JP2001342223A - Method for producing indene-styrene-based graft polymer, molding material, film or additive using polymer obtained by the same production method and optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a graft polymer excellent in low hygroscopicity, heat resistance, mechanical strength and photocharacterization and a molding material, a film or additive obtained by above production method and optical components using the above materials. SOLUTION: This method for producing a graft polymer is characterized by starting a cation polymerization of (a) a monomer component which is an indene or indene-based monomer represented by a formula I, wherein R1 to R5 are each H, a halogen, C, O, N, P or Si; (n) is an integer of 1-5 by using an activating agent containing aluminium in the presence of a reaction initiator and a base and then adding (b) a copolymer represented by a formula II wherein R6 and R7 are each H, a halogen, C, O, N, P or Si; (n) is an integer of 1-5 thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a graft polymer having novel properties and, in particular, excellent compatibility.
The present invention relates to a molding material, a film or an additive obtained by this manufacturing method and an optical component using the same.

[0002]

2. Description of the Related Art Indene and its derivatives (indene-based monomers) are contained in large quantities in the C9 fraction and are mainly available as inexpensive compounds, mainly as raw materials for chemicals (Japanese Patent Application Laid-Open No. 7-2582).
No. 39). Polymers incorporating these monomers are expected to have properties such as improved heat resistance and low hygroscopicity. However, because of their low radical polymerization reactivity, the N-substituted maleimide is at least equimolar to the indene derivative. And maleic anhydride are essential components (Japanese Unexamined Patent Publication No.
-301930 gazette). However, the resin obtained by this method has a high water absorption due to the hydrophilic substituent contained in the N-substituted maleimide or maleic anhydride.
On the other hand, even in cationic polymerization, a high molecular weight product can be obtained only at a polymerization temperature of −40 ° C. or lower, which makes industrialization difficult.

[0003] As with the indene derivative, a cycloolefin is a raw material for a polymer having a cyclic structure double bond. From this cycloolefin, an alicyclic polyolefin resin obtained by ring-opening polymerization has excellent properties such as high heat resistance, transparency, and low moisture absorption, and is used for optical parts, electronic materials, medical equipment, and the like. Used as a material. However, when producing this alicyclic polyolefin, it is necessary to use a rare metal such as molybdenum or tungsten chloride as a polymerization catalyst, and in most cases, an organic metal cocatalyst such as triethylaluminum is used. Due to restrictions such as the use of an aqueous compound, it cannot be easily produced. Optical parts such as lenses, which are the main applications of alicyclic polyolefins, are manufactured by an injection molding method. At this time, there is a problem that large birefringence occurs in the molded article.

With respect to the birefringence, by randomly copolymerizing monomers having positive and negative birefringence in a specific acrylic resin, birefringence hardly occurs even when injection molding is performed or the entire molded article is produced. (Optics, Vol. 20, No. 2, p. 80)
(30), 1991). Such acrylic resin,
It can be easily produced by a suspension polymerization method or the like. However, the acrylic resin has high water absorption and low heat resistance, and therefore has a limited range of application to optical parts and the like, despite having excellent optical characteristics. The heat resistance of an acrylic resin can be obtained by introducing a cyclic structure into the main chain by using an N-substituted maleimide as a monomer (Japanese Patent Application Laid-Open No. SHO 61-61).
-95011) has a problem in terms of water absorption.

[0005] Therefore, it is possible to industrially obtain inexpensively, and as a result of diligent search for monomers having heat resistance and low hygroscopicity, indene and its derivatives can introduce a cyclic structure into the polymer structure. Further, it has been found that since the polymer is composed only of carbon and hydrogen atoms, the polymer has a characteristic of extremely low water absorption.
Indene can obtain a (co) polymer by cationic polymerization. However, in the generally known cationic polymerization, a catalyst having a strong activity (that is, generates heat or ignites strongly with moisture in the air) such as tin tetrachloride, titanium tetrachloride, boron trifluoride, concentrated sulfuric acid and alkylaluminum is used. Done.

In the cationic polymerization, the activation energy of the chain transfer reaction and the termination reaction is larger than that of the growth reaction. Therefore, the polymerization is carried out at a low temperature. For example, the cationic polymerization of isobutene requires The reaction is carried out at a temperature around 100 ° C. (Introduction to Polymer Chemistry, Chemical Doujin, p.
249, 1984). However, it is difficult to easily synthesize a high molecular weight polymer by ordinary cationic polymerization, and it is necessary to find a production method for obtaining an indene polymer with an industrially simple system.

For the purpose of increasing the molecular weight of the indene-containing polymer, the following method has been carried out. (1) A method utilizing indene and an N-substituted maleimide and / or maleic anhydride to give an alternating copolymer by radical polymerization (JP-A-5-301930). (2) Method by living cationic polymerization (JMS-PURE A
PPL. CHEM., A30 (4), PP.253-267 (1993)).

However, in the method (1), the N-substituted maleimide and / or maleic anhydride having an equivalent amount of indene or more must be used as a monomer component. There is. In the method (2), an extremely pure compound must be used in order to suppress the chain transfer reaction and the termination reaction. Therefore, the C9 fraction cannot be used as it is as a raw material for producing a polymer. Very low temperature (about -80 ° C)
Therefore, an industrially inexpensive polymer cannot be supplied.

As a method for producing a bifunctional polymer, a method is known in which a metal halide and a dihalogen-containing compound are used as a cationic polymerization initiator, and polymer chains are grown at both ends of the dihalogen-containing compound. Also in this method, the molecular weight of the obtained polymer is not as large as about 8,000 (JP-A-62-79203).
Therefore, it is necessary to find a method for obtaining a high molecular weight indene-based polymer.

[0010]

DISCLOSURE OF THE INVENTION The present invention relates to a method of preparing a specific monomer mixture containing indene or an indene-based monomer as an essential component by using an activator containing aluminum in the presence of a specific reaction initiator and a base. The present invention provides a method for producing a graft polymer in which a styrene-based polymer having a phenolic hydroxyl group is added after initiating cationic polymerization using the same. Also,
An object of the present invention is to provide a molded material, a film or an additive and an optical component using the graft polymer obtained by this production method.

[0011]

According to the present invention, the following monomer component (a) is cationically polymerized by using an activator containing aluminum in the presence of a reaction initiator and a base. The present invention relates to a method for producing a graft polymer characterized by adding a polymer (b), and a molding material, a film or an additive, and an optical component using a polymer obtained by this method. (A) Indene or an indene-based monomer represented by the general formula (I).

Embedded image However, R _{1 to} R ₅ are a hydrogen atom, a halogen atom, a carbon atom,
It represents a substituent containing any of an oxygen atom, a nitrogen atom, a phosphorus atom and a silicon atom, and n represents an integer of 1 to 5. However, when n is plural, R ₅ may be the same or different. (b) A copolymer represented by the general formula (II).

Embedded image Here, R ₆ and R ₇ represent a substituent containing any of a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom and a silicon atom, m is a weight fraction, and n is 1 to 5 Indicates an integer. However, when n is plural, R ₆ and R ₇ may be the same or different.

In the present invention, the monomer component (a) 10
The amount of the copolymer (b) added was 0.1% to 0 parts by weight.
It is preferably about 500% by weight.

In the present invention, the reaction initiator is preferably a compound selected from water, acetic acid and an adduct of isobutyl vinyl ether acetic acid.

In the present invention, the base is preferably a compound selected from methyl dichloroacetate, methyl chloroacetate, 1,4-dioxane, diethyl ether, tetrahydrofuran and N, N-dimethylsulfoxide (DMSO).

In the present invention, the activator is preferably a compound selected from ethylaluminum dichloride, diethylaluminum chloride and aluminum chloride.

In the present invention, the monomer component (a) is
It is preferably a compound selected from the group consisting of indene, alkylindenes, halogenated indenes, arylindenes, alkoxyindenes, alkoxycarbonylindenes, acyloxyindenes, alkylsilylindenes and alkylstannylindenes. .

In the present invention, the polymerization temperature is -100
It is preferably in the range of ５０50 ° C.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of a method for producing a graft polymer according to the present invention, and a molding material, a film or an additive and an optical component using the graft polymer obtained by the production method will be specifically described. explain.

The indene represented by the general formula (I) or the indene monomer (a) used in the present invention includes indene, 1-methylindene, 2-methylindene,
-Methylindene, 4-methylindene, 5-methylindene, 6-methylindene, 7-methylindene,
1,4-dimethylindene, 1,5-dimethylindene, 1,6-dimethylindene, 1,7-dimethylindene, 4-ethylindene, 5-ethylindene, 6-
Alkylindenes such as ethylindene and 7-ethylindene, 4-chloroindene, 5-chloroindene, 6
-Chloroindene, 7-chloroindene, 4-bromoindene, 5-bromoindene, 6-bromoindene, 7
-Bromoindene, 4-iodoindene, 5-iodoindene, 6-iodoindene, 7-iodoindene, 4
Halogenated indenes such as -fluoroindene, 5-fluoroindene, 6-fluoroindene and 7-fluoroindene, arylindenes such as 4-phenylindene, 5-phenylindene, 6-phenylindene and 7-phenylindene, Alkoxyindenes such as 4-methoxyindene, 5-methoxyindene, 6-methoxyindene, and 7-methoxyindene; 4-methoxycarbonylindene; 5-methoxycarbonylindene;
Alkoxycarbonylindenes such as methoxycarbonylindene and 7-methoxycarbonylindene; acyloxyindenes such as 4-methylcarbonyloxyindene, 5-methylcarbonyloxyindene, 6-methylcarbonyloxyindene and 7-methylcarbonyloxyindene; -Trimethylsilylindene, 5-
Alkylsilylindenes such as trimethylsilylindene, 6-trimethylsilylindene, 7-trimethylsilylindene, 4-tree n-butylstannylindene, 5-tree n-butylstannylindene, 6-tree n-butylstannylindene, 7 And alkylstannylindenes such as -tree n-butylstannylindene. These can be used alone or in combination of two or more.

In the present invention, indene, alkylindenes, halogenated indenes, arylindenes, alkoxyindenes, alkoxycarbonylindenes, acyloxyindenes in the above-mentioned indene or indene-based monomer (a). And a compound selected from the group consisting of alkylsilylindenes and alkylstannylindenes. Among these,
In terms of heat resistance and low hygroscopicity, indene and alkyl-substituted indene are more preferred, and indene, methylindene,
Ethylindene is more preferred.

In the present invention, the monomer having a phenolic hydroxyl group contained in the copolymer (b) represented by the general formula (II) includes 4-hydroxystyrene, 4-hydroxy-3-methylstyrene, 4-hydroxy-3,
5-dimethylstyrene, 4-hydroxy-3-ethylstyrene, 4-hydroxy-3,5-diethylstyrene,
4-hydroxy-3-chlorostyrene, 4-hydroxy-3,5-dichlorostyrene, 4-hydroxy-3-methoxystyrene, 4-hydroxy-3,5-dimethoxystyrene, 4-hydroxy-3-N, N-dimethylaminostyrene and the like No. These can be used alone or
More than one species can be used in combination.

Among these, 4-hydroxystyrene is more preferred from the viewpoint of heat resistance and reactivity.

In the present invention, the monomer having no phenolic hydroxyl group contained in the copolymer (b) represented by the general formula (II) includes styrene, m-methylstyrene, p-methylstyrene, o-methylstyrene, 2,4
-Dimethylstyrene, 2,5-dimethylstyrene, 3,
4-dimethylstyrene, 3,5-dimethylstyrene, p
Alkylstyrenes such as -tert-butylstyrene, p-tert-butoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p- Fluorostyrene, m-fluorostyrene, o
-Fluorostyrene, halogenated styrenes such as o-methyl-p-fluorostyrene, 4-vinylbiphenyl,
Vinyl biphenyls such as 3-vinyl biphenyl and 2-vinyl biphenyl, 1- (4-vinylphenyl) naphthalene, 2- (4-vinylphenyl) naphthalene, 1- (3
-Vinylphenyl) naphthalene, 2- (3-vinylphenyl) naphthalene, 2- (3-vinylphenyl) naphthalene, 1- (2-vinylphenyl) naphthalene, 2-
Vinylphenylnaphthalenes such as (2-vinylphenyl) naphthalene, 1- (4-vinylphenyl) anthracene, 2- (4-vinylphenyl) anthracene, 9-
(4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 2- (3-vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene,
Vinylphenylanthracenes such as-(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, 9- (2-
Vinylphenylphenanthrenes such as 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) pyrene and the like Vinylphenylpyrenes, 4
-Vinyl-p-terphenyl, 4-vinyl-m-terphenyl, 4-vinyl-o-terphenyl, 3-vinyl-p-terphenyl, 3-vinyl-m-terphenyl, 3
Vinyl terphenyls such as -vinyl-o-terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl and 2-vinyl-o-terphenyl;
Vinylphenyl terphenyls such as -vinylphenyl) -p-terphenyl, 4-vinyl-4'-methylbiphenyl, 4-vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4-vinyl Vinylalkylbiphenyls such as biphenyl and 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'-bromobiphenyl, 4-vinyl-3'-bromobiphenyl, 4-vinyl-2'-bromobiphenyl, 4-
Halogenated vinyl biphenyls such as vinyl-2-bromobiphenyl and 4-vinyl-3-bromobiphenyl;
Vinyl-4'-methoxybiphenyl, 4-vinyl-3'-
Methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4-vinyl-2-methoxybiphenyl, 4-vinyl-3-methoxybiphenyl, 4-vinyl-4'-ethoxybiphenyl, 4-vinyl-3'-ethoxybiphenyl, 4-vinyl-2 Alkoxybiphenyls such as' -ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl, 4-vinyl-3-ethoxybiphenyl, and alkoxycarbonylbiphenyls such as 4-vinyl-4'-methoxycarbonylbiphenyl and 4-vinyl-4'-ethoxycarbonylbiphenyl , Alkoxyalkylbiphenyls such as 4-vinyl-4'-methoxymethylbiphenyl, and trialkylstannylbi such as 4-vinyl-4'-trimethylstannylbiphenyl and 4-vinyl-4'-tributylstannylbiphenyl Eniru acids, trialkylsilyl methyl vinyl biphenyl and 4-vinyl-4'-trimethylsilylmethyl-biphenyl, 4-vinyl-4'-trimethylstannyl-methylbiphenyl, 4
Trialkylstannylmethylbiphenyls such as vinyl-4'-tributylstannylmethylbiphenyl, p-
Chloroethylstyrene, m-chloroethylstyrene, o
-Halogen-substituted alkylstyrenes such as chloroethylstyrene, p-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, m
-Alkoxystyrenes such as -ethoxystyrene, o-ethoxystyrene, p-methoxycarbonylstyrene, m
Alkoxycarbonylstyrenes such as -methoxycarbonylstyrene, acetyloxystyrene, ethanoyloxystyrene, acyloxystyrenes such as benzoyloxystyrene, alkyl ether styrenes such as p-vinylbenzylpropyl ether, and alkylsilyls such as p-trimethylsilylstyrene. Styrenes, p-trimethylstannylstyrene, p-tributylstannylstyrene, alkylstannylstyrenes such as p-triphenylstannylstyrene, ethyl vinylbenzenesulfonate, vinylbenzyldimethoxyphosphide,
vinyl styrenes such as p-vinyl, α-methyl styrene, α-alkyl styrenes such as α-ethyl styrene,
and β-alkylstyrenes such as β-methylstyrene and β-ethylstyrene. These can be used alone or in combination of two or more.

Among these, styrene, alkyl styrenes, halogenated styrenes, vinyl biphenyls, vinyl phenyl naphthalenes, vinyl phenyl anthracenes, vinyl phenyl phenanthrenes, vinyl phenyl pyrenes, vinyl terphenyls, vinyl phenyl Terphenyls, vinylalkylbiphenyls, halogenated vinylbiphenyls, alkoxybiphenyls, alkoxycarbonylbiphenyls, alkoxyalkylbiphenyls, trialkylstannylbiphenyls, alkylsilylmethylvinylbiphenyls, trialkylstannylmethylbiphenyls , Halogen-substituted alkylstyrenes, alkoxystyrenes, acyloxystyrenes, alkoxycarbonylstyrenes, alkylether styrenes Alkylsilyl styrenes, alkyl stannyl styrenes, vinyl styrenes, is preferably at least one compound selected from the group consisting of α- alkyl styrenes and β- alkyl styrenes.

Of these, styrene, alkyl styrene, para-substituted alkoxy styrene, para-substituted alkyl styrene, and α-methyl styrene are more preferable in terms of heat resistance and low hygroscopicity, and styrene, 4-methyl styrene, and 2-methyl styrene are more preferable. Styrene, 4-t-butylstyrene, 4
-Methoxystyrene and α-methylstyrene are more preferred.

In the present invention, the amount of the copolymer (b) to be added is 0.1 to 50 relative to the total amount of the monomer component (a).
It is preferably 0% by weight, more preferably 10 to 100% by weight. When the amount of the copolymer (b) added is
If the amount is less than 0.1% by weight, the termination reaction tends not to proceed sufficiently. If the amount exceeds 500% by weight, the obtained graft polymer tends to have high hygroscopicity.

The reaction initiator in the present invention includes water,
Compounds such as acetic acid, chloroacetic acid, trichloroacetic acid, trifluoroacetic acid and adducts of isobutyl vinyl ether acetic acid are used alone or in combination of two or more. However, the compounds shown here are examples, and the present invention is not limited to these compounds.

Among these, water, acetic acid and adducts of isobutyl vinyl ether acetic acid are more preferable in view of the reactivity of living polymerization.

The addition amount of the reaction initiator in the present invention is preferably 0.01 to 10% by weight based on the total amount of the monomer component (a). If the amount of the initiator is less than 0.01% by weight, living polymerization of the polymerization reaction tends to be lost, and if it exceeds 10% by weight, the molecular weight tends to be small.

As the base in the present invention, methyl dichloroacetate, methyl chloroacetate, methyl acetate, ethyl acetate, 1,4-dioxane, diethyl ether, tetrahydrofuran, DMSO, DMF, DMAc, NMP, diethyl carbonate, dimethylthioether, diethyl Compounds such as thioether, triallylphosphine, triethylamine, 1-methylpyrrolidine and tetrahydrothiophene are used alone or in combination of two or more. However, the compounds shown here are examples, and the present invention is not limited to these compounds.

Of these, methyl dichloroacetate, methyl chloroacetate,
4-Dioxane, diethyl ether, tetrahydrofuran and DMSO are more preferred.

In the present invention, the amount of the base added is preferably 0.001 to 1000% by weight based on the total amount of the monomer component (a). If the amount of the base is less than 0.001% by weight, the reactivity of living polymerization in the polymerization reaction tends to be lost, and if it exceeds 1000% by weight, the progress of the polymerization reaction tends to be delayed.

As the activating agent in the present invention, compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, ethylaluminum dichloride, diethylaluminum chloride and aluminum chloride are used alone or in combination of two or more. Used. However, the compounds shown here are examples, and the present invention is not limited to these compounds.

Among these, ethyl aluminum dichloride, diethyl aluminum chloride and aluminum chloride are more preferable from the viewpoint of reactivity.

The polymerization temperature in the present invention is from -100 to
It is preferably in the range of 50 ° C, more preferably in the range of -78 to 30 ° C. When the polymerization temperature is -10
Below 0 ° C., the activator tends to precipitate,
When the temperature exceeds 0 ° C., living polymerizability tends to be lost.

In the cationic polymerization reaction of the present invention, an inhibitor for suppressing the initiation reaction by a trace amount of water present in the reaction system may be added. Examples of the inhibitor include pyridine, 2,6-dimethylpyridine, 2,6-diethylpyridine, 2,6-di-t-butylpyridine and the like. However, the compounds shown here are examples, and the present invention is not limited to these compounds.

The amount of these inhibitors to be added is preferably 0.001 to 1000% by weight based on the amount of the activator. If the amount of the inhibitor is less than 0.001% by weight, the effect tends not to be exhibited. If the amount exceeds 1000% by weight, the cationic polymerization reaction does not proceed, and (graft)
There is a tendency that a polymer cannot be obtained.

In the present invention, when the copolymer (b) is polymerized, known methods such as radical polymerization, cationic polymerization and anionic polymerization can be used. Among them, the radical polymerization method is preferred from the viewpoint of reactivity. preferable.

In the present invention, when performing the radical polymerization of the copolymer (b), a known radical polymerization initiator can be used. Examples of the radical polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, and 1,1-t-butylperoxy-3. , 3,5-trimethylcyclohexane, t
Organic peroxides such as -butylperoxyisopropyl carbonate, azobisisobutyronitrile, azobis-4
Azo compounds such as -methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile and azodibenzoyl; water-soluble catalysts such as potassium persulfate and ammonium persulfate; and peroxides or persulfates and reducing agents Any of those that can be used for ordinary radical polymerization, such as a redox catalyst by a combination of the above, can be used. The polymerization initiator is 0.01% based on the total amount of the monomers.
It is preferably used in the range of 10 to 10% by weight.

In the present invention, a mercaptan compound, thioglycol, carbon tetrachloride, α-methylstyrene dimer, or the like can be added as necessary as a molecular weight regulator in the radical polymerization of the copolymer (b).

In the present invention, when the copolymer (b) is obtained by thermal polymerization, the polymerization temperature can be appropriately selected from 0 to 200 ° C., and particularly preferably from 40 to 120 ° C.

In the present invention, the molecular weight of the copolymer (b) is not particularly limited, but preferably has a number average molecular weight (in terms of polystyrene) of 1 × 10 ⁴ to 1 × 10 ⁶ , A range of × 10 ^{4 to} 7 × 10 ⁵ is particularly preferred. If the number average molecular weight is less than 1 × 10 ⁴ , it tends to be mechanically brittle, and if it exceeds 1 × 10 ⁶ , precision transferability tends to be lost.

In the present invention, the weight fraction m of the monomer having a phenolic hydroxyl group and the monomer having no phenolic hydroxyl group in the copolymer (b) is from 0.001 to 0.001.
It is preferably in the range of 0.7. The weight fraction m is 0.
When it is less than 001, the graft ratio tends to decrease, and when it exceeds 0.7, the hygroscopicity tends to increase.

The solvent in the cationic polymerization of the present invention includes:
Hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, chloromethane, dichloromethane,
Halogenated hydrocarbons such as chloroform, carbon tetrachloride, bromobenzene, chlorobenzene, and dichlorobenzene, nitromethane, nitroethane, nitrobenzene, and the like may be used alone or in combination of two or more. However, the compounds shown here are examples, and the present invention is not limited to these compounds.

In the graft polymer of the present invention, an appropriate additive can be used if necessary, and there is no particular limitation. For example, known antioxidants, ultraviolet absorbers, plasticizers and the like can be used. As a mixing method, for example, they can be uniformly mixed by melt-kneading them together with a resin under heating. Alternatively, a uniform mixture can also be obtained by dissolving each in a solvent, casting the solution on a substrate, and heating and drying the solvent.

The method for processing the graft polymer in the present invention is not particularly limited, and any known method can be used. For example, a melt molding method such as an injection molding method or a compression molding method, or a varnish dissolved in an organic solvent. It can also be processed into a film by a casting method or melt extrusion.

The graft polymer obtained according to the present invention can be used for, for example, A
Additives for increasing the strength of molded products made of resins such as BS and AAS resins, additives such as epoxy resin flexibility additives, and optical components such as projection lenses for liquid crystal projectors, laser pickup lenses for optical discs, and magneto-optics Laser pickup lens for disc, optical disc,
Injection molded products such as magneto-optical disks, DVD disks, liquid crystal cell substrates, light diffusion sheets, projector screens and prisms, semiconductor-related materials, paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal collectors, Ion exchange resins, antistatic agents, antioxidants, antifogging agents, rust inhibitors, antistaining agents, bactericides, insect repellents, medical materials, flocculants, surfactants,
It can also be applied to lubricants, binders for solid fuels, conductive treatment agents, and the like.

The lens or sheet using the graft polymer of the present invention is coated with an inorganic compound such as MgF ₂ or SiO ₂ by a vacuum deposition method, a sputtering method, an ion plating method, or the like, or is formed on the surface of a molded product. Organosilicon compounds such as silane coupling agents, vinyl monomers, melamine resins, epoxy resins, fluororesins,
By hard coating a silicone resin or the like, moisture resistance, optical properties, chemical resistance, abrasion resistance, anti-fog, and the like can be improved.

[0049]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 1) Synthesis of styrene-4-hydroxystyrene copolymer In a 200 mL round bottom flask, 90 g of styrene and 4-t
10 g of ert-butoxy styrene and 0.25 g of benzoyl peroxide were weighed and stirred for 60 minutes while performing nitrogen bubbling to obtain a uniform mixed solution. Thereafter, the mixed solution was poured into a test tube, and the mixture was heated at 90 ° C. for 7 hours and further at 120 ° C. for 2 hours.
The polymerization was carried out by heating for a period of time, and the resulting mass was treated with THF 100
Dissolved in ml. The solution was reprecipitated with 1 liter of methanol to obtain 9.5 g of a styrene-4-tert-butoxystyrene copolymer (Mw = 30 × 10 ⁴ ). Next, the styrene-4-tert-butoxystyrene copolymer 10 obtained above was placed in a 500 ml round bottom flask.
g and 333 ml of dioxane were weighed and stirred until a uniform solution was obtained. 8.6N oxalic acid 1.3 was added to this solution.
Then, the reaction was carried out at 60 ° C. for 3 hours. The solution obtained was concentrated to 100 ml on a rotary evaporator and the concentrate was poured into 1 l of water. The resulting precipitate was collected by filtration, washed sufficiently with water, and then washed with dioxane 6
Dissolved in 0 ml. This solution was poured into 1 liter of hexane, the resulting precipitate was collected by filtration, and the precipitate was dried under reduced pressure to obtain 9.0 g of a styrene-4-hydroxystyrene copolymer (Mw = 30 × 10 ⁴ ). Was.

2) Purification of Compound Used for Cationic Polymerization Indene: Calcium chloride was added to 25 ml of indene and allowed to stand overnight. Next, calcium chloride was added to remove calcium chloride, refluxed under dry nitrogen for 2 hours,
Distilled under reduced pressure. -Bromine benzene: Calcium hydride was added to bromobenzene and left overnight. Next, except for calcium hydride, calcium hydride was newly added, and the mixture was dried under dry nitrogen.
After refluxing for an hour, distillation was performed under reduced pressure. Benzene chloride: Diphosphorus pentoxide was added to benzene chloride and left overnight. Next, diphosphorus pentoxide was newly added except for diphosphorus pentoxide, and refluxed under dry nitrogen for 2 hours, followed by distillation under reduced pressure. -Methyl dichloroacetate: Calcium hydride was added to methyl dichloroacetate and left overnight. Next, except for calcium hydride, diphosphorus pentoxide was added and dried under dry nitrogen.
After refluxing for an hour, distillation was performed under reduced pressure. 1,4-dioxane: Calcium hydride was added to 1,4-dioxanemethyl and left overnight. Next, except for calcium hydride, calcium hydride was newly added, refluxed under dry nitrogen for 2 hours, and distilled under normal pressure. Acetic acid: Diphosphorus pentoxide was added to acetic acid and left overnight. Next, diphosphorus pentoxide was newly added except for diphosphorus pentoxide, and the mixture was refluxed under dry nitrogen for 2 hours and distilled under normal pressure. This acetic acid was dissolved in chlorobenzene to obtain a 40 mM solution. Ethyl aluminum dichloride: Ethyl aluminum dichloride is dissolved in benzene chloride under dry nitrogen,
A 0 mM solution was used.

3) Cationic polymerization Under a reduced pressure, the mixture was sufficiently heated with a drier, and after the heating was completed, 0.508 g of indene, 4.45 g of methyl dichloroacetate, and
0.5 ml of mM acetic acid (chlorobenzene solution) and 0.398 g of bromide benzene were weighed and mixed in a 0 degree bath until uniform. Next, 0.5 ml of 20 mM ethylaluminum dichloride (chlorobenzene solution), which had been cooled in a 0 ° bath in advance, was added dropwise to initiate polymerization. Three minutes after the start of the polymerization, 100 g of a 1% chlorobenzene solution of the previously synthesized styrene-4-hydroxystyrene copolymer was added dropwise to the polymerization system, and the polymerization was terminated. The operations up to this point were performed under a dry nitrogen stream. The solution thus obtained was reprecipitated with methanol. The precipitate was collected by filtration and dried under reduced pressure to obtain a graft. The obtained graft was melted at about 260 ° C. and compression molded to obtain a sample for evaluation. In order to measure the molecular weight of the graft chain, the polymerization was stopped by adding methanol instead of adding the copolymer. As a result, 1.3 g of polyindene (Mw = 2.5 × 10 ⁴ ) was obtained.

4) Method for evaluating graft polymer (1) Average molecular weight The molecular weight of the prepared sample was determined by GPC (L-4000 manufactured by Hitachi, Ltd.).
The average molecular weight in terms of styrene was measured using a UV Detector. (2) Graft rate The graft rate of the produced sample was calculated from the following equation. Graft rate (%) = (weight of graft polymer−weight of polymer before graft) / (weight of monomer) × 100 (3) Transmittance The transmittance of the prepared sample was measured at 500 nm using V-570 manufactured by JASCO Corporation. Was measured. A sample having a thickness of 2 mm was selected and produced by compression molding. (4) Birefringence Using an Ellipsometer AEP-100 manufactured by Shimadzu Corporation, 25
The temperature was measured at 632.8 nm at a laser light wavelength of 632.8 nm. A sample with a thickness of 2 mm was selected and produced by compression molding.
The sheet stretched 1.5 times was evaluated as a test piece. (5) Glass transition temperature (Tg) The powdery polymer was measured using a differential scanning calorimeter (Rigaku Thermo Co., Ltd.).
Plus DSC8230) was used to measure the glass transition temperature (Tg). (6) Saturated water absorption The test piece (10 × 10 × 3 mm) was dried in an oven (90 ° C., 24 h), weighed, left in water at 70 ° C., allowed to absorb saturated water, and then weighed. Was measured, and the saturated water absorption was calculated by the following equation. Saturated water absorption (%) = (weight after saturated water absorption-weight before water absorption) / (weight before water absorption) x 100 (7) Flexural breaking strength The flexural strength of the test piece was measured using AGS-1000G manufactured by Shimadzu Corporation. went. Test at room temperature, test speed 0.5mm
/ min, span 20 mm, specimen width 10 mm.

Example 2 In cationic polymerization, instead of methyl dichloroacetate, 0.5 ml of 12 mM 1,4-dioxane (chlorobenzene solution) was added to 3.99 chlorobenzene before the start of polymerization.
g of polyindene (Mw = 1.8 × 10 ⁴ ) as a result of performing the same procedure as in Example 1 except that the time until the addition of the copolymer was changed to 24 hours after the start of the polymerization.
I got

Comparative Example 1 A 200 ml flask was charged with 45 g of toluene and indene 1
5 g was added and stirred in a 25 ° C. bath until uniform. 0.15 g of aluminum chloride is added to this solution,
The polymerization was started. 30 minutes after the start of polymerization, Mw 300,
6.4 g of polystyrene of 000 was added, and at the stage when the polystyrene was dissolved in the polymerization solution, a small amount of methanol was added to stop the polymerization, and the polymerization solution was dried by an evaporator. This was dissolved in 100 ml of THF, reprecipitated using methanol, and a sample (Mw = 1.7 × 1)
0 ⁴⁾ was obtained 20g.

The evaluation results of the polymers obtained from Examples 1 and 2 and Comparative Example 1 are summarized in Table 1.

[0057]

[Table 1]

[0058]

As a molding material, film or additive using the graft polymer obtained by the production method of the present invention,
Excellent in low moisture absorption, heat resistance, mechanical strength, and optical properties, and can be suitably used for optical parts.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuro Yamanaka 14 Goi Minami Coast, Ichihara-shi, Chiba Hitachi Chemical Co., Ltd. Goi Office (72) Inventor Keiko Ushikubo 14 Goi-minami Coast, Ichihara-shi, Chiba Hitachi Chemical F-term (reference) at Goi Works Co., Ltd.

Claims (11)

[Claims] After the cationic polymerization of the following monomer component (a) is started using an activator containing aluminum in the presence of a reaction initiator and a base, the following copolymer (b) is added. A method for producing a graft polymer, comprising: (A) Indene or an indene-based monomer represented by the general formula (I). Embedded image However, R _{1 to} R ₅ are a hydrogen atom, a halogen atom, a carbon atom,
It represents a substituent containing any of an oxygen atom, a nitrogen atom, a phosphorus atom and a silicon atom, and n represents an integer of 1 to 5. However, when n is plural, R ₅ may be the same or different. (b) A copolymer represented by the general formula (II). Embedded image Here, R ₆ and R ₇ represent a substituent containing any of a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom and a silicon atom, m is a weight fraction, and n is 1 to 5 Indicates an integer. However, when n is plural, R ₆ and R ₇ may be the same or different. 2. The copolymer (b) is added in an amount of 0.1 to 500% by weight based on 100 parts by weight of the monomer component (a).
The method for producing a graft polymer according to claim 1, wherein 3. The method for producing a graft polymer according to claim 1, wherein the reaction initiator is a compound selected from water, acetic acid and an adduct of isobutyl vinyl ether acetic acid. 4. The compound according to claim 1, wherein the base is a compound selected from methyl dichloroacetate, methyl chloroacetate, 1,4-dioxane, diethyl ether, tetrahydrofuran and N, N-dimethylsulfoxide (DMSO). A method for producing the graft polymer according to claim 1. 5. The method for producing a graft polymer according to claim 1, wherein the activator is a compound selected from ethylaluminum dichloride, diethylaluminum chloride and aluminum chloride. 6. The monomer component (a) is selected from the group consisting of indene, alkylindenes, halogenated indenes, arylindenes, alkoxyindenes, alkoxycarbonylindenes, acyloxyindenes, alkylsilylindenes and alkylstannylindenes. The method for producing a graft polymer according to any one of claims 1 to 5, which is a compound selected from the group consisting of: 7. The method for producing a graft polymer according to claim 1, wherein the polymerization temperature is in the range of −100 to 50 ° C. 8. A molded material using a polymer obtained by the method for producing a graft polymer according to claim 1. Description: 9. A film using a polymer obtained by the method for producing a graft polymer according to any one of claims 1 to 7. 10. An additive using a polymer obtained by the method for producing a graft polymer according to any one of claims 1 to 7. 11. An optical component using the molding material, film or additive according to claim 8. Description: