JP2000319319A - Terminal-modified syndiotactic styrene-based polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject styrene-based polymer excellent in heat resistance and moldability and processability and useful as a raw material for various high-performance functional resins by constituting the polymer so as to have a specific molecular weight and increase the modification ratio of molecular terminals. SOLUTION: This polymer is a (co)polymer having a structural unit of formula I [R1 is H, a halogen, a 1-3C hydrocarbon, O, N or the like; (m) is 0-5]. In the polymer, tacticity of C1 carbon of phenyl group containing a substituent group is limited to >=30% based on racemic pentad by 13C-NMR and the number-average molecular weight (Mn) is limited to 1,000 to 10,000,000 and weight-average molecular weight (Mw)/Mn is limited to <=2.5 and the molecular chain having functional group at the molecular terminals is limited to >=30% in total molecular chain. The polymer is preferably obtained by previously bringing a transition metal compound into contact with an organic aluminum oxy compound at -50 deg.C to 50 deg.C for 5 sec to 10 hr and further bringing a compound of formula II into contact with the resultant catalyst at -50 deg.C to 50 deg.C for 30 sec to 36 hr to polymerize the compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a terminal-modified syndiotactic styrene polymer having a narrow molecular weight distribution, a high syndiotacticity and a high content of a functional group at the molecular terminal, and its production. It is about the method.

[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. As a solution to the drawbacks of the styrene-based polymer having an atactic structure, a styrene-based polymer having a high syndiotactic structure and a styrene-based copolymer obtained by copolymerizing the styrene-based monomer and other components have been developed. (JP-B-3-7685, JP-B1-37403, JP-A-63-24)
No. 1009).

[0003] These polymers are excellent in heat resistance, chemical resistance and electrical properties, and are expected to be applied in various fields. However, the syndiotactic polystyrene according to the technology disclosed in these publications has no functional group, and is therefore not suitable for application as a functional material such as an adhesive, a resin modifier, and a compatibilizer. There was no resin material. As a technique for compensating the above-mentioned drawbacks of syndiotactic polystyrene, JP-A-5-320251 and JP-A-5-320448 disclose a styrene-based polymer having a syndiotactic structure having a functional group at a terminal end. ing. However, in the technology disclosed in the above-mentioned publication, there is no description about the living property of polymerization, the rate of introduction of a functional group into a polymer, and the molecular weight distribution. Therefore, in the technology disclosed in the examples of the patent publication, due to the lack of living properties of polymerization, the functional group introduction rate into the polymer is low, so even if the terminal modification is performed However, its reforming effect was insufficient for industrial implementation.

[0004] On the other hand, a method for synthesizing living polystyrene has been known for a relatively long time. For example, J.Amer.Ch
em.Soc., 1957, Vol. 78, pp. 2026-2027 and Makromol. Che
m., 1960, Vol. 36, pp. 200-208, a production method of subjecting a monomer such as styrene to living anion polymerization,
Polymer Bullentin, 1990, Vol. 24, pp. 201-206 and Macr
omolecules, 1993, Vol. 26, pp. 744-751 describes a method of subjecting monomers such as styrene to living cationic polymerization.
Macromolecules, 1993, 26, 2987-2988, M
Acromolecules, 1994, Vol. 27, pp. 7228-7229, proposes a production method in which a monomer such as styrene is subjected to living radical polymerization. However, the three-dimensional structure of the styrene-based resin obtained by these living anionic polymerization, living cationic polymerization, living radical polymerization, etc. has an atactic structure, and its heat resistance,
There was a disadvantage that the chemical resistance was poor.

[0005] As described above, according to the technology disclosed in the related art, a styrene monomer is developed into a syndiotactic structure while undergoing living polymerization to introduce a functional group into a terminal. In addition, a terminal-modified syndiotactic styrene polymer having a narrow molecular weight distribution and a high terminal modification rate could not be obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a terminal-modified syndiotactic styrene polymer which is excellent in heat resistance and moldability and is useful as a raw material for various high-performance resins and functional resins. It is to provide a manufacturing method.

[0007]

Means for Solving the Problems As a result of diligent studies to solve the above problems, the present inventors have found that the number average molecular weight in a specific range, the molecular weight distribution is reduced, and the terminal modification rate is reduced. The inventors have found that an enhanced terminal-modified syndiotactic styrene-based polymer can solve the problems of the present invention, and have completed the present invention.

That is, the present invention provides the following general formula (1)

Embedded image (In the formula, R ¹ is a hydrogen atom, a halogen atom, and has 1 to 3 carbon atoms.
0 represents a hydrocarbon group or a substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m represents an integer of 0 to 5. . However, when m is plural, each R ¹ may be the same or different. A) a (co) polymer having at least one structural unit represented by the formula ( ₁ ), wherein the phenyl group (containing a substituent) has a C ₁ -carbon tacticity of ¹³ C-
Racemic pentad by NMR is 30% or more, and the number average molecular weight (Mn) is in the range of the following formula (2);
The relationship between the number average molecular weight (Mn) and the weight average molecular weight (Mw) satisfies the following formula (3), and the molecular chain having a functional group at the molecular terminal is 30% or more of the total molecular chain. The present invention relates to a terminal-modified syndiotactic styrene polymer. 1000 ≦ Mn ≦ 10000000 (2) Mw / Mn ≦ 2.5 (3)

[0009] The present invention, as a catalyst component, (A) the following general formula (4) and / or _{^{(5) MR 1 a R 2}} b R 3 c X 1 4- (a + b + c) (4) _{^{MR 1 d R 2 e X 1}} 3- (d + e) (5) ( wherein, R ^1, R ^2, and R ³ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms Aryl group, alkylaryl group, arylalkyl group, C 1-20 acyloxy group, C 1-20 alkoxy group, C 1-20 thioalkoxy group, C 6-6
20 thioaryloxy groups, cyclopentadienyl groups,
It represents a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group. M is a transition metal selected from the group consisting of titanium (Ti), zirconium (Zr) or hafnium (Hf), and X ¹ is a halogen atom. These R ¹ , R ² and R ³ may be the same or different. A, b, and c each represent an integer of 0 to 4,
D and e each represent an integer of 0 to 3. A) a transition metal compound represented by

(B) the following (a) to (d): (a) an organoaluminum oxy compound; (b) an ionic compound capable of forming a cationic transition metal compound by reacting with the transition metal compound; It mainly comprises at least one cocatalyst selected from a Lewis acid compound capable of forming a cationic transition metal compound by reacting with a metal compound, and (d) an organometallic compound of a metal belonging to Group 1, 2 or 13 of the periodic table. Using what is contained as a catalyst component, the component (A) and the component (B) are brought into contact with each other in advance at a temperature of −50 ° C. to 50 ° C. for 5 seconds to 10 hours. One or more styrenic monomers represented

Embedded image (In the formula, R ¹ is a hydrogen atom, a halogen atom, and has 1 to 3 carbon atoms.
0 represents a hydrocarbon group or a substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m represents an integer of 0 to 5. . However, when m is plural, each R ¹ may be the same or different. Is polymerized at a temperature of 0 ° C. or lower, and then a terminal modifier capable of reacting with a living polymer having a transition metal derived from the component (A) at a molecular terminal is brought into contact with the polymer. The present invention also relates to a method for producing the terminal-modified syndiotactic styrene polymer according to item 1.

[0011]

Embodiments of the present invention will be described below in detail. The terminal-modified syndiotactic styrene-based polymer in the present invention has at least one structural unit (repeating unit) represented by the general formula (1). Here, R ¹ of the structural unit represented by the general formula (1) is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, a nitrogen atom, a sulfur atom,
It indicates a substituent containing at least one of a phosphorus atom, a selenium atom, a silicon atom and a tin atom.

Here, the halogen atom includes fluorine,
Chlorine, bromine and iodine can be mentioned. Also,
Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a tertiary butyl group; a hydrogen atom on a benzene ring having 6 to 30 carbon atoms; Aryl group having a substituent containing halogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom or tin atom, chloroethyl group, bromomethyl group, bromoethyl group, etc. And 20 halogen-substituted alkyl groups.

Here, a substituent containing a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, a tin atom, or the like is added to a benzene ring having 6 to 30 carbon atoms. Examples of the aryl group having a benzene ring, naphthalene ring, phenanthrene ring, anthracene 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, pleiadene ring, picene ring, perylene ring, pentaphene ring, pentacene ring, rubicene ring, corocene ring, pyranthrene ring, ovalene ring, and alkyl substituents thereof ( Methyl group, ethyl group, isopropyl group Such as a tertiary butyl group),

A halogen-substituted alkyl group (such as a chloroethyl group or a bromoethyl group), a substituent containing an oxygen atom (such as a methoxy group, an ethoxy group, an isopropoxy group, a methoxycarbonyl group or an acyloxy group), or a substituent containing a silicon atom (such as a trimethylsilyl group) Such as trimethylstannyl group, tributylstannyl group,
A substituent containing a nitrogen atom (such as a dimethylamino group, a diazo group, a nitro group, or a cyano group); a substituent containing a sulfur atom (such as a sulfone group, a sulfonic acid methyl ester group, a phenylthio group, or a methylthio group). Group,
A selenium atom-containing substituent (methylseleno group, phenylseleno group, methylselenoxyl group,
Phenyl selenoxyl group, etc.), substituents containing phosphorus atoms (eg, phosphoric acid methyl ester group, phosphite ester group, dimethyl phosphino group, diphenyl phosphino group, methyl phosphinyl group, phenyl phosphinyl group, etc.) At any position.

The substituent containing an oxygen atom includes a methoxy group, an ethoxy group, an isopropoxy group, a methoxycarbonyl group, an acyloxy group and the like. Examples of the substituent containing a silicon atom include a trimethylsilyl group. Examples of the substituent containing a tin atom include a trimethylstannyl group, a tributylstannyl group, and a triphenylstannyl group. Examples of the substituent containing a nitrogen atom include a dimethylamino group, a diazo group, a nitro group, and a cyano group.

Examples of the substituent containing a sulfur atom include a sulfone group, a sulfonic acid methyl ester group, a phenylthio group, a methylthio group, and a mercapto group. Examples of the substituent containing a selenium atom include a methylseleno group, a phenylseleno group, a methylselenoxyl group, and a phenylselenoxyl group. Examples of the substituent containing a phosphorus atom include a phosphoric acid methyl ester group, a phosphite ester group, a dimethyl phosphino group, a diphenyl phosphino group, a methyl phosphinyl group, and a phenyl phosphinyl group.

In the structural unit represented by the general formula (1), m is an integer of 0 to 5, and when m is plural, m R ^1s are the same. Or different ones. Specific examples of the structural unit represented by the general formula (1) having such a substituent include styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5 Alkyl styrenes such as -dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene and p-tert-butylstyrene; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene,
halogenated styrenes such as p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene;

Vinyl biphenyls such as 4-vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl;
1- (4-vinylphenyl) naphthalene, 2- (4-vinylphenyl) naphthalene, 1- (3-vinylphenyl) naphthalene, 2- (3-vinylphenyl) naphthalene, 1-
Vinylphenylnaphthalenes such as (2-vinylphenyl) naphthalene and 2- (2-vinylphenyl) naphthalene; 1- (4-vinylphenyl) anthracene, 2- (4-
(Vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 2- (3-vinylphenyl) anthracene, 9-
Vinyl anthracenes such as (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, 2- (2-vinylphenyl) anthracene and 9- (2-vinylphenyl) anthracene; 1- (4-vinylphenyl) )
Phenanthrene, 2- (4-vinylphenyl) phenanthrene,

3- (4-vinylphenyl) phenanthrene, 4- (4-vinylphenyl) phenanthrene, 9-
(4-vinylphenyl) phenanthrene, 1- (3-vinylphenyl) phenanthrene, 2- (3-vinylphenyl) phenanthrene, 3- (3-vinylphenyl) phenanthrene, 4- (3-vinylphenyl) phenanthrene,
9- (3-vinylphenyl) phenanthrene, 1- (2-vinylphenyl) phenanthrene, 2- (2-vinylphenyl) phenanthrene, 3- (2-vinylphenyl) phenanthrene, 4- (2-vinylphenyl) phenanthrene,
Vinylphenylphenanthrenes such as 9- (2-vinylphenyl) phenanthrene; 1- (4-vinylphenyl)
Pyrene, 2- (4-vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 2- (2-vinylphenyl) Vinylphenylpyrenes such as pyrene;

4-vinyl-p-terphenyl, 4-vinyl-
m-terphenyl, 4-vinyl-o-terphenyl, 3-vinyl-p-terphenyl, 3-vinyl-m-terphenyl,
Vinyl terphenyls such as 3-vinyl-o-terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl, 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-vinyl Biphenyl, 3-methyl
Vinylalkylbiphenyls such as -4-vinylbiphenyl; 4-vinyl-4'-fluorobiphenyl, 4-vinyl-
3′-fluorobiphenyl, 4-vinyl-2′-fluorobiphenyl, 4-vinyl-2-fluorobiphenyl, 4-vinyl-3-fluorobiphenyl, 4-vinyl-4′-chlorobiphenyl,

4-vinyl-3'-chlorobiphenyl, 4-vinyl-2'-chlorobiphenyl, 4-vinyl-2-chlorobiphenyl, 4-vinyl-3-chlorobiphenyl, 4-vinyl
-4'-bromobiphenyl, 4-vinyl-3'-bromobiphenyl, 4-vinyl-2'-bromobiphenyl, 4-vinyl
Halogenated vinyl biphenyls such as -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-
Alkoxybiphenyls such as vinyl-3'-ethoxybiphenyl, 4-vinyl-2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl, 4-vinyl-3-ethoxybiphenyl; 4-vinyl-4'-methoxycarbonyl Biphenyl,

Alkoxycarbonylvinyl biphenyls such as 4-vinyl-4'-ethoxycarbonylbiphenyl; alkoxyalkylvinylbiphenyls such as 4-vinyl-4'-methoxymethylbiphenyl; 4-vinyl-
Trialkylsilylvinylbiphenyls such as 4'-trimethylsilylbiphenyl; trialkylstannylvinylbiphenyls such as 4-vinyl-4'-methylstannylbiphenyl and 4-vinyl-4'-tributylstannylbiphenyl; 4-vinyl Trialkylsilylmethylvinylbiphenyls such as -4'-trimethylsilylmethylbiphenyl; trialkylstannylmethylvinyls such as 4-vinyl-4'-trimethylstannylmethylbiphenyl and 4-vinyl-4'-tributylstannylmethylbiphenyl Arylstyrenes such as biphenyls; p-
Chloroethylstyrene, m-chloroethylstyrene, o-
Halogen-substituted alkylstyrenes such as chloroethylstyrene;

P-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, m-
Alkoxystyrenes such as ethoxystyrene and o-ethoxystyrene; alkoxycarbonylstyrenes such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene; acyloxystyrenes such as acetyloxystyrene, ethanoyloxystyrene and benzoyloxystyrene; p-vinylbenzyl Alkyl ether styrenes such as propyl ether; alkyl silyl styrenes such as p-trimethylsilyl styrene; alkyl stannyl styrenes such as p-trimethylstannyl styrene, p-tributylstannyl styrene, p-triphenylstannyl styrene; vinylbenzene sulfonic acid Examples include vinyl styrene such as ethyl, vinylbenzyl dimethoxy phosphide, and p-vinyl styrene.

The terminal-modified syndiotactic styrene-based polymer of the present invention is a polymer comprising a combination of two or more kinds of one or more different structural units represented by the above general formula (1). It is a copolymer. In other words, the terminal-modified syndiotactic styrene-based polymer of the present invention does not necessarily show only one kind, but also contains two or more kinds of structural units. Therefore, the polymer of the present invention is a homopolymer and a two-dimensional polymer. In addition to copolymers, terpolymers,
Also included are multi-component copolymers such as multi-component copolymers.

In the present invention, if necessary, other monomers copolymerizable with the styrene monomer may be copolymerized with the styrene polymer as long as the effects of the present invention are not impaired. May be used. Other monomers copolymerizable with the styrene monomer in this case include:
Olefins such as ethylene, propylene, 1-butene,
Cyclic olefins such as cyclopentene and 2-norbornene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene; 3-pentadiene,
Conjugated dienes such as 1,3-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, non-conjugated dienes such as 5-ethylidene-2-norbornene, methyl methacrylate,
(Meth) acrylic acid esters such as methyl acrylate are included.

The terminal-modified syndiotactic styrene-based polymer of the present invention has the above structural units (repeating units). That is, a phenyl group having a substitution or no substitution which is a side chain with respect to a main chain formed from carbon-carbon bonds has a steric structure alternately located in the opposite direction, and its tacticity is determined by nuclear magnetic resonance. Quantified by the NMR method. Specifically, the analysis is based on the analysis of a C ₁ carbon signal, a methine / methylene carbon signal, or a ¹ H-NMR proton signal of an aromatic ring by ¹³ C-NMR (nuclear magnetic resonance spectroscopy using isotope carbon).

The tacticity determined by NMR is the abundance ratio of a plurality of continuous structural units (ie, the abundance ratio of a relative conformational relationship of continuous structural units). In the case of the formula (1), triads and in the case of five (5) pentads can be represented by a pentad. Is slightly variable, but is usually 75% or more, preferably 85% by racemic dyad in a chain of styrenic repeating units.
Those having a syndiotacticity of 30% or more, preferably 50% or more as a racemic pentad are shown.

In the terminal-modified syndiotactic styrenic polymer of the present invention, not only one type of structural unit represented by the general formula (1) but also two or more types of both structural units are bonded. Have a syndiotactic structure (cosyndiotactic structure). In addition, copolymers composed of these structural units include various modes such as block copolymerization, random copolymerization, and alternating copolymerization.

The styrenic polymer mainly having a syndiotactic structure according to the present invention does not necessarily have to be a single polymer. As long as the syndiotacticity is within the above range, a mixture with an isotactic or atactic styrene polymer or an atactic styrene polymer may be incorporated in the polymer chain.

The terminal-modified syndiotactic styrenic polymer of the present invention must have a number average molecular weight (Mn) and a weight average molecular weight (Mw) satisfying the above formulas (2) and (3).

In the terminal-modified syndiotactic styrenic polymer obtained in the present invention, the number average molecular weight (M
n) is preferably from 1,000 to 10,000,000, more preferably
5,000 to 5,000,000, more preferably 10,000 to 2,000,00
0, particularly preferably 15,000 to 800,000. If the molecular weight is too small, the physical properties as a polymer such as low mechanical strength will be insufficient.On the other hand, if the molecular weight is too large, molding will be difficult, or it will be difficult to modify the terminal of the polymer or synthesize the block copolymer. Problem arises.

The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), of the terminal-modified syndiotactic styrene polymer of the present invention is 2.5.
It is essential that: Preferably, it is 1.8 or less. Especially preferably, it is 1.5 or less. If the molecular weight distribution is too wide, problems such as deterioration of physical properties such as abrasion resistance, terminal modification of the polymer, and difficulty in synthesizing the block copolymer occur, which is not preferable.

The terminal modification rate of the terminal-modified syndiotactic styrenic polymer of the present invention is 30% or more, preferably 50% or more, more preferably 70% or more, and further preferably 80% or more. is there. When the terminal modification ratio is less than 30%, the effect of improving the strength properties and the like becomes insufficient when used as a resin modifier, and the reactivity is insufficient when a macromonomer and a reactive prepolymer are used. Becomes

The terminal modification rate (F,%) is defined as the percentage of the number of terminally modified molecular chains to the total number of molecular chains. The terminal modification ratio can be determined by measuring the number average molecular weight (Mn) and the terminal modifying group concentration of the polymer. The number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC) or the like. Method of measuring the terminal modified group concentration varies depending on the type of terminal modifier, but infrared absorption spectrum, UV absorbers spectrum, ¹ H
-NMR spectrum, ¹³ C-NMR spectrum, a method such as GPC equipped with an ultraviolet detector and a differential refractive index detector can be used.

In order to produce the terminal-modified syndiotactic styrene polymer of the present invention, a catalyst component is selected from the compounds represented by the general formulas (4) and (5) of the component (A). A compound containing, as a main catalyst component, a reaction product of at least one selected transition metal compound and at least one cocatalyst selected from components (a) to (d) of component (B), The component (A), one or more transition metal components, and the component (B), one or more cocatalyst components, are contacted in advance at a temperature of -50 ° C to 50 ° C for 5 seconds to 10 hours. Under the (aged) state, one or more styrene-based monomers represented by the above-mentioned general formula (6) are polymerized at a temperature of 0 ° C. or less, and then (A)
An efficient production can be achieved by bringing a reagent capable of reacting with a living polymer having a transition metal derived from a component at the molecular terminal into contact with the polymer.

Here, as the transition metal compound of the component (A), various ones can be used. Usually, for example, the transition metal compound represented by the general formulas (4) and (5) is used. It is preferably at least one compound selected from the group. R ¹ , R ² , and R ³ in the general formula (4) or (5) each represent a hydrogen atom, a carbon number of 1 to 2,
0 alkyl group (specifically, methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group, 2-ethylhexyl group, etc.), aryl group having 6 to 20 carbon atoms, alkyl Aryl group, arylalkyl group (specifically, phenyl group, tolyl group, xylyl group, benzyl group, etc.), acyloxy group having 1 to 20 carbon atoms (specifically, heptadecylcarbonyloxy group, etc.), 20 alkoxy groups (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, 2-ethylhexyloxy group, etc.), and a thioalkoxy group having 1 to 20 carbon atoms (specifically, Thiomethoxy group etc.),

A thioaryloxy group having 6 to 20 carbon atoms (specifically, a thiophenoxy group or the like), a cyclopentadienyl group, a substituted cyclopentadienyl group (specifically, a methylcyclopentadienyl group, 2-dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, etc.), indenyl group, substituted indenyl group, fluorenyl group, or substituted fluorenyl group. M is titanium (Ti), zirconium (Zr) or hafnium (Hf)
X ¹ represents a halogen atom (specifically, chlorine, bromine, iodine, or fluorine). These R ¹ , R ² and R ³ may be the same or different. A, b, and c are each 0 to 4
And d and e each represent an integer of 0 to 3.

Among these transition metal compounds, a titanium compound is most preferably used in terms of polymerization activity.
More preferable titanium compounds include a mono (cyclopentadienyl) titanium compound, a mono (indenyl) titanium compound and a mono (fluorenyl) titanium compound represented by the general formula (7). TiR ⁴ XYZ (7) (wherein, R ⁴ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, etc., and X, Y and Z each independently represent a hydrogen atom , An alkyl group having 1 to 12 carbon atoms,
12 alkoxy groups, thioalkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, thioaryloxy group having 6 to 20 carbon atoms, 6 to 20 carbon atoms Represents an arylalkyl group or a halogen atom. )

The substituted cyclopentadienyl group represented by R ⁴ in this formula is, for example, an alkyl group having 1 to 6 carbon atoms,
A cyclopentadienyl group substituted by at least two, specifically a methylcyclopentadienyl group; a 1,3-dimethylcyclopentadienyl group; a 1,2,4-trimethylcyclopentadienyl group; 3,4-tetramethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3-di (trimethylsilyl) cyclopentadienyl group; tert-butylcyclopentadienyl group; 1,3-di (tertiary) Butyl) cyclopentadienyl group; and pentamethylcyclopentadienyl group.

X, Y and Z each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (specifically, methyl, ethyl, propyl, n-butyl, isobutyl, amyl, Isoamyl group, octyl group, 2-ethylhexyl group, etc., alkoxy group having 1 to 12 carbon atoms (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group, 2 -Ethylhexyloxy group, etc.), a thioalkoxy group having 1 to 20 carbon atoms (specifically, thiomethoxy group, etc.), an aryl group having 6 to 20 carbon atoms (specifically, phenyl group, naphthyl group, etc.), 6 carbon atoms. An aryloxy group of 20 to 20 (specifically, a phenoxy group, etc.);
A thioaryloxy group of 20 (specifically, a thiophenol group or the like), an arylalkyl group having 6 to 20 carbon atoms (specifically, a benzyl group) or a halogen atom (specifically, chlorine, bromine, iodine or fluorine) Is shown.

Specific examples of the titanium compound represented by the general formula (7) include cyclopentadienyltrimethyltitanium; cyclopentadienyltriethyltitanium;
Cyclopentadienyltripropyltitanium; cyclopentadienyltributyltitanium; methylcyclopentadienyltrimethyltitanium; 1,2-dimethylcyclopentadienyltrimethyltitanium; 1,2,4-trimethylcyclopentadienyltrimethyltitanium; , 2,3,4
-Tetramethylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltriethyltitanium;

Pentamethylcyclopentadienyltripropyltitanium; pentamethylcyclopentadienyltributyltitanium; cyclopentadienylmethyltitanium dichloride; cyclopentadienylethyltitanium dichloride; pentamethylcyclopentadienylmethyltitanium dichloride; Cyclopentadienyl ethyl titanium dichloride; cyclopentadienyl dimethyl titanium monochloride; cyclopentadienyl diethyl titanium monochloride; cyclopentadienyl titanium trimethoxide; cyclopentadienyl titanium triethoxide;

Cyclopentadienyltitanium tripropoxide; cyclopentadienyltitanium triphenoxide;
Pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide; pentamethylcyclopentadienyl titanium tripropoxide; pentamethylcyclopentadienyl titanium tributoxide; pentamethylcyclopentadienyl titanium Trifenoxide;

Cyclopentadienyl titanium trichloride; pentamethylcyclopentadienyl titanium trichloride; cyclopentadienyl methoxy titanium dichloride; cyclopentadienyl dimethoxy titanium chloride;
Pentamethylcyclopentadienylmethoxytitanium dichloride; cyclopentadienyltribenzyltitanium; pentamethylcyclopentadienylmethyldiethoxytitanium; indenyltitanium trichloride; indenyltitaniumtrimethoxide; indenyltitaniumtriethoxide; Nyltrimethyltitanium; indenyltribenzyltitanium; pentamethylcyclopentadienyltitanium trithiomethoxide; pentamethylcyclopentadienyltitanium trithiophenoxide.

Further, as the titanium compound, a condensed titanium compound represented by the following general formula (8) may be used.

Embedded image (Wherein, R ⁵ and R ⁶ each represent a halogen atom,
Represents an alkoxy group or an acyloxy group of -20, and k is 2
Represents an integer of up to 20. The trivalent titanium compound represented by the general formula (8) typically includes a titanium trihalide such as titanium trichloride and a cyclopentadienyl titanium compound such as cyclopentadienyl titanium dichloride. Other examples include those obtained by reducing a tetravalent titanium compound. These trivalent titanium compounds may be those which form a complex with an ester, an ether or the like.

The zirconium compound as the transition metal compound includes tetrabenzyl zirconium, zirconium tetraethoxide, zirconium tetrabutoxide,
Bisindenyl zirconium dichloride, triisopropoxy zirconium chloride, zirconium benzyl dichloride, tributoxy zirconium chloride and the like, and the hafnium compound is tetrabenzyl hafnium,
Examples include hafnium tetraethoxide and hafnium tetrabutoxide, and vanadium compounds include vanadyl bisacetylacetonate, vanadyl triacetylacetonate, triethoxyvanadyl, and tripropoxyvanadyl. Among these transition metal compounds, titanium compounds are particularly preferred. Further, as the above-mentioned titanium compound and the like, a compound which forms a complex with an ester or an ether may be used.

The transition metal compound as the component (A) includes a transition metal compound having two ligands having conjugated π electrons, for example, a group consisting of a transition metal compound represented by the following general formula (9). There is at least one compound selected from M ¹ R ⁷ R ⁸ R ⁹ R ¹⁰ (9) (wherein, M ¹ represents titanium, zirconium or hafnium, and R ⁷ and R ⁸ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group Or R ⁹ and R ¹⁰ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or a thioalkoxy group having 1 to 20 carbon atoms. Wherein R ⁷ and R ⁸ are a hydrocarbon group having 1 to 5 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms, or 1 to 2 carbon atoms.
It may be cross-linked by 0 and germanium-containing hydrocarbon groups having 1 to 5 germanium. )

In the general formula (9), R ⁷ and R ⁸ are a cyclopentadienyl group or a substituted cyclopentadienyl group (specifically, a methylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl) 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group;
1,3-di (trimethylsilyl) cyclopentadienyl group; 1,2,4-tri (trimethylsilyl) cyclopentadienyl group; tert-butylcyclopentadienyl group; 1,3-di (tert-butyl) cyclo Pentadienyl group; 1,2,4-tri (tert-butyl)
Cyclopentadienyl group),

R ⁸ represents an indenyl group, a substituted indenyl group (specifically, a methylindenyl group; a dimethylindenyl group; a trimethylindenyl group, etc.), a fluorenyl group or a substituted fluorenyl group (eg, a methylfluorenyl group); , R ⁹ may be the same or different, and furthermore, R ⁷ and R ⁸
Is an alkylidene group having 1 to 5 carbon atoms (specifically, a methine group, an ethylidene group, a propylidene group, a dimethylcarbyl group, etc.) or an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms (specifically, May have a structure cross-linked by a dimethylsilyl group, a diethylsilyl group, a dibenzylsilyl group, etc.).

On the other hand, R ⁹ and R ¹⁰ are as described above, but more specifically, are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, n- A butyl group, an isobutyl group, an amyl group, an isoamyl group, an octyl group, a 2-ethylhexyl group and the like; an aryl group having 6 to 20 carbon atoms (specifically, a phenyl group and a naphthyl group); Arylalkyl group (specifically, benzyl group, etc.), alkoxy group having 1 to 20 carbon atoms (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group , 2-ethylhexyloxy group), an aryloxy group having 6 to 20 carbon atoms (specifically, a phenoxy group, etc.), and an amino group or a thioalkoxy having 1 to 20 carbon atoms. Shows the sheet group.

Specific examples of the transition metal compound represented by the general formula (9) include biscyclopentadienyl titanium dimethyl; biscyclopentadienyl titanium diethyl; biscyclopentadienyl titanium dipropyl; Cyclopentadienyl titanium dibutyl; bis (methylcyclopentadienyl) titanium dimethyl; bis (tertiary butyl cyclopentadienyl) titanium dimethyl;
Bis (1,3-dimethylcyclopentadienyl) titanium dimethyl; bis (1,3-ditert-butylcyclopentadienyl) titanium dimethyl; bis (1,2,4-
Trimethylcyclopentadienyl) titanium dimethyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethyl; biscyclopentadienyltitanium dimethyl; bis (trimethylsilylcyclopentadienyl) titanium dimethyl;

Bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethyl; bis (1,2,2
4-tri ((trimethylsilyl) cyclopentadienyl) titanium dimethyl; bisindenyltitanium dimethyl;
Bisfluorenyltitanium dimethyl; methylenebiscyclopentadienyltitanium dimethyl; ethylidenebiscyclopentadienyltitanium dimethyl; methylenebis (2
3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; ethylidenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; dimethylsilylbis (2,3,4,5-tetra) Methylcyclopentadienyl) titanium dimethyl; methylenebisindenyltitanium dimethyl; ethylidenebisindenyltitanium dimethyl; dimethylsilylbisindenyltitanium dimethyl;

Methylenebisfluorenyltitanium dimethyl; ethylidenebisfluorenyltitanium dimethyl; dimethylsilylbisfluorenyltitanium dimethyl; methylene (tert-butylcyclopentadienyl) (cyclopentadienyl) titanium dimethyl; Pentadienyl) (indenyl) titanium dimethyl; ethylidene (cyclopentadienyl) (indenyl) titanium dimethyl; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethyl; methylene (cyclopentadienyl) (fluorenyl) titanium dimethyl; Ethylidene (cyclopentadienyl) (fluorenyl) titanium dimethyl; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dimethyl; methylene (indenyl)
(Fluorenyl) titanium dimethyl;

Ethylidene (indenyl) (fluorenyl) titanium dimethyl; dimethylsilyl (indenyl)
(Fluorenyl) titanium dimethyl; biscyclopentadienyltitanium dibenzyl; bis (tert-butylcyclopentadienyl) titanium dibenzyl; bis (methylcyclopentadienyl) titanium dibenzyl; bis (1,
3-dimethylcyclopentadienyl) titanium dibenzyl; bis (1,2,4-trimethylcyclopentadienyl) titanium dibenzyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dibenzyl Bispentamethylcyclopentadienyltitanium dibenzyl;
Bis (trimethylsilylcyclopentadienyl) titanium dibenzyl; bis (1,3-di- (trimethylsilyl) cyclopentadienyl) titanium dibenzyl;

Bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; bisindenyl titanium dibenzyl; bisfluorenyl titanium dibenzyl; methylenebiscyclopentadienyl titanium dibenzyl; ethylidene Biscyclopentadienyltitanium dibenzyl; methylenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; ethylidenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl Benzyl; dimethylsilylbis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; methylenebisindenyltitanium dibenzyl; ethylidenebisindenyltitanium dibenzyl; dimethylsilylbisindenyltitanium dibenzyl;
Methylenebisfluorenyltitanium dibenzyl;

Ethylidenebisfluorenyltitanium dibenzyl; dimethylsilylbisfluorenyltitanium dibenzyl; methylene (cyclopentadienyl) (indenyl)
Titanium dibenzyl; ethylidene (cyclopentadienyl) (indenyl) titanium dibenzyl; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dibenzyl; methylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; ethylidene (cyclo Pentadienyl) (fluorenyl) titanium dibenzyl; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dibenzyl; methylene (indenyl) (fluorenyl)
Titanium dibenzyl; ethylidene (indenyl) (fluorenyl) titanium dibenzyl; dimethylsilyl (indenyl) (fluorenyl) titanium dibenzyl;

Biscyclopentadienyl titanium dimethoxide; biscyclopentadienyl titanium diethoxide;
Biscyclopentadienyl titanium dipropoxide; biscyclopentadienyl titanium dibutoxide; biscyclopentadienyl titanium diphenoxide; bis (methylcyclopentadienyl) titanium dimethoxide; bis (1,
3-dimethylcyclopentadienyl) titanium dimethoxide; bis (1,2,4-trimethylcyclopentadienyl) titanium dimethoxide; bis (1,2,3,4-taylamethylcyclopentadienyl) titanium dimethoxide ;
Bispentamethylcyclopentadienyl titanium dimethoxide; bis (trimethylsilylcyclopentadienyl)
Bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethoxide;

Bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dimethoxide; bisindenyltitanium dimethoxide; bisfluorenyltitanium dimethoxide; methylenebiscyclopentadienyltitanium dimethoxide; ethylidene Biscyclopentadienyl titanium dimethoxide; methylene bis (2,3,4,5
-Tetramethylcyclopentadienyl) titanium dimethoxide; ethylidenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide; dimethylsilylbis (2,3,4,5-tetramethylcyclopenta Dienyl) titanium dimethoxide; methylenebisindenyltitanium dimethoxide; methylenebis (methylindenyl) titanium dimethoxide; ethylidenebisindenyltitanium dimethoxide; dimethylsilylbisindenyltitanium dimethoxide;

Methylenebisfluorenyltitanium dimethoxide; methylenebis (methylfluorenyl) titanium dimethoxide; ethylidenebisfluorenyltitanium dimethoxide; dimethylsilylbisfluorenyltitanium dimethoxide; methylene (cyclopentadienyl) ( Indenyl) titanium dimethoxide; ethylidene (cyclopentadienyl) (indenyl) titanium dimethoxide; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethoxide; methylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide; ethylidene (Cyclopentadienyl) (fluorenyl) titanium dimethoxide; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dimethoxide; methylene (indenyl)
(Fluorenyl) titanium dimethoxide; ethylidene (indenyl) (fluorenyl) titanium dimethoxide; dimethylsilyl (indenyl) (fluorenyl) titanium dimethoxide.

The zirconium compound includes ethylidene biscyclopentadienyl zirconium dimethoxide, dimethylsilyl biscyclopentadienyl zirconium dimethoxide, and the like, and the hafnium compound is ethylidene biscyclopentadienyl hafnium dimethoxide. And dimethylsilylbiscyclopentadienylhafnium dimethoxide. Among these, a titanium compound is particularly preferable. Further, in addition to these combinations, 2,2'-thiobis (4-methyl-6-t-butylphenyl) titanium diisopropoxide; 2,2'-thiobis (4-methyl-6-t-butylphenyl) titanium It may be a bidentate complex such as dimethoxide. Among these transition metal compounds, a transition metal compound having one π ligand as shown by the general formula (7) is particularly preferably used.

In the polymerization catalyst used in the present invention, the transition metal compound as the component (A) may be used alone or in combination of two or more. on the other hand,
The component (B) contains a component obtained from at least one cocatalyst selected from the following (a) to (d). (A) an organoaluminum oxy compound (b) an ionic compound capable of producing a cationic transition metal compound by reacting with the transition metal compound (c) a Lewis acid capable of producing a cationic transition metal compound by reacting with the transition metal compound Compounds (d) Organometallic compounds of metals of Groups 1, 2 and 13 of the Periodic Table

First, the organoaluminum oxy compound (a) is preferably a linear or cyclic polymer represented by the following general formula (10), and is a so-called aluminoxane. In ^{(-Al (R 11) O-)} n (10) formula, R ¹¹ is a hydrocarbon group having 1 to 10 carbon atoms, also R ¹¹ itself is replaced with a halogen atom and / or R ¹² -O group May be used. Here, specific examples of R ¹¹ or R ¹² include alkyl groups such as methyl, ethyl, propyl, and isobutyl, and among them, a methyl group is preferable. n indicates the degree of polymerization, and is preferably 5 or more, more preferably 10 to 100, and most preferably 10 to 50. If the degree of polymerization n is less than 5, the polymerization activity is undesirably reduced, and if it is more than 100, problems such as a decrease in polymerization activity and difficulty in demineralization are caused.

The ionic compound (b) capable of forming a cationic transition metal compound by reacting with the transition metal compound represented by the general formula (4) and / or the general formula (5) is a non-coordinating compound. Examples include anions and cations. Here, as the non-coordinating anion, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( (Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xyyl) borate, triphenylpentafluorophenyl borate, tris (pentafluorophenyl) phenyl borate, and the like.

Among these non-coordinating anions, those which are tetrakis (pentafluorophenyl) borate are particularly preferred. Specific examples include, for example, triphenylcarbenium tetrakis (pentafluorophenyl) borate; 4,4 ′, 4 ″ -tri (methoxyphenyl) carbenium tetrakis (pentafluorophenyl) borate; tri (tolyl) carbenium tetrakis (pentane) 4,4 ', 4 "-tri (chlorophenyl) carbeniumtetrakis (pentafluorophenyl) borate; triphenylsilyltetrakis (pentafluorophenyl) borate; trimethoxysilyltetrakis (pentafluorophenyl) borate; tri (Thioisopropyl) silyltetrakis (pentafluorophenyl) borate; trimethylsilyltetrakis (pentafluorophenyl) borate;
4 ', 4 "-tri (methoxyphenyl) silyltetrakis (pentafluorophenyl) borate; tri (toluyl) silyltetrakis (pentafluorophenyl) borate; 4,4', 4" -tri (chlorophenyl) silyltetrakis (pentane Fluorophenyl) borate and the like.

Examples of the cation include a) a carbonium cation, b) an oxonium cation, c) an ammonium cation, d) a phosphonium cation, and e) a ferrocenium cation having a transition metal. a) Specific examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

B) Specific examples of oxonium cations include alkyloxonium cations such as hydroxonium cation OH ₃ +, methyloxonium cation CH ₃ OH ₂ +, and dimethyloxonium cation (CH ₃ ) ₂
Examples thereof include a dialkyloxonium cation such as OH +, a trialkyloxonium cation (CH ₃ ) ₃ O +, and a trialkyloxonium cation such as triethyloxonium cation (C ₂ H ₅ ) ₃ O +.

C) Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation and tributylammonium cation, N, N-diethylanilinium cation, N, N-2 And N, N-dialkylanilinium cations such as 1,4,6-pentamethylanilinium cation, dialkylammonium cations such as di (i-propyl) ammonium cation and dicyclohexylammonium cation.

D) Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As the ionic compound (b), those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be used. Of the above, especially triphenylcarbonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetra (pentafluorophenyl) borate and the like Ionic compounds can be more preferably used.

Specific examples of the Lewis acid compound (c) capable of producing a cationic transition metal compound by reacting with the transition metal compound represented by the general formula (4) and / or the general formula (5) include tris (Pentafluorophenyl) boron, tris (monofluorophenyl) boron, tris (difluorophenyl) boron, and triphenylboron.

The organometallic compounds of Group 1, 2 and 13 element metals in the Periodic Table (d) include not only organic metal compounds in a narrow sense but also organometallic halogen compounds of Group 1, 2 and 13 element metals. And hydrogenated organometallic compounds. Here, the element metals of the periodic table 1 are: Li, Na. The element metals of the periodic table 2 are: Mg, Be. The element metals of the periodic table 13 are: Al and B. Of these, preferred element metals are Li, M
g, Al, particularly preferably Al.

Examples of the organometallic compound (d) include methyllithium, butyllithium, phenyllithium, dibutylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. Is preferred.
Examples of the organometallic halogen compound (d) include ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride, and ethyl aluminum dichloride. Examples of the hydrogenated organometallic compound (d) include diethyl aluminum hydride and sesquiethyl aluminum hydride.

In the present invention, the above-mentioned (a) to (a)
(D) may be used alone or in combination.
Preferred promoters are (a) alone, (c) alone, (a) and (d), (b) and (d), and (c) and (d). Particularly preferred is a combination of (c) and (d).

The catalyst for producing a syndiotactic styrene resin used in the present invention contains, as a main component, the reaction product of the above-mentioned components (A) and (B). Other catalyst components may be added within a range not impairing the above. Component (A) and component (B) in the catalyst of the present invention
The compounding ratio of the components differs depending on the type of the compound and various polymerization conditions, and is not uniquely defined.
It is desirable that the molar ratio of the transition metal compound of the components (b), (c), (d) and (A) be within the following range.

The molar ratio of aluminum / (A) transition metal compound in the (a) organoaluminum oxy compound is usually 1
~ 1000,000, preferably 10-50000, more preferably 1
00 to 5,000. The molar ratio of (b) the ionic compound / (A) the transition metal compound is usually from 0.01 to 100, preferably from 0.1 to 10.

The molar ratio of (c) Lewis acidic compound / (A) transition metal compound is usually from 0.01 to 100, preferably from 0.1 to 1
0. Here, when a Lewis acid compound is used as the co-catalyst component, it is preferable to use an organometallic compound of a metal belonging to Group 1 or 2 of the periodic table in combination. When the (d) organometallic compound is used, the molar ratio of (d) organometallic compound / (A) transition metal compound is usually 0.1
1010,000, preferably 11,0001,000. Outside the above range, the polymerization activity is undesirably reduced.

In the present invention, the metal hydride compound may be further used in combination with the above-mentioned organometallic compounds of the metals of Group 1, 2, and 13 of the periodic table, organometallic halogen compounds, hydrogenated organometallic compounds, and the like. A system monomer may be polymerized. Here, as the metal hydride compound, for example, N
aH, LiH, CaH ₂ , LiAlH ₄ , NaBH _{4 and the} like. Examples of the organometallic compounds, organometallic halogen compounds, and hydrogenated organometallic compounds of the main element metals of the Group 1, 2, and 13 element metals include those described above.

In the present invention, the transition metal compound represented by the general formula (4) and / or the general formula (5) alone,
Alternatively, this and at least one cocatalyst selected from the above (a) to (d) can be used by being supported on a carrier. Examples of the carrier include an inorganic compound and an organic polymer compound. As the inorganic compound, inorganic oxides, inorganic chlorides, inorganic hydroxides and the like are preferable, and a small amount of carbonate,
It may contain a sulfate. Preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia and calcia, and inorganic chlorides such as magnesium chloride. These inorganic compounds are preferably porous fine particles having an average particle diameter of 5 to 150 µm and a specific surface area of 2 to 800 m2 / g, and can be used after being heat-treated at, for example, 100 to 800 ° C.

The organic polymer compound preferably has an aromatic ring, a substituted aromatic ring, or a functional group such as a hydroxy group, a carboxyl group, an ester group, or a halogen atom in the side chain. Specific examples of the organic polymer compound include α, which has a functional group obtained by chemically modifying a polymer having units such as ethylene, propylene, and butene.
-Olefin homopolymers, α-olefin copolymers, polymers having units of acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene, and the like, and chemically modified products thereof. These organic polymer compounds have an average particle size of 5 to 25.
0 μm spherical microparticles are used. By supporting the transition metal compound and the co-catalyst on a simple substance, contamination due to adhesion of the catalyst to the polymerization reactor can be prevented.

The terminal-modified syndiotactic styrene polymer of the present invention can be obtained by the following production method using the above-mentioned styrene monomer, transition metal compound, cocatalyst and the like. <Method for Producing Syndiotactic Styrene-Based Resin> In the present invention, the component (B) is a transition metal compound of the component (A) and at least one cocatalyst selected from the components (a) to (d). Is polymerized in the presence of a catalyst which has been contacted (aged) in advance. Specifically, aging and polymerization may be performed by the following methods (I) to (V). In the following description, the component (A) represents a transition metal compound, and the component (B) represents a promoter.

(I) The components (A) and (B) are brought into contact with each other in advance, and then contacted with a monomer component such as a styrene monomer to carry out polymerization. (II) After the component (A), the component (B) and a small amount of the styrene monomer component are brought into contact in advance, the polymerization is carried out by bringing the component into contact with a monomer component such as a styrene monomer.

(III) The components (A) and (B) are mixed, brought into contact with a carrier, the produced supported catalyst is separated, and the supported catalyst is contacted with a monomer component such as a styrene monomer. Then, polymerization is performed. (IV) After contacting the component (A) with the carrier, the component (B) is further contacted with the component (B) to separate the generated supported catalyst,
Polymerization is carried out by bringing the supported catalyst into contact with a monomer component such as a styrene monomer. (V) After contacting the component (B) with the carrier, (A)
The catalyst is brought into contact with the components, the generated supported catalyst is separated, and the supported catalyst is brought into contact with a monomer component such as a styrene-based monomer to carry out polymerization.

Among the methods (I) to (V), the methods (I) and (I) are intended to improve the efficiency of the initiator and the polymerization activity and to further narrow the molecular weight distribution of the obtained polymer.
Method I) is preferred. More preferably, the method (II) is used. By performing aging, the efficiency of the initiator can be improved and the molecular weight distribution can be narrowed. Further, as described later, the polymerization reaction of the present invention in which a specific polymerization temperature is applied is a so-called living polymerization system. Therefore, due to the synergistic effect of aging and polymerization temperature, a terminal-modified syndiotactic styrene-based polymer having a sufficiently high molecular weight, a narrow molecular weight distribution, and a high terminal modification rate can be efficiently obtained.

The contact temperature between the components (A) and (B) is -5.
Must be in the range of 0 ° C to 50 ° C, -40 ° C to 4 ° C
A range of 0 ° C. is preferred. The contact time between the component (A) and the component (B) differs depending on the contact temperature and cannot be determined uniquely, but is usually 5 seconds to 10 hours. Preferably 1 minute to 3
Time range. If the contact temperature is too high, the desired aging effect cannot be obtained, and if the contact temperature is too low, it is disadvantageous in economy. An excessively long contact time is not preferable because the polymerization activity is low, and an aging time of less than 5 seconds is not preferable because control of the reaction becomes difficult.

The component (A) and the component (B) can be used in the state of either a solution or a slurry, respectively, but are preferably in the form of a solution in order to obtain higher polymerization activity. The solvent used for preparing the solution or slurry is a hydrocarbon solvent such as butane, pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene, or chloroform, methylene chloride, dichloroethane, chlorobenzene, etc. It is a halogenated hydrocarbon solvent. Preferred solvents are aromatic hydrocarbons such as toluene and benzene. Further, two or more solvents may be mixed and used.

The polymerization temperature is usually in the range of -50 to 0 ° C. from the viewpoint of promoting living polymerization and producing a terminal-modified syndiotactic styrene polymer having a high terminal modification rate. It is preferably carried out at a temperature of -40 to 0 ° C, more preferably at a temperature of -35 to -5 ° C. If the polymerization temperature is lower than -50 ° C, the syndiotacticity decreases, which is not preferable. On the other hand, if the polymerization temperature is higher than 0 ° C, the molecular weight distribution (Mw / Mn) becomes unfavorably wide. Typical polymerization times are from 30 seconds to 36 hours, preferably
It is 1 minute to 20 hours, more preferably 5 minutes to 10 hours. The optimal time required to produce the desired polymer will vary with the temperature, solvent and other polymerization conditions employed.

The polymerization can be carried out at sub-atmospheric pressures as well as at super-atmospheric pressures. It is also carried out at reduced pressure until the lowest component of the polymerization mixture evaporates. However, it is preferred to use a pressure near atmospheric pressure. The polymerization method is usually performed by a solution polymerization method in an inert solvent, a slurry polymerization method, or a bulk polymerization method using a monomer as a diluent. Among these methods, a solution polymerization method and a bulk polymerization method are preferable.

Inert solvents used in the polymerization include aliphatic, cycloaliphatic, aromatic and halogenated aromatic hydrocarbons, and mixtures thereof. Preferred inert solvents for the polymerization are C4 -C26 alkanes, especially branched alkanes, toluene, ethylbenzene, and mixtures thereof. Suitable solvents are used to give a monomer concentration of 2 to 100% by weight.

Also, anisole, diphenyl ether,
A polymerization reaction may be carried out by adding a small amount of a polar compound such as an ether such as ethyl ether, diglyme, tetrahydrofuran or dioxane or an amine such as triethylamine or tetramethylethylenediamine within a range not to impair the effects of the present invention.

In the method for producing a terminal-modified syndiotactic styrene-based polymer of the present invention, when the polymerization reaction reaches a predetermined polymerization conversion, a transition metal derived from the component (A) is provided at the molecular terminal. A reagent capable of reacting with the living polymer (hereinafter, referred to as “terminal modifier”) is added to the polymerization system and brought into contact with the living polymer. As a terminal modifier, oxygen molecules, carbon monoxide, carbon dioxide, carbon disulfide,
In addition to carbonyl sulfide, sulfur dioxide and the like, the following compounds may be mentioned.

For example, halogen molecules such as chlorine, bromine and iodine; organic halides such as vinylbenzyl chloride and bromodichloromethane; ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, epoxidized natural rubber, epichlorohydric Epoxy compounds such as phosphorus and epibromohydrin; thiirane compounds such as thiirane, methylthiirane and phenylthiirane; ethyleneimine derivatives such as ethyleneimine, propyleneimine, N-phenylethyleneimine and N- (β-cyanoethyl) ethyleneimine; A hetero three-membered ring compound containing

4-dimethylaminoacetophenone, 4-
Diethylaminoacetophenone, 1,3-bis (diphenylamino) -2-propanone, 1,7-bis (methylethylamino) -4-heptanone, 4-dimethylaminobenzophenone, 4-di-t-butylaminobenzophenone, 4- Diphenylaminobenzophenone, 4,4 '
-Bis (dimethylamino) benzophenone, 4,4'-
N-substituted aminoketones such as bis (diethylamino) benzophenone and 4,4′-bis (diphenylamino) benzophenone and ketone compounds such as N-substituted aminothioketone; bromoacetone, α-bromoacetophenone, 1-bromo-2- Ketones having a halogen such as butanone, 2'-bromoacetophenone, 3'-bromoacetophenone, and 4-bromoacetophenone

4-dimethylaminobenzaldehyde, 4
Aldehyde compounds such as N-substituted benzaldehydes and N-substituted benzthioaldehydes such as -diphenylaminobenzaldehyde and 4-divinylaminobenzaldehyde; ethyl (thio) ketene, butyl (thio) ketene, phenyl (thio) ketene and toluyl ( Ketene compounds such as thio) ketene and thioketene compounds; ester compounds and lactone compounds such as ethyl acetate and γ-butyrolactone; acid halide compounds such as bromoacetyl chloride, m-bromobenzoyl chloride, propionic chloride, octanoic chloride; Carbodiimide compounds such as N'-diphenylcarbodiimide, N, N'-diethylcarbodiimide;

2-amino-6-chloropyridine, 2,5
-Dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, 3,6-
Dichloro-4-methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4,6- Dichloropyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 2-
Chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2- (methylthio) pyrimidine, 2,4,5,6-tetrachloropyrimidine,

2,4,6-trichloropyrimidine, 2-
Amino-6-chloropyrazine, 2,6-dichloropyrazine, 2,4-bis (methylthio) -6-chloro-1,
3,5-triazine, 2,4,6-trichloro-1,
Pyridine compounds having a halogen on a carbon atom adjacent to a nitrogen atom such as 3,5-triazine, 2-bromo-5-nitrothiazole, 2-chlorobenzothiazole, 2-chlorobenzoxazole; methyl-2-pyridyl ketone; Methyl-4-pyridyl ketone, propyl-2-pyridyl ketone, di-4-pyridyl ketone, propyl-3-
Pyridyl-substituted ketones such as pyridyl ketone and 2-benzoyl pyridine; pyridines including vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine

N, N-dimethylformamide, acetamide, N, N-diethylacetamide, aminoacetamide, N, N-dimethyl-N ', N'-dimethylacetamide, N, N-dimethylacetamide, N, N-ethylacetamide , N, N-dimethyl-N'-ethylacetamide, acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, nicotinamide, isonicotinamide, picolinamide, N, N
Dimethylisonicotinamide, succinamide, phthalamide, N, N, N ′, N′-tetramethylphthalamide, oxamide, N, N, N ′, N′-tetramethyloxamide,

2-furancarboxylic amide, N, N-dimethyl-2-furancarboxylic amide, quinoline-2-
Carboxylic acid amide, N-ethyl-N-methyl-quinoline carboxylic acid amide, N-methyl-β-propiolactam, N-phenyl-β-propiolactam, N-phenyl-2-pyrrolidone, Nt -Butyl-2-pyrrolidone, N-phenyl-5-methyl-2-pyrrolidone, N
Amide compounds such as N-substituted lactams such as -methyl-2-piperidone, N-phenyl-2-piperidone, N-methyl-ε-caprolactam and N-substituted thiolactams;

1,3-Diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,1
-Dipropyl-2-imidazolidinone, 1-methyl-3
-Ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, 1-methyl-3- (2-methoxyethyl)- 2-imidazolidinone, 1-methyl-
3- (2-ethoxyethyl) -2-imidazolidinone,
Urea compounds such as N-substituted cyclic ureas such as 1,3-di- (2-methoxyethyl) -2-imidazolidinone and N-substituted cyclic thioureas;

Imide compounds such as succinimide, N-methylsuccinimide, maleimide, N-methylmaleimide, phthalimide, N-methylphthalimide; methyl carbamate, methyl N, N-diethylcarbamate, isocyanuric acid, N, N Carbamic acid compounds including isocyanuric acid derivatives such as', N'-trimethylisocyanuric acid, isocyanuric acid compounds and thiocarbonyl-containing compounds corresponding thereto;

Isocyanate compounds such as phenyl isocyanate, butyl isocyanate and phenylthioisocyanate, and thioisocyanate compounds; trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, t-butyldimethylchlorosilane,
Tetrachlorosilane, methyltrichlorosilane, chlorodimethylsilane, trimethylethoxysilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, ethylmethyldichlorosilane, phenylmethyldichlorosilane, dimethylchlorosilane, phenyltrichlorosilane, tetramethoxysilane, methyltrimethoxy Silane, dimethyldimethoxysilane, trimethylmethoxysilane, ethylmethyldimethoxysilane, dimethylmethoxysilane, phenylmethyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyldiethoxysilane, dimethyldisilane Ethoxysilane, methyltriisopropoxysilane, dimethyldiisopropoxy Silane, phenyl methyl diisopropoxy silane, methyl triacetoxy silane, dimethyl diacetoxy silane, phenyl methyl diacetoxy silane,

Allyloxytrimethylsilane, 2-methyl-1- (trimethylsilyloxy) -1-propene,
3-divinyltetramethyldisiloxane, 1,1,3
5,5-pentaphenyltrimethyltrisiloxane,
1,1,5,5-tetraphenyltetramethyltrisiloxane, tris (trimethylsiloxy) silane, phenyltriethoxysilane, 1,4-bis (dimethylsilyl) benzene, N, N-dimethylaminotrimethylsilane, (ethylthio) A silicon compound having a hydrogen atom such as trimethylsilane, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a substituent containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom;

Germanium compounds such as trimethylgermanium chloride, triethylgermanium chloride, triphenylgermanium chloride, trimethylgermanium bromide; trimethyltin chloride;
Tin compounds such as triethyltin chloride, triphenyltin chloride, trimethyltin bromide, triethyltin bromide, triphenyltin fluoride, and tributyltin chloride; dimethylchlorophosphine, diethylchlorophosphine, di-t-butylchlorophosphine, dicyclohexylchlorophosphine, Phosphorus compounds such as diphenylchlorophosphine, diphenylphosphinic chloride, diphenylchlorophosphate, bis (dimethylamino) phosphoryl chloride;
Halogens such as -bromophenethyl alcohol, 4-bromophenol, 3-bromo-1-propanol, 2-bromobenzyl alcohol, 4-bromo-2,6-dimethylphenol, 2-bromoethanol, and 4-bromo-2-naphthol Substituted alcohols and phenols;

Α-bromo-p-toluic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid,
Succinic anhydride, 2-bromo-n-butyric acid, 6-bromohexanoic acid, α-bromoisobutyric acid, 2-bromoisobutyric acid, 2
-Bromopropionic acid, 3-bromopropionic acid, 11
Carboxylic acids such as -bromoundecanoic acid, 5-bromovaleric acid, chloroacetic acid, and bromoacetic acid, and ester compounds thereof; o-bromobenzonitrile, m-bromobenzonitrile, p-bromobenzonitrile, α-bromotolunitrile, Nitriles such as 3-bromopropionitrile and 4-bromobutyronitrile; ethers such as o-bromoanisole, 4-bromodiphenyl ether, 2-bromoethylethyl ether and bromomethyl ether; o-bromoaniline, m- Amines such as bromoaniline, p-bromoaniline, 4-bromo-N, N-dimethylaniline, 2-bromo-4-methylaniline, 3-bromophenylhydrazine hydrochloride, and 3-bromopropylamine; o-bromonitrobenzene Nitro compounds such as 2-bromosulfur Sodium phosphate, and the like sulfonic acids such as 2-bromo-sulfonic acid.

In order to obtain a terminal-modified polymer which is preferable as a macromonomer, a reagent having both a reactive site capable of binding to a living polymer and a polymerizable site is selected as a terminal-denaturing agent. Vinylbenzyl chloride, 4-bromo-1-butene, 2-bromo-2
-Butene, 5-bromo-1-pentene, 3-bromo-1
-Propene, 3-chloro-1-propene, 3-bromo-
Examples include olefins such as 1-propene and chloromethylstyrene, and acetylenes. When a terminal-modified polymer that is preferable as a macromonomer is obtained, a reagent having both a reactive site capable of binding to a living polymer and a polymerizable site is selected as a terminal modifier, and specific examples thereof include vinylbenzyl chloride. And the like.

The amount of the terminal modifier used is usually 0.1 to 1000 mol, preferably 0.2 to 500 mol, more preferably 0.5 to 500 mol per 1 mol of the transition metal compound (A).
It is in the range of 100 moles. The terminal modifier is usually added when the polymerization conversion exceeds 5%. It is not preferable from the viewpoint of cost to add at a point when the conversion does not exceed 5%. In addition, as the polymerization proceeds, the polymerization rate decreases, and the living terminal is easily deactivated. From the viewpoint of increasing the terminal modification rate, the terminal conversion agent is added after the polymerization conversion rate exceeds 5%. It is not preferable to leave the reaction solution for a long period of time.

Although the temperature of the terminal modification reaction is not particularly limited,
It is usually -80 to 60C, preferably -50 to 50C, particularly preferably -40 to 40C. The terminal modification reaction time depends on the reaction temperature and cannot be unambiguously determined.
It is usually 1 minute to 600 minutes, preferably 2 minutes to 300 minutes. Termination of the terminal modification reaction is usually performed by adding a reaction terminator to the reaction system when a predetermined terminal modification ratio is reached. As the reaction terminator, for example, alcohols such as methanol, ethanol, propanol, butanol, and isobutanol are used, and they may contain an acid such as hydrochloric acid. After termination of the terminal reaction, the method of recovering the polymer is not particularly limited, for example,
A steam stripping method, precipitation with a poor solvent, or the like may be used.

In order to control the molecular weight of the polymer, a chain transfer agent may be added within a range that does not impair the effects of the present invention. As the chain transfer agent, allenes such as 1,2-butadiene, cyclic dienes such as cyclooctadiene, and hydrogen are preferably used.

[0108]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. First,
Each evaluation and measurement method used in the examples of the present invention will be described. 1) Catalytic activity 1 mmol of catalytic metal was represented by the amount of polymer produced (gram) per hour. 2) Molecular weight and molecular weight distribution of polymer The measurement was performed using SSC-7100 type gel permeation chromatography manufactured by Senshu Kagaku with a differential refractometer attached as a detector. 3)% syndiotacticity It was determined by measuring pentads (racemic pentads) by ¹³ C-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. 4) Terminal functional group introduction ratio It was determined by ¹ H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL Ltd.

Example 1 A polymerization reaction was carried out in a nitrogen atmosphere using a three-neck glass flask having an inner volume of 300 ml, which was dried and purged with nitrogen. 168 ml of toluene and 0.4 mmol of trioctylaluminum were charged into a three-necked flask, and aged at room temperature for 10 minutes. Here, 0.2 mmol of (trimethyl) pentamethylcyclopentadienyltitanium and then 0.2 mmol of tris (pentafluorophenyl) boron were charged at room temperature.
Aged for 10 minutes. Next, keep the temperature at -20 ° C.
Aging was performed for 60 minutes.

Finally, 20 ml of a toluene solution of 6.0 mmol of p-methylstyrene was charged and a polymerization reaction was carried out at -20 ° C. for 5 minutes. After adding 20 ml of a toluene solution of 20.0 mmol of tert-butyl isocyanate and reacting for 2 hours at the same temperature, further raising the temperature to room temperature and reacting for 2 hours, the reaction was stopped by adding a small amount of methanol. Then, the polymerization solution was poured into a large amount of methanol to precipitate a polymer. The obtained polymer is washed, separated by filtration, dried, then further dissolved in toluene, separated by filtration, and precipitated again in a large amount of methanol.The obtained polymer is washed, separated by filtration, dried, and weighed. Thus, 0.049 g (yield: 6.9 wt%) of a polymer was obtained.
The polymerization activity was 4.9 ((g of PS) / (mmol Ti) × hr). The weight average molecular weight (Mw) of the obtained polymer was 35200
, The number average molecular weight (Mn) is 28400, and the molecular weight distribution (Mw
/ Mn) was 1.24. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more for racemic pentad. Further, ¹ H-NMR
The terminal functional group introduction rate determined from the measurement was 94.3%.

Example 2 A polymerization reaction was carried out in a nitrogen atmosphere using a 200 ml glass three-necked flask which had been dried and purged with nitrogen. 68 ml of toluene and 0.2 mmol of trioctylaluminum were charged into a three-necked flask and aged at room temperature for 10 minutes. Here, 0.1 mmol of (trimethyl) pentamethylcyclopentadienyltitanium and subsequently 0.1 mmol of tris (pentafluorophenyl) boron were charged and added at room temperature.
Aging was performed for 0 minutes. Next, keep the temperature at -20 ° C.
After aging for 10 minutes, p-methylstyrene was added in 0.1 ml.
A toluene solution containing 1 mmol was added and aged for 60 minutes. Finally, 20 ml of a toluene solution of 6.0 mmol of p-methylstyrene was charged and a polymerization reaction was carried out at -20 ° C for 5 minutes. After adding 20 ml of a toluene solution of 10.0 mmol of tert-butyl isocyanate and reacting for 2 hours at the same temperature, further raising the temperature to room temperature and reacting for 2 hours, the reaction was stopped by adding a small amount of methanol, The polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The obtained polymer was washed, separated by filtration, dried, and further dissolved in toluene. After separated by filtration, the polymer was precipitated again in a large amount of methanol, and the obtained polymer was washed, separated by filtration, and dried. After that, it is weighed and 0.071 g of polymer (yield: 9.9 wt%)
I got The polymerization activity was 8.6 ((gof PS) / (mmol Ti) × hr). The weight average molecular weight (Mw) of the obtained polymer was 518.
00, number average molecular weight (Mn) is 42300, molecular weight distribution (Mw
/ Mn) was 1.23. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more for racemic pentad. Further, the terminal functional group introduction ratio determined by ¹ H-NMR measurement was 84.7%.

Example 3 A polymerization reaction was carried out in a nitrogen atmosphere using a three-neck glass flask having an inner volume of 200 ml, which was dried and purged with nitrogen. 67 ml of toluene and 0.2 mmol of trioctylaluminum were charged into a three-necked flask and aged at room temperature for 10 minutes. Here, 0.1 mmol of (trimethyl) pentamethylcyclopentadienyltitanium and subsequently 0.1 mmol of tris (pentafluorophenyl) boron were charged and aged at room temperature for 10 minutes. Next, the temperature was kept at −20 ° C., and aging was performed for 10 minutes. Then, a toluene solution containing 0.1 mmol of p-methylstyrene was added, and aging was performed for 60 minutes. Finally, 20 ml of a toluene solution containing 3.0 mmol of styrene and 3.0 mmol of p-methylstyrene was charged, and a polymerization reaction was performed at -20 ° C for 5 minutes. After adding 20 ml of a toluene solution of 10.0 mmol of tert-butyl isocyanate and reacting for 2 hours at the same temperature, further raising the temperature to room temperature and reacting for 2 hours, the reaction was stopped by adding a small amount of methanol. The polymerization solution was poured into a large amount of methanol to precipitate a polymer.

The obtained polymer was washed, separated by filtration, dried, further dissolved in toluene, separated by filtration, precipitated again in a large amount of methanol, and the obtained polymer was washed, separated by filtration, and dried. Thereafter, it was weighed to obtain 0.039 g of a polymer (yield: 5.8 wt%). The polymerization activity was 4.7 ((g of PS) / (mmol Ti) × hr). The weight average molecular weight (Mw) of the obtained polymer was 322.
00, number average molecular weight (Mn) is 25,000, molecular weight distribution (Mw
/ Mn) was 1.29. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more for racemic pentad. Further, ¹ H-NMR
The copolymer composition obtained from the measurement is styrene: 30.0 mol
%, P-methylstyrene: 70.0 mol%, and the introduction ratio of terminal functional groups was 63.3%.

Comparative Example 1 A polymerization reaction was carried out under a nitrogen atmosphere by using a 200 ml glass three-necked flask which had been dried and purged with nitrogen. A toluene solution (manufactured by Tosoh Akzo) of 77 ml of toluene and 5.0 mmol of methylaluminoxane was charged and the temperature was kept at 23 ° C. Were charged toluene solution 20ml containing p- methylstyrene 18.0mmol herein, after aging 10 minutes, cyclopentadienyl trichloro titanium (C _P TiCl ₃₎ 0.01
A toluene solution containing mmol was added, and a polymerization reaction was performed at 23 ° C. for 5 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of acidic methanol to precipitate a polymer.

The obtained polymer was washed, separated by filtration, dried and weighed to obtain 0.091 g of polymer (yield 4.3%). The polymerization activity is
110 ((g of PS) / (mmol Ti) × hr). The weight average molecular weight (Mw) of the obtained polymer was 19100, the number average molecular weight (Mn) was 10300, and the molecular weight distribution (Mw / Mn) was 1.85.
Met. The syndiotacticity determined by ¹³ C-NMR measurement was 95% for racemic pentad.
That was all. Further, the terminal functional group introduction ratio determined by ¹ H-NMR measurement was 16.5%.

[0117]

The terminal-modified syndiotactic styrenic polymer of the present invention has a narrow molecular weight distribution, has a high syndiotacticity, and has a high content of a functional group at the molecular terminal, so that it can be used in home electric appliances. , Plastic materials used in a wide range of fields such as OA equipment, various high-performance resins and functional resins such as resin modifiers, and macromonomers or reactive resins that are raw materials for various high-performance resins and functional resins. It is extremely useful as a polymer. Further, by polymerizing a styrene-based monomer using the production method of the present invention, the molecular weight of the present invention is sufficiently high, the molecular weight distribution is narrow, the syndiotacticity is high, and a functional group is provided at the molecular terminal. A terminal-modified syndiotactic styrene-based polymer having a high content of a group can be produced with high efficiency.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahide Murata 2-3-15-504, Suido, Bunkyo-ku, Tokyo (72) Inventor Toshio Kase 5-2-2302, Matsushiro, Tsukuba, Ibaraki Prefecture (72) Inventor Hiroyuki Ozaki 4-6-202 Onogawa Tsukuba, Ibaraki Prefecture (72) Inventor Yoshifumi Fukui 4-63-507 Ninomiya 4-chome, Tsukuba City, Ibaraki Prefecture (72) Hideaki Hagiwara 2-Akubo, Tsukuba City, Ibaraki Prefecture 6-14 Sakurai Heights 203 (72) Inventor Jin Jiju 2-2-7 Kodateno, Kanazawa-shi, Ishikawa Prefecture (72) Inventor Satoshi Miyazawa 1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref. Inventor Kenji Tsuchihara 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Yasumi Suzuki 1-1-1, Higashi, Tsukuba, Ibaraki Institute of Materials Science and Technology (72) Inventor Michihiko Asai 1-1-1, Higashi, Tsukuba, Ibaraki Pref.Institute of Materials Science and Technology, Institute of Industrial Science (72) Kazuo Soga 1-1-1, Higashi, Tsukuba, Ibaraki F-term in Materials Engineering and Technology Laboratory (reference) 4J028 AA01A AB00A AB01A AC01A AC02A AC03A AC08A AC10A AC13A AC15A AC20A AC23A AC25A AC26A AC28A BA00A BA01B BA02B BA03B BA04B BB00A BB01B BB02B03BCBBC BCBC BCBC BCBC BCBC EB12 EB13 EB15 EB18 EB21 EB22 EB25 FA01 FA02 GA01 GA06 GA12 GB01 4J100 AA02Q AA03Q AA04Q AB02P AB04P AB07P AB08P AB09P AB10P AB16P AL03Q AR22Q AS02Q AS11Q AS15Q BA02P BA04P BA05P BA06P BA10P BA12P BA31P BA40P BA41P BA45P BA52P BA53P BA58P BA63P BA65P BA67P BA72P BA89P BA94P BB01P BB03P BB07P BC08Q BC42P BC43P BC44P BC48P BC49P CA01 CA04 CA12 CA27 DA01 DA04 JA43

Claims (2)

[Claims] [Claim 1] The following general formula (1) (In the formula, R ¹ is a hydrogen atom, a halogen atom, and has 1 to 3 carbon atoms.
0 represents a hydrocarbon group or a substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m represents an integer of 0 to 5. . However, when m is plural, each R ¹ may be the same or different. A) a (co) polymer having at least one structural unit represented by the formula ( ₁ ), wherein the phenyl group (containing a substituent) has a C ₁ -carbon tacticity of ¹³ C-
Racemic pentad by NMR is 30% or more, and the number average molecular weight (Mn) is in the range of the following formula (2);
The relationship between the number average molecular weight (Mn) and the weight average molecular weight (Mw) satisfies the following formula (3), and the molecular chain having a functional group at the molecular terminal is 30% or more of the total molecular chain. Terminal-modified syndiotactic styrenic polymer. 1000 ≦ Mn ≦ 10000000 (2) Mw / Mn ≦ 2.5 (3) As wherein catalyst component, (A) the following general formula (4) and / or _{^{(5) MR 1 a R 2}} b R 3 c X 1 4- (a + b + c) (4) MR 1 d _{^{R 2 e X 1 3- (d}} + e) (5) ( wherein, R ^1, R ^2, and R ³ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms , An alkylaryl group, an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms
20 thioaryloxy groups, cyclopentadienyl groups,
It represents a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group. M is a transition metal selected from the group consisting of titanium (Ti), zirconium (Zr) or hafnium (Hf), and X ¹ is a halogen atom. These R ¹ , R ² and R ³ may be the same or different. A, b, and c each represent an integer of 0 to 4,
D and e each represent an integer of 0 to 3. ), (B) the following (a) to (d) (a) an organoaluminum oxy compound, and (b) an ionic compound capable of producing a cationic transition metal compound by reacting with the transition metal compound. At least one selected from a compound, (c) a Lewis acid compound capable of forming a cationic transition metal compound by reacting with the transition metal compound, and (d) an organometallic compound of a metal belonging to Group 1, 2 or 13 of the periodic table. Using a component containing a kind of cocatalyst as a main catalyst component, the component (A) and the component (B) are contacted in advance at a temperature of -50 ° C to 50 ° C for 5 seconds to 10 hours, At least one styrene monomer represented by the following general formula (6): (In the formula, R ¹ is a hydrogen atom, a halogen atom, and has 1 to 3 carbon atoms.
0 represents a hydrocarbon group or a substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m represents an integer of 0 to 5. . However, when m is plural, each R ¹ may be the same or different. Is polymerized at a temperature of 0 ° C. or lower, and then a terminal modifier capable of reacting with a living polymer having a transition metal derived from the component (A) at a molecular terminal is brought into contact with the polymer. Item 6. A method for producing a terminal-modified syndiotactic styrene polymer according to item 1.