JP3026678B2 - Styrene polymer, method for producing the same, and multilayer material using the polymer - Google Patents

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
While retaining the crystallinity characteristic of syndiotactic polystyrene, a terminally functionalized styrenic polymer having a high syndiotactic structure imparted with compatibilizing ability and adhesion ability, and a method for efficiently producing the same, and The present invention relates to a multilayer material using the styrene-based polymer.

[0002]

2. Description of the Related Art Conventionally, a styrene-based polymer produced by a radical polymerization method or the like is molded into various shapes by various molding methods, and is used for household electric appliances, office equipment, household goods, packaging containers, toys, Although widely used as furniture, synthetic paper, and other industrial materials, it has a drawback that its three-dimensional structure has an atactic structure and is inferior in 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 as a solution to the disadvantage of the styrene-based polymer having an atactic structure, and further developing this polymer. A styrenic copolymer in which a styrenic monomer and another monomer are copolymerized has also been developed (JP-A-62-104).
Nos. 818, 62-187708, 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 the disadvantages of poor compatibility with other resins and little adhesion to metals and the like. Incidentally, copolymers of unsaturated carboxylic acid esters and the like and syndiotactic polystyrene are known (JP-A-3-7705, JP-A-2-314327, JP-A-3-89509). . However, these copolymers, when the comonomer content is low, a highly crystalline copolymer is obtained, but when the comonomer content is increased, an amorphous polymer is generated, and syndiotactic polystyrene Mechanical, thermal, and chemical properties cannot be fully utilized. Therefore, in order to maintain high syndiotacticity, the amount of comonomers that can be copolymerized is limited, and materials that take advantage of the characteristics of syndiotactic polystyrene by complexing with other thermoplastic resins and fillers are used. There is a disadvantage that it cannot be obtained in a wide range. It is also conceivable to use a resin compatibilizing agent as the third component, but the molding temperature of syndiotactic polystyrene is high, not only there is no suitable one, but there is a possibility that the addition of the third component may lower the performance, Not preferred.

[0003]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention provides a high degree of synthiotactic styrenic resin which retains its inherent crystallinity and has a compatibilizing ability and an adhesive ability. The purpose of the present invention is to develop a styrenic polymer having a syndiotactic structure.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a highly syndiotactic having a terminal functional group and a reduced viscosity in a specific range. It has been found that a styrenic polymer having a structure can be suitable for the purpose. The present invention has been completed based on such findings. That is, the present invention provides a compound represented by the general formula (I)

[0005]

Embedded image

[Wherein, 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, 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 together with a benzene ring. A styrenic polymer having a functional group at the terminal end of the structural unit represented by the formula:
0.0 measured in trichlorobenzene at a temperature of 135 ° C.
The reduced viscosity at a concentration of 5 g / deciliter is 0.01 to 20.
The present invention provides a styrene-based polymer having a syndiotactic structure having a deciliter / g and a high stereoregularity of a chain of the structural unit, and a multilayer material having at least one layer made of the styrene-based polymer. Is what you do. Further, the present invention provides a compound represented by the general formula (II):

[0007]

Embedded image

[Wherein R ¹ and m are the same as above]
A (a) a transition metal compound and (b) a catalyst containing aluminoxane as main components, or (b) a (a) transition metal compound and (c) the transition metal compound. Polymerization is carried out in the presence of a catalyst containing a compound capable of forming an ionic complex by reaction as a main component to substantially form a polymer, which has a halogen atom or active hydrogen, an oxygen atom, nitrogen 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. To provide.

The styrene monomer represented by the general formula (II) used as a raw material of the styrene polymer of the present invention includes, for example, styrene; p-methylstyrene;
2,4-dimethylstyrene; 3,4-dimethylstyrene; 3,5-dimethylstyrene; alkylstyrene such as p-tert-butylstyrene, p-methylstyrene;
Chlorostyrene; m-chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene;
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
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
-(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-
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, vinylphenyl 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;
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; trialkylsilylvinyl biphenyls such as 4-vinyl-4'-trimethylsilylbiphenyl;4-vinyl-4'-trimethylstannylbiphenyl; 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-dimethyltert-butylsilylstyrene, p-dimethylphenylsilylstyrene; p-methyldiphenylsilylstyrene; p-triphenylsilylstyrene and the like. Phenyl group-containing silylstyrenes, p-dimethylchlorosilylstyrene; p-methyldichlorosilylstyrene; p-trichlorosilylstyrene; p-dimethylbromosilylstyrene; halogen-containing silylstyrenes such as p-dimethyliodosilylstyrene; Examples thereof include silyl group-containing silylstyrenes such as (p-trimethylsilyl) dimethylsilylstyrene. These styrene 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 comprising (a) (a) a transition metal compound and (b) an aluminoxane as main components, or (b)
A compound mainly composed of (a) a transition metal compound and (c) a compound capable of forming an ionic complex by reacting with the transition metal compound is used. There are various types of the transition metal compound as the component (a), but preferably, the general formula (III) M ¹ R ² ... R ^k (III) wherein M ¹ is Ti , Zr, Cr, V, Nb, Ta or Hf, wherein 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, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms;
Acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, acetylacetonate group, substituted acetylacetonate group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen molecule, Lewis base, chain unsaturated Ligands such as hydrocarbon or cyclic unsaturated hydrocarbon, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group,
It represents a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. K represents the valence of the metal, and usually represents an integer of 2 to 5].

Here, examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadi An enyl group and a trimethylsilylcyclopentadienyl group. Further, 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,
An iodine atom; examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an octyl group, and a 2-ethylhexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group. Examples of the aryl group having 6 to 20 carbon atoms, and examples of the alkylaryl group and the arylalkyl group include a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of the acyloxy group having 1 to 20 carbon atoms, such as a group, include a heptadecylcarbonyloxy group, a substituent containing a silicon atom, such as a trimethylsilyl group and a (trimethylsilyl) methyl group; and Lewis bases, such as 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 such as amines such as 2,2′-bipyridine and phenanthroline, and phosphines such as triethylphosphine and triphenylphosphine include
Examples of cyclic unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene, and derivatives thereof include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, and cyclooctatetra. And ene and derivatives thereof. Examples of the crosslink by a covalent bond include a methylene bridge, a dimethylmethylene bridge,
Ethylene crosslinking, dimethylsilylene crosslinking, dimethylstannylene crosslinking and the like can be mentioned.

Specific examples of the titanium compound include tetramethoxytitanium, tetraethoxytitanium, tetra-n
-Butoxytitanium, tetraisopropoxytitanium, titanium tetrachloride, titanium trichloride, titanium dichloride, titanium hydride, cyclopentadienyltrimethyltitanium, cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadi Enyltributyltitanium, methylcyclopentadienyltrimethyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium Titanium, pentamethylcyclopentadienyl tributyl titanium, cyclopentadienyl methyl titanium dichloride, cyclopentadienyl ethyl titanium dichloride, pentamethyl cyclopen 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 Enylmethoxytitanium dichloride, cyclopentadienyldimethoxytitanium chloride, pentamethylcyclopentadienylmethoxytitanium 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 the zirconium compound in which M ¹ is zirconium include dicyclopentadienyl zirconium dichloride, tetrabutoxy zirconium, zirconium tetrachloride, Phenyl zirconium, cyclopentadienyl zirconium trimethoxide, pentamethylcyclopentadienyl zirconium trimethoxide, cyclopentadienyl tribenzyl zirconium,
Pentamethylcyclopentadienyl tribenzyl zirconium, bisindenyl zirconium dichloride, zirconium dibenzyl dichloride, zirconium tetrabenzyl, tributoxy zirconium chloride, triisopropoxy zirconium chloride, (pentamethyl cyclopentadienyl) trimethyl zirconium, (pentamethyl (Cyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) trichlorozirconium, (Cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethylzil , (Methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclo (Pentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, bis (cyclopentadienyl) dimethylzirconium, bis ( Cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzyl Zirconium,
Bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) ) Dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium , Bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclo (Natadienyl) 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) dimethyl zirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-fluorenyl) (cyclo Pentadienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3
5-trimethylcyclopentadienyl) dimethyl zirconium and the like.

Specific examples of the hafnium compound include cyclopentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyl tribenzyl hafnium, pentamethylcyclopentadienyl 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. Specific examples of vanadium include:
Vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclo Pentadienyl vanadium dichloride, cyclopentadienyl vanadium dichloride, dicyclopentadienyl methyl vanadium and the like can be mentioned. Specific examples of the niobium compound include:
Examples include niobium pentachloride, tetrachloromethyl niobium, dichlorotrimethyl niobium, dicyclopentadienyl niobium dichloride, dicyclopentadienyl niobium trihydride, pentaboxyniobium and the like. Specific examples of the tantalum compound include tantalum pentachloride, dichlorotrimethyl tantalum, dicyclopentadienyl tantalum trihydride, and pentabutoxy niobium. Specific examples of the chromium compound include chromium trichloride, tetrabutoxychrome, and the like.
Tetramethylchromium, dicyclopentadienylchromium,
Dibenzene chromium and the like.

Further, as other transition metal compounds,
What carried the transition metal compound on a carrier such as a magnesium compound or a silicon compound can be used,
A compound obtained by modifying the above transition compound with an electron donating compound can also be used. Particularly preferred among these transition metal compounds are titanium compounds and zirconium compounds. For the catalyst (a), aluminoxane (b) is used together with the transition metal compound (a). This aluminoxane is obtained by contacting an organoaluminum compound with a condensing agent, and has the general formula (IV)

[0016]

Embedded image

[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. Aluminoxane represented by the general formula (V):

[0018]

Embedded image

Wherein R ³ is the same as above and q is 2
-50, preferably 5-30. And the like. Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum. Of these, trimethylaluminum is preferred. Also,
Typical examples of the condensing agent include water, and any other condensing agent capable of condensing trialkylaluminum, such as copper sulfate pentahydrate, water adsorbed on inorganic and organic substances, and the like. No.

In general, the contact product of an organoaluminum compound such as a trialkylaluminum and water is mixed with an unreacted trialkylaluminum and various condensation products together with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane. Are molecules in which these are intricately associated, and these are various products depending on the contact conditions between the trialkylaluminum and water as a condensing agent. The method of contacting the alkyl aluminum compound with water at this time 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 then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and water is added later, and furthermore, a metal salt or the like is contained. There is a method of reacting water of crystallization, water adsorbed on inorganic or organic substances with an organoaluminum compound. The water may contain up to about 20% of amines such as ammonia and ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphite. Although this reaction proceeds even without solvent, it is preferable to carry out the reaction in a solvent. Preferred solvents include hexane, heptane and
Examples thereof include aliphatic hydrocarbons such as decane and aromatic hydrocarbons such as benzene, toluene and xylene.

When an aluminoxane (for example, an alkylaluminoxane) is used, if a hydrated compound or the like is used after the above-mentioned contact reaction, the solid residue is filtered off, and the filtrate is subjected to a temperature of 30 to 200 ° C. under normal pressure or reduced pressure. Preferably 40
At a temperature of で 150 ° C. for 20 minutes to 8 hours, preferably 30 minutes
Those heat-treated while distilling off the solvent in the range of minutes to 5 hours are preferred. In this heat treatment, the temperature may be appropriately determined depending on various conditions, but is usually in the above range. Generally, at a temperature lower than 30 ° C., no effect is exhibited,
On the other hand, when the temperature exceeds 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and neither is preferable. The reaction product is obtained as a colorless solid or solution depending on the conditions of the heat treatment. The product thus obtained can be dissolved or diluted with a hydrocarbon solvent, if necessary, and used as a catalyst solution.

A preferred example of an aluminoxane, particularly an alkylaluminoxane, which is a contact product of an organoaluminum compound used as a catalyst component and a condensing agent is an aluminum-methyl group (Al- The high magnetic field component in the methyl proton signal region based on the CH ₃ ) bond is 50% or less. In other words, at room temperature of the above contact product, when observing the proton nuclear magnetic resonance ⁽¹ H-NMR) spectra in toluene solvent, methyl proton signal based on the "Al-CH _3" is tetramethylsilane (TMS) standard In the range of 1.0 to -0.5 ppm. TMS
Is located in the methyl proton observation region based on “Al—CH ₃ ”.
—CH ₃ ”, the TMS
Methyl proton signal of toluene 2.35
ppm and the high magnetic field component (i.e., -0.1 to -0.0.
5 ppm) and other magnetic field components (ie, 1.0 to -0.1 pp)
m), the component having the high magnetic field component of 50% or less, preferably 45 to 5% of the whole can be suitably used as the catalyst component.

The (b) catalyst includes the above (a) transition metallization
(C) reacts with the transition metal compound together with
A compound capable of forming a sex complex is used. This compound
Although there is no particular limitation, the cation and the
Compound consisting of an anion bonded to
(C) is group IIIB, VB, VIB, VIIB, VI of the periodic table
II, IA, IB, IIA, IIB, IVA and VIIA
Cation containing an element selected from
VB, VIB, VIIB, VIII, IB, IIB, IIIA
Anion bonded to an element selected from group IV, group IVA and group VA
Compounds, especially cations and multiple groups
A coordination complex consisting of bound aonin is preferably used
Can be For example, general formula (VI) or (VII) [L¹-R^Four]^{U +})_V (M^TwoZ¹Z^Two... Z^e]^(ef)-)_W ... (VI) or ([L^Two]^{U +})_V (M^ThreeZ¹Z^Two... Z^e]^(ef)-)_W ... (VII) (However, L^TwoIs M^Four, R^FiveR⁶M^Five, R⁷ _ThreeC or R⁸M
^FiveWhere L¹Is a Lewis base, M^TwoAnd M^ThreeIs
VB, VIB, VIIB, VIII,
Selected from IB, IIB, IIIA, IVA and V
Element, M^FourAnd M^FiveAre IIIB and IV, respectively.
, V, VIB, VIIB, VIII, I, IB, II
An element selected from the group A, IIB and VIIA, Z¹~ Z^e
Is a hydrogen atom, a dialkylamino group, an alkoxy
Group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 20 carbon atoms
Aryloxy group, alkyl group having 1 to 20 carbon atoms, carbon
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
Z represents a group or a halogen atom;¹~ 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
A group represented by R^FiveAnd R⁶Are cyclopentadienyl
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
Represents a group. R⁸Is tetraphenylporphyrin, phthalo
Shows macrocyclic ligands such as cyanine. f is M^Two, M^Threeof
E is an integer of 1 to 7, e is an integer of 2 to 8, and u is [L¹
-R^Four], [L ^TwoIs an integer of 1 to 7, and v is
An integer of 1 or more, w = (v × u) / (ef). ]
It is a compound represented by these.

[0024] Here, specific examples of the Lewis base represented by L ^1, ammonia, methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, tri -n- butylamine, N , N-dimethylaniline, methyldiphenylamine, pyridine;
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 the like.

Also, M^TwoAnd M^ThreeAs a specific example,
B, Al, Si, P, As, Sb, etc., M^FourExamples of
Li, Na, Ag, Cu, Br, I, I_ThreeWhat
Th, M^FiveAs specific examples of Mn, Fe, Co, Ni,
Zn and the like can be mentioned. Z¹~ Z ^eAs a specific example,
For example, a dimethylamino group as a dialkylamino group,
Diethylamino group; an alkoxy group having 1 to 20 carbon atoms
Methoxy group, ethoxy group, n-butoxy group, carbon number 6
A phenoxy group as an aryloxy group,
-Dimethylphenoxy group, naphthyloxy group, carbon number 1
A methyl group, an ethyl group, an n-
Ropyl, iso-propyl, n-butyl, n-o
Octyl group, 2-ethylhexyl group, C 6-20
Reel, alkylaryl or arylalkyl
Phenyl, p-tolyl, benzyl,
Pentafluorophenyl group, 3,5-di (trifluoro
Tyl) phenyl group, 4-tert-butylphenyl
Group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group
Phenyl, 2,4-dimethylphenyl, 2,3-dimethyl
Tylphenyl group, 1,2-dimethylphenyl group, carbon number
P-fluoro as 1 to 20 halogen-substituted hydrocarbon groups
Phenyl group, 3,5-difluorophenyl group, pentac
Lorophenyl group, 3,4,5-trifluorophenyl
Group, pentafluorophenyl group, 3,5-di (trifur
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, dicyclohexylantimony
And a diphenylboron group. R^Four, R⁷Concrete
Examples include those similar to those mentioned above.
R^FiveAnd R⁶Specific examples of the substituted cyclopentadienyl group of
A methylcyclopentadienyl group, a butylcyclo
Pentadienyl group, pentamethylcyclopentadienyl
And those substituted with an alkyl group such as a group. This
Here, the alkyl group usually has 1 to 6 carbon atoms and is substituted.
The number of the substituted alkyl groups can be selected from an integer of 1 to 4.
You.

Among the compounds of the above general formulas (VI) and (VII), those in which M ² and M ³ are boron are preferred. Among the compounds of the general formulas (VI) and (VII), specifically, the following compounds can be particularly preferably used. For example, compounds of the general formula (VI) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyltri (n-butyl) tetraphenylborate. Ammonium, benzyltriphenylborate tri (n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, Dimethylsulfonium, 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] borate, tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], methyldiphenylammonium tetra (pentafluorophenyl) borate, 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-d Roanilinium), dimethyl tetra (pentafluorophenylmethyl) borate (p-bromoanilinium), 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-
And dimethylanilinium ditrifluoromethylphenyl) borate and triethylammonium tow hexafluoroarsenate.

On the other hand, compounds of the general formula (VII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetra (pentafluorophenyl) borate, 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) borate (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) borate (zinc tetraphenylporphyrin), silver tetrafluoroborate , Silver hexafluoroarsenate, silver hexafluoroantimonate and the like. 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 and the like are also used. be able to.

In the present invention, an organometallic compound can be used as the component (d), if desired, together with the above-mentioned catalyst (a) or (b). As the (d) organometallic compound that is optionally used in combination, a compound represented by the general formula M ⁶ (R ⁹ ) _r ... (VIII) is used. In the general formula (VIII), R ⁹ represents 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 represents an aralkyl group. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Examples thereof include an n-butyl group, an i-butyl group, a hexyl group, a 2-ethylhexyl group, and a phenyl group. And M
⁶ is lithium, sodium, potassium, magnesium,
Zinc, cadmium, aluminum, boron, gallium,
Indicates silicon or tin. 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 Dialkyl zinc compounds such as trimethyl gallium, triethyl gallium, and tripropyl gallium; alkyl boron compounds such as triethyl boron, tripropyl boron, and tributyl boron; alkyl tin compounds such as tetraethyl tin, tetrapropyl tin, and tetraphenyl tin And the like. Also, M ⁶
There are various compounds as aluminum. Specific examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trioctylaluminum.

Regarding the use ratio of each component in the catalyst,
Although there is no particular limitation, in the catalyst (a),
The molar ratio of the component (a) to the component (b) is 1:20 to 1: 1.
0000, preferably 1: 100 to 1: 2000
Thus, it is preferable to use both components. On the other hand, (b)
In other words, the molar ratio of the component (a) to the component (c) is 1: 0.0.
1-1: 100, preferably 1: 1 to 1:10
Thus, both components are preferably used. In this case, the component (a)
(C) The components are brought into contact in advance, and the treated product is separated and washed.
And may be brought into contact in a polymerization system. Also,
(B) in the catalyst or (b) the catalyst, if desired
The amount of component (d) used is based on 1 mole of component (a).
Then, it is usually selected in the range of 0 to 100 mol. this
Improvement of polymerization activity by using component (d)
Can be used, but even if used too much, it is equivalent to the amount added
No effect is exhibited. The component (d) is the component (a)
And the contact between component (c) or component (a) and component (c).
It may be used in contact with a contact treatment product. This contact is
May be brought into contact with each other,
You may. Also, the ratio of styrene monomer to catalyst used
Is not particularly limited, but usually a styrene monomer /
The transition metal compound has a molar ratio of 10 to 10.⁹, Preferably 1
0 ^Two-10⁷Is chosen to be in the range

In order 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 200C, preferably 30 to 100
At a temperature of 1 ° C. for 1 second to 10 hours, preferably 1 minute to
The polymerization is carried out for about 6 hours. Also, as the polymerization method,
Any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, and a gas phase polymerization method can be used, and any of continuous polymerization and discontinuous polymerization may be used. Here, in the solution polymerization, one or more solvents such as aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane and octane are used as solvents. Can be used in combination. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. Control of the molecular weight and composition of the polymer may be performed 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 substantially forming the polymer in this way, a functionalization treatment of the polymerization terminal is performed. In this functionalization treatment, the resulting polymer has a halogen atom or active hydrogen and has a substituent containing at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a halogen atom. The reaction is performed by reacting a compound, or carbon dioxide or carbon disulfide. Examples of the compound having the above substituent include 4-bromophenethyl alcohol, 4-bromophenol, 3-bromo-1-propanol, 2-bromobenzyl alcohol, 4-bromo-2,6-dimethylphenol, and 2-bromophenol. Halogen-substituted alcohols such as ethanol and 4-bromo-2-naphthol and phenols,
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, 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 Ketones such as o-bromoanisole, epichlorohydrin, 4-bromodiphenyl ether, epibromohydrin, 2-bromoethylethyl ether, and bromomethyl ether;
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
Sulfonic acids such as sodium-bromosulfonate, 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 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 isocyanate compounds. These compounds are
One type may be used, or two or more types may be used in combination.

The conditions for the functionalization treatment of the polymerization terminal are not particularly limited, but are usually -80 to 100 ° C, preferably-
The reaction may be performed at a temperature of 30 to 80 ° C. for 0.1 second to 3 hours, preferably for about 1 second to 1 hour. In addition, the amount of the terminal functionalizing agent used is usually based on 1 mole 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, a terminally functionalized styrenic polymer having a high syndiotactic structure is obtained.
The syndiotactic structure as used herein 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 a main chain formed from carbon-carbon bonds, is alternately arranged in opposite directions. The tacticity is determined by nuclear magnetic resonance ( ¹³ C-NMR) using isotope carbon. ¹³ C
-Tacticity measured by the NMR method can be represented by the abundance ratio of a plurality of continuous structural units, for example, dyad for two, triad for three, and pentad for five. The styrenic polymer having a high syndiotactic structure as referred to in the present invention is preferably a racemic diad in a chain of styrenic repeating units of 75% or more, more preferably 85% or more.
Above or a racemic pentad having a syndiotacticity of preferably 30% or more, more preferably 50% or more. However, the degree of syndiotacticity slightly varies depending on the type of the substituent and the like.

The styrene polymer of the present invention has a reduced viscosity of 0.01 to 20 deciliters at a concentration of 0.05 g / deciliter measured at 135 ° C. in 1,2,4-trichlorobenzene. / G. When the reduced viscosity is less than 0.01 deciliter / g, the physical properties as a polymer are not sufficiently exhibited. On the other hand, when it exceeds 20 deciliters / g, the moldability becomes poor. The multilayer material of the present invention has at least one layer composed of the above-mentioned terminally functionalized styrene-based polymer having a high syndiotactic structure, and the material of the other layers is not particularly limited. Any of plastic resin, thermosetting resin, metal and other materials can be used. Various types of thermoplastic resins,
For example, a polyolefin resin, a polystyrene resin, a condensation type polymer, an addition polymerization type polymer, or the like can be used. 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 using octene-1, 4-methylpentene-1, 3-methylbutene-1, and the like, and chemically modified products thereof, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer And ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ethylene ionomer polypropylenes, and chemically modified products thereof. Specific examples of the polystyrene resin include general-purpose polystyrene, isotactic polystyrene, other syndiotactic polystyrene, and high-impact polystyrene (modified with rubber). Specific examples of the condensation polymer include polyacetal resins, polycarbonate resins, polyamide resins such as nylon 6, nylon 6.6, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resins, polyimide resins, and polysulfone resins. , Polyether sulfone resin, polyphenylene sulfide resin and the like. Examples of the addition polymerization type polymer include a polymer obtained from a polar vinyl monomer and a polymer obtained from a diene monomer, specifically, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, An acrylonitrile-butadiene-styrene copolymer, a diene-based polymer obtained by hydrogenating a diene chain, and a thermoplastic elastomer may be used.

As the thermosetting resin, for example, phenol resin, epoxy resin, unsaturated polyester resin,
Alternatively, these fiber reinforced materials and the like can be mentioned. 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, and wood. And the like. These materials can be used alone or in combination of two or more depending on the purpose of use. The shape and state of each layer or portion constituting the multilayer material of the present invention are various, and include, for example, films, sheets, fibers (woven fabric, non-woven fabric), various molded products, sintered products, single products. There are crystals, foams, and porous bodies. The method of forming each material into a multilayer is not particularly limited, and various methods conventionally used 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. When the other material is a metal, particularly when the metal to be laminated is relatively thin. For example, a lamination method, a metal evaporation method, an electrostatic coating method, or the like is used. Further, in the case of laminating on a molded article or a thick material, a method of coating the surface by heat fusion, impregnation, application 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, the surface of a film, a sheet, a fiber, a cloth, a molded body, a sintered body, a single crystal, a foam, or a porous body may be used. A layer composed of the styrene-based polymer, which is laminated, impregnated, or coated and coated, or a composite thereof. Further, the multilayer material of the present invention is widely used in various fields such as films, sheets (especially stampable sheets), containers, packaging materials, automobile parts, electric / electronic parts, and the like.

[0035]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Glass container of Example 1 (1) of methylaluminoxane prepared purged with argon inner volume 500 ml, 200 ml of toluene, copper sulfate pentahydrate _{(CuSO 4 · 5H 2 O)} 17.7g (71 mmol) and trimethyl aluminum Twenty-four milliliters (250 mmoles) were added and reacted 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 were obtained. Its molecular weight measured by freezing point depression method was 610. Also, Japanese Patent Application Laid-Open No. 62-32539
High magnetic field components by ¹ H-NMR measurement based on 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 (-0.1 to -0.5 ppm) and other magnetic field components (i.e., 1.0 to -0.1 ppm), the high magnetic field component was 43% of the whole.

(2) Polymerization of p-methylstyrene In a 1-liter three-necked flask, under a nitrogen atmosphere,
150 ml of toluene, the medium prepared in (1) above
40 mmol of tilluminoxane, p-methylstyrene
20 ml was charged, and the temperature was raised to 80 ° C. 80 ℃
For 5 minutes, then cyclopentadienyl titanium
Mutrimethoxide [CpTi (OMe) _Three] 100 My
Chromol was added to initiate polymerization. Polymerize for 8 minutes
After that, add 1 to the terminating agent (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: 30 ml toluene, temperature: 40-50 ° C. Reduced viscosity: 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 based on carboxylic acid was recognized in the infrared absorption spectrum. Further ¹³ C-
As a result of NMR analysis, C ₁ carbon signal was 142.1 pp.
m was confirmed, and it was confirmed that it had a syndiotactic structure.

Examples 2 to 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 developed using thin-layer chromatography using hexane / chloroform (50/50 volume ratio) as a developing solution. In all cases, the R _f value was smaller than that of the syndiotactic polystyrene that was not used. Therefore, Examples 2 to
The polymer obtained in 4 was found to have a higher polarity than ordinary syndiotactic polystyrene and was considered to be end-functionalized.

Examples 5 to 7 Under the conditions shown in Table 3, high molecular weight end-functionalized syndiotactic polystyrene was produced. Although the solvent resistance was high and the terminal as shown in Examples 2 to 4 could not be confirmed, it can be assumed that the terminal was similarly functionalized.

[0046]

[Table 4]

Note) Toluene: 50 ml, styrene: 10 ml, methylaluminoxane: 3
Mmol Cp ^* Ti (OMe) ₃ (pentamethylcyclopentadienyl trimethoxide): 5 micromol Temperature: 70 ° C.

[0048]

[Table 5]

Example 8 (1) Tri-n-tetra (pentafluorophenyl) borate
Preparation of butyl ammonium Pentafluorophenyl lithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) was reacted with 45 mmol of boron trichloride in hexane to convert tri (pentafluorophenyl) boron to white. Obtained as a solid. By reacting 41 mmol of this tri (pentafluorophenyl) boron with 41 mmol of lithium pentafluorophenyl, lithium tetra (pentafluorophenyl) borate was obtained as a white solid. Next, 16 mmol of lithium tetra (pentafluorophenyl) borate and 16 mmol of tri-n-butylammonium hydrochloride were reacted in water to obtain 12.8 mmol of tri-n-butylammonium tetra (pentafluorophenyl) borate as a white solid. Could be obtained.

(2) Production of epichlorohydrin-stopped syndiotactic polystyrene 150 ml of toluene and 200 ml of styrene were added to a dry container at room temperature under an argon atmosphere, and triisobutylaluminum (TIBA) was used as a catalyst component. 5 mmol was added and left for 30 minutes.
Thereafter, 5 μmol of tri-n-butylammonium tetra (pentafluorophenyl) borate and 5 μmol of pentamethylcyclopentadienyltrimethyltitanium prepared in the above (1) were added, and the polymerization reaction was carried out for 2 hours. Thereafter, 2 mmol of epichlorohydrin was added,
The reaction was performed for 10 minutes. After the reaction is completed, methanol is added,
The reaction was stopped and, after filtration, further washed three times with methanol. The polymer was dried under reduced pressure to obtain 79 g of a polymer. The reduced viscosity of this polymer in 1,2,4-trichlorobenzene at a concentration of 0.05 g / deciliter measured at a temperature of 135 ° C. was 1.92 deciliter / g, and the melting point was 269 ° C. In addition, as in Examples 5 to 7, the terminal was not confirmed due to the high molecular weight, but it can be assumed that the terminal was similarly functionalized.

Example 9 (Multilayer Material) A sheet (dimensions: 5 × 5) of nylon 6.6 (trade name: 202B) manufactured by Ube Industries, Ltd. was placed in a mold of 5 × 5 × 0.2 cm.
× 0.1 cm), and the powder of the terminal-modified syndiotactic polystyrene obtained in Example 8- (2) was uniformly and tightly packed. This is heated to 290 ° C on a press plate,
Melted for 5 minutes. Thereafter, the resultant was cooled to obtain a multilayer material composed of nylon and syndiotactic polystyrene. The bonding state of the interface was good.

[0052]

The styrenic polymer of the present invention has a high syndiotactic structure and is functionalized at its terminal, and retains the crystallinity characteristic of syndiotactic polystyrene. It has excellent adhesive ability and compatibilizing ability, and is suitably used, for example, in fields requiring adhesion to metal (evaporated films, multilayer materials) and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-13707 (JP, A) JP-A-4-11605 (JP, A) JP-A-4-214715 (JP, A) JP-A-62-1987 212403 (JP, A) JP-A-5-287022 (JP, A) JP-A-5-230126 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/00-8 / 50 C08F 12/06-12/30

Claims (4)

(57) [Claims] 1. A compound of the general formula [Wherein, 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, m is an integer of 1 to 5, and when m is plural, R ¹ may be the same or different, and R ¹ may form a condensed ring together with a benzene ring. A styrene-based polymer having a functional group at the terminal end of the structural unit represented by the formula: reduced viscosity in 1,2,4-trichlorobenzene at a concentration of 0.05 g / deciliter measured at a temperature of 135 ° C. Is 0.01 to 20 deciliters / g and a styrenic polymer having a syndiotactic structure in which the stereoregularity of the chain of the structural units is high. 2. The method according to claim 1, wherein the terminal functional group is at least one selected from carboxylic acid group, carboxylic acid ester group, hydroxyl group, halogen, cyano group, nitro group, amino group, ether group and thioether group. 2. The styrene polymer according to 1. 3. A compound of the general formula [Wherein, 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, m is an integer of 1 to 5, and when m is plural, R ¹ may be the same or different, and R ¹ may form a condensed ring together with a benzene ring. ] (A) (a)
A catalyst mainly composed of a transition metal compound and (b) an aluminoxane, or (b) a catalyst mainly composed of (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 contains a halogen atom or active hydrogen, and contains an oxygen atom, a nitrogen atom, a sulfur atom,
2. A compound having a substituent containing at least one selected from a phosphorus atom and a halogen atom, or carbon dioxide or carbon disulfide.
Or the method for producing a styrenic polymer according to 2. 4. A multilayer material having at least one layer made of the styrenic polymer according to claim 1.