JP2001342224A - Method for producing indene-styrene-based graft polymer, molded material, film or additive using polymer obtained by the same 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 carrying out cation polymerization of (a) a monomer component which is an indene or indene-based polymer 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 1-4 with (b) the following copolymer represented by a formula II, wherein R6 to R8 are each H, a halogen, C, O, N, P or,Si; (n) is an integer of 1-5 in the presence of an activating agent containing boron.

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 for preparing a specific monomer mixture containing indene or an indene monomer as an essential component by using a boron-containing activator in the presence of a specific copolymer. An object of the present invention is to provide a method for producing a graft polymer obtained by performing cationic polymerization. Another object of the present invention is to provide a molding 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, there is provided a graft polymer characterized in that the following monomer component (a) and the following copolymer (b) are cationically polymerized in the presence of an activator containing boron. And a molded material, film or additive using the polymer obtained by this method, and an optical component. (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 However, R _{6 to} R ₈ 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, m represents a weight fraction, and n represents an integer of 1 to 5. 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 activator is boron trifluoride, boron trifluoride acetic acid complex, boron trifluoride te
rtbutyl methyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride diethyl ether complex, boron trifluoride dimethyl ether complex, boron trifluoride ethylamine complex, boron trifluoride methanol complex, boron trifluoride dimethyl sulfide complex And a compound selected from boron trifluoride phenol complex, boron trifluoride propanol complex and boron trifluoride tetrahydrofuran complex.

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 -100 ° C.

[0016]

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, in the above indene or indene monomer (a), indene, alkylindenes, halogenated indenes, arylindenes, alkoxyindenes, alkoxycarbonylindenes, acyloxyindenes 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 methyl ether group contained in the copolymer (b) represented by the general formula (II) may be 2-methoxymethylstyrene or 3-methoxymethylstyrene.
Methoxymethylstyrene, 4-methoxymethylstyrene, 2-ethoxymethylstyrene, 3-ethoxymethylstyrene, 4-ethoxymethylstyrene, 3-n-propoxymethylstyrene, 4-n-propoxymethylstyrene, 4-i-propoxymethyl Examples include styrene, 4-n-butoxymethylstyrene, 4-i-butoxymethylstyrene, 4-tert-butoxymethylstyrene, 4-vinyl-4′-methoxymethylbiphenyl, and 4-phenoxymethylstyrene. These, alone,
Alternatively, two or more kinds can be used in combination.

Of these, 4-methoxymethylstyrene and 4-ethoxymethylstyrene are particularly preferred in terms of heat resistance and reactivity.

In the present invention, the monomer having no methyl ether 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, pt
alkylstyrenes such as tert-butylstyrene, p-tert-butoxystyrene, p-chlorostyrene, m
-Chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p
Halogenated styrenes such as -fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, vinyl biphenyls such as 4-vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl, 1- (4-vinylphenyl) naphthalene, 2
-(4-vinylphenyl) naphthalene, 1- (3-vinylphenyl) naphthalene, 2- (3-vinylphenyl)
Naphthalene, 2- (3-vinylphenyl) naphthalene,
Vinylphenylnaphthalenes such as 1- (2-vinylphenyl) naphthalene and 2- (2-vinylphenyl) naphthalene; 1- (4-vinylphenyl) anthracene;
(4-vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 2- (3-vinylphenyl) anthracene, 9
Vinylphenylanthracenes such as-(3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, 2- (2-vinylphenyl) anthracene, 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-
Vinylphenylphenanthrenes such as (2-vinylphenyl) 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
Vinylphenylpyrenes such as -vinylphenyl) pyrene and 2- (2-vinylphenyl) pyrene; 4-vinyl-p-terphenyl; 4-vinyl-m-terphenyl;
-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 and 2-vinyl-o-terphenyl; vinylphenyl terphenyls such as 4- (4-vinylphenyl) -p-terphenyl; 4-vinyl-4'-methylbiphenyl , 4-
Vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4-vinylbiphenyl,
Vinylalkylbiphenyls such as 3-methyl-4-vinylbiphenyl, 4-vinyl-4′-fluorobiphenyl, 4-vinyl-3′-fluorobiphenyl, 4-vinyl-2′-fluorobiphenyl, 4-vinyl-2-fluorobiphenyl, -Vinyl-3-fluorobiphenyl, 4-vinyl-4'-chlorobiphenyl, 4-vinyl-3'-chlorobiphenyl, 4-vinyl-2'-chlorobiphenyl, 4-vinyl-2-chlorobiphenyl, 4-
Vinyl-3-chlorobiphenyl, 4-vinyl-4'-bromobiphenyl, 4-vinyl-3'-bromobiphenyl, 4-vinyl-2'-bromobiphenyl, 4-vinyl-2-bromobiphenyl, 4-vinyl-3-bromobiphenyl and the like Halogenated vinyl biphenyls, 4-vinyl-4'-methoxybiphenyl, 4-vinyl-3'-methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4-vinyl-2-methoxybiphenyl, 4-vinyl-3-methoxybiphenyl, 4 -Alkoxybiphenyls such as -vinyl-4'-ethoxybiphenyl, 4-vinyl-3'-ethoxybiphenyl, 4-vinyl-2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl, 4-vinyl-3-ethoxybiphenyl, and 4-vinyl- 4'-methoxycarbonyl bife And alkoxyalkylbiphenyls such as alkoxycarbonylbiphenyls such as 4-vinyl-4'-ethoxycarbonylbiphenyl, and trialkylstannes such as 4-vinyl-4'-trimethylstannylbiphenyl and 4-vinyl-4'-tributylstannylbiphenyl. Nylbiphenyls, trialkylsilylmethylvinylbiphenyls such as 4-vinyl-4'-trimethylsilylmethylbiphenyl, 4-vinyl-4'-trimethylstannylmethylbiphenyl,
Trialkylstannylmethylbiphenyls such as vinyl-4'-tributylstannylmethylbiphenyl, p
-Chloroethylstyrene, m-chloroethylstyrene,
halogen-substituted alkylstyrenes such as o-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, hydroxystyrenes, alkylstyrenes, halogenated styrenes,
Vinyl biphenyls, vinyl phenyl naphthalenes, vinyl phenyl anthracenes, vinyl phenyl phenanthrenes, vinyl phenyl pyrenes, vinyl terphenyls, vinyl phenyl terphenyls, vinyl alkyl biphenyls, halogenated vinyl biphenyls, alkoxy biphenyls, Alkoxycarbonylbiphenyls, alkoxyalkylbiphenyls, trialkylstannylbiphenyls, alkylsilylmethylvinylbiphenyls, trialkylstannylmethylbiphenyls, halogen-substituted alkylstyrenes, alkoxystyrenes, acyloxystyrenes, alkoxycarbonylstyrenes , Alkyl ether styrenes, alkyl silyl styrenes, alkyl stannyl styrenes, vinyl styrenes, α It is preferably a compound selected from the group consisting of 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 moisture absorption, 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 based on 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.

As the activator in the present invention, boron trifluoride, boron trifluoride acetate complex, boron trifluoride t
ert butyl methyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride diethyl ether complex, boron trifluoride dimethyl ether complex, boron trifluoride ethylamine complex, boron trifluoride methanol complex, boron trifluoride dimethyl sulfide complex , Boron trifluoride phenol complex, boron trifluoride propanol complex, boron trifluoride tetrahydrofuran complex, boron tribromide, boron tribromide dimethyl sulfide complex, boron trichloride, boron trichloride dimethyl sulfide complex and boron triiodide 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, boron trifluoride, boron trifluoride acetate complex, boron trifluoride tertbutyl methyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride diethyl ether complex, boron trifluoride dimethyl ether Complex, boron trifluoride ethylamine complex, boron trifluoride methanol complex, boron trifluoride dimethyl sulfide complex, boron trifluoride phenol complex, boron trifluoride propanol complex, and boron trifluoride tetrahydrofuran complex are living polymerizable so,
More preferred.

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.

The polymerization temperature in the present invention is from -100 to
Preferably in the range of 100 ° C, -78 to 50 ° C
More preferably, it is within the range. When the polymerization temperature is -10
Below 0 ° C., the activator tends to precipitate,
When the temperature exceeds 00 ° C., living polymerizability tends to be lost.

In the cationic polymerization reaction of the present invention, a stabilizer for stabilizing living polymerization may be added. This stabilizer includes methyl dichloroacetate, methyl chloroacetate, methyl acetate, ethyl acetate, 1,4-dioxane, diethyl ether, tetrahydrofuran, DMS
Compounds such as O, DMF, DMAc, NMP, diethyl carbonate, dimethylthioether, diethylthioether, triallylphosphine, triethylamine, 1-methylpyrrolidine, and tetrahydrothiophene are used alone or in combination of two or more. However,
The compounds shown here are only examples and the present invention is not limited to these.

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 monomer having a methyl ether group and the monomer having no methyl ether group in the copolymer (b) is 0.001 to 0.9. It is preferably within the range. When the weight fraction m is less than 0.001, the graft ratio tends to be low,
If it is larger, 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 may be 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 may be 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.

[0043]

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 4-methoxymethylstyrene In a 100 ml round bottom flask, 20 g of 4-chloromethylstyrene, 50 g of methanol and 0.1 g of potassium iodide were placed.
And stirred until uniform. To this solution, 40 ml of 5M sodium methoxide (methanol solution) was added dropwise and refluxed for 1 hour. This solution was added dropwise to a dilute aqueous hydrochloric acid solution containing ice, and the resulting organic phase was extracted with toluene. The toluene phase was washed with 1M sodium hydrogen carbonate and water, and toluene was distilled off by an evaporator. Obtained.
The obtained oily organic matter is fractionated by distillation under reduced pressure,
19 g of methoxymethylstyrene were obtained.

2) Synthesis of styrene-4-methoxymethylstyrene copolymer In a 200 ml round bottom flask, 99 g of styrene, 1 g of 4-methoxymethylstyrene and 0.1 g of benzoyl peroxide were added.
25 g was 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 heated and polymerized at 90 ° C. for 7 hours and further at 120 ° C. for 2 hours, and the obtained mass was dissolved in 100 ml of THF. The solution was reprecipitated with 1 l of methanol to obtain 93 g of a styrene-4-methoxymethylstyrene copolymer (Mw = 31 × 10 ⁴ ).

3) Purification of Compound Used for Cationic Polymerization Indene: Calcium chloride was put in 25 ml of indene and left overnight. Next, calcium chloride was added to remove calcium chloride, refluxed under dry nitrogen for 2 hours,
Distilled under reduced pressure. -Dichloromethane: Calcium chloride was added to dichloromethane and left overnight. Next, except for calcium chloride, calcium hydride was added, and the mixture was refluxed under dry nitrogen for 2 hours and distilled under normal pressure. -Boron trifluoride ether complex: A commercially available complex was dissolved in dichloromethane to obtain a 20 mM solution.・ N, N-dimethylsulfoxide (DMSO): DMS
Molecular sieves 4A was added to O and left overnight. Next, calcium hydride was added except for the molecular sieves 4A, and the mixture was distilled under reduced pressure under dry nitrogen.

4) Cationic polymerization Under a reduced pressure, the mixture was sufficiently heated with a drier, and after completion of heating, 0.508 g of indene and a styrene-4-methoxymethylstyrene copolymer were placed in a 200 ml round bottom flask which was returned to normal pressure with dry nitrogen. 218 g, DMSO 0.00089 m
1, 4.24 ml of dichloromethane was weighed and mixed in a -40 degree bath until uniform. Next, 0.5 ml of 20 mM boron trifluoride ether complex (dichloromethane solution), which had been cooled in a bath at −40 ° C. in advance, was added dropwise to initiate polymerization. Three hours after the start of the polymerization, a small amount of methanol was added to terminate the polymerization. The operations up to this point were performed under a dry nitrogen stream. The solution thus obtained was reprecipitated with methanol. The precipitate is collected by filtration,
By drying under reduced pressure, 0.65 g of a graft was obtained. 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, polymerization was performed using 4-methoxymethyltoluene as a model compound as a polymerization initiator. As a result, the Mw of polyindene under these polymerization conditions was 2
It was 0000.

5) 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.

Comparative Example 1 A 200 ml flask was charged with 45 g of toluene and 15 g of indene.
g and 6.4 g of polystyrene (Mw = 300,000) were added and stirred in a 25 ° C. bath until uniform. 0.15 g of aluminum chloride was added to this solution to initiate polymerization. Thirty minutes after the initiation of the polymerization, 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 and reprecipitated using methanol to obtain a 20 g sample. In addition,
As a result of measuring the molecular weight of the polyindene, the Mw of the polyindene under these polymerization conditions was 17,000.

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

[0051]

[Table 1]

[0052]

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 Goi Works Co., Ltd.

Claims (9)

[Claims] 1. A method for producing a graft polymer, comprising cationically polymerizing the following monomer component (a) and the following copolymer (b) in the presence of an activator containing boron. (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 However, R _{6 to} R ₈ 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, m represents a weight fraction, and n represents an integer of 1 to 5. 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. An activator comprising: boron trifluoride, boron trifluoride acetic acid complex, boron trifluoride tertbutyl methyl ether complex, boron trifluoride dibutyl ether complex,
Boron trifluoride diethyl ether complex, boron trifluoride dimethyl ether complex, boron trifluoride ethylamine complex, boron trifluoride methanol complex, boron trifluoride dimethyl sulfide complex, boron trifluoride phenol complex, boron trifluoride propanol complex The method for producing a graft polymer according to claim 1, wherein the compound is a compound selected from the group consisting of: and boron trifluoride tetrahydrofuran complex. 4. The monomer component (a) is composed 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 3, which is a compound selected from the group consisting of: 5. The method for producing a graft polymer according to claim 1, wherein the polymerization temperature is in the range of −100 to 100 ° C. 6. A molded material using a polymer obtained by the method for producing a graft polymer according to any one of claims 1 to 5. 7. A film using a polymer obtained by the method for producing a graft polymer according to any one of claims 1 to 5. 8. An additive using a polymer obtained by the method for producing a graft polymer according to claim 1. Description: 9. An optical component using the molding material, film or additive according to claim 6. Description: