styrene were added at room temperature to a dry container under an argon atmosphere, and triisobutylaluminum (TIBA) as a catalyst component was added. 5 mmol was added and the mixture was allowed to stand for 30 minutes.
Thereafter, 5 μmol of tri-n-butylammonium tetra (pentafluorophenyl) borate and 5 μmol of pentamethylcyclopentadienyltrimethyltitanium prepared in (1) above were added, and a polymerization reaction was carried out for 2 hours. Then, add 2 mmol of epichlorohydrin,
Reacted for 10 minutes. After completion of the reaction, add methanol,
The reaction was stopped, the mixture was filtered, and then washed with methanol three times. It was dried under reduced pressure to obtain 79 g of a polymer. This polymer had a reduced viscosity of 1.92 deciliter / g and a melting point of 269 ° C in 1,2,4-trichlorobenzene at a concentration of 0.05 g / deciliter measured at a temperature of 135 ° C. Further, since the high molecular weight was the same as in Examples 5 to 7, the terminal was not confirmed, but it can be inferred that the terminal was functionalized similarly.

Example 9 (multilayer material) A sheet of nylon 6.6 (trade name: 202B) manufactured by Ube Industries, Ltd. (size: 5 × 5) was placed on a 5 × 5 × 0.2 cm mold.
X 0.1 cm), and the powder of the terminal-modified syndiotactic polystyrene obtained in Example 8- (2) was uniformly and tightly packed therein. Heat this to 290 ° C on a press plate,
Melt processed for 5 minutes. Then, it cooled and obtained the multilayer material which consists of nylon and syndiotactic polystyrene. The adhesive state of the interface of this product was good.

[0052]

The styrenic polymer of the present invention has a high degree of syndiotactic structure and is functionalized at the end, and retains the crystallinity characteristic of syndiotactic polystyrene. It has excellent adhesiveness and compatibilizing ability, and is suitably used, for example, in fields requiring adhesiveness with metals (evaporated film, multilayer material).

Claims (4)

[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. ] A styrene-based polymer having a functional group at the terminating end of the structural unit represented by the following formula, which has a reduced viscosity at a concentration of 0.05 g / deciliter measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C. Is 0.01 to 20 deciliters / g, and the styrene polymer has a syndiotactic structure in which the stereoregularity of the chain of the structural units is high. 2. The functional group at the terminal position is at least one selected from a carboxylic acid group, a carboxylic acid ester group, a hydroxyl group, a halogen, a cyano group, a nitro group, an amino group, an ether group and a thioether group. 1. The styrene-based polymer described in 1. 3. 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. ] The styrene-based monomer represented by
A catalyst containing a transition metal compound and (b) an aluminoxane as a main component, or (b) containing (a) a transition metal compound and (c) a compound capable of reacting with the transition metal compound to form an ionic complex. Polymerized in the presence of a catalyst, substantially
After the polymer is formed, it has a halogen atom or active hydrogen, and has an oxygen atom, a nitrogen atom, a sulfur atom,
A compound having a substituent containing at least one selected from a phosphorus atom and a halogen atom, or carbon dioxide or carbon disulfide is reacted.
Or the method for producing a styrene-based polymer according to item 2. 4. A multilayer material having at least one layer comprising the styrene-based polymer according to claim 1.