JP3107251B2 - Styrene block copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel styrenic block copolymer and a method for efficiently producing the same. More specifically, the present invention has excellent heat resistance, chemical resistance, and electrical properties, and has good toughness, elongation, adhesiveness, and compatibility. Styrenic block copolymer useful as a polymer, and a method for efficiently producing the same.

[0002]

2. Description of the Related Art Polystyrene resins are generally obtained by radical polymerization of styrene monomers by a method such as bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization. The polystyrene-based resin obtained by such radical polymerization usually has an atactic structure, does not have stereoregularity, and has insufficient heat resistance and chemical resistance depending on the application. It is rare.

Incidentally, polystyrene resins having stereoregularity include those having an isotactic structure and those having a syndiotactic structure. The former isotactic structure is mainly composed of a polymer using a Ziegler-type catalyst. On the other hand, the latter having a syndiotactic structure can be polymerized in the presence of a catalyst consisting mainly of a combination of a titanium compound such as titanium halide or alkoxytitanium and an alkylaluminoxane. (Japanese Patent Application Laid-Open No. Sho 62-104818).

[0004] These polystyrene resins having stereoregularity have a higher melting point and better chemical resistance than polystyrene resins having an atactic structure having no stereoregularity. Although it is expected to be used as a polymer having high chemical resistance, polystyrene resins having an isotactic structure have a drawback that the crystallization rate is extremely low, and are not practical. In contrast, polystyrene resins having a syndiotactic structure have a high crystallization rate, are excellent in heat resistance, chemical resistance, and have improved electrical properties. Development has been attempted (JP-A-62-104818, JP-A-63-24109), and applications in various fields are expected.

[0005] However, this polystyrene resin having a syndiotactic structure is excellent in heat resistance and chemical resistance, but has the same impact resistance as that of a general atactic structure. Attempts have been made to blend rubber, inorganic fillers, and the like to improve the viscosity, but in this case, the use is inevitably limited.

On the other hand, in recent years, a high-molecular-weight monomer having a polymerizable functional group at a terminal, a so-called macromonomer, has been developed and has begun to be applied to various uses. By co-polymerizing this macromonomer with other monomers, it is possible to easily give a polymer having the properties of the branch component, for example, compatibility, adhesion, lubricity, etc., while maintaining the properties of the trunk component. Can be.

As such a polymer using a macromonomer, for example, a homopolymer using a specific macromonomer having a styryl group at a terminal and a copolymer of the macromonomer with a styrene-based monomer have been proposed. (JP-A-4-13707). In this case, the homopolymer or copolymer using the macromonomer can sufficiently exhibit the desired effect, but in the copolymer of the macromonomer and the styrene monomer, the repeating unit of the styrene monomer and the The sequence of the repeating units of the monomer was not particularly specified, and the copolymer was practically a random copolymer.

[0008]

SUMMARY OF THE INVENTION The present invention has excellent heat resistance, chemical resistance, electrical properties, and good toughness,
An object of the present invention is to provide a styrene-based block copolymer having elongation, adhesiveness, and compatibility and useful as a material for a composite material, a heat-resistant elastomer, and the like.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a styrenic block copolymer having excellent physical properties, and as a result, have found that a high-grade syndigo having a specific styrenic monomer as a repeating unit is obtained. A styrene-based block containing a polymer segment having a tactic structure and a polymer segment derived from a macromonomer having a specific molecular weight having a polymerization active vinyl group at a terminal at a predetermined ratio, and having an intrinsic viscosity in a specific range. The copolymer shows excellent heat resistance, chemical resistance, and electrical properties, and has good toughness, elongation,
Having adhesion and compatibility, and polymerizing the styrenic monomer in the presence of a specific catalyst;
By adding and polymerizing a macromonomer having a specific molecular weight having a polymerization active vinyl group at a terminal, the styrene-based block copolymer can be easily obtained, and further, a macromonomer having a styryl group at a terminal. Of course, they have found that those having an acryloyl group or a methacryloyl group can also be used, and based on this finding, have completed the present invention.

That is, the present invention relates to (A) a compound represented by the general formula: CH ₂ ＣＨCH—Ar— (R ¹ ) p (I) (wherein Ar is a divalent aromatic group, R ¹ is a hydrogen atom, a halogen atom Or a substituent containing at least one selected from a carbon atom and a silicon atom, p is an integer of 1 to 5, and when p is 2 or more, R ¹ may be the same or different. (B) a polymer segment having a high degree of syndiotactic structure having a repeating unit of a styrenic monomer represented by the formula (B):
After polymerizing an anionic polymerizable monomer using an anionic polymerization initiator, a macromonomer having a number average molecular weight of 300 to 10,000 having a polymerization active vinyl group at a terminal obtained by reacting this with a halogen-containing unsaturated compound. Polymer segment derived from 20-0.1% by weight and in a 1,2,4-trichlorobenzene solution at a temperature of 135 ° C.
And a styrene-based block copolymer characterized by having an intrinsic viscosity [η] of 0.07 to 20 dl / g.

According to the present invention, the styrenic block copolymer comprises (a) a styrenic monomer represented by the above general formula (I) formed from (a) a transition metal compound and (b) an aluminum condensed compound. Or a catalyst consisting of (a) a transition metal compound and (c) a compound capable of reacting with the transition metal compound to form an ionic complex. It can be produced by adding and polymerizing.

In the styrenic block copolymer of the present invention, (A) the styrenic monomer forming the polymer segment is represented by the following general formula: CH ₂ −CH—Ar— (R ¹ ) p (I) Ar, R ¹ and p have the same meanings as described above). Specific examples of such a styrene monomer include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-
Alkylstyrenes such as dimethylstyrene and pt-butylstyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-
Halogenated styrenes such as bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, 4-vinylbiphenyl, 3-vinylbiphenyl, 2- Vinyl biphenyls such as vinyl biphenyl, 1- (4-vinylphenyl) -naphthalene, 2-
(4-vinylphenyl) -naphthalene, 1- (3-vinylphenyl) -naphthalene, 2- (3-vinylphenyl) -naphthalene, 1- (2-vinylphenyl) -naphthalene, 2- (2-vinylphenyl) -Vinylphenylnaphthalenes such as naphthalene, 1- (4-vinylphenyl) -anthracene, 2- (4-vinylphenyl)-
Anthracene, 9- (4-vinylphenyl) -anthracene, 1- (3-vinylphenyl) -anthracene, 2
-(3-vinylphenyl) -anthracene, 9- (3-
(Vinylphenyl) -anthracene, 1- (2-vinylphenyl) -anthracene, 2- (2-vinylphenyl)
Vinylphenylanthracenes such as -anthracene and 9- (2-vinylphenyl) -anthracene;
-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)-
Vinylphenylphenanthrenes such as phenanthrene, 4- (2-vinylphenyl) -phenanthrene, 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, 3-vinyl-o
-Terphenyl, 2-vinyl-p-terphenyl, 2-
Vinyl terphenyls such as vinyl-m-terphenyl, 2-vinyl-o-terphenyl, vinylphenyl terphenyls such as 4- (4-vinylphenyl) -p-terphenyl, 4-vinyl-4'- Methyl biphenyl, 4
-Vinyl-3'-methylbiphenyl, 4-vinyl-2 '
Vinylalkylbiphenyls such as -methylbiphenyl, 2-methyl-4-vinylbiphenyl, 3-methyl-4-vinylbiphenyl, 4-vinyl-4'-fluorobiphenyl, 4-vinyl-3'-fluorobiphenyl, 4-
Vinyl-2'-fluorobiphenyl, 4-vinyl-2-
Fluorobiphenyl, 4-vinyl-3-fluorobiphenyl, 4-vinyl-4'-chlorobiphenyl, 4-vinyl-3'-chlorobiphenyl, 4-vinyl-2'-chlorobiphenyl, 4-vinyl-2-chlorobiphenyl , 4
-Vinyl-3-chlorobiphenyl, 4-vinyl-4'-
Halogenated vinyl biphenyls such as bromobiphenyl, 4-vinyl-3'-bromobiphenyl, 4-vinyl-2'-bromobiphenyl, 4-vinyl-2-bromobiphenyl, 4-vinyl-3-bromobiphenyl, 4- Trialkylsilylvinylbiphenyls such as vinyl-4'-trimethylsilylbiphenyl; trialkylstannylvinylbiphenyls such as 4-vinyl-4'-trimethylstannylbiphenyl and 4-vinyl-4'-tributylstannylbiphenyl; 4 Trialkylsilylmethylvinylbiphenyls such as 4-vinyl-4'-trimethylsilylmethylbiphenyl, halogen-substituted alkylstyrenes such as p-chloroethylstyrene, m-chloroethylstyrene and o-chloroethylstyrene, p-trimethylsilylstyrene m- trimethylsilyl styrene,
Alkylsilylstyrenes such as o-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene, o-triethylsilylstyrene, p-dimethyl-t-butylsilylstyrene, p-dimethylphenylsilylstyrene, p-methyldiphenyl Phenyl group-containing silylstyrenes such as silylstyrene and p-triphenylsilylstyrene, p-dimethylchlorosilylstyrene, p-methyldichlorosilylstyrene, p
Halogen-containing silylstyrenes such as -trichlorosilylstyrene, p-dimethylbromosilylstyrene and p-dimethyliodosilylstyrene; and silyl group-containing silylstyrenes such as p- (p-trimethylsilyl) dimethylsilylstyrene.

These styrene monomers may be used alone or in combination of two or more as long as the properties of the syndiotactic styrene polymer are not impaired. It may be copolymerized with a monomer.

On the other hand, in the styrenic block copolymer of the present invention, the macromonomer forming the polymer segment (B) has a polymerization-active vinyl group such as a styryl group, an acryloyl group, or a methacryloyl group at a terminal. Then, an anionic polymerizable monomer is subjected to anionic polymerization using an anionic polymerization initiator, and then the obtained polymer is reacted with a halogen-containing unsaturated compound.

As the anionic polymerizable monomer, any one can be selected from those known as monomers capable of anionic polymerization.
"Polymer Handbook (Polymer HandBo)
ok) "(published by John Wiley & Sons),
Among the monomers described in Chapter 2, the Q (resonance factor) value is 0.
A conjugated monomer having an e (polar factor) value of not less than 2 and -1.50 or more is preferable. Examples of such conjugated monomers include olefins such as diphenylethylene and indene, isoprene, 1,3-butadiene,
Fluoro-1,3-butadiene, 2,3-dichloro-
Dienes such as 1,3-butadiene and 1,3-cyclohexadiene, alkyl, halogen, haloalkyl-substituted styrene such as α-methylstyrene and 2,4,6-trimethylstyrene, 1-vinylnaphthalene, 2-isopropenyl Aromatic vinyl compounds such as naphthalene, 4-chloro-1-vinylnaphthalene, methyl and ethyl acrylates and methacrylates, n-butyl, sec-butyl, t
Esters such as -butyl, isobutyl, 2-chloroethyl, 2-nitropropyl, 2,3-epoxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, octyl, cyclohexyl, benzyl, phenyl, and magnesium of acrylic acid and methacrylic acid , Unsaturated carboxylic acids such as metal salts such as potassium salts, acrylamide derivatives such as N, N-dimethylacrylamide, N, N-diallyl-substituted acrylamide and acrylamide, and methacrylamide derivatives corresponding thereto, and further benzyl cinnamate; Acrolein, N-substituted maleimide, acrylonitrile, methacrylonitrile and the like can be mentioned.

In addition to the conjugated monomers, non-conjugated monomers such as ethylene, vinyl acetate, vinyl chloride and vinylidene chloride can be used.

These anionic polymerizable monomers may be used alone or in combination of two or more.

Examples of the anionic polymerization initiator include, for example, alkali metals such as cesium, rubidium, potassium, sodium and lithium, alkali metal alkyls or alkaline earth metal alkyls such as n-butyllithium, octyl potassium and benzyl barium; Complexes of alkali metal aromatic compounds such as naphthalene, alkali metal amides such as potassium amide and diethyllithium amide, and magnesium compounds (C ₆ H ₅ ) ₂ C—O ⁻ such as phenylmagnesium bromide and diethylmagnesium
Alkali metal ketyl such as Na ⁺ , lithium aluminum hydride (LiAlH ₄ ), dimethoxyethoxy sodium aluminum hydride [NaAlH ₂ (O—CH
₂ CH ₂ OCH ₃ ) ₂ ], an alkoxide such as n-butoxy potassium, a functional group-containing metal compound such as p-vinylbenzylmagnesium chloride, or the like, depending on the type of monomer used. . For example, when using ethylene as a monomer,
A combination of an alkyl metal compound and a tertiary diamine compound is effective.

The anionic polymerizable monomer is anionically polymerized by using these anionic polymerization initiators. In this case, a solvent may or may not be used. When using a solvent, for example, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, cyclohexane,
Nonpolar solvents such as alicyclic hydrocarbons such as cyclopentane and aromatic hydrocarbons such as benzene and toluene are preferably used. These solvents may be used singly or as a mixture of two or more.

The temperature of the anionic polymerization is usually from -78 to 20.
In the range of 0 ° C., it is appropriately selected according to the type of the monomer used. For example, in the case of using ethylene in the range of 30 to 70 ° C, and in the case of using dienes, in the range of 0 to 60 ° C,
-78 to -20 when using an unsaturated carboxylic acid derivative
It is advantageous to choose in the range of ° C.

Further, the anionic polymerizable monomer is usually used at a ratio of 2 mol times or more based on the anionic polymerization initiator. When ethylene is used as the anionic polymerizable monomer, 1.5 moles per 1 mole of the polymerization initiator is used.
It is desirable to add the tertiary diamine compound at a ratio of about 2.5 mol from the viewpoint of improving the catalytic activity.

A polymerization active vinyl group is introduced into the terminal of the polymer obtained by such anionic polymerization. Examples of the polymerization active vinyl group include a styryl group, an acryloyl group, and a methacryloyl group.

When the styryl group is introduced, a halogen-containing styrene derivative may be allowed to act upon completion of the polymerization of the anionic polymerizable monomer. As the halogen-containing styrene derivative used at this time, for example,

Embedded image (In the formula, R ² is a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom, a halogen atom, a halogenated alkyl group or an aryl group having 1 to 20 carbon atoms, At least one is a halogen atom or a halogenated alkyl group or aryl group having 1 to 20 carbon atoms, n is an integer of 1 to 3, and when n is 2 or 3, R ³ is the same. Or different ones).

Examples of such halogen-containing styrene derivatives include 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,5-dichlorostyrene,
2,3-dichlorostyrene, 3,4-dichlorostyrene, 3,5-dichlorostyrene, 2-chloro-5-methylstyrene, 4-chloro-5-methylstyrene, 2-chloro-3,4-dimethylstyrene, 2,3,4-trichlorostyrene, 2,4,5-trichlorostyrene, 4-
Chlorine-containing derivatives such as chloromethylstyrene and 4-chloromethyl-4'-vinylbiphenyl, and corresponding bromine-containing derivatives and iodine-containing derivatives can be given.

These halogen-containing styrene derivatives are generally used in an amount of 0.05 to 5 mol, preferably 0.5 to 5 mol, per 1 mol of the anionic polymerization initiator used in the anionic polymerization.
It is used in a proportion of 3 mol, more preferably 1.0 to 2.0 mol. This halogen-containing styrene derivative may be added to the reaction system as it is, or may be added after diluting in an appropriate solvent. At this time, a catalyst may be used, but it is better not to use it for preventing polymerization. The temperature at which the halogen-containing styrene derivative is added to the reaction system and reacted with the polymer of the anionic polymerizable monomer may be the polymerization temperature, but is preferably in the range of -78 to 50 ° C. When p-vinylbenzylmagnesium chloride is used as an anionic polymerization initiator, a bifunctional macromonomer is obtained.

In this way, a macromonomer having a polymerization-active styryl group at a terminal is obtained. The structure of this macromonomer, for example, in the case of monosubstituted styrene,

Embedded image In the case of trisubstituted styrene

Embedded image (Wherein R ³ ′, R ³ ″, and R ³ ″ are groups or mere bonds in which only halogen is lost in the substituents of the halogen-containing styrene derivative, M is an anionic polymerizable monomer unit, and R ⁴ is an anionic polymerization initiator. And m is the degree of polymerization).

On the other hand, when an acryloyl group or a methacryloyl group is introduced,

Embedded image (Wherein R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a halogen atom, a halogenated alkoxy group or a halogenated aryloxy group having 1 to 20 carbon atoms) or an acrylic acid derivative or a methacrylic acid derivative represented by the following formula: . Examples of the acrylic acid derivative include chlorine-containing derivatives such as acrylic acid chloride, 2-chloroethyl acrylate, 3-chloropropyl acrylate, 4-chlorobutyl acrylate, p-chlorophenyl acrylate and the like, and bromine-containing derivatives corresponding thereto. Examples thereof include iodine-containing derivatives. Examples of the methacrylic acid derivative include a methacrylic acid derivative corresponding to the acrylic acid derivative.

In the present invention, the macromonomer having a polymerization-active vinyl group at its terminal must have a number average molecular weight in the range of 300 to 10,000, preferably 500 to 6,000. This number average molecular weight is 300
Below, the properties of the resulting macromonomer polymer,
For example, adhesion and compatibility are not sufficiently exhibited. That is, it is important that this macromonomer be a pentamer or more when methyl methacrylate is used as the anion-polymerizable monomer, and a 15-mer or more when ethylene is used.

The styrenic block copolymer of the present invention comprises
(A) a polymer segment having a high syndiotactic structure having the styrene-based monomer as a repeating unit, and (B) a polymer segment derived from a macromonomer having a polymerization-active vinyl group at the terminal. It is.

The term “high syndiotactic structure” as used herein means that the stereochemical structure is mainly a syndiotactic structure, that is, a substituted aryl group which is a side chain to a main chain formed from carbon-carbon bonds is alternately opposite. Having a three-dimensional structure positioned in the direction (racemic), and its tacticity is determined by nuclear magnetic resonance ( ¹³ C) using isotope carbon.
-NMR method).

Tacticity determined by the ¹³ C-NMR method is determined based on the abundance ratio of a plurality of continuous structural units (ie, the abundance ratio of a relative conformational relationship of continuous structural units), for example, in the case of two Can be indicated by a dyad, a triad in the case of three, a pentad in the case of five, and having a high syndiotactic structure in the present invention means that the type of the substituent and the content ratio of each repeating unit Although the degree of syndiotacticity varies slightly depending on the type, a chain of styrenic repeating units usually has a syndiotacticity of 75% or more in racemic dyad or 30% or more in racemic pendant.

The styrenic block copolymer has (A) a content of the polymer segment of 80 to 99.9% by weight, and (B) a content of the polymer segment of 20 to 0.1%.
It must be in the range of weight percent. If the ratio of the (A) segment to the (B) segment is out of the above range, the object of the present invention cannot be sufficiently achieved.

Further, the styrene-based block copolymer is used in a 1,2,4-trichlorobenzene solution at a temperature of 135.
Intrinsic viscosity [η] measured at 0 ° C is 0.07 to 20 dl / g
Must be in the range of If the intrinsic viscosity [η] is less than 0.07 dl / g, mechanical properties are insufficient, and if it exceeds 20 dl / g, molding becomes difficult.

In order to produce such a styrene-based block copolymer, according to the present invention, the styrene-based monomer is first prepared by using a catalyst comprising (a) a transition metal compound and (b) an aluminum condensate compound, or ( Polymerization is carried out in the presence of a catalyst comprising a) a transition metal compound and (c) a compound capable of forming an ionic complex by reacting with the transition metal compound.

As the transition metal compound of the component (A),
For example, the general formula

Embedded image (In the formula, R ⁷ to R ¹⁸ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
0 alkoxy group, C6-20 aryl group, C7-20 arylalkyl group, C6-20 aryloxy group, C1-20 acyloxy group, acetylacetonyl group, cyclopentane Dienyl group, substituted cyclopentadienyl group or indenyl group, a, b and c
Is an integer of 0 or 1 to 4 each satisfying a relational expression of 0 ≦ a + b + c ≦ 4, and d and e are respectively 0 ≦ d + e ≦ 3
Is an integer of 0 or 1 to 3 that satisfies the relational expression, f is 0, 1 or 2, g and h are each an integer of 0 or 1 to 3 that satisfies the relational expression of 0 ≦ g + h ≦ 3, M ¹ and M ² Represents titanium, zirconium, hafnium or vanadium, respectively, M ³
And M ⁴ are each vanadium). Among them, the compounds represented by the general formula (VI) wherein M ¹ is titanium or zirconium are exemplified. It is suitable. One of these transition metal compounds may be used, or two or more thereof may be used in combination.

In the above general formulas (VI) to (IX),
Among those represented by R ⁷ to R ¹⁸ , chlorine, bromine, iodine or fluorine is used as the halogen atom, and cycloalkyl substituted with one or more alkyl groups having 1 to 6 carbon atoms is used as the substituted cyclopentadienyl group. Pentadienyl group,
Specifically, a methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and the like, as an alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, n-propyl group,
An isopropyl group, an n-butyl group, an isobutyl group, an amyl group, an isoamyl group, an octyl group, a 2-ethylhexyl group and the like, and examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. , An amyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyl group, etc., as an aryl group having 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group, etc., and an arylalkyl group having 7 to 20 carbon atoms. ,
For example, a benzyl group, a phenethyl group, a 9-anthrylmethyl group and the like, as an aryloxy group having 6 to 20 carbon atoms, for example, a phenoxy group and the like, and as an acyloxy group having 1 to 20 carbon atoms, for example, an acetyloxy group, And a stearoyloxy group.

The above general formulas (VI) to (I)
Among the transition metal compounds represented by X), specific examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-butoxytitanium, tetraisopropoxytitanium, cyclopentadienyltrimethyltitanium, titanium tetrachloride, Titanium trichloride, dimethoxytitanium dichloride, methoxytitanium trichloride, trimethoxytitanium chloride, cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadienyltributyltitanium, methylcyclopentadienyltrimethyltitanium, methylcyclo Pentadienyltribenzyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, tetramethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium Titanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium, pentamethylcyclopentadienyltributyltitanium, pentamethylcyclopentadienyltitanium triphenyl, pentamethylcyclopentadienyltribenzyltitanium, Cyclopentadienylmethyltitanium dichloride, cyclopentadienylethyltitanium dichloride, pentamethylcyclopentadienylmethyltitanium dichloride, pentamethylcyclopentadienylethyltitanium dichloride, cyclopentadienyldimethyltitanium monochloride, cyclopentadienyldiethyl Titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclopentadienyl Titanium tripropoxide, cyclopentadienyl titanium triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethylcyclopentadienyl titanium tripropoxide, pentamethylcyclopenta Dienyl titanium tributoxide, pentamethyl cyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethyl cyclopentadienyl titanium trichloride, cyclopentadienyl methoxy titanium dichloride, cyclopentadienyl dimethoxy titanium chloride, Pentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltribenzyltitanium, cyclopentadienyldimethylmethoxytitanium , Methylcyclopentadienyldimethylmethoxytitanium, pentamethylcyclopentadienylmethyldiethoxytitanium, indenyltitanium trichloride, indenyltitaniumtrimethoxide, indenyltitaniumtriethoxide, indenyltrimethyltitanium, indenyltribenzyl Titanium and the like can be mentioned. Bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) diethyltitanium, bis (cyclopentadienyl) Dienyl) dibenzyltitanium, bis (methylcyclopentadienyl) dimethyltitanium, bis (pentamethylcyclopentadienyl) dimethyltitanium, bis (methyldicyclopentadienyl) dibenzyltitanium, bis (pentamethylcyclopentadi Enyl) dibenzyltitanium, bis (pentamethylcyclopentadienyl) chloromethyltitanium,
Bis (pentamethylcyclopentadienyl) hydridomethyltitanium and the like can be mentioned. Further, titanium compounds containing a cross-linkable ligand such as ethylenebis (indenyl) dimethyltitanium, ethylenebis (tetrahydroindenyl) dimethyltitanium, and dimethylsilylenebis (cyclopentadienyl) dimethyltitanium may also be used. These transition metal compounds may be those which form a complex with a Lewis base.

Of these titanium compounds, when it is necessary to increase the molecular weight of the styrenic polymer, titanium compounds having an alkoxide or a substituted π-electron ligand are preferred. When the molecular weight is reduced, a titanium compound having a π-electron ligand or a halogen ligand is preferable.

The compounds represented by the above general formulas (VI) to (IX)
Among the transition metal compounds represented by the following, specific examples of the zirconium compound include cyclopentadienyl zirconium trimethoxide, pentamethylcyclopentadienyl zirconium trimethoxide, cyclopentadienyl tribenzyl zirconium, and pentamethylcyclopentadiene. Examples include enyltribenzyl zirconium, bisindenyl zirconium dichloride, zirconium benzyl dichloride, zirconium tetrabenzyl, tributoxy zirconium chloride, triisopropoxy zirconium chloride and the like.

Similarly, specific examples of the hafnium compound include cyclopentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyl tribenzyl hafnium, and pentamethylcyclopentadienyl trimethoxide. Benzyl hafnium, bisindenyl hafnium dichloride,
Examples include hafnium dibenzyl dichloride, hafnium tetrabenzyl, tributoxy hafnium chloride, and triisopropoxy hafnium chloride.

Similarly, specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetate. Nart and the like.

The aluminum condensate compound of component (b) used in combination with these transition metal compounds is a contact product of organoaluminum and a condensing agent. Here, as the organic aluminum compound, usually the general formula _{^{AlR 19 3 (X) (R}} 19 in the formula a halogen atom, an alkyl group or a halogenated alkyl group having 1 to 8 carbon atoms, the three ^{R 19}
May be the same or different), specifically, trimethylaluminum, dimethylaluminum chloride, triethylaluminum, triisobutylaluminum, etc., of which trimethylaluminum is preferred .

As the condensing agent, water is typically mentioned. In addition to the above, various compounds such as copper sulfate pentahydrate, water adsorbed on inorganic or organic substances, and the like, which cause the above-mentioned organic aluminum to undergo a condensation reaction, can be used. No.

A typical example of the aluminum condensed compound is a compound represented by the following general formula:

Embedded image (Wherein R ²⁰ is an alkyl group having 1 to 8 carbon atoms, and q is 0 to 0)
Aluminoxane represented by the formula:
General formula

Embedded image (Wherein R ²⁰ has the same meaning as described above, and r is 2 to 50)
And a cyclic aluminoxane represented by

In general, the contact product of an organoaluminum compound such as a trialkylaluminum and water is mixed with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, as well as a mixture of unreacted trialkylaluminum and various condensation products, Are molecules in which these are intricately associated, and these are various products depending on the contact conditions between the trialkylaluminum and water as a condensing agent.

The method of contacting the alkylaluminum compound with water at this time is not particularly limited, and the reaction may be performed according to a known method. For example, (1) a method of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water, (2) a method of adding an organoaluminum compound initially during polymerization and then adding water, and (3) There is a method of reacting water of crystallization contained in a metal salt or the like and water adsorbed on an inorganic or organic substance with an organoaluminum compound. The water may contain up to about 20% of ammonia, amines such as ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphite. In addition, this reaction proceeds even without solvent,
It is preferably carried out in a solvent, and suitable solvents include aliphatic hydrocarbons such as hexane, heptane and decane, and aromatic hydrocarbons such as benzene, toluene and xylene.

When an aluminoxane (eg, an alkylaluminoxane) is used, if a hydrated compound or the like is used after the above-mentioned contact reaction, the solid residue is filtered off, and the filtrate is subjected to a temperature of 30 to 200 ° C. under normal pressure or reduced pressure. , Preferably 40
At a temperature of で 150 ° C. for 20 minutes to 8 hours, preferably 30 minutes
Those heat-treated while distilling off the solvent in the range of minutes to 5 hours are preferred.

In this heat treatment, the temperature may be appropriately determined according to various conditions, but is usually in the above range. Generally, at a temperature lower than 30 ° C., no effect is exhibited,
On the other hand, when the temperature exceeds 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and neither is preferable.

The reaction product is obtained as a colorless solid or solution depending on the conditions of the heat treatment. The product thus obtained can be dissolved or diluted with a hydrocarbon solvent, if necessary, and used as a catalyst solution.

A preferred example of the aluminoxane, particularly an alkylaluminoxane, which is a contact product of an organoaluminum compound used as a catalyst component and a condensing agent is an aluminum-methyl group (Al- High magnetic field components in the methyl proton signal region based on CH ₃ ) bonds are 50% or less. In other words, at room temperature of the above contact product, when observing the proton nuclear magnetic resonance ^{(1 H-NMR)} spectra in toluene solvent, methyl proton signal based on the "Al-CH _3" is tetramethylsilane (TMS) standard In the range of 1.0 to -0.5 ppm. T
The MS proton signal (0 ppm) is “Al-C
Since it is in the methyl proton observation region based on “H ₃ ”, the methyl proton signal based on “Al—CH ₃ ” is measured based on 2.35 ppm of the methyl proton signal of toluene based on TMS, and the high magnetic field component (ie,
−0.1 to −0.5 ppm) and other magnetic field components (ie,
(1.0 to -0.1 ppm), those having the high magnetic field component of 50% or less, preferably 45 to 5% of the whole can be suitably used as the catalyst component.

In the present invention, the catalyst (a)
If desired, another catalyst component can be added as a component (d) to the combination of the component and the component (b) to improve the catalytic activity.

[0052] The (D) As the catalyst component, for example, the general formula ^{_{R 21 k AlY 3-k (}} XIII) (R 21 in the formula 1 to 18 carbon atoms, preferably 1 to 12
A hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkoxy group, Y is a hydrogen atom or a halogen atom, and k is a number of 1 to 3). Specific examples of such a substance include one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, diethylaluminum ethoxide and the like. Can be. Moreover, in which Konawa range not stereoregularity, the general formula ^{W-R 22 - (P)} s-R 23 -W '(XI
V) (In the formula, R ²² and R ^{23 each} have a hydrocarbon group having 1 to 20 carbon atoms, a substituted aromatic hydrocarbon group having 7 to 30 carbon atoms, or a substituent containing a hetero atom such as oxygen, nitrogen, or sulfur. Represents a substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, P is a hydrocarbon group having 1 to 20 carbon atoms,

Embedded image R ²⁴ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, W and W ′ are a hydroxyl group, an aldehyde group or a carboxyl group, and s is an integer of 0 or 1 to 5). Organic compounds having two hydroxyl, aldehyde or carboxyl groups can be added.

Specific examples of the organic compound represented by the general formula (XIV) include 2,2'-dihydroxy-3
3'-di-t-butyl-5,5'-dimethyldiphenyl sulfide, 2,2'-dihydroxy-3,3'-di-
t-butyl-5,5'-dimethyldiphenyl ether and the like.

In the present invention, the component (a) and the component (b)
When a catalyst composed of a combination of components is used, the proportion of these components varies depending on the type of each component, the type of the styrene-based monomer used as the raw material, and other conditions, and cannot be unambiguously determined. b) the molar ratio of aluminum in component (b) to the transition metal in component 10 ^6, preferably chosen to be 10 to 10 ^4.

The ratio of the raw material styrene monomer to the catalyst may be determined as appropriate, but usually the molar ratio of the styrene monomer to aluminum in the component (ii) is from 1 to 10 ⁶ , preferably 10 to 10 ⁶ . It is chosen to be ² to 10 ^4.

In the present invention, a combination of (a) a transition metal compound and (c) a compound capable of reacting with the transition metal compound to form an ionic complex is used as the catalyst in addition to the above combination. Can be. If desired, a combination obtained by further adding the component (d) to this combination can be used.

In this catalyst, the transition metal compound used as the component (A) may be appropriately selected from those described above, but is preferably selected from the compounds represented by the general formulas (VI) and (VI).
The transition metal compounds represented by I), (VIII) and (IX) are desirable, and particularly those having 6 to 20 carbon atoms.
Compounds having at least one aryl group are preferred. The component (d) optionally used includes those described above, and among them, the general formula (XI)
Organoaluminum compounds represented by II) are preferred.

Further, the component (c) is a compound in which a cation and a plurality of groups are composed of groups VB, VIB, VIIB and VII of the periodic table.
Groups I, IB, IIB, IIIA, IVA and V
It is a coordination complex compound comprising an anion bonded to an element selected from Group A. The type of the coordination complex compound is not particularly limited, and may be, for example, a general formula ([L ¹ -H] ^{u +} ) v ([M ⁵ X ^{1 X 2 ... X i] (} it) -) w (XV) or ^{([L 2] u +)} v ([M 6 X 1 X 2 ... X i] (it) -) w (XVI) ( where, L ^{2 M 7, R 25} R a 26 ^{M 8} or ^{R 27} ₃ C) [VB group wherein ^{L 1} is a Lewis base, ^{M 5} and ^{M 6,} respectively periodic table, VIB group, VIIB group, VIII group , I
An element selected from Group B, Group IIB, Group IIIA, Group IVA or Group VA, M ⁷ is Group IB, Group IIB, V
Metal selected from Group III, ^{M 8} is of the Periodic Table VIII
X ^{1 to} X ⁱ each represent a hydrogen atom,
A dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group,
It represents a substituted alkyl group, an organic metalloid group or a halogen atom, R ²⁵ and R ²⁶ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ²⁷ represents a hydrocarbon group. t is an integer of 1 to 7 in valences of M ⁵ and M ⁶ , i is an integer of 2 to 8, u is an integer of 1 to 7 in ionic valence of L ¹ -H and L ² ,
v is an integer of 1 or more, w = u × v / (it)].

[0059] Specific examples of the Lewis base represented by the above L ^1, dimethyl ether, diethyl ether, ethers such as tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, acetonitrile, nitriles such as benzonitrile Amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, 2,2'-bipyridine, and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; ethylene and butadiene as chain unsaturated hydrocarbons; 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof, benzene, toluene, xylene, cycloheptatriene, cyclooctadiene as cyclic unsaturated hydrocarbons , Cyclooctatriene, cyclooctatetraene and derivatives thereof.

Specific examples of M ⁵ and M ⁶ include B, Al,
Si, P, As, Sb, etc. Specific examples of ^{M 7} L
i, Na, Ag, Cu, etc. Specific examples of ^{M 8} F
e, Co, Ni and the like. Specific examples of X ^{1 to} X ⁱ include, for example, a dimethylamino group, a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group, a phenoxy group, 2,6-dimethyl as an aryloxy group Phenoxy group, naphthyloxy group, alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, carbon number 6 A phenyl group, a p-tolyl group, a benzyl group, a pentafluorophenyl group, a 3,5-di (trifluoromethyl) phenyl group as an aryl group, an alkylaryl group or an arylalkyl group of
4-tert-butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 1,2-dimethylphenyl group, F, Cl, Br, l as halogen, Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. R
Specific examples of the substituted cyclopentadienyl group ²⁵ and R ^26, methylcyclopentadienyl group, butylcyclopentadienyl group, and pentamethylcyclopentadienyl group.

Among the compounds of the above formulas [14] and [15], the following compounds can be particularly preferably used.
For example, as the compound of the formula [14], triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (n-butyl) ammonium tetrakis (o, p-dimethylphenyl) borate , Trimethylammonium tetraphenylborate, tetrakis (p-
Tri (n-butyl) ammonium trifluoromethyl) borate, triphenylphosphonium tetraphenylborate,
Tri (methylphenyl) phosphonium tetraphenylborate, tri (dimethylphenyl) phosphonium tetraphenylborate, isopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Tri (n-butyl) ammonium phenyl) borate, triethylammonium hexafluoroarsenate, dimethylanilinium tetrakis (pentafluorophenyl) borate, diethylanilinium tetrakis (pentafluorophenyl) borate, di-n-tetrakis (pentafluorophenyl) borate Butylanilinium, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Rakisu (pentafluorophenyl) borate p- bromo -N, N-dimethyl anilinium and the like.

On the other hand, among the compounds represented by formula (XVI), preferred are, for example, ferrocenium tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, decamethylferrocenium tetrakis (pentafluorophenyl) borate , Cetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, cyanoferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate ,
Examples include trityl tetraphenylborate, trityl tetrakis (pentafluorophenyl) borate, silver hexafluoroarsenate, silver hexafluoroantimonate, and silver tetrafluoroborate.

The proportion of the component (a) to the component (c) is not particularly limited, but the molar ratio of the component (c) to the component (a) is usually 0.01 to 100, preferably 1 to 100.
Is chosen to be The component (a) and the component (c) may be brought into contact with each other in advance, and the contact product may be separated and washed before use, or may be brought into contact in a polymerization system. Further, the amount of the component (d) used as desired is usually selected in the range of 0 to 100 mol per 1 mol of the component (a). The use of the component (d) can improve the polymerization activity, but the effect corresponding to the added amount is not exhibited even if the amount is too large. The component (d) may be used in contact with the component (a), the component (c) or the contact product of the component (a) with the component (c). This contact may be carried out in advance, or may be added sequentially into the polymerization system and brought into contact.

[0064] The amount of the (C) component, the raw material monomer / component (iii) the molar ratio of generally 1 to 10 ^9, preferably chosen to be 100 to 10 ^7.

In the present invention, in the presence of such a catalyst, the styrene-based monomer represented by the above general formula (I) is first polymerized to form a styrene-based polymer having a high syndiotactic structure (including oligomers). ), A desired styrene block copolymer is obtained by a two-stage polymerization method in which the macromonomer is copolymerized. The polymerization temperature, polymerization time, polymerization method and the like in these steps may be appropriately selected, but generally, the polymerization temperature is 0 to 120 ° C, preferably 10 to 80 ° C, and the polymerization time is 1 second to 10 ° C. What is necessary is just to select within the time range. As the polymerization method, any of bulk, solution and suspension polymerization is possible. Further, in the solution polymerization, usable solvents include aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, benzene,
There are aromatic hydrocarbons such as toluene and xylene.
Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferred. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected.

[0066]

The styrenic block copolymer of the present invention retains the excellent heat resistance, chemical resistance and electrical properties inherent in syndiotactic polystyrene, as well as toughness, elongation, adhesion and olefin resin. It has improved compatibility with a diene-based resin and is useful as a material for a composite material or a heat-resistant elastomer.

According to the method of the present invention, the styrene-based block copolymer can be produced efficiently.

[0068]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The melting point, intrinsic viscosity and adhesive strength of the polymer were determined as follows. (1) Melting point device: DSC-200 differential scanning calorimeter manufactured by Seiko Electronics Measurement conditions: 300 ° C, 5 minutes hold, 7 ° C up to 30 ° C
/ Minute cooling (fast cooling), holding at 30 ° C. for 5 minutes, heating up to 300 ° C. at 20 ° C./minute (second heating). The melting point was determined during the second heating. (2) Intrinsic viscosity It was measured in 1,2,4-trichlorobenzene at 135 ° C. (3) Adhesive strength Two aluminum plates (thickness: 50 μm) having a width of 15 mm were prepared, and 40 mg of the copolymer was sandwiched therebetween. After melting at a temperature of 300 ° C., pressing was performed at a pressure of 10 kg / cm ² for 2 minutes. The adhesive strength of the test piece thus prepared was measured at a pulling speed of 2 cm / min.

Production Example 1 (1) Production of isoprene-type macromonomer After replacing a 0.5-liter internal volume reactor with a stirrer with nitrogen, 260 ml of sufficiently dried heptane and 50 ml of isoprene were added thereto, and the mixture was heated to 50 ° C. Heat, then se
38.4 mmol of c-butyllithium in 40 m of heptane
and diluted gradually into the reaction system. After the dropwise addition, the reaction was continued for 3 hours while stirring, and immediately after the reaction was completed, the reaction system was immediately cooled to −78 ° C. in a dry ice-methanol bath. Next, a heptane solution of 4-chloromethylstyrene (46 mmol / 40 ml heptane) was added dropwise through a dedicated inlet tube, and the mixture was further stirred for 1 hour while maintaining the liquid temperature at -78 ° C, and then alcohol was introduced. The reaction was stopped to obtain 40.7 g of an isoprene-type macromonomer. Gel permeation chromatography (solvent; chloroform, temperature 35 ° C)
As a result of the measurement, the product had a weight average molecular weight of 890 (Mn = 593) in terms of polyethylene and a molecular weight distribution of 1.5.
It was 0.

The infrared absorption spectrum (KBr method) of this macromonomer was measured.
Cis-1,4 of the isoprene chain near 377 cm ^-1
Absorption of methyl group by structure, peaks due to C = C of the same structure in 1660 cm ^-1, but also in the 1645 cm ^-1 was observed peak suggesting the presence of a terminal vinyl groups based on the styryl group.

Further, ¹³ C-NMR measurement [CDCl
₃ solution] As a result, the absorption derived from the terminal vinyl group at around 135 ppm and 112 ppm was 124 to 125 ppm,
The absorption of the methylene carbon of the double bond in the isoprene main chain structure at around 135 ppm,
The absorption of methylene carbon at around 2.3 ppm was 23.0 p.
The absorption of methyl carbon was confirmed near pm. Carbon on the benzene ring was sequentially observed between 120 and 148 ppm.

(2) In the above (1), a heptane solution of methacrylic acid chloride (48 mmol / 40 ml heptane) was used in place of 4-chloromethylstyrene, and 33.4 mmol / 4 sec-butyllithium was used.
The procedure was performed in the same manner as in (1) except that a 0 ml heptane solution was used.

The yield of the obtained macromonomer was 31.6.
g, the weight average molecular weight was 1020 in terms of polyethylene, and the molecular weight distribution was 1.60. Furthermore, was measured for IR, is observed a new absorption of carbonyl in the vicinity of 1725 cm ^-1, the 1640 cm ^-1 were observed peaks indicating the presence of unsaturated bonds due to a methacryloyl group.

(3) In the above (1), 60 ml of ethyl acrylate was used instead of isoprene, the solvent was changed to tetrahydrofuran (THF), and the initiator was t-butyllithium (34.6 mmol / 40 ml hexane). 4-chloromethylstyrene (40 mmol / 40m
lTHF), except that the polymerization was carried out at -78 ° C.
It carried out similarly to (1). The yield of the obtained macromonomer was 44.8 g, the weight average molecular weight was 1480 in terms of polystyrene, and the molecular weight distribution was 1.40.

(4) In the above (1), 50 ml of 1,3-butadiene was used instead of isoprene, and the solvent was T
HF and t-butyllithium (37.
(3 mmol / 40 ml heptane) at 0 ° C. After the polymerization, acrylic acid chloride (44.
(7 mmol / 40 ml THF) to produce an acryloyl-terminated butadiene macromonomer. The processing procedure is the same as in the above (1).

The yield of the macromonomer was 25.3 g,
The weight average molecular weight is 860, the molecular weight distribution is 1.36, and the IR c-butadiene is around 740 cm ^-1.
A peak due to the is-1,4 structure, a characteristic peak of carbonyl in an acryloyl group near 1725 cm ⁻¹ ,
Further, a peak due to unsaturated bonds was observed at around 1640 cm ^-1 .

(5) In the above (1), 30 g / 200 ml of methacrylic acid (2,4,6-tribromophenyl) was used instead of isoprene, and sec-butyllithium (7.5 mmol / 40 ml) was used as an initiator.
After polymerization at -78 ° C using heptane, 4-chloromethylstyrene (9 mmol / 40 ml) was added thereto.
THF) to give 27.8 g of the desired terminal styrene-type macromonomer. This had a weight average molecular weight of 3,850 and a molecular weight distribution of 1.41.

Preparation Example 2 Preparation of Aluminum Condensation Compound (Methylaluminoxane) In a 500-ml glass container purged with nitrogen, 200 ml of toluene and copper sulfate pentahydrate (CuSO ₄ .5H) were added.
₂ O) placed 17.7 g (71 mmol) and trimethyl aluminum 24 ml (250 mmol), and allowed to react for 8 hours at 40 ° C.. Thereafter, toluene is distilled off from the solution obtained by removing the solid component under reduced pressure, and the contact product is obtained.
7 g were obtained. Its molecular weight measured by freezing point depression method was 610. Also, Japanese Patent Application Laid-Open No. 62-32539
High magnetic field components by ¹ H-NMR measurement based on No. ¹
That is, observing the proton nuclear magnetic resonance spectrum at room temperature the toluene solution (Al-CH ₃₎ methyl proton signal based on the binding seen in the range of 1.0 to-0.5 ppm in tetramethylsilane standard. The proton signal of tetramethylsilane (0 ppm) is A
Since it is in the observation region based on the methyl proton based on the l-CH ₃ bond, the methyl proton signal based on this Al-CH ₃ bond was measured based on 2.35 ppm of the methyl proton signal of toluene based on tetramethylsilane. The magnetic field component (i.e., -0.0 to -0.
5 ppm) and other magnetic field components (i.e., 1.0--0.
1 ppm), the high magnetic field component is 4% of the total.
3%.

Example 1 100 ml of toluene and 4 mmol of the methylaluminoxane obtained in Production Example 2 as a catalyst component were added to a dried 500 ml reaction vessel under a nitrogen atmosphere at room temperature, and 100 ml of styrene was further added. Let stand for 30 minutes. Then, 10 μmol of 1,2,3,4,5-pentamethylcyclopentadienyltitanium trimethoxide was added thereto to initiate polymerization.

After reacting for 30 minutes, Production Example 1
A toluene solution (10 g / 50 ml toluene) of the isoprene-type macromonomer obtained in (1) was added, and polymerization was performed for 2 hours. Thereafter, the reaction product was added to a methanol-hydrochloric acid mixture, the reaction was stopped, and demineralized. Thereafter, the resultant was further washed with methanol and dried. Further, in order to remove the non-quality polymer, Soxhlet extraction was performed for 8 hours with methyl ethyl ketone, and the insoluble portion was dried to obtain 39.5 g of a polymer. The intrinsic viscosity [η] of this polymer is 0.90 dl /
g.

When ¹³ C-NMR was measured, 14
A sharp peak was observed at 5.2 ppm. This indicates that the styrene chain has a syndiotactic structure. The infrared absorption spectrum (IR) shows 13
Absorption of cis-1,4 isoprene unit was observed around 80 cm ⁻¹ , and it was determined by ¹ H-NMR. The isoprene unit content was found to be 9.7% by weight. The results are shown in Table 2.

The syndiotacticity of racemic pentad was 90% or more. The syndiotacticity was determined from ¹³ C-NMR.

Example 2 A copolymer was produced in the same manner as in Example 1 except that the conditions shown in Table 1 were changed. Table 2 shows the results.

The syndiotacticity determined by ¹³ C-NMR was 92% or more for racemic pentad.

Examples 3 to 6 Block copolymers were produced in the same manner as in Example 1 except that the conditions shown in Table 1 were changed. Table 2 shows the results. The syndiotacticity calculated from ¹³ C-NMR was 87% or more for racemic pentad.

Example 7 In Example 1, the polymerization catalyst was 30 micromoles of triisobutylaluminum, 5 micromoles of triethylammonium tetrakis (pentafluorophenyl) borate and 1,2,3,4,5-pentamethylcyclopentadienyl. A block copolymer was produced in the same manner as in Example 1 except that the system was changed to a system comprising 5 micromoles of titanium trimethotyl. Table 2 shows the results.

Examples 8 to 10 Block copolymers were produced in the same manner as in Example 7 except that the conditions shown in Table 1 were changed. Table 2 shows the results.

Comparative Example 1 In a nitrogen atmosphere, 100 ml of toluene, 4 mmol of the methylaluminoxane obtained in Production Example 2 as a catalyst component were added to a 500-ml dry reaction vessel at room temperature, and 100 ml of styrene was further added. For 30 minutes.

In this container, 1,2,3,4,5-pentamethylcyclopentadienyltitanium trimethoxide 1
0 μmol was added, and a toluene solution (10 g / 50 ml toluene) of the ethyl acrylate type macromonomer obtained in Production Example 1 (3) was further added, and polymerization was performed for 3 hours. Thereafter, the reaction product was added to a methanol-hydrochloric acid mixture, the reaction was stopped, and decalcification was performed. Thereafter, the resultant was further washed with methanol and dried to obtain 28.5 g of a polymer.
The intrinsic viscosity [η] of this polymer was 0.48 dl / g.

When ¹³ C-NMR was measured, it was found that 14
A sharp peak was observed at 5.1 ppm. This indicates that the styrene chain has a syndiotactic structure. In addition, absorption of carbonyl was observed at around 1730 cm ^-1 in IR, and it was found that the content of ethyl acrylate unit determined by ¹ H-NMR was 4.6% by weight. Table 2 shows the results.

The syndiotacticity of the product was determined by ¹³ C-NMR to be 72% for racemic pentad.

Comparative Example 2 Comparative Example 1 was carried out in the same manner as in Comparative Example 1 except that the macromonomer obtained in Production Example 1 (5) was used instead of the macromonomer obtained in Production Example (3). did. Table 2 shows the results.

[0094]

[Table 1]

Note 1) Polymerization catalyst (I) 1,2,3,4,5-pentamethylcyclopentadienyltitanium trimethoxide-methylaluminoxane (II) 1,2,3,4,5-pentamethylcyclo Pentadienyltitanium trimethyl-tri (pentafluorophenyl) triethylammonium borate-triisobutylaluminum 2) IP-CMS: isoprene chain terminal styryl group IP-AC: isoprene chain terminal acryloyl group EA-CMS: acrylic ester chain terminal styryl group BD-MC: 1,3-butadiene chain terminal methacryloyl group BPMA-CMS: 2,4,6-tribromophenyl methacrylic acid chain terminal styryl group 3) Polymerization time before addition of macromonomer (however, 120 minutes after addition) 4) Total polymerization time

[0096]

[Table 2]

Claims (3)

(57) [Claims] (A) The general formula CH ₂ CH—Ar— (R ¹ ) p (wherein Ar is a divalent aromatic group, R ¹ is a hydrogen atom, a halogen atom or a carbon atom and a silicon atom) A substituent containing at least one member selected from the group consisting of p and an integer of 1 to 5; when p is 2 or more, R ¹ may be the same or different; 80 to 99.9% by weight of a polymer segment having a high syndiotactic structure having a monomer as a repeating unit, and (B)
After polymerizing an anionic polymerizable monomer using an anionic polymerization initiator, a macromonomer having a number average molecular weight of 300 to 10,000 having a polymerization active vinyl group at a terminal obtained by reacting this with a halogen-containing unsaturated compound. Polymer segment derived from 20-0.1% by weight and in a 1,2,4-trichlorobenzene solution at a temperature of 135 ° C.
A styrene-based block copolymer characterized by having an intrinsic viscosity [η] of 0.07 to 20 dl / g measured in (1). 2. (a) General formula CH ₂ ＣＨCH—Ar— (R ¹ ) p (wherein Ar is a divalent aromatic group, R ¹ is a hydrogen atom, a halogen atom or a carbon atom and a silicon atom) A styrene monomer represented by the following formula: wherein p is an integer of 1 to 5, and when p is 2 or more, R ¹ may be the same or different. Is polymerized in the presence of a catalyst consisting of (a) a transition metal compound and (b) an aluminum condensate compound, and then
(B) After polymerizing an anionic polymerizable monomer using an anionic polymerization initiator, this is reacted with a halogen-containing unsaturated compound, and has a number-average molecular weight of 300 to 10,000 having a polymerization active vinyl group at a terminal obtained. The method for producing a styrenic block copolymer according to claim 1, wherein the polymerization is carried out by adding a macromonomer. (A) a compound represented by the general formula CH ₂ ＣＨCH—Ar— (R ¹ ) p (wherein Ar is a divalent aromatic group, R ¹ is a hydrogen atom, a halogen atom or a carbon atom and a silicon atom) A styrene monomer represented by the following formula: wherein p is an integer of 1 to 5, and when p is 2 or more, R ¹ may be the same or different. Is polymerized in the presence of a catalyst consisting of (a) a transition metal compound and (c) a compound capable of forming an ionic complex by reacting with the transition metal compound. After polymerization using an agent,
This is reacted with a halogen-containing unsaturated compound, and has a number-average molecular weight of 300-
The method for producing a styrenic block copolymer according to claim 1, wherein the polymerization is carried out by adding 10,000 macromonomers.