JPH05320250A - Chemically modified styrene polymer and its production - Google Patents

Abstract

PURPOSE:To produce a chemically modified styrene polymer having various functional groups introduced for improving the performance by reacting a specific syndiotactic styrene polymer with a specific reagent. CONSTITUTION:A syndiotactic styrene polymer comprising repeating units of formula I (wherein R<1> is H, alkyl, etc.) or comprising repeating units of formula I and formula H (wherein R<2> is a 1-20C hydrocarbon group; R<3> and R<4> are each H, halogen, alkyl, etc.; and n is 1-4) and/or formula III (wherein R5 and R6 are each halogen, etc.; and p is 1-4) is chemically modified by reacting it with at least one reagent selected from the group consisting of a substitution reagent which reacts with a benzene ring, a reagent which substitutes for a hydrogen atom at the alpha-position, and a reagent which is added to a double bond in a side chain to such an extent that the amt. of modification of 10<-4>-15mol% is obtd., thus giving the objective polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel crystalline chemically modified styrene polymer and a method for producing the same.
More specifically, the present invention is a method for efficiently producing a crystalline chemically modified styrene-based polymer by optimally and simply chemically modifying a styrene-based polymer having a crystalline syndiotactic structure, depending on the application, Further, the present invention relates to a crystalline chemically modified styrene-based polymer which is provided with compatibilizing ability, adhesiveness, printability, antistatic property and the like and is useful as a material for composite materials and the like.

[0002]

2. Description of the Related Art Styrene-based polymers conventionally produced by radical polymerization or the like are molded into various shapes by various molding methods, and are used for household appliances, office equipment, household products, packaging containers, toys, It is widely used as furniture, synthetic paper, and other industrial materials, but its three-dimensional structure has an atactic structure, which has the drawback of poor heat resistance and chemical resistance. The research group of the present inventors has succeeded in developing a styrene-based polymer having a high syndiotactic structure so far by solving such drawbacks of the styrene-based polymer having an atactic structure. We have also developed a styrenic copolymer in which a styrenic monomer and other monomers are copolymerized. For example, a syndiotactic copolymer of styrene and substituted styrene (JP-A-63-241009), a syndiotactic copolymer of styrene and a polar monomer (JP-A-2-2588).
No. 10, gazette and No. 2-258805 gazette) were succeeded in development. However, the production of syndiotactic copolymer by such copolymerization has the following problems. (1) Amorphous solvent-soluble by-products may be produced, or the crystallinity, which is a characteristic feature of syndiotactic styrene resins, may be impaired. (2) The copolymerization comonomer species is limited, and the introduction of various functional groups and substituents for the purpose of improving the performance of the syndiotactic styrene resin is unavoidable. (3) Since monomers having different copolymerizability are used, it is necessary to set optimum polymerization conditions for each, and the operation is complicated.

[0003]

Under the above circumstances, the present invention provides a syndyne having a small amount of an amorphous by-product polymer into which various functional groups or substituents for high performance have been introduced. It was made for the purpose of developing a method for easily and efficiently producing a styrene polymer having an tactic structure without impairing the crystallinity.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have identified a specific styrene-based polymer or copolymer having a syndiotactic structure by a specific chemical method. It has been found that the object can be achieved by modifying with a modifier at a predetermined ratio.
The present invention has been completed based on such findings. That is, the present invention provides (A) general formula (I)

[0005]

[Chemical 9]

[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 ^1's are They may be the same or different. ] A styrene-based polymer having a syndiotactic structure comprising a repeating unit represented by the above, or the above-mentioned (A) repeating unit and (B) general formula (II)

[0007]

[Chemical 10]

[In the formula, R ² represents 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, and n is 1 to 1 Is an integer of 4, and when n is plural, n R ^{4 s} may be the same or different. ] And / or (C) the general formula (III)

[0009]

[Chemical 11]

[In the formula, 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 is plural. The R ^{6 s} may be the same or different. ] A styrene-based polymer having a syndiotactic structure containing a repeating unit represented by the following formulas, a benzene ring substitution reaction reagent, an α-position hydrogen substitution reaction reagent and a side chain carbon-carbon double bond addition reaction reagent A method for producing a crystalline chemically modified styrenic polymer, characterized in that at least one selected from the group is allowed to act to chemically modify so that the modification amount is 10 ⁻⁴ to 15 mol%. is there. The present invention also provides (A) general formula (I)

[0011]

[Chemical formula 12]

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

[0013]

[Chemical 13]

[In the formula, X is -NO ₂ , -SO ₃ H, -S
OCl ₂ , —COR ⁷ (provided that 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 above. ] The repeating unit represented by
General formula (V)

[0015]

[Chemical 14]

[In the formula, Y represents a monovalent metal atom, a halogen atom, an —OOH group or a maleic anhydride residue, and R ¹ and m are the same as defined above. ] The repeating unit represented by the formula (c), the general formula (VI)

[0017]

[Chemical 15]

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

[0019]

[Chemical 16]

[Wherein Z²And V²Are each halogen
Atom, monovalent metal atom or carbon atom, oxygen atom, nitrogen
Any of elementary atom, sulfur atom, silicon atom and tin atom
A substituent containing one or more groups, which may be the same as each other
May be different, R ^Five, R⁶And p are
Are the same]
Containing at least one chemically modified unit,
The content of the (D) chemically modified unit is 10^-Four~ 15 mol
%, In 1,2,4-trichlorobenzene at a temperature of 135 ° C.
Reduced viscosity at a concentration of 0.05 g / deciliter measured in degrees
Degree 0.01 ~ 20 deciliter / g and crystal melting temperature
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 styrene polymer having a syndiotactic structure composed of the 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 styrene-based copolymer having a syndiotactic structure consisting 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 or a tertiary butyl group. And the like, and the alkoxy group includes alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, and isopropoxy group. As the aryl group, a benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, chrysene ring, biphenyl ring, terphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, heptalen ring, biphenylene ring, as-indacene ring, s-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring, acephenanthrene ring, aceanthrylene ring, triphenylene ring, naphthacene ring, preaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring, Rubisen ring,
Substituents containing a corosene ring, a pyrantrene ring and an ovarene ring are shown. 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 trialkyl group. Examples thereof include alkoxysilyl groups such as methoxysilyl group, and siloxysilyl group.

Among the styrene-based monomers forming the repeating unit represented by the 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-
Dimethyl styrene; p-ethyl styrene; m-ethyl styrene; p-tert-butyl styrene; alkyl styrenes such as p-phenyl 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 aryl styrene monomer in which R ¹ is an aryl group include vinylphenyls such as 4-vinylbiphenyl, 3-vinylbiphenyl and 2-vinylbiphenyl; 1- (4-vinylphenyl) naphthalene, 2- (4-Vinylphenyl) naphthalene, 1-
Vinylphenyl naphthalenes 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-
Vinyl such as (2-vinylphenyl) phenanthrene, 2- (2-vinylphenyl) phenanthrene, 3- (2-vinylphenyl) phenanthrene, 4- (2-vinylphenyl) phenanthrene, 9- (2-vinylphenyl) phenanthrene Phenylphenanthrenes; 1- (4
Vinylphenylpyrenes such as -vinylphenyl) pyrene, 2- (4-vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene; 4-vinyl-4'-bromobiphenyl, 4-vinyl-3'-bromo Biphenyl, 4-
Vinyl-2'-bromobiphenyl, halogenated vinylbiphenyls such as 4-vinyl-2-bromobiphenyl, 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; 4-Vinyl-4'-trimethylstannylbiphenyl, 4-vinyl-4'-tributylstannylbiphenyl and other trialkylstannylvinylbiphenyls; 4
-Vinyl-4'-trimethylsilylmethylbiphenyl and other trialkylsilylmethylvinylbiphenyls; 2-
Vinylphenylpyrenes such as (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 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
-Terphenyl, vinyl terphenyls such as 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 , Vinyl alkyl biphenyls such as 3-methyl-4-vinylphenyl; 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;
Examples thereof include trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4′-trimethylstannylmethylbiphenyl and 4-vinyl-4′-tributylstannylmethylbiphenyl. Further, 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, o-triethyl. Alkylsilylstyrenes such as silylstyrene, p-dimethyltert-butylsilylstyrene, phenylstyrene-containing silylstyrenes such as p-dimethylphenylsilylstyrene, p-methyldiphenylsilylstyrene, p-triphenylsilylstyrene, p-
Hydro group-containing silylstyrenes such as dimethylhydrosilylstyrene, p-methyldihydrosilylstyrene, p-trihydrosilylstyrene, p-dimethylchlorosilylstyrene, p-methyldichlorosilylstyrene, p-trichlorosilylstyrene, p-dimethylbromosilyl Styrene, halogen-containing silylstyrenes such as p-dimethyliodosilylstyrene, p-dimethylmethoxysilylstyrene, p-methyldimethoxysilylstyrene, p-
Alkoxy group-containing silylstyrenes such as trimethoxysilylstyrene, silyl group-containing silylstyrenes such as p- (p-trimethylsilyl) dimethylsilylstyrene, 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
Examples thereof include silyl-substituted alkyl) styrenes and siloxysilylstyrenes such as p-trimethylsiloxydimethylsilylstyrene. These styrene-based monomers forming the repeating unit represented by the general formula (I) may be used alone 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, or a carbon number. 6-20 arylene groups, C7-20 alkylarylene groups, arylalkylene groups, etc. are shown. Specific examples thereof 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 are each a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or a carbon number 1
~ 8 monovalent hydrocarbon groups (for example, saturated hydrocarbon groups represented by alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group or unsaturated hydrocarbon groups such as vinyl group) And n is an integer of 1 to 4.
When n is plural, n R ⁴ may be the same or different.

The styrene-based monomer forming the repeating unit represented by the general formula (II) is represented by the general formula (I
When R ^{2 of} 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. 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 can be mentioned.

Further, it is represented by the general formula (III).
(C) R in the repeating unit^FiveAnd R ⁶Is the general formula
R in (II)³And R^FourIs the same as
It is an integer of 1 to 4. When p is plural, p
R⁶May be the same or different. This general formula (III)
A styrenic monomer forming a repeating unit represented by
For example, p-divinylbenzene, m-divinyl
Rubenzene, trivinylbenzene, p-isopropenyl
Examples include styrene. In the present invention, the
Form repeating units represented by general formulas (II) and (III)
These monomers may be used alone or in combination of two or more.

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

The syndiotactic structure referred to here is
It is possible to obtain a compound whose stereochemical structure has a syndiotactic structure. 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, is alternately located in the opposite direction with respect to the main chain formed from carbon-carbon bonds. It has a three-dimensional structure, and its tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, two diads, three triads, and five pentads. .. The styrenic polymer having a high syndiotactic structure referred to in the present invention is, in the chain of styrenic repeating units, preferably 75% or more by racemic dyad, more preferably 85% or more, or preferably racemic pentad. Indicates those having a syndiotacticity of 30% or more, more preferably 50% or more. However, the degree of syndiotacticity varies slightly depending on the type of substituent. The molecular weight of the styrene-based polymer may be various depending on the polymerization conditions and the like. Generally, the weight-average molecular weight in GPC [1,2,4-trichlorobenzene, 135 ° C, polystyrene conversion] measurement is 1,000 to 300,000, preferably 5
It is 000 to 250,000. Further, those having a reduced viscosity of 0.01 to 20 deciliter / g at a concentration of 0.05 g / deciliter measured at a temperature of 135 ° C. in 1,2,4-trichlorobenzene are preferable.

The styrene-based polymer having the syndiotactic structure is a styrene-based monomer forming the (A) unit, or a styrene-based monomer forming the (B) unit with the styrene-based monomer and / or (C). A catalyst containing, as a main component, a styrene-based monomer forming a unit, (a) a transition metal compound and (b) a contact product of an organoaluminum compound and a condensing agent, or (a) a transition metal compound and (c) It can be produced by polymerizing in the presence of a catalyst whose main component is a compound capable of reacting with a transition metal compound to form an ionic complex. There are various transition metal compounds of the above-mentioned component (a), but it is preferable to use the general formula (VIII) M ¹ R ⁸ ... R ^k ... (VIII) [wherein M ¹ is Ti. , Zr, Cr, V, Nb, Ta or Hf, and 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 having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group;
C1-C20 acyloxy group, allyl group, substituted allyl group, acetylacetonato group, substituted acetylacetonato group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen molecule, Lewis base, chain unsaturated Ligands such as hydrocarbons or cyclic unsaturated hydrocarbons, cyclopentadienyl groups, substituted cyclopentadienyl groups, indenyl groups, substituted indenyl groups, tetrahydroindenyl groups,
A substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. In addition, k represents the valence of the metal, and generally includes an integer of 2 to 5).

Examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group Examples thereof include an enyl group and a trimethylsilylcyclopentadienyl group. Further, the ligands of R ⁸ to R ^k may form crosslinked by covalent bonds between the ligands.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a carbon number of 1 to 20.
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, and an alkoxy group having 1 to 20 carbon atoms includes a methoxy group, 6 to 20 carbon atoms such as ethoxy group, propoxy group, butoxy group, phenoxy group
Examples of the aryl group, alkylaryl group or arylalkyl group include a phenyl group, a tolyl group, a xylyl group, a benzyl group and the like, and an acyloxy group having 1 to 20 carbon atoms includes a heptadecylcarbonyloxy group and the like containing a silicon atom. As the group, a trimethylsilyl group,
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, phosphines such as triethylphosphine and triphenylphosphine,
Chain unsaturated hydrocarbons include ethylene, butadiene,
Examples of cyclic unsaturated hydrocarbons such as 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and their derivatives. Examples thereof include derivatives. Examples of the crosslink by a covalent bond include methylene crosslink, dimethylmethylene crosslink, ethylene crosslink, dimethylsilylene crosslink, and dimethylstannylene crosslink.

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

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

Specific examples of the hafnium compound include cyclopentadienyl hafnium 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, cyclopenta Examples thereof include dienyl vanadium dichloride and dicyclopentadienylmethyl vanadium.

Specific examples of the niobium compound include niobium pentachloride, tetrachloromethylniobium, dichlorotrimethylniobium, dicyclopentadienylniobium dichloride, dicyclopentadienylniobium trihydride, pentabtoxniobium and the like. Specific examples of the tantalum compound include tantalum pentachloride, dichlorotrimethyltantalum, dicyclopentadienyltantalum trihydride, pentabtoxniobium, and the like, and specific examples of the chromium compound include chromium trichloride, tetrabutoxychromium, and tetramethyl. Examples include chromium, dicyclopentadienyl chromium, dibenzene chromium and the like. Further, as the other transition metal compound, those obtained by supporting the above transition metal compound on a carrier such as a magnesium compound or a silicon compound can be used, and those obtained by modifying the above transition compound with an electron donating compound can also be used. .. Particularly preferable among these transition metal compounds are titanium compounds and zirconium compounds. The contact product of the organoaluminum compound used as the contact component (b) with the condensing agent is obtained by contacting various organoaluminum compounds with the condensing agent. Here, the organoaluminum compound is usually a general formula (IX) AlR ⁹ ₃ ... (IX) [In the formula, R ⁹ represents an alkyl group having 1 to 8 carbon atoms. ] An organoaluminum compound represented by Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum. Of these, trimethylaluminum is preferable. In addition, as the condensing agent, water can be mentioned as a typical one, but in addition to this, any compound in which a trialkylaluminum is subjected to a condensation reaction, for example, copper sulfate pentahydrate,
Various kinds of water such as water adsorbed on an inorganic substance or an organic substance can be used. Specific examples of the contact product of the organoaluminum compound and the condensing agent include general formula (X)

[0035]

[Chemical 17]

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

[0037]

[Chemical 18]

[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 defined above. ] A cyclic alkylaluminoxane represented by

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

This contact product (for example, alkylaluminoxane), after the above-mentioned contact reaction, when a hydrous compound or the like is used, the solid residue is filtered off, and the filtrate is heated 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
What was heat-treated while distilling off the solvent for 5 hours is preferable. In this heat treatment, the temperature may be appropriately determined depending on various situations, but it is usually performed in the above range. Generally, at a temperature of less than 30 ° C., the effect does not appear, and 2
If the temperature exceeds 00 ° C, thermal decomposition of the alkylaluminoxane itself occurs, which is not preferable. Then, depending on the treatment conditions of the heat treatment, the reaction product is obtained in the form of a colorless solid or solution. The product thus obtained can be used as a catalyst solution by dissolving or diluting it with a hydrocarbon solvent, if necessary.

A preferable example of the contact product of the organoaluminum compound used as the catalyst component (b) and the condensing agent, particularly an alkylaluminoxane, is an aluminum-methyl group (A) observed in a proton nuclear magnetic resonance spectrum.
The high magnetic field component in the methyl proton signal region based on the 1-CH ₃ ) bond is 50% or less. That is, when the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum of the above contact product is observed in a toluene solvent at room temperature, the methyl proton signal based on “Al—CH ₃ ” is a tetramethylsilane (TMS) standard. 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 (that is, -0.1 to -0.5 ppm) and the other magnetic field component (that is, 1.0 to -0.1 ppm) are measured based on the standard, the high magnetic field component is the whole. 50% or less, preferably 45 to 5%, can be suitably used as the catalyst component.

Next, (c) transition used as a contact component
Capable of reacting with a metal transfer compound to form an ionic complex
There is no particular limitation on the compound, but a cation and multiple groups
A compound consisting of an anion bound to an element, especially
An array consisting of an on and an anion in which multiple groups are bound to an element.
A complex compound can be preferably used. Such a power
Composed of thione and anion in which multiple groups are bound to an element
The compounds include IIIB group, IVB group, VB group and VI of the periodic table.
B, VIIB, VIII, IA, IB, IIA, IIB,
Cations and complexes containing elements selected from the IVA and VIIA groups
The bases of the numbers are VB, VIB, VIIB, VIII, and IB of the periodic table
Group II, IIIB, IIIA, IVA and VA elements
A compound consisting of an anion bound to
(XII) or (XIII) ([L¹-R^Ten]^{u +})_V (M²Z¹Z²... Z^e]^(ef)-)_W ... (XII) or ([L²]^{u +})_V (M³Z¹Z²... Z^e]^(ef)-)_W ... (XIII) (However, L²Is M^Four, R¹¹R¹²M^Five, R¹³ ₃C or R¹⁴
M^Five[Wherein L¹Is Lewis base, M²And M³
Are the VB group, VIB group, VIIB group, and VIII of the periodic table, respectively.
Group, IB, IIB, IIIA, IVA, and V
Element, M^FourAnd M^FiveIs the IIIB group of the periodic table,
Group IV, Group V, Group VIB, Group VIIB, Group VIII, Group I, Group IB,
Element selected from IIA group, IIB group and VIIA group, Z¹~ Z
^eAre a hydrogen atom, a dialkylamino group, and an alkoxy group, respectively.
Si group, C1-C20 alkoxy group, C6-C20
Aryloxy group, C1-C20 alkyl group, charcoal
Aryl groups, alkylaryl groups, and ants having a prime number of 6 to 20
Alkyl group, halogen-substituted hydrocarbon having 1 to 20 carbon atoms
Elementary group, C1-C20 acyloxy group, organic metalloy
Z group or halogen atom, Z¹~ Z^eHaha 2 and above
The above may be bonded to each other to form a ring. R^TenIs water
Elementary atom, C1-C20 alkyl group, C6-C20
Aryl group, alkylaryl group or arylalkyl of
R group, R¹¹And R¹²Are each cyclopentadiene
Nyl group, substituted cyclopentadienyl group, indenyl group or
Is a fluorenyl group, R¹³Is alkyl having 1 to 20 carbons
Group, aryl group, alkylaryl group or arylal
Indicates a kill group. R¹⁴Is tetraphenylporphyrin,
A macrocyclic ligand such as tarocyanine is shown. f is M², M
³Is an integer of 1 to 7, e is an integer of 2 to 8, and u is
[L¹-R^Ten], [L ²] With an ionic valence of 1 to 7
Number, v is an integer of 1 or more, and w = (v × u) / (ef)
is there. ] It is a compound represented by these.

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

Also, M²And M³As a concrete example of
B, Al, Si, P, As, Sb, M, etc.^FourWith a concrete example of
Then, Li, Na, Ag, Cu, Br, I, I₃Na
Th, M^FiveAs specific examples of Mn, Fe, Co, Ni,
Zn etc. are mentioned. Z¹~ Z ^eAs a concrete example of
For example, a dimethylamino group as the dialkylamino group,
Diethylamino group; as an alkoxy group having 1 to 20 carbon atoms
Methoxy group, ethoxy group, n-butoxy group, carbon number 6
A phenoxy group as the aryloxy group of -20, 2,6
-Dimethylphenoxy group, naphthyloxy group, carbon number 1
~ 20 alkyl groups as methyl, ethyl, n-type
Ropyl group, iso-propyl group, n-butyl group, n-o
Octyl group, 2-ethylhexyl group, C6-20
Reel group, alkylaryl group or arylalk
Group as a phenyl group, p-tolyl group, benzyl group,
Interfluorophenyl group, 3,5-di (trifluoromethine)
Tyl) phenyl group, 4-tert-butylphenyl
Group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group
Phenyl group, 2,4-dimethylphenyl group, 2,3-dimethyl
Cylphenyl group, 1,2-dimethylphenyl group, carbon number
1-20 halogen-substituted hydrocarbon groups as p-fluoro
Phenyl group, 3,5-difluorophenyl group, pentac
Lolophenyl group, 3,4,5-trifluorophenyl
Group, pentafluorophenyl group, 3,5-di (triflu
Oromethyl) phenyl group, F, C as halogen atom
l, Br, I; pentamethylanti as an organic metalloid group
Mon group, trimethylsilyl group, trimethylgermyl group,
Diphenylarsine group, dicyclohexyl antimony
Group, a diphenylboron group. R^Ten, R¹³Concrete
Examples include those similar to those listed above.
R¹¹And R¹²Specific examples of the substituted cyclopentadienyl group of
Is a methylcyclopentadienyl group, butylcyclo
Pentadienyl group, pentamethylcyclopentadienyl
Examples thereof include those substituted with an alkyl group such as a group. This
Here, the alkyl group usually has 1 to 6 carbon atoms and is not substituted.
The number of alkyl groups can be selected from an integer of 1 to 4
It

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

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

In the present invention, an organometallic compound as a component (d) may be used in combination with the above (a) catalyst component and (b) catalyst component, or (a) catalyst component and (c) catalyst component, if desired. it can. As the (d) organometallic compound optionally used in combination, a compound represented by the general formula (XIV) M ⁶ (R ¹⁵ ) _S (XIV) is used. In this general formula (XIV), R ¹⁵ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom. Number 7
~ 20 aralkyl groups are shown. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group,
Examples thereof include n-butyl group, i-butyl group, hexyl group, 2-ethylhexyl group and phenyl group. And M
⁶ is lithium, sodium, potassium, magnesium,
Zinc, cadmium, aluminum, boron, gallium,
Indicates silicon or tin. In addition, 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. Such as dialkylzinc compounds, alkylgallium compounds such as trimethylgallium, triethylgallium and tripropylgallium, alkylboron compounds such as triethylboron, tripropylboron and tributylboron, alkyltin compounds such as tetraethyltin, tetrapropyltin and tetraphenyltin And so on. Also, M ⁶ is
There are various compounds in the case of aluminum. Specific examples thereof include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trioctylaluminum.

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

The ratio of the styrene-based monomer to the catalyst used is not particularly limited, but the molar ratio of styrene-based monomer / transition metal compound is usually 10 to 10 ¹² , preferably 10 ² to 10 ^8. To be chosen. In the polymerization reaction of the present invention, generally, the polymerization temperature may be 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. The polymerization method may be bulk, solution or suspension polymerization. In solution polymerization, usable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, alicyclic hydrocarbons such as cyclohexane, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene.
Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferable. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected.

In the present invention, the styrene polymer having a syndiotactic structure comprising the (A) repeating unit thus obtained, or the (A) repeating unit and the (B) repeating unit and / or Alternatively, a styrene-based polymer having a syndiotactic structure containing (C) a repeating unit is chemically modified by acting a chemical modifier. As the chemical modifier, a benzene ring substitution reaction reagent, α
At least one selected from a position hydrogen substitution reaction reagent and an addition reaction reagent to a side chain carbon-carbon double bond is used. Here, when a polymer composed of the repeating unit (A) is used as the styrene-based polymer, both a benzene ring substitution reaction reagent and an α-position hydrogen substitution reaction reagent are used as the chemical modifier. When a copolymer containing the repeating unit (A) and the repeating unit (B) and / or the repeating unit (C) is used, the chemical modifier may be a benzene ring substitution reaction agent, α Both a position hydrogen substitution reaction reagent and a side chain carbon-carbon double bond addition reaction reagent can be used.

Examples of the substitution reaction reagent for the benzene ring include nitration reagent, acylation reagent, sulfonation reagent,
A metallizing agent and a chlorosulfonating agent are preferably used. When a nitro group is introduced using a nitration reagent, it can be converted into an amino group if desired.
Further, when metallized using a metallizing agent, for example, lithiated, it can be converted into an aldehyde, a carboxylic acid, a thiol, an alcohol, a ketone or the like, if desired. Further, as the α-position hydrogen substitution reaction reagent, for example, a radical reaction reagent and a metallization reagent are preferably used. Examples of the reaction using a radical reaction reagent include a bromination reaction with N-bromosuccinimide, a reaction with maleic anhydride, and other radical reactions. Further, when metallized by using a metallizing agent, it can be converted into an aldehyde, a carboxylic acid, a thiol, an alcohol, a ketone or the like as desired in the same manner as described above. Further, examples of the addition reaction reagent to the side chain carbon-carbon double bond include, for example, a hydroxylation reagent (for example, potassium permanganate), a radical addition reagent,
A metallizing agent (eg, alkyl lithium), a borohydride agent, a hydrogen sulfate alkylating agent, a halogenating agent (eg, halogen element, hydrogen halide), etc. are preferably used. Further, when metallized 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 syndiotactic styrene-based polymer is preferably in the form of powder having an average particle diameter of 150 μm or less. Both a homogeneous system and a swelling system can be used. When the reaction is carried out in a homogeneous system, trichlorobenzene, decalin, pyridine, etc. are usually used as a solvent for dissolving the polymer, but in the case of a relatively low molecular weight compound, chloroform, methyl chloride, etc. can also be used. .. When the reaction is carried out in a heterogeneous system, water, alcohol, other polar solvent, etc. 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, but in the case of a relatively high molecular weight monomer, chloroform, methylene chloride or the like can also be used. .. Among these, the heterogeneous system and the swelling system are preferable.

There are no particular restrictions on the temperature, time, amount of reaction reagent used, etc. in this chemical modification treatment, and each reaction can be carried out according to the conditions generally used in atactic polystyrene. In this way, a crystalline chemically modified styrene-based polymer is obtained, but its modification amount must be in the range of 10 ⁻⁴ to 15 mol%. When the modification amount is less than 10 ⁻⁴ mol%, the object of the present invention cannot be sufficiently achieved, and when it exceeds 15 mol%, the crystallinity is impaired. Next, the crystalline chemically modified styrenic polymer of the present invention is (A) general formula (I)

[0054]

[Chemical 19]

[In the formula, R ¹ and m are the same as defined above. A repeating unit having a syndiotactic structure represented by the formula (D) (a) and the general formula (IV)

[0056]

[Chemical 20]

[In the formula, X is --NO ₂ , --SO ₃ H, --S
OCl ₂ , —COR ⁷ (provided that 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 above. ] The repeating unit represented by
General formula (V)

[0058]

[Chemical 21]

[In the formula, Y represents a monovalent metal atom, a halogen atom, an —OOH group or a maleic anhydride residue, and R ¹ and m are the same as defined above. ] The repeating unit represented by the formula (c), the general formula (VI)

[0060]

[Chemical formula 22]

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

[0062]

[Chemical formula 23]

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

In this crystalline chemically modified styrene polymer, the content (chemically modified amount) of the (D) chemically modified unit must be in the range of 10 ⁻⁴ to 15 mol%. If this 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 was 0.01 to 20 deciliter /
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 workability is deteriorated.
Further, the polymer has a syndiotactic structure in the main chain and has crystallinity, and its crystal melting temperature is in the range of 230 to 350 ° C. Here, the crystal melting temperature refers to a melting temperature observed by a differential scanning calorimeter in the process of once melting in a nitrogen atmosphere, returning to normal temperature, and then raising the temperature. This crystalline chemically modified styrene-based polymer can be easily manufactured by appropriately selecting and chemically modifying the raw material syndiotactic styrene-based polymer and the chemical modifier according to the above-described manufacturing method of the present invention.

[0065]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 (Production of acylated modified product of syndiotactic polystyrene) Weight average molecular weight of 430,00 produced according to a known method.
1.0 g of syndiotactic polystyrene of 0 (particle size of 149 μm or less), 1.84 mmol of aluminum chloride,
Add to a slurry solution of 5 ml of carbon disulfide containing 1.84 mmol of acetyl chloride and, while stirring, 2
The reaction was carried out at 0 ° C for 15 minutes. After the reaction was completed, the reaction was stopped by pouring it into a large amount of methanol, thoroughly washing, and then drying. The yield was 1.053g. ^{From 1} H-NMR, 2.
A methyl group derived from acetyl chloride was found around 36 ppm, and the acylation rate determined from this was 13.0 mol%. The melting point of this product was measured by a differential scanning calorimeter (DSC) under the following conditions [melting point (T observed in (4) (T
m) is calculated. ] Was 236.7 ° C. Measurement conditions of differential scanning calorimeter (1) 30 to 305 ° C 20 ° C / min (temperature increase) (2) 305 ° C 5 minutes hold (3) 305 to 30 ° C 7 ° C / min (temperature decrease) (4) 30 to 300 C. 20.degree. C./min (temperature increase) 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. In addition, 1, 2,
Concentration measured at 135 ° C in 4-trichlorobenzene.
The reduced viscosity of 05 g / deciliter was 2.02 deciliter / g.

Example 2 (Production of Nitrated Modified Product of Syndiotactic Polystyrene) Syndiotactic polystyrene 2.0 shown in Example 1
20 g of 98% by weight concentrated sulfuric acid and 67% by weight
Disperse in a mixed solution with 20 ml of nitric acid and
The reaction was allowed for 0 minutes. After the reaction was completed, the polymer powder was collected, 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 rate was 2.1 mol%, the melting point was 267.9 ° C., and the MEK insoluble portion was 98 wt%. 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) With a stirrer having an inner volume of 0.5 liter After purging 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 mmol of p- (3-butenyl) styrene was added thereto, and 12 mmol of aluminoxane and 12 mmol of TIBA were added. Was added and stirred for 30 minutes. Then, 15 μmol of pentamethylcyclopentadienyltitanium trimethoxide was added and the reaction was carried out for 2 hours. After 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. The obtained copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, and 98% by weight was insoluble. In addition, 1, 2,
The reduced viscosity at a concentration of 0.05 g / deciliter measured at 135 ° C in a 4-trichlorobenzene solution was 2.0 deciliter / g. Further, a differential scanning calorimeter [DSC-200 manufactured by Seiko Denshi KK] was used to sample 5.7 mg of the above copolymer at 50 to 310 ° C. at 20 ° C. /
After the temperature was raised at a rate of minutes, the temperature was lowered to 310 to 30 ° C at a rate of 20 ° C / minute. Furthermore, the endothermic pattern was observed when the temperature was raised again to 30 to 315 ° C. at a rate of 20 ° C./min. As a result, it was confirmed that the above copolymer had a melting temperature of 245 ° C. The syndiotacticity of the racemic pentad was 92% or more as measured by ¹³ C-NMR. In IR, a stretching vibration of a carbon-carbon double bond due to a styrene unit was observed at 1630 cm ^-1 , and a copolymerization reaction with styrene mainly proceeded with an olefin unit of p- (3-butenyl) styrene. It turned out that The content of 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 nitrogen bubbling. did. To this, 5 mmol of n-butyllithium was added and reacted at 70 ° C. for 30 minutes. A part of the metal compound thus obtained was added to a reaction reagent shown in Table 1 to carry out further reaction. After completion of the reaction, methanol was added and the polymer was recovered. The results are shown in Table 1.

[0069]

[Table 1]

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

Comparative Example 1 In Example 1, 30 ml of carbon disulfide, 37.5 mmol of aluminum chloride and 37.
Acylation was performed 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 of this product was 37.5 mol%, it showed no melting point, and the MEK insoluble portion was 20 wt%.

Comparative Example 2 The nitration was carried out in the same manner as in Example 2 except that the reaction time was 30 minutes. As a result, 2.23 g of a nitrate was obtained. This product 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, a styrene-based polymer having a syndiotactic structure or a styrene-based copolymer having a double bond in a side chain is chemically modified with a chemical modifier to improve performance. A variety of functional groups and substituents for the purpose of producing a styrene-based polymer having a syndiotactic structure with less amorphous by-product polymer simply and efficiently without impairing the crystallinity. be able to. The crystalline chemically modified styrene-based polymer thus obtained is provided with compatibilizing ability, adhesiveness, printability, antistatic property, etc., and is useful as a material for composite materials and the like.

Claims (3)

[Claims] 1. (A) General formula: [In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group,
It 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 styrene-based polymer having a syndiotactic structure comprising a repeating unit represented by the above, or the above-mentioned (A) repeating unit and (B) a general formula: [In the formula, 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 number 1
~ 8 hydrocarbon groups, n is an integer of 1 to 4,
Is plural, n R ^{4 s} may be the same or different. ] And / or (C) the general formula: [In the formula, R ⁵ and R ⁶ are each a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and p is 1
Is an integer from 4 to 4, and when p is plural, p R ^{6 s} may be the same or different. ] A styrene-based polymer having a syndiotactic structure containing a repeating unit represented by the following formulas, a benzene ring substitution reaction reagent, an α-position hydrogen substitution reaction reagent and a side chain carbon-carbon double bond addition reaction reagent A method for producing a crystalline chemically modified styrene-based polymer, which comprises chemically reacting at least one selected from the above so that the modification amount is 10 ⁻⁴ to 15 mol%. 2. A benzene ring substitution reaction reagent is a nitration reagent, an acylation reagent, a sulfonation reagent, a metallation reagent or a chlorosulfonation reagent, and the α-position hydrogen substitution reaction reagent is a radical reaction reagent or a metalation reagent. And the addition reaction reagent to the side chain carbon-carbon double bond is a hydroxylation reagent, a radical addition reagent, a metallation reagent, a borohydride agent, a hydrogen sulfate alkylating agent or a halogenating agent. A process for producing a crystalline chemically modified styrene polymer. 3. (A) General formula:[In the formula, R¹Is 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 R¹Are the same or different
It may be one. ] The syndiotactic
Repeating unit having a general structure and (D) (a) general formula:[In the formula, X is -NO₂, -SO₃H, -SOCl₂,-
COR⁷(However, R⁷Is a hydrocarbon group having 1 to 8 carbon atoms)
Represents a monovalent metal atom, R¹And m are the same as above.
It A repeating unit represented by the formula (b), a general formula:[In the formula, Y is a monovalent metal atom, a halogen atom, -OOH
A group or a maleic anhydride residue, R¹And m are
Is the same. ] The repeating unit represented by
Formula[In the formula, Z¹And V¹Are halogen atom and monovalent
Metal atom or carbon atom, oxygen atom, nitrogen atom, sulfur source
Contains one or more of child, silicon atom and tin atom
Represents a substituent, which may be the same or different from each other.
May be R²Is a hydrocarbon group having 1 to 20 carbon atoms, R³
And R^FourAre respectively hydrogen atom, halogen atom or carbon
Indicates a hydrocarbon group of the number 1 to 8, n is an integer of 1 to 4.
And when n is multiple, n R^FourAre the same or different
May be ] The repeating unit represented by
(D) General formula:[In the formula, Z²And V²Are halogen atom and monovalent
Metal atom or carbon atom, oxygen atom, nitrogen atom, sulfur
Containing one or more of atom, silicon atom and tin atom
Substituents, which may be the same or different from each other.
May be there, R ^FiveAnd R⁶Are the hydrogen atom and
Rogen atom or a hydrocarbon group having 1 to 8 carbon atoms, p is
Is an integer of 1 to 4, and when p is plural, p R⁶Is the same
It may be one or different. Also, R²Is as above
Is the same. ] Selected from repeating units
Containing at least one chemically modified unit,
In addition, the content of the (D) chemically modified unit is 10^-Four~ 15 mol
%, In 1,2,4-trichlorobenzene at a temperature of 135 ° C.
Reduced viscosity at a concentration of 0.05 g / deciliter measured in degrees
Degree 0.01 ~ 20 deciliter / g and crystal melting temperature
Crystallinity characterized by being in the range of 230 to 350 ° C
Chemically modified styrene polymer.