JP3115944B2 - Chemically modified styrenic polymer and method for producing the same - 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 crystalline chemically modified styrenic polymer and a method for producing the same.
More specifically, the present invention provides a method for efficiently producing a crystalline chemically modified styrene-based polymer by optimally and easily chemically modifying a styrene-based polymer having a crystalline syndiotactic structure according to the application, Also, the present invention relates to a crystalline chemically modified styrene-based polymer which is imparted with compatibilizing ability, adhesiveness, printability, antistatic property and the like, and is useful as a material such as a composite material.

[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. For example, a syndiotactic copolymer of styrene and substituted styrene (JP-A-63-24109), a syndiotactic copolymer of styrene and a polar monomer (JP-A-2-2588)
No. 10, JP-A-2-258805). However, the production of syndiotactic copolymers by such copolymerization has the following problems. (1) An amorphous solvent-soluble by-product may be formed, or crystallinity, which is a characteristic feature of the syndiotactic styrene resin, may be impaired. (2) The types of copolymerized comonomers are limited, and the introduction of various types of functional groups and substituents for improving the performance of the syndiotactic styrene resin is inevitably limited. (3) Since monomers having different copolymerizabilities are used, it is necessary to set optimum polymerization conditions for each, and the operation is complicated.

[0003]

SUMMARY OF THE INVENTION Under these circumstances, the present invention provides a syndio with a small amount of amorphous by-product polymer into which various kinds of functional groups and substituents for high performance have been introduced. An object of the present invention is to develop a method for easily and efficiently producing a styrenic polymer having an tactic structure without impairing crystallinity.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have been able to convert a specific styrenic polymer or copolymer having a syndiotactic structure into a specific chemical compound. It has been found that the purpose can be achieved by denaturing at a predetermined ratio using a denaturing agent.
The present invention has been completed based on such findings. That is, the present invention relates to (A) a compound represented by the general formula (I)

[0005]

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[Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a silicon-containing group, m is an integer of 1 to 5, and when m is plural, m R ^1s are They may be the same or different. A styrenic polymer having a syndiotactic structure comprising a repeating unit represented by the following formula (A):

[0007]

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Wherein R ² is a hydrocarbon group having 1 to 20 carbon atoms, R ³ and R ⁴ are each a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and n is 1 to 4 is an integer, and when n is plural, n R ^{4 s} may be the same or different. And / or (C) a general formula (III)

[0009]

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Wherein R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, p is an integer of 1 to 4, and when p is plural, p R ⁶ may be the same or different. A styrenic polymer having a syndiotactic structure including a repeating unit represented by], nitration agent, acyl Ka試
Agent, sulfonating agent, metalating agent or chlorosulfone
Reagent for substitution reaction to benzene ring as a chemical reagent, radical reaction
応試agent or α-position hydrogen substituent reactants and hydroxylated reagent is metalated reagent, radical addition reagents, metal Ka試
Agents, borohydride agents, hydrogen sulfate alkylating agents or halogens
The chemical modification is carried out by reacting at least one agent selected from addition reaction reagents to the side chain carbon-carbon double bond, which is an agent, so that the amount of modification is 10 ^-4 to 15 mol%. And a method for producing a crystalline chemically modified styrenic polymer. Further, the present invention relates to (A) a compound represented by the general formula (I):

[0011]

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Wherein R ¹ and m are as defined above.
A repeating unit having a syndiotactic structure represented by the following formula: (D) (a) a general formula (IV)

[0013]

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[Wherein X is -NO ₂ , -SO ₃ H, -S
OCL ₂ , —COR ⁷ (where R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms) or a monovalent metal atom, and R ¹ and m are the same as described above. (B)
General formula (V)

[0015]

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[In the formula, Y represents a monovalent metal atom, a halogen atom, a —OOH group or a maleic anhydride residue, and R ¹ and m are the same as those described above. And (c) a general formula (VI)

[0017]

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[In the formula, Z ¹ and V ¹ each represent a halogen atom, a monovalent metal atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and a tin atom. And they may be the same or different from each other, and R ² , R ³ , R ⁴ and n are the same as described above. And a repeating unit represented by the formula (d):
General formula (VII)

[0019]

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[Wherein, Z^TwoAnd V^TwoIs halogen
Atom, monovalent metal atom or carbon atom, oxygen atom, nitrogen atom
Any of elemental, sulfur, silicon and tin atoms
Denotes one or more substituents, even if they are identical to each other
May be different, R ^Five, R⁶And p are
Is the same).
Containing at least one chemically modified unit,
The content of the (D) chemically modified unit is 10^-Four~ 15mol
% In 1,2,4-trichlorobenzene at 135 ° C.
Reduced viscosity at a concentration of 0.05 g / deciliter measured in degrees
The degree is 0.01-20 deciliter / g and the crystal melting temperature is
Crystallinity characterized by being in the range of 230 to 350 ° C
It also provides a chemically modified styrenic polymer.

In the method of the present invention, as a raw material, a styrenic polymer having a syndiotactic structure comprising a repeating unit (A) represented by the general formula (I),
Alternatively, the repeating unit (A) and the repeating unit (B) represented by the general formula (II) and / or the general formula (II)
A styrenic copolymer having a syndiotactic structure composed of the repeating unit (C) represented by (I) is used. In the general formula (I), R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a silicon-containing group, wherein the alkyl group is a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group. And an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group. Examples of the aryl group include benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, chrysene ring, biphenyl ring, terphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, heptalene ring, biphenylene ring, as-indacene ring, s-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring, acephenanthrene ring, aceanthrylene ring, triphenylene ring, naphthacene ring, pleiaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring, pentacene ring, Rubycene ring,
It represents a substituent containing a corocene ring, a pyranthrene ring, and an ovalene ring. Further, the silicon-containing group includes a group having a silicon-carbon bond, a silicon-silicon bond or a silicon-oxygen bond, and specifically, an alkylsilyl group such as a trimethylsilyl group, an arylsilyl group such as a phenylsilyl group, and a trisilyl group. Examples include an alkoxysilyl group such as a methoxysilyl group, and a siloxysilyl group.

Among the styrene monomers forming the repeating unit represented by the above general formula (I), specific examples of the alkylstyrene monomer in which R ¹ is an alkyl group include p-methylstyrene; m-methylstyrene; o -Methylstyrene; 2,4-dimethylstyrene; 2,5-dimethylstyrene; 3,4-dimethylstyrene; 3,5-
Alkyl styrene such as dimethyl styrene; p-ethyl styrene; m-ethyl styrene; p-tert-butyl styrene; Further, specific examples of the alkoxystyrene monomer in which R ¹ is an alkoxy group include p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene, pn-propoxystyrene, and pn-butoxystyrene. it can. Further, specific examples of the arylstyrene monomer in which R ¹ is an aryl group include vinylphenyls such as 4-vinylbiphenyl, 3-vinylbiphenyl, and 2-vinylbiphenyl; 1- (4-vinylphenyl) naphthalene, (4-vinylphenyl) naphthalene, 1-
Vinylphenylnaphthalenes such as (3-vinylphenyl) naphthalene, 2- (3-vinylphenyl) naphthalene, 1- (2-vinylphenyl) naphthalene, 2- (2-vinylphenyl) naphthalene; 1- (4-vinyl Phenyl) 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-
Vinyls such as (2-vinylphenyl) phenanthrene, 2- (2-vinylphenyl) phenanthrene, 3- (2-vinylphenyl) phenanthrene, 4- (2-vinylphenyl) phenanthrene, and 9- (2-vinylphenyl) phenanthrene Phenylphenanthrenes; 1- (4
Vinylphenylpyrenes such as -vinylphenyl) pyrene, 2- (4-vinylphenyl) pyrene and 1- (3-vinylphenyl) pyrene; 4-vinyl-4'-bromobiphenyl, 4-vinyl-3'-bromo Biphenyl, 4-
Halogenated vinyl biphenyls such as vinyl-2'-bromobiphenyl, 4-vinyl-2-bromobiphenyl and 4-vinyl-3-bromobiphenyl; 4-vinyl-4 '
-Methoxybiphenyl, 4-vinyl-3'-methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4
-Vinyl-2-methoxybiphenyl, 4-vinyl-3-
Methoxybiphenyl, 4-vinyl-4'-ethoxybiphenyl, 4-vinyl-3'-ethoxybiphenyl, 4-
Vinyl-2'-ethoxybiphenyl, 4-vinyl-2-
Alkoxyvinylphenyls such as ethoxybiphenyl and 4-vinyl-3-ethoxybiphenyl; 4-vinyl-
4'-methoxycarbonylbiphenyl, 4-vinyl-
Alkoxycarbonylvinylbiphenyls such as 4'-ethoxycarbonylbiphenyl; alkoxyalkylvinylbiphenyls such as 4-vinyl-4'-methoxymethylbiphenyl; trialkylsilylvinylbiphenyls such as 4-vinyl-4'-trimethylsilylbiphenyl; Trialkylstannylvinylbiphenyls such as 4-vinyl-4'-trimethylstannylbiphenyl and 4-vinyl-4'-tributylstannylbiphenyl; 4
Trialkylsilylmethylvinylbiphenyls such as -vinyl-4'-trimethylsilylmethylbiphenyl; 2-
Vinylphenylpyrenes such as (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene and 2- (2-vinylphenyl) pyrene; 4-vinyl-p-terphenyl, 4-vinyl-m-ter Phenyl, 4-vinyl-o
-Terphenyl, 3-vinyl-p-terphenyl, 3-
Vinyl-m-terphenyl, 3-vinyl-o-terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m
Vinyl terphenyls such as -terphenyl and 2-vinyl-o-terphenyl; 4- (4-vinylphenyl)-
vinylphenyl terphenyls such as p-terphenyl; 4-vinyl-4'-methylbiphenyl, 4-vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4-vinylphenyl , 3-methyl-4-vinylphenyl and other vinylalkyl biphenyls; 4-vinyl-4'-fluorobiphenyl, 4-vinyl-3'-fluorobiphenyl, 4-vinyl-2'-
Fluorobiphenyl, 4-vinyl-2-fluorobiphenyl, 4-vinyl-3-fluorobiphenyl, 4-vinyl-4'-chlorobiphenyl, 4-vinyl-3'-chlorobiphenyl, 4-vinyl-2'-chlorobiphenyl ,
4-vinyl-2-chlorobiphenyl, 4-vinyl-3-
Halogenated vinyl biphenyls such as chlorobiphenyl;
And trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-trimethylstannylmethylbiphenyl and 4-vinyl-4'-tributylstannylmethylbiphenyl. Specific examples of the silicon-containing styrene monomer in which R ¹ is a silicon-containing group include p-trimethylsilylstyrene, m-trimethylsilylstyrene, o-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene, and o-triethyl. Alkyl silyl styrenes such as silyl styrene and p-dimethyl tertiary butyl silyl styrene; phenyl group-containing silyl styrenes such as p-dimethyl phenyl silyl styrene, p-methyl diphenyl silyl styrene and p-triphenyl silyl styrene;
Hydro-containing silyl styrenes such as dimethylhydrosilylstyrene, p-methyldihydrosilylstyrene, p-trihydrosilylstyrene, p-dimethylchlorosilylstyrene, p-methyldichlorosilylstyrene, p-trichlorosilylstyrene, p-dimethylbromosilyl Halogen-containing silyl styrenes such as styrene, p-dimethyliodosilylstyrene, p-dimethylmethoxysilylstyrene, p-methyldimethoxysilylstyrene, p-
Alkoxy group-containing silyl styrenes such as trimethoxysilyl styrene, silyl group-containing silyl styrenes such as p- (p-trimethylsilyl) dimethylsilyl styrene, p
-Bis (trimethylsilyl) methylstyrene, silyl group-containing methylstyrenes such as p-trimethylsilylmethylstyrene, p- (2-trimethylsilylethyl) styrene, p- (3-trimethylsilylpropyl) styrene,
p- (4-trimethylsilylbutyl) styrene, p-
(Ω- such as (8-trimethylsilyloctyl) styrene)
Silyl-substituted alkyl) styrenes, and siloxysilylstyrenes such as p-trimethylsiloxydimethylsilylstyrene. These styrene monomers forming the repeating unit represented by the general formula (I) may be used singly or in combination of two or more.

Next, in the repeating unit (B) represented by the general formula (II), R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, for example, an alkylene group having 1 to 20 carbon atoms, It represents an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms or an arylalkylene group. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentenylene group, a hexylene group, a phenylene group and a tolylene group. R ³ and R ⁴ each represent a hydrogen atom, a halogen atom (eg, chlorine, bromine, fluorine, iodine) or a carbon atom
To 8 monovalent hydrocarbon groups (for example, a saturated hydrocarbon group represented by an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, or an unsaturated hydrocarbon group such as a vinyl group). And n is an integer from 1 to 4.
When n is plural, n R ^{4 s} may be the same or different.

The styrenic monomer forming the repeating unit represented by the general formula (II) includes a styrene monomer represented by the general formula (I)
When R ^{2 in} I) is an alkylene group, for example, p- (2
-Propenyl) styrene, m- (2-propenyl) styrene, p- (3-butenyl) styrene, m- (3-butenyl) styrene, o- (3-butenyl) styrene, p-
(4-pentenyl) styrene, m- (4-pentenyl)
Styrene, o- (4-pentenyl) styrene, p- (7
-Octenyl) styrene, p- (1-methyl-3-butenyl) styrene, p- (2-methyl-3-butenyl) styrene, m- (2-methyl-3-butenyl) styrene,
o- (2-methyl-3-butenyl) styrene, p- (3
-Methyl-3-butenyl) styrene, p- (2-ethyl-3-butenyl) styrene, p- (2-ethyl-4-pentenyl) styrene, p- (3-butenyl) -α-methylstyrene, m- (3-butenyl) -α-methylstyrene, o- (3-butenyl) -α-methylstyrene and the like can be mentioned. Further, when R ² in the general formula (II) is an arylene group, for example, 4-vinyl-4′-
(3-butenyl) biphenyl, 4-vinyl-3 '-(3
-Butenyl) biphenyl, 4-vinyl-4 '-(pentenyl) biphenyl, 4-vinyl-2'-(4-pentenyl) biphenyl, 4-vinyl-4 '-(2-methyl-3
-Butenyl) biphenyl and the like.

Also, represented by the above general formula (III)
(C) R in the repeating unit^FiveAnd R ⁶Is the general formula
R in (II)^ThreeAnd R^FourAnd p is
It is an integer of 1 to 4. And when p is plural, p
R⁶May be the same or different. This general formula (III)
Styrene monomer forming a repeating unit represented by
Examples of p-divinylbenzene, m-divinyl
Rubenzene, trivinylbenzene, p-isopropenyl
Styrene and the like. In the present invention,
Forming repeating units represented by general formulas (II) and (III)
The monomers used may be one kind or two or more kinds.

In the method of the present invention, the styrene-based polymer used as a raw material may be a styrene-based polymer comprising the above-mentioned (A) repeating unit, or (A) a repeating unit, (B) a repeating unit and And / or a styrene copolymer containing (C) a repeating unit. When the latter styrene-based copolymer is used, it is preferable that the content of the repeating unit (A) in the copolymer is 85 mol% or more. The content of the repeating unit (B) is 10 ^-4.
To 15 mol%, preferably 10 ^-4 to 10 mol%, while the content of the repeating unit (C) is 10 ^-4.
To 5 mol%, preferably 10 ^-4 to 2 mol%. Further, the copolymerization mode may be either a random copolymer or a block copolymer. In the method of the present invention, the styrenic polymer used as a raw material is a polymer having a syndiotactic structure, particularly preferably a high syndiotactic structure, in which the main chain has a stereoregularity.

The syndiotactic structure referred to herein is:
Those whose stereochemical structure has a syndiotactic structure can be obtained. Here, the syndiotactic structure 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, are alternately located in opposite directions. It has a three-dimensional structure, and its tacticity is quantified by nuclear magnetic resonance ( ^13C -NMR) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method can be represented by the proportion of a plurality of continuous constituent units, for example, a dyad for two, a triad for three, and a pentad for five. . The styrenic polymer having a high syndiotactic structure referred to in the present invention is preferably 75% or more, more preferably 85% or more, or racemic pentad in a chain of styrene-based repeating units, preferably in a racemic diad. Indicates those having a syndiotacticity of 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. Various molecular weights of the styrenic polymer can be obtained depending on polymerization conditions and the like. Generally, the weight average molecular weight in GPC [1,2,4-trichlorobenzene, 135 ° C., polystyrene conversion] measurement is 1000 to 1000. 300,000, preferably 5
2,000 to 250,000. Further, those having a reduced viscosity of 0.01 to 20 deciliters / g at a concentration of 0.05 g / deciliter measured at a temperature of 135 ° C. in 1,2,4-trichlorobenzene are preferred.

The styrene-based polymer having a syndiotactic structure may be a styrene-based monomer forming the unit (A) or a styrene-based monomer forming the unit (B) and / or (C) A styrene-based monomer forming a unit is reacted with (a) a catalyst mainly composed of a contact product of a transition metal compound and (b) an organoaluminum compound with a condensing agent, or (a) a transition metal compound and (c) It can be produced by polymerizing in the presence of a catalyst containing a compound capable of forming an ionic complex by reacting with a transition metal compound as a main component. There are various types of the transition metal compound as the component (A), and preferably, the general formula (VIII) M ¹ R ⁸ ... R ^k (VIII) wherein M ¹ is Ti , Zr, Cr, V, Nb, Ta or Hf, wherein R ^{8 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, the substituted cyclopentadienyl group includes, for example, 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, pentamethylcyclopentadi An enyl group and a trimethylsilylcyclopentadienyl group. Further, the ligands of R ^{8 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 and an iodine atom;
Examples of the alkyl group 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. C6-C20 such as ethoxy, propoxy, butoxy, phenoxy, etc.
Examples of the aryl group, alkylaryl group or arylalkyl group include phenyl, tolyl, xylyl, and benzyl groups; and acyloxy groups having 1 to 20 carbon atoms include silicon atoms such as a heptadecylcarbonyloxy group. The group includes a trimethylsilyl group,
Examples of Lewis bases such as (trimethylsilyl) methyl group include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as benzonitrile, trimethylamine, triethylamine and tributylamine. N, N-
Dimethylaniline, pyridine; 2,2′-bipyridine,
Amines such as phenanthroline, and phosphines such as triethylphosphine and triphenylphosphine;
Examples of chain unsaturated hydrocarbons include ethylene, butadiene,
Examples of cyclic unsaturated hydrocarbons such as 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and cyclooctatetraene. Derivatives and the like. Examples of the crosslink by a covalent bond include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a dimethylsilylene crosslink, and a dimethylstannylene crosslink.

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 (VIII), 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,
Cyclopentadienyltribenzylhafnium, pentamethylcyclopentadienyltribenzylhafnium,
Examples include bisindenyl hafnium dichloride, hafnium dibenzyl dichloride, hafnium tetrabenzyl, tributoxy hafnium chloride, triisopropoxy hafnium chloride, hafnium tetrachloride, dicyclopentadienyl hafnium dichloride, and tetraethoxy hafnium. Specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride,
Vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentane Dienyl vanadium dichloride, dicyclopentadienyl methyl vanadium and the like can be mentioned.

Specific examples of the niobium compound include niobium pentachloride, tetrachloromethyl niobium, dichlorotrimethyl niobium, dicyclopentadienyl niobium dichloride, dicyclopentadienyl niobium trihydride, pentaboxy niobium 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 tetramethyl. Chromium, dicyclopentadienyl chromium, dibenzene chromium and the like can be mentioned. Further, as the other transition metal compound, those in which the above transition metal compound is supported on a carrier such as a magnesium compound or a silicon compound can be used, and those in which the above transition compound is modified with an electron donating compound can also be used. . Particularly preferred among these transition metal compounds are titanium compounds and zirconium compounds. In addition, (b) a contact product of an organoaluminum compound and a condensing agent used as a contact component is obtained by bringing various organoaluminum compounds into contact with a condensing agent. Here, as the organic aluminum compound, usually the general formula _{^{(IX) AlR 9 3 ··· (}} IX) wherein, R ⁹ represents an alkyl group having 1 to 8 carbon atoms. And an organoaluminum compound represented by the formula: Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum. Of these, trimethylaluminum is preferred. Examples of the condensing agent include water as a typical one, and any other condensing agent capable of condensing trialkylaluminum, such as copper sulfate pentahydrate,
Various substances such as water adsorbed on inorganic substances and organic substances are exemplified. Specific examples of the contact product between the organoaluminum compound and the condensing agent include those represented by the general formula (X)

[0035]

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Wherein q represents an integer of 0 to 50, preferably an integer of 5 to 30, and R ⁹ is the same as described above. A chain alkylaluminoxane represented by the general formula (XI)

[0037]

Embedded image

[In the formula, r represents an integer of 2 to 50, preferably an integer of 5 to 30, and R ⁹ is the same as described above. And the like.

In general, the contact product of an organoaluminum compound such as a trialkylaluminum and water is mixed with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, as well as a mixture of unreacted trialkylaluminum and various condensation products, and 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.

After the above contact reaction, when a hydrated compound or the like is used, this contact product (for example, an alkylaluminoxane) is filtered off from the solid residue, and the filtrate is treated at 30 to 200 ° C. under normal pressure or reduced pressure. Temperature, preferably 40-1
At a temperature of 50 ° C., 20 minutes to 8 hours, preferably 30 minutes to
It is preferable to heat-treat the solvent within 5 hours while distilling off the solvent. In this heat treatment, the temperature may be appropriately determined depending on various conditions, but is usually in the above range. Generally, at temperatures below 30 ° C., no effect is exhibited and
If the temperature exceeds 00 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and both are not preferred. 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 such a contact product of an organoaluminum compound used as a catalyst component with a condensing agent, particularly an alkylaluminoxane, is an aluminum-methyl group (A
l-CH ₃₎ high magnetic field component in the methyl proton signal region based on the binding is of 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 At 1.0
It is found in the range of -0.5 ppm. Because TMS proton signals (0 ppm) is in the methyl protons observation area based on the "Al-CH _3", the methyl proton signal based on the "Al-CH _3", the methyl proton signal 2.35ppm toluene in TMS standard When the high magnetic field component is divided into a high magnetic field component (i.e., -0.1 to -0.5 ppm) and another magnetic field component (i.e., 1.0 to -0.1 ppm), the high magnetic field component is 50% or less, preferably 45 to 5% of the above can be suitably used as a catalyst component.

Next, (c) transition used as a contact component
Reaction with metal transfer compounds to form ionic complexes
There are no particular restrictions on the compound, but the cation and multiple
With an anion bonded to an element, especially
And an anion in which a plurality of groups are bonded to an element.
A complex complex compound can be suitably used. Such a mosquito
Consists of thione and an anion in which multiple groups are bonded to an element
Compounds include IIIB, IVB, VB, VI
Group B, VIIB, VIII, IA, IB, IIA, IIB,
Cations containing elements selected from Group IVA and Group VIIA
Numbers are groups VB, VIB, VIIB, VIII, IB of the periodic table
Selected from group III, IIB, IIIA, IVA and VA
A compound comprising an anion bonded to, for example, a general formula
(XII) or (XIII) ([L¹-R^Ten]^{u +})_V (M^TwoZ¹Z^Two... Z^e]^(ef)-)_W ... (XII) or ([L^Two]^{u +})_V (M^ThreeZ¹Z^Two... Z^e]^(ef)-)_W ... (XIII) (However, L^TwoIs M^Four, R¹¹R¹²M^Five, R¹³ _ThreeC or R¹⁴
M^FiveWhere L¹Is a Lewis base, M^TwoAnd M^Three
Are the VB, VIB, VIIB, and VIII of the periodic table, respectively.
Selected from group IV, group IB, group IIB, group IIIA, group IVA and group V
Element, M^FourAnd M^FiveIs the IIIB group of the periodic table,
IV, V, VIB, VIIB, VIII, I, IB,
An element selected from Group IIA, IIB and VIIA, Z¹~ Z
^eAre hydrogen, dialkylamino, alkoxy
Si group, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl group having 1 to 20 carbon atoms, charcoal
Aryl group, alkylaryl group, ant having a prime number of 6 to 20
Alkyl group, halogen-substituted hydrocarbon having 1 to 20 carbon atoms
Element group, acyloxy group having 1 to 20 carbon atoms, organic metalloy
Z or a halogen atom;¹~ Z^eHaha 2 or more
The upper portions may be bonded to each other to form a ring. R^TenIs water
Elemental atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl, alkylaryl or arylalkyl
And R represents¹¹And R¹²Are cyclopentadie
Nyl group, substituted cyclopentadienyl group, indenyl group or
Is a fluorenyl group, R¹³Is alkyl having 1 to 20 carbon atoms
Group, aryl group, alkylaryl group or arylal
Represents a kill group. R¹⁴Is tetraphenylporphyrin,
Shows macrocyclic ligands such as tarocyanines. f is M^Two, M
^ThreeIs an integer of 1 to 7, e is an integer of 2 to 8, and u is
[L¹-R^Ten], [L ^Two] With an ionic valence of 1 to 7
The number, v is an integer of 1 or more, w = (v × u) / (ef)
is there. ] It is a compound represented by these.

[0043] 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^Ten, R¹³Concrete
Examples include those similar to those mentioned above.
R¹¹And R¹²Specific 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 general formulas (XII) and (XIII), those in which M ² and M ³ are boron are preferred. Among the compounds of the general formulas (XII) and (XIII), specifically, the following compounds can be particularly preferably used. For example, compounds of the general formula (XII) 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, benzyl 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 (XIII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate, 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 (XII) and (XIII), 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, if desired, an organometallic compound may be used as the component (d) together with the catalyst component (a) and the catalyst component (b) or the catalyst component (a) and the catalyst component (c). it can. As the (d) organometallic compound which is optionally used in combination, a compound represented by the general formula (XIV) M ⁶ (R ¹⁵ ) _S (XIV) is used. In the general formula (XIV), R ¹⁵ 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. S represents the valence of M ⁶ . There are various compounds represented by the general formula (XIV). 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.

When the components (a) and (b) are used as catalysts, the proportion of each component in the catalyst used in the method of the present invention is based on the transition metal (for example, titanium) in the component (a). the molar ratio of aluminum in component (b) is 1 to 10 ^6, preferably 10 to 10 to use both components is desired at a rate such that the ⁴ range. On the other hand, when the components (a) and (c) are used,
The molar ratio of the component (c) to the component (a) is 0.01 to 10
It is desirable to use both components in proportions such as to be in the range of 0, preferably 1-10. In this case, the component (a) and the component (c) may be brought into contact with each other in advance, and the contact-treated product may be separated and used linearly, or may be brought into contact in a polymerization system. The amount of component (d) used as desired is usually selected in the range of 0 to 100 mol per 1 mol of component (a). By using the component (d), the polymerization activity can be improved. However, even if it is used in an excessively large amount, the effect corresponding to the added amount is not exhibited. This (d)
The components may be used in contact with the component (a), the component (c) or the contact product of the component (a) with the component (c).
This contact may be carried out in advance, or may be carried out by sequentially adding the components into the polymerization system.

There is no particular limitation on the ratio of the styrene monomer to the catalyst, but the molar ratio of the styrene monomer to the transition metal compound is usually 10 to 10 ¹² , preferably 10 ² to 10 ^8. Is chosen as In the polymerization reaction in the present invention, the polymerization temperature may be generally selected in the range of 0 to 120 ° C, preferably 10 to 80 ° C, and the polymerization time may be selected in the range of 1 second to 10 hours. As the polymerization method, any of bulk, solution and suspension polymerization can be used. In the case of solution polymerization, usable solvents include aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, benzene, and the like.
There are aromatic hydrocarbons such as toluene and xylene.
Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferred. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected.

In the present invention, the styrenic polymer having a syndiotactic structure comprising the repeating unit (A) thus obtained, or the repeating unit (A), and the repeating unit (B) Alternatively, a styrene-based polymer having a syndiotactic structure containing a repeating unit (C) is chemically modified with a chemical modifier. Examples of the chemical modifier include a reagent for substitution reaction on a benzene ring, α
At least one member selected from the group consisting of a hydrogen substitution reagent and an addition reagent to the side chain carbon-carbon double bond is used. Here, when a polymer comprising the repeating unit (A) is used as the styrene-based polymer, any of a benzene ring substitution reagent and an α-position hydrogen substitution reagent are used as the chemical modifier. When a copolymer containing (A) a repeating unit and (B) a repeating unit and / or (C) a repeating unit is used, as a chemical modifying agent, a benzene ring substitution reactant, α Any of a hydrogen substitution reagent and an addition reagent to the side chain carbon-carbon double bond can be used.

[0051] As substitution reactant to the benzene ring, two <br/> Toro reduction agent, acylation reagent, sulfonated reagent is needed use metalated reagent or chlorosulphonated Ka試agent. When a nitro group is introduced using a nitrating reagent, it can be converted to an amino group if desired. Also, in the case of metallization using a metallization reagent, for example, lithiation,
If desired, it can be converted to aldehyde, carboxylic acid, thiol, alcohol, ketone and the like. As the α-position hydrogen substitution reaction reagent, La radical reactants or meta <br/> Le of trial agent is use. The reaction by the radical reaction reagent, for example, N- bromosuccinimide bromination reaction by reaction with maleic anhydride, and other radical reactions like. When metalation is performed using a metalation reagent, if desired, an aldehyde,
It can be converted to carboxylic acids, thiols, alcohols, ketones and the like. Further, the side chain carbon - The addition reactant to carbon double bond, arsenide Dorokishiru reduction agent (e.g., potassium permanganate, etc.), radical addition reagent,
Metalated reagent (e.g., alkyl lithium), borohydride agent, hydrogen sulfate alkylating agent or halogenating agent (e.g., halogen, hydrogen halide) is needed use.
When metalation is performed by an alkyllithium addition reaction or the like, it can be converted to an aldehyde, a carboxylic acid, a thiol, an alcohol, a ketone, or the like, if desired, as described above.

In the chemical modification treatment with these chemical modifiers, the raw material of the syndiotactic styrene-based polymer is preferably in the form of a powder having an average particle size of 150 μm or less. Either a homogeneous system or a swelling system can be used. When the reaction is carried out in a homogeneous system, trichlorobenzene, decalin, pyridine and the like are usually used as a solvent for dissolving the polymer, but in the case of a relatively low molecular weight compound, chloroform and methyl chloride can also be used. . When the reaction is carried out in a heterogeneous system, water, alcohol, other polar solvents and the like are used as a solvent for suspending the polymer. On the other hand, when the reaction is carried out in a swelling system, carbon disulfide is usually used as a solvent for swelling the polymer. In the case of a relatively high molecular weight monomer, chloroform, methylene chloride and the like can also be used. . Of these, heterogeneous and swollen systems are preferred.

There are no particular restrictions on the temperature, time, amount of reagent used, etc. in this chemical modification treatment, and each reaction can be carried out in accordance with the conditions generally used for atactic polystyrene. In this way, a crystalline chemically modified styrenic polymer is obtained, and the amount of modification must be in the range of 10 ^-4 to 15 mol%. If the amount of modification is less than 10 ^-4 mol%, the object of the present invention cannot be sufficiently achieved, and if it exceeds 15 mol%, the crystallinity is impaired. Next, the crystalline chemically modified styrenic polymer of the present invention comprises (A) a compound represented by the general formula (I):

[0054]

Embedded image

Wherein R ¹ and m are the same as above. A repeating unit having a syndiotactic structure represented by the formula (D) (a):

[0056]

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[Where X is -NO ₂ , -SO ₃ H, -S
OCL ₂ , —COR ⁷ (where R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms) or a monovalent metal atom, and R ¹ and m are the same as described above. (B)
General formula (V)

[0058]

Embedded image

[In the formula, Y represents a monovalent metal atom, a halogen atom, a —OOH group or a maleic anhydride residue, and R ¹ and m are the same as those described above. And (c) a general formula (VI)

[0060]

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[Wherein, Z ¹ and V ¹ each represent a halogen atom, a monovalent metal atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and a tin atom. And they may be the same or different, and R ² , R ³ , R ⁴ and n are the same as described above. And a repeating unit represented by the general formula (VII):

[0062]

Embedded image

[Wherein Z ² and V ² each represent a halogen atom, a monovalent metal atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and a tin atom] And they may be the same or different, and R ⁵ , R ⁶ and p are the same as described above. And a chemically modified unit composed of at least one selected from the repeating units represented by the formula:

In this crystalline chemically modified styrenic polymer, the content (D) of the chemically modified unit (chemically modified amount) must be in the range of 10 ^-4 to 15 mol%. If the content is less than 10 ^-4 mol%, the object of the present invention cannot be sufficiently achieved, and if it exceeds 15 mol%, the crystallinity is impaired. Further, the reduced viscosity at a concentration of 0.05 g / deciliter measured at a temperature of 135 ° C. in 1,2,4-trichlorobenzene is 0.01 to 20 deciliter / d.
It must be in the range of g. This reduced viscosity is 0.0
If it is less than 1 deciliter / g, the physical properties are insufficient, while if it exceeds 20 deciliter / g, the processability is reduced.
Further, the polymer has a crystal structure in which the main chain has a syndiotactic structure and has a crystal melting temperature in the range of 230 to 350 ° C. Here, the crystal melting temperature refers to a melting temperature observed in a process of once melting in a nitrogen atmosphere, returning to normal temperature, and then raising the temperature by a differential scanning calorimeter. The crystalline chemically modified styrene-based polymer can be easily produced by appropriately selecting the raw materials of the syndiotactic styrene-based polymer and the chemical modifying agent according to the production method of the present invention and chemically modifying the same.

[0065]

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. Example 1 (Production of acylated modified product of syndiotactic polystyrene) Weight average molecular weight 430,00 produced according to a known method
1.0 g of syndiotactic polystyrene (particle size of 149 μm or less) of 1.8 g of aluminum chloride, 1.84 mmol,
Add to a slurry solution of 5 ml of carbon disulfide containing 1.84 mmol of acetyl chloride and, with stirring, add 2 ml of acetyl chloride.
The reaction was performed at 0 ° C. for 15 minutes. After completion of the reaction, the reaction was stopped by pouring it into a large amount of methanol, washed sufficiently, and dried. The yield was 1.053 g. ^{From 1} H-NMR, 2.
A methyl group derived from acetyl chloride was observed at around 36 ppm, and the acylation ratio determined from this was 13.0 mol%. The melting point of this product was measured under the following conditions using a differential scanning calorimeter (DSC) [melting point (T
m). ] Was 236.7 ° C. Measurement conditions of differential scanning calorimeter (1) 30 to 305 ° C. 20 ° C./min (heating) (2) Hold at 305 ° C. for 5 minutes (3) 305 to 30 ° C. 7 ° C./min (cooling) (4) 30 to 300 20 ° C./min (temperature rise) The methyl ethyl ketone (MEK) insoluble portion was 97% by weight, which was almost the same as 98% by weight of the syndiotactic polystyrene before chemical modification. Furthermore, 1, 2,
Concentration measured in 4-trichlorobenzene at 135 ° C.
The reduced viscosity of 05 g / deciliter was 2.02 deciliter / g.

Example 2 (Production of a nitrated modified product of syndiotactic polystyrene) Syndiotactic polystyrene 2.0 shown in Example 1
g in 20 ml of 98% by weight concentrated sulfuric acid and 67% by weight
Disperse in a mixed solution with 20 ml of nitric acid,
The reaction was performed for 0 minutes. After completion of the reaction, the polymer powder was recovered, washed with sufficient water, replaced with methanol, and dried. As a result, 2.02 g of chemically modified polystyrene was obtained.
As a result of elemental analysis, the nitration ratio was 2.1 mol%, the melting point was 267.9 ° C., and the MEK insoluble portion was 98% by weight. The reduced viscosity was 1.93 deciliter / g.

Example 3 (Production of Chemically Modified Syndiotactic Polystyrene Using Unsaturated Group) (1) (Production of Syndiotactic Polystyrene Copolymer Having Unsaturated Group) Equipped with a 0.5 L internal volume stirrer After replacing the reaction vessel with nitrogen, the mixture was heated to 70 ° C., and a sufficiently dried mixture of 300 milliliters of toluene, 200 milliliters of styrene, and 30 millimoles of p- (3-butenyl) styrene was added thereto, and 12 millimoles of aluminoxane and 12 millimoles of TIBA were added. Was added and stirred for 30 minutes. Next, 15 μmol of pentamethylcyclopentadienyltitanium trimethoxide was added, and the reaction was performed for 2 hours. After the completion of the reaction, the mixture was poured into a large amount of methanol, washed and dried to obtain 10.5 g of a copolymer. When the obtained copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, 98% by weight was an insoluble portion. In addition, the insoluble part is 1, 2,
The reduced viscosity at a concentration of 0.05 g / deciliter measured at 135 ° C. in the 4-trichlorobenzene solution was 2.0 deciliter / g. Further, using a differential scanning calorimeter (DSC-200, manufactured by Seiko Denshi Co., Ltd.), a 5.7 mg sample of the copolymer was prepared at 50 to 310 ° C. at 20 ° C. /
After the temperature was raised at a rate of 20 minutes per minute, the temperature was lowered to 310 to 30 ° C. at a rate of 20 ° C./minute. Further, an endothermic pattern when the temperature was raised again to 30 to 315 ° C. at a rate of 20 ° C./min was observed. As a result, it was confirmed that the copolymer had a melting temperature of 245 ° C. According to the measurement of ¹³ C-NMR, the syndiotacticity was at least 92% for racemic pentad. In the IR, a stretching vibration of a carbon-carbon double bond due to the styrene unit is observed at 1630 cm ⁻¹ , and the copolymerization reaction with styrene proceeds mainly with the olefin unit of p- (3-butenyl) styrene. Turned out to be. The content of the p- (3-butenyl) styrene unit is 3.
It was 0 mol%.

(2) Production of Chemically Modified Product 2.0 g of the styrene copolymer (particle size of 149 μm or less) produced in (1) was dispersed in 50 ml of hexane, and water in the system was removed by bubbling with nitrogen. did. To this was added 5 mmol of n-butyllithium and reacted at 70 ° C. for 30 minutes. A portion of the metallized product thus obtained was thrown into the reaction reagents shown in Table 1 and further reacted. After completion of the reaction, methanol was added to recover the polymer. Table 1 shows the results.

[0069]

[Table 1]

In the table (Note): 20 ml of toluene, 70 ° C., time 30 minutes 3- (2) -1 and 3- (2) -1
In the infrared absorption spectrum of (2) -2, the absorption at 1630 cm ^-1 observed in 3- (1) disappeared, and a new absorption shown in Table 1 appeared.

Comparative Example 1 In Example 1, 30 ml of carbon disulfide, 37.5 mmol of aluminum chloride and 37.
Acylation was carried out as in Example 1, except that 5 mmol was used. As a result, 1.14 g of an acylated product was obtained. The acylation ratio was 37.5 mol%, it did not show a melting point, and the MEK-insoluble portion was 20% by weight.

Comparative Example 2 Nitration was carried out in the same manner as in Example 2, except that the reaction time was changed to 30 minutes. As a result, 2.23 g of a nitrated product was obtained. It had a nitration rate of 31.0 mol%, no melting point, and a MEK-insoluble portion of 62% by weight.
Met.

[0073]

As described above, according to the present invention, high performance can be obtained by chemically modifying a styrene polymer having a syndiotactic structure or a styrene copolymer having a double bond in a side chain with a chemical modifier. For the purpose of easily and efficiently producing a styrene-based polymer having a syndiotactic structure with a small amount of amorphous by-products, in which various functional groups and substituents are introduced, without impairing the crystallinity. be able to. The crystalline chemically modified styrenic polymer thus obtained has compatibility, adhesiveness, printability, antistatic properties and the like, and is useful as a material such as a composite material.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-146912 (JP, A) JP-A-62-104818 (JP, A) JP-A-1-95113 (JP, A) JP-A-4-104 88004 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/00-8/50 C08F 12/00-12/36

Claims (2)

(57) [Claims] (A) General formula (1) [Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryl group or a silicon-containing group, m is an integer of 1 to 5, and when m is plural, m R ^{1 s} may be the same or different. A styrenic polymer having a syndiotactic structure comprising a repeating unit represented by the formula (A) or a repeating unit (A) and a general formula (B) Wherein R ² is a hydrocarbon group having 1 to 20 carbon atoms, R ³ and R ⁴ are each a hydrogen atom, a halogen atom or a carbon atom
Represents a hydrocarbon group of from 8 to 8, wherein n is an integer of from 1 to 4,
In the case where there are a plurality of groups, n R ^{4 's} may be the same or different. And / or (C) a general formula: [Wherein, R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms;
And p is a plurality, and when p is plural, p R ⁶ may be the same or different. ] A styrene-based polymer having a syndiotactic structure containing a repeating unit represented by the following formula: is substituted with a benzene ring that is a nitrating, acylating, sulfonating, metalating, or chlorosulfonating agent. Α-position hydrogen-substitution reagent, hydroxylation reagent, radical addition reagent, metallation reagent, borohydride agent, hydrogensulfate alkylating agent or side chain carbon-carbon which is a halogenating agent By reacting at least one selected from reagents for addition reaction to the double bond, the amount of denaturation is 10 ^-4 to 15
A method for producing a crystalline chemically modified styrenic polymer, characterized in that it is chemically modified to have a molar percentage. (A) a general formula: [Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryl group or a silicon-containing group, m is an integer of 1 to 5, and when m is plural, m R ^{1 s} may be the same or different. And a repeating unit having a syndiotactic structure represented by the formula (D) (a): Wherein, X is _{-NO 2, -SO 3 H, -SOCl} 2, -
COR ⁷ (where R ⁷ is a hydrocarbon group having 1 to 8 carbon atoms) or a monovalent metal atom, and R ¹ and m are the same as described above. A repeating unit represented by the general formula (b): [Wherein Y is a monovalent metal atom, a halogen atom, -OOH
Represents a group or a maleic anhydride residue, and R ¹ and m are the same as described above. A repeating unit represented by the formula (c): [Wherein, Z ¹ and V ¹ each represent a halogen atom, a monovalent metal atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a tin atom; well be different even identical to one another, R ² is a hydrocarbon group having 1 to 20 carbon atoms, R ³
And R ⁴ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 1 to 4, and when n is plural, n different R ⁴ are the same or different. It may be. And a repeating unit represented by the formula (d): [Wherein, Z ² and V ² each represent a halogen atom, a monovalent metal atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a tin atom; ^May be the same or different from each other, and R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, p is an integer of 1 to 4, and p is In the case of a plurality, p R ⁶ may be the same or different. R ² is the same as above. And a chemically modified unit consisting of at least one selected from the repeating units represented by
And a reduced viscosity at a concentration of 0.05 g / deciliter measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C. in a content of the chemically modified unit (D) of 10 ⁻⁴ to 15 mol%. A crystalline chemically modified styrenic polymer characterized by having a crystal melting temperature in the range of 0.01 to 20 deciliters / g and a crystal melting temperature of 230 to 350 ° C.