JP6900663B2 - Copolymer - Google Patents

Description

The present invention relates to a copolymer having both excellent heat resistance and melt molding processability.

A methacrylic resin such as polymethylmethacrylate is transparent and has properties that are well-balanced in mechanical strength, molding processability, weather resistance, etc., and is widely used as a sheet material or a molding material. However, methacrylic resin has a problem of low heat resistance, and there are some applications in which its use is restricted. In particular, when used for films, lenses, disks, optical transmission materials, etc., heat resistance superior to that of polymethyl methacrylate is required.

In recent years, many polymerizable monomers that impart heat resistance to (meth) acrylic copolymers have been developed (for example, Patent Documents 1 to 3).
However, the degree of improvement in heat resistance by copolymerization of the polymerizable monomer imparting heat resistance and the (meth) acrylic monomer proposed in Patent Documents 1 to 3 is generally set to Tg. It is desired to develop a technique for realizing heat resistance corresponding to applications that require higher heat resistance, which is not sufficient at about several ° C to 30 ° C.

On the other hand, as a polymerizable monomer that also improves heat resistance, a polymerizable monomer having a plurality of reaction points in the monomer has been proposed. For example, in Non-Patent Document 1, Tg is improved by adding a polymerizable monomer having two (meth) acrylate substituents to the cyclohexane ring into the polymerization system of the acrylate. This is due to the cross-linking effect due to the incorporation of a plurality of reaction sites in the sex monomer into different polymer chains. Such crosslinked polymers are generally difficult to mold after polymerization and cannot be used in industrial applications where melt molding processability is required.

In addition, Non-Patent Document 2 describes a method for synthesizing a compound represented by the following formula (3), which is a raw material for synthesizing a compound suitable as the monomer (1) used in the present invention. An example of polyurethane production using a diol derived from 3) has been disclosed, but there is no mention of a (meth) acrylic copolymer.

Japanese Unexamined Patent Publication No. 60-90204 JP-A-2002-308941 Japanese Unexamined Patent Publication No. 2013-227496

J.E. Elliott et al. Polymer 44 (2003) 327-332 S. Okamoto, S. Onoue, M. Kobayashi, A. Sudo, J. Polym. Sci., Part A: Polym. Chem. 2014, 24, 3498-3505.

An object of the present invention is to provide a copolymer which has excellent heat resistance as compared with the conventional one and at the same time retains melt molding processability which is important for industrial use.

As a result of diligent studies by the present inventor, the two reaction points contained in the polymerizable monomer represented by the following formula (1) in the copolymerization with other vinyl-based monomers are continuous in the molecule. It is possible to realize a copolymer having extremely excellent heat resistance, and since these reaction points are oriented in a specific direction, intermolecular cross-linking does not occur and the molecule It has been found that the inner ringing keeps the thermoplasticity and does not impair the melt molding processability.

That is, the gist of the present invention is as follows.

[1] Coweight of a monomer represented by the following formula (1) (hereinafter referred to as "monomer (1)") and a vinyl-based monomer different from the monomer (1). Combined.

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. Q ¹ is a trivalent group or 3 which may contain a hetero atom having 1 to 20 carbon atoms. It indicates a valence atom. Z indicates a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms.)

[2] The copolymer according to [1], wherein the monomer (1) is a compound represented by the following (2).

(In the formula (2), Q ² represents an atom of Group 14 of the periodic table. R ¹ , R ² , and Z are synonymous with those in the above formula (1). R ³ is a hydrogen atom or the number of carbon atoms. Indicates a hydrocarbon group that may contain 1 to 19 heteroatoms.)

[3] In the formula (2), characterized in that Q ² is a carbon atom or a silicon atom, a copolymer described in [2].

[4] In the formula (2), characterized in that Q ² is a carbon atom, the copolymer according to [3].

[5] The copolymer according to any one of [2] to [4], wherein ^{R 3} is a hydrogen atom or a methyl group in the above formula (2).

[6] The copolymer according to any one of [1] to [5], wherein Z is represented by the following formula (X).
YO- (X)
(In the formula (X), Y represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms.)

[7] In the above formula (X), the hydrocarbon group which may contain a heteroatom having 1 to 20 carbon atoms is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon-substituted carbonyl group, or a hydrocarbon-substituted oxy. The copolymer according to [6], which is a carbonyl group or a hydrocarbon trisubstituted silyl group.

[8] The copolymer according to any one of [1] to [7], wherein the monomer (1) is derived from myo-inositol.

[9] The copolymer according to any one of [1] to [8], wherein the vinyl-based monomer is a (meth) acrylic acid ester.

[10] A copolymer containing a structural unit represented by the following formula (A) and a structural unit represented by the following formula (B), and a structure represented by the formula (A) in the copolymer. A copolymer in which the molar ratio of the unit and the structural unit represented by the formula (B) is 1: 1 to 1: 1000.

(In formulas (A) and (B), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. Z is a hydrogen atom, a hydroxyl group, or a hetero with 1 to 20 carbon atoms. Indicates a hydrocarbon group that may contain an atom.)

[11] The copolymer according to [10], wherein Z is represented by the following formula (X) in the formula (A).
YO- (X)
(In the formula (X), Y represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms.)

[12] In the formula (A), the hydrocarbon group which may contain a heteroatom having 1 to 20 carbon atoms is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon-substituted carbonyl group, or a hydrocarbon-substituted oxycarbonyl group. The copolymer according to [11], which is a group or a hydrocarbon trisubstituted silyl group.

According to the present invention, there is provided a copolymer having very excellent heat resistance without impairing melt molding processability.

^{6 is a 1 1} H-NMR chart of the copolymer-1 obtained in Example 1.

Hereinafter, embodiments of the present invention will be described in detail.

In this specification, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid. Acrylic acid ester and methacrylic acid ester are collectively referred to as (meth) acrylic acid ester. Acrylate and methacrylate are collectively referred to as (meth) acrylate. The same applies to (meth) acrylamide and (meth) acrylonitrile.
Further, in the present specification, the carbon number of each substituent refers to the total number of carbon atoms including the substituent when the substituent further has a substituent.

The copolymer of the present invention has a monomer represented by the following formula (1) (hereinafter, may be referred to as "monomer (1)") and a vinyl different from the monomer (1). A copolymer obtained by copolymerizing a system monomer (hereinafter, may be referred to as "another vinyl-based monomer") (hereinafter, this copolymer is referred to as "copolymer (I)"). It referred sometimes.), and the monomer (1) is -C as represented by the following formula (1A) in the copolymerization reaction system with other vinyl monomer (= O) R ¹ group And -C (= O) R ² groups are bonded and cyclized, and copolymerized with other vinyl-based monomers to form a copolymer (I). Hereinafter, such a copolymer may be referred to as a "cyclized copolymer".

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. Q ¹ is a trivalent group or 3 which may contain a hetero atom having 1 to 20 carbon atoms. It indicates a valence atom. Z indicates a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms.)

(In the formula ^{(1A), R 1, R} 2, Q 1, Z has the same meaning as in the formula (1).)

The copolymer of the present invention also has a structural unit represented by the following formula (A) (hereinafter sometimes referred to as "structural unit (A)") and a structural unit represented by the following formula (B) (hereinafter referred to as "structural unit (A)"). It is a copolymer containing "structural unit (B)"), and the molar ratio of the structural unit (A) to the structural unit (B) is 1: 1 to 1: 1000. It is a copolymer (hereinafter, this copolymer may be referred to as "copolymer (II)").

(In formulas (A) and (B), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. Z is synonymous with the formula (1).)

The copolymer of the present invention includes these copolymers (I) and copolymers (II).

<Monomer (1)>
The monomer (1) imparts excellent heat resistance to the obtained copolymer when used as a polymerization component. As the monomer (1), a commercially available product may be used, or a separately synthesized monomer (1) may be used.

A suitable Z in the formula (1) will be described later as Z in the following formula (2).

In the formula (1), when Q ¹ is a trivalent atom, a specific example thereof is an atom of Group 13 of the periodic table. It is preferably a boron atom or an aluminum atom.

In the present invention, the monomer (1) is preferably a compound represented by the following formula (2) (hereinafter, may be referred to as “compound (2)”).

(In the formula (2), Q ² represents an atom of Group 14 of the periodic table. R ¹ , R ² , and Z are synonymous with those in the above formula (1). R ³ is a hydrogen atom or the number of carbon atoms. Indicates a hydrocarbon group that may contain 1 to 19 heteroatoms.)

In the above formula (2), preferably Q ² is carbon atom, silicon atom, particularly preferably a carbon atom.

R ³ is a hydrogen atom, a hydrocarbon group which may contain a hetero atom with carbon number from 1 to 19, preferably a hydrogen atom, a hydrocarbon group of 1 to 19 carbon atoms. Preferably, it is an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group, and these alkyl group, cycloalkyl group, alkenyl group and aryl group are further substituted alkyl group, cycloalkyl group, alkenyl group and aryl group. You may have any of. Here, specific examples of the alkyl group and the cycloalkyl group include a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a t-butyl group, a 1-pentyl group and a 1-hexyl group. Group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1,1-dimethylpropyl group, 1,1 , 2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl Group, 2-ethylhexyl group, 2-hepyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl Group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2 ] Examples include octyl group, nonyl group, decahydronaphthyl group, mentyl group, neomentyl group, neopentyl group, 5-decyl group and the like.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cinnamyl group, a styryl group and the like.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group and the like. Examples of substituents that can be substituted for the aromatic ring of these aryl groups include alkyl groups, aryl groups, fused aryl groups, phenylcyclohexyl groups, phenylbutenyl groups, tolyls, xsilyl groups, p-ethylphenyl groups and the like. Can be mentioned.

Among these, R ^3, a hydrogen atom or a methyl group, is most preferred.

In Z, as the heteroatom of the hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, a selenium atom, a silicon atom, a fluorine atom and a boron atom are used. For example, Z may contain a plurality of these heteroatoms. Of these heteroatoms, oxygen atoms and silicon atoms are preferable. The way in which the heteroatom is contained in the hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and the heteroatom may be contained between the carbon chains or at the end of the hydrocarbon group having 1 to 20 carbon atoms. Alternatively, it may be bonded to any carbon atom contained in the hydrocarbon group having 1 to 20 carbon atoms by a double bond.

Among the heteroatom-containing groups containing these heteroatoms, examples of the oxygen atom-containing group include an alkoxy group, an aryloxy group, an acyl group, an aroyl group, a carboxylate group, and a carbonate group. Examples of the nitrogen atom-containing group include an amide group and a carbamate group. Examples of the sulfur atom-containing group include a thioalkoxy group and a thioaryroxy group. Examples of the phosphorus atom-containing group include a phosphino group. Examples of the selenium atom-containing group include a selenyl group. Examples of the silicon atom-containing group include a trialkylsilyl group, a dialkylarylsilyl group, and an alkyldiarylsilyl group. In particular, as a group containing both a silicon atom and an oxygen atom, a siloxy group such as a trialkylsiloxy group, a dialkylarylsiloxy group or an alkyldiarylsiloxy group, an alkoxy such as a trialkoxysilyl group, a dialkylalkoxysilyl group or an alkyldialkoxysilyl group A silyl group can be mentioned. Examples of the fluorine atom-containing group include a fluoroalkyl group and a fluoroaryl group. Examples of the boron atom-containing group include an alkylboron group and an arylboron group.

More specific examples of heteroatom-containing groups are as follows.
Oxygen atom-containing groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, phenoxy group, benzyloxy group, p-methylphenoxy group and p-methoxyphenoxy group. , P-methoxybenzyloxy group, methoxymethyloxy group, 2-tetrahydropyranyloxy group, acetyl group, benzoyl group, acetoxy group, ethylcarboxylate group, t-butyl carboxylate group, phenyl carboxylate group, methoxycarbonyloxy Examples thereof include a group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, a phenoxycarbonyloxy group and the like.
The nitrogen atom-containing group includes a dimethylamino group, a diethylamino group, a di-n-propylamino group, a cyclohexylamino group, an acetamide group, a benzamide group, a cyclohexanecarboxamide group, a methoxycarbonylamino group, a dimethylaminocarbonyloxy group, and a t-butoxy. Examples thereof include a carbonylamino group and a benzyloxycarbonylamino group.
Sulfur atom-containing groups include thiomethoxy group, thioethoxy group, thio-n-propoxy group, thioisopropoxy group, thio-n-butoxy group, thio-t-butoxy group, thiophenoxy group, p-methylthiophenoxy group, p. -Methoxythiophenoxy group and the like can be mentioned.
Examples of the phosphorus atom-containing group include a dimethylphosphino group, a diethylphosphino group, a di-n-propylphosphino group, a cyclohexylphosphino group and the like.
Examples of the selenium atom-containing group include a methylselenyl group, an ethylserenyl group, an n-propylserenyl group, an n-butylserenyl group, a t-butylserenyl group, a phenylserenyl group and the like.
Examples of the silicon atom-containing group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a t-butyldimethylsilyl group, a dimethylphenylsilyl group, and a methyldiphenylsilyl group.
Examples of the group containing both a silicon atom and an oxygen atom include a trisubstituted siloxy group such as a trimethylsiloxy group, a triethylsiloxy group, a triisopropylsiloxy group, a t-butyldimethylsiloxy group, a dimethylphenylsiloxy group and a methyldiphenylsiloxy group. Examples thereof include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethylethoxysilyl group and a methyldiethoxysilyl group.

Among the above-mentioned heteroatom-containing groups, the trisubstituted silyl group of a trisubstituted siloxy group such as t-butyldimethylsiloxy group and the alkoxyalkyl group such as a methoxymethyloxy group and a 2-tetrahydropyranyloxy group are hydroxyl groups. It also functions as a protecting group for the above, and after the copolymerization reaction of the monomer (1) with another vinyl-based monomer, the obtained copolymer is deprotected by hydrolysis or the like to cause a deprotection reaction. It can be converted to a hydroxyl group.

Z is particularly preferably a hydrocarbon group containing a hydrogen atom, a hydroxyl group, a hydrocarbon group, or a hydrocarbon atom and / or a silicon atom as a hetero atom.
Among the above, Z is preferably represented by the following formula (X).
YO- (X)
(In the formula (X), Y represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms.)
In the formula (X), the hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms is a hydrocarbon group (-R) having 1 to 20 carbon atoms and a hydrocarbon-substituted carbonyl group (-C (-C ()). = O) -R), hydrocarbon-substituted oxycarbonyl groups (-C (= O) -OR), or hydrocarbon tri-substituted silyl groups (-Si (-R) ₃ ) are preferred. Here, R is a hydrocarbon group, and _{the three Rs (-Si (-R) 3} ) may be the same or different.
Among these, when Y is a hydrogen atom, it is preferable because it can enhance the affinity with other resins and can be functionalized by treating it with a reactive compound such as isocyanate. Further, when Y is a hydrocarbon-substituted carbonyl group, it is preferable because it has a high effect of increasing heat resistance and can reduce the water absorption rate of the entire resin. It is preferable that Y is a hydrocarbon trisubstituted silyl group because it can impart high hydrophobicity and can easily convert Y to a hydrogen atom by a post-polymerization treatment (for example, tetrabutylammonium fluoride or the like).

The R is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and these alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups are further substituted with an alkyl group, a cycloalkyl group, and the like. It may have either an alkenyl group or an aryl group. Here, specific examples of the alkyl group and the cycloalkyl group include a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a t-butyl group, a 1-pentyl group and a 1-hexyl group. Group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1,1-dimethylpropyl group, 1,1 , 2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl Group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl Group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2 ] Examples include octyl group, nonyl group, decahydronaphthyl group, mentyl group, neomentyl group, neopentyl group, 5-decyl group and the like.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cinnamyl group, a styryl group and the like.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group and the like. Examples of substituents that can be substituted for the aromatic ring of these aryl groups include alkyl groups, aryl groups, condensed aryl groups, phenylcyclohexyl groups, phenylbutenyl groups, trill groups, xsilyl groups, p-ethylphenyl groups and the like. Can be mentioned.

Among these, as R, an aryl group is preferable from the viewpoint of enhancing heat resistance, and a phenyl group is more preferable from the viewpoint of easiness of synthesis. From the viewpoint of reducing the water absorption rate, an alkyl group is preferable, an alkyl group having 4 to 15 carbon atoms is more preferable, and a t-butyl group and a cyclohexyl group are more preferable. Similarly, from the viewpoint of reducing the water absorption rate, when Y is a hydrocarbon trisubstituted silyl group, it is preferable that one or more R contained in the hydrocarbon trisubstituted silyl group is an alkyl group, and the number of carbon atoms is 4 to 15. The alkyl group is more preferable, and the t-butyl group and cyclohexyl group are more preferable.

Among the compounds (2) suitable as the monomer (1), the compound in the formula (2) in which Q ² is a carbon atom and R ³ is a methyl group is not described above, for example, using myo-inositol as a starting material. According to the synthesis method described in Patent Document 2, a triol (myo-inositol orthoester) represented by the above formula (3) can be synthesized and synthesized from this triol.
As a method for synthesizing from this triol, in general, the 4- and 6-position hydroxyl groups of the above-mentioned triol are selectively (meth) acrylated to di (meth) acrylate, and then the 2-position hydroxyl group is arbitrarily removed. A method for converting to a polymerizable functional group, or a synthesis in which the 2-position hydroxyl group of the above-mentioned triol is converted to a non-polymerizable functional group, and then the 4- and 6-position hydroxyl groups are (meth) acrylated to di (meth) acrylate. The method is used. Both are preferably used as synthetic methods, but from the viewpoint of selectivity, the 2-position hydroxyl group of triol is converted into a non-polymerizable functional group, and then the 4- and 6-position hydroxyl groups are (meth) acrylated to di (meth). A synthetic method of acrylate is preferably used. The non-polymerizable functional group is a substituent having no carbon-carbon double bond that can be polymerized by radical polymerization, and preferred substituents include those exemplified in Z. As a method for converting to a non-polymerizable functional group, generally known organic synthetic methods such as hydride reduction, alkyl substitution with an alkyl metal, (thio) etherification, silylation, esterification, and amidation can be used. it can.

In the production of the copolymer of the present invention, only one type of monomer (1) may be used, or two or more types may be used in combination.

<Other vinyl-based monomers>
The other vinyl-based monomer copolymerized with the monomer (1) is not particularly limited as long as it can be copolymerized. Specific examples of other vinyl-based monomers include aromatic compounds such as styrene, α-methylstyrene, t-butylstyrene, and chlorostyrene, (meth) acrylic acid, methyl (meth) acrylate, and (meth) acrylic. (Meta) acrylates such as ethyl acid, butyl (meth) acrylate, glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- N-substituted maleimides such as cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-chlorophenylmaleimide, maleic acid, maleic anhydride, unsaturated dibasic acid of fumaric acid or a derivative thereof, vinyl acetate, (meth) acrylamide. , And (meth) acrylonitrile and the like. Further, polyfunctional vinyl-based monomers such as divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate can also be used. Only one of these may be used, or two or more thereof may be used in combination.

Among them, other preferable vinyl-based monomers are monofunctional vinyl-based monomers from the viewpoint of copolymerizability, compatibility, moldability, and functional imparting, and more preferably (meth) acrylic acid. It is an ester, particularly preferably methyl (meth) acrylate.

<Method for producing copolymer>
A known polymerization method can be used when producing the copolymer of the present invention. Examples of the polymerization system include a massive polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. Further, as the polymerization method, a radical polymerization method or an anion polymerization method is preferable, and a radical polymerization method is more preferable.

Examples of the radical polymerization initiator used in the radical polymerization method include peroxide-based initiators such as benzoyl peroxide and di-t-butyl peroxide, 2,2'-azobisisobutyronitrile, and 2,2'. -Azobis-2,4-dimethylvaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile and other azo initiators Can be mentioned. Among the radical polymerization initiators, benzoyl peroxide, 2,2'-azobisisobutyronitrile, and 2,2'-azobis-2,4-dimethylvaleronitrile are preferable from the viewpoint of handleability. Only one kind of these radical polymerization initiators may be used, or two or more kinds thereof may be used in combination.
Further, in order to produce the copolymer of the present invention, a living radical polymerization method such as an atom transfer radical polymerization (ATRP) method, a reversible non-cleavable chain transfer polymerization (RAFT) method, and a nitroxide-mediated polymerization (NMP) method is used. It can also be used. In particular, the RAFT method, which does not require the use of heavy metal compounds, is preferable. Examples of the chain transfer agent used in the RAFT method include compounds having a thiocarbonylthio group (dithioester structure or trithiocarbonate structure), and specifically, cyanomethyl-N-methyl-N-phenyldithiocarbamate. , S-Cyanomethyl-S-dodecyltrithiocarbonate, 2-cyanopropan-2-ylbenzothioate, 4-cyano-4- (thiobenzoylthio) valerate, 2-cyano-2-propyldodecyltrithiocacarbonate, Examples thereof include 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] valeric acid, 2- (dodecylthiocarbonotioilthio) -2-methylpropionic acid.

The amount of the radical polymerization initiator used is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more per 100 parts by mass of the total amount of the monomers used in the production of the copolymer. The amount of the radical polymerization initiator used is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, per 100 parts by mass of the total amount of the monomers used in the production of the copolymer.

In the production of the copolymer, a chain transfer agent such as mercaptan may be used in order to adjust the molecular weight of the obtained copolymer.

Radical polymerization for obtaining a copolymer can be carried out without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbon solvents such as methylene chloride and chloroform, acetone, methyl ethyl ketone and methyl isobutyl ketone. Ketone solvents, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol and other alcohol solvents, acetonitrile, propionitrile, benzonitrile and other nitrile solvents, ethyl acetate, n-butyl acetate and the like. Examples thereof include ester solvents and carbonate solvents such as ethylene carbonate and propylene carbonate. As the solvent, one type may be used alone, or two or more types may be used in combination.

In addition, polymerization can also be carried out in an emulsion system or a system using supercritical CO _{2 as a medium.}

The atmosphere of the polymerization is not particularly limited, but an oxygen-free atmosphere such as an inert gas atmosphere is preferable. This is because oxygen easily reacts with radicals and inhibits polymerization.

The polymerization temperature is preferably 0 ° C. or higher, more preferably 25 ° C. or higher. The polymerization temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.

After the above polymerization reaction, the obtained copolymer can be converted into a hydroxyl group by removing a protecting group such as a trisubstituted silyl group by hydrolysis or the like according to a conventional method as described above.

In this case, the deprotection reaction is carried out when the protecting group is a trisubstituted silyl group, for example, acetic acid, a pyridinium salt of p-toluenesulfonic acid, tetrabutylammonium fluoride, cesium fluoride, hydrofluoric acid, hydrogen fluoride-pyridine. It is preferably carried out by using, for example, water, tetrahydrofuran, dioxane, acetone, acetonitrile or the like as a reaction solvent. The reaction is usually carried out in a temperature range of 0 to 100 ° C. for about 0.1 to 100 hours. When the protecting group is an alkoxyalkyl group, it is carried out under acidic conditions such as coexistence with trifluoroacetic acid in the above-mentioned reaction solvent at the same temperature for the same period of time.

That is, the copolymer (I) is produced by a copolymerization reaction of the above-mentioned monomer (1) with another vinyl-based monomer, and then, if necessary, a deprotection reaction by hydrolysis is carried out. May be good.
Further, as the copolymer (II), it is sufficient that a copolymer containing a structural unit (A) and a structural unit (B) can be obtained, and in the above formula (2), Z is the above-mentioned hydrogen atom and hydroxyl group. , A group other than the hydrocarbon group which may contain a heteroatom having 1 to 20 carbon atoms. By performing a deprotection reaction such as hydrolysis after the copolymerization reaction with methyl (meth) acrylate, Z Uses a compound that can be a hydrocarbon group that may contain a hydrogen atom, a hydroxyl group, and a heteroatom having 1 to 20 carbon atoms and methyl (meth) acrylate, and a deprotection reaction by hydrolysis or the like after the copolymerization reaction. Can also be produced in the same manner as in the above-mentioned method for producing a copolymer.

<Copolymerization composition of copolymer>
The copolymerization composition of the copolymer can be controlled by the amount of the polymerizable monomer used in the production of the copolymer.

The copolymer composition of the copolymer (I) of the present invention is not particularly limited, but in order to improve the heat resistance of the copolymer, the amount of the monomer (1) used is used in the production of the copolymer. Of the total amount of the monomer to be obtained, 0.1% by mass or more is preferable, and 1% by mass or more is more preferable. Further, in order to improve the melt molding processability of the copolymer, the amount of the monomer (1) used is preferably 80% by mass or less, preferably 70% by mass or less, based on the total amount of the monomers used in the production of the copolymer. More preferably, it is by mass or less.

Further, the molar ratio of the structural unit derived from the monomer (1) contained in the copolymer (I) to the structural unit derived from another vinyl-based monomer is simply determined from the viewpoint of improving heat resistance. Constituent unit derived from the polymer (1): Constituent unit derived from another vinyl-based monomer = 1: 1000 or less, particularly preferably 1: 100 or less, from the viewpoint of improving melt molding processability. It is preferably 1: 1 or more, particularly 1: 2 or more.

Further, the molar ratio of the structural unit (A) and the structural unit (B) contained in the copolymer (II) is such that the structural unit (A): the structural unit (B) = 1: from the viewpoint of improving the heat resistance. It is preferably 1000 or less, particularly 1: 100 or less, and from the viewpoint of improving melt molding processability, it is preferably 1: 1 or more, particularly 1: 2 or more.

<Molecular weight of copolymer>
The mass average molecular weight (Mw) of the copolymer of the present invention is preferably 1,000 to 500,000. When the mass average molecular weight is 1,000 or more, the physical properties and handleability of the copolymer are good. Further, when the mass average molecular weight is 500,000 or less, the processability is good. Here, the mass average molecular weight is a value calculated by gel permeation chromatography (GPC) described later.

The mass average molecular weight of the copolymer can be controlled by appropriately changing the amount of the polymerization initiator used in the polymerization reaction, the amount of the chain transfer agent, the polymerization temperature, the polymerization time and the like.

<Use of copolymer>
The copolymer of the present invention has excellent heat resistance and sufficient melt molding processability, and is extremely useful industrially as a molding material in various fields where heat resistance is required.
Specific applications include, but are not limited to, films, lenses, disks, optical transmission materials, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the scope of the present invention is not limited to these Examples, and can be arbitrarily modified without departing from the gist of the present invention. Can be carried out.

The copolymer was evaluated according to the following method.

JEOL's JNM-AL400 ( ¹ H observation frequency 400 MHz, ¹³ C observation frequency 100.6 MHz) was used for the NMR measurement.

<Glass transition temperature (Tg) of copolymer>
The glass transition temperature (Tg) as an index of the heat resistance of the copolymer was measured under the following conditions.
Using "EXSTAR6000" manufactured by Seiko Electronics Co., Ltd., the temperature is raised to 30 to 300 ° C at 10 ° C / min, isothermal at 300 ° C for 30 minutes, and lowered to 300 to 30 ° C at 20 ° C / min under a nitrogen atmosphere. It was measured by data acquisition during the temperature rise from 30 to 300 ° C. at 10 ° C./min.

<Molecular weight of copolymer>
The mass average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the copolymer obtained in Example 1 were calculated by GPC by the following apparatus and conditions (standard polystyrene). Conversion).
Equipment: Tosoh HLC-8120GPC
Column: Tosoh TSKgel-SuperHM-H (15 cm x 6.0 mmφ)
Oven temperature: 40 ° C
Eluent: tetrahydrofuran
Sample concentration: 5 mg / mL
Flow velocity: 0.6 mL / mim
Injection volume: 20 μL
Detector: Refractive index detector and UV detector (measurement wavelength 254 nm)
The mass average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the copolymer obtained in Example 2-9 were calculated by GPC by the following apparatus and conditions. (Standard polystyrene conversion).
Equipment: Tosoh HLC-8120GPC
Column: Tosoh TSKgel-SuperHM-H (15 cm x 6.0 mmφ)
Oven temperature: 40 ° C
Eluent: N, N-dimethylformamide solution of lithium bromide (weight percent concentration 1%)
Sample concentration: 5 mg / mL
Flow velocity: 0.6 mL / mim
Injection volume: 20 μL
Detector: Refractive index detector

[Synthesis Example 1]
Triol (myo-inositol orthoester) represented by the following formula (3) was synthesized according to Non-Patent Document 2 using myo-inositol as a starting material.

[Synthesis Example 2]
Triol (5.54 g; 27.1 mmol) represented by the above formula (3) and N, N-dimethyl-4-aminopyridine (37.6 mg; 0.308 mmol) obtained in Synthesis Example 1 were added. It was dissolved in viridin (145 mL) under an argon atmosphere and the solution was cooled to 0 ° C. Benzoyl chloride (3.20 mL; 28.0 mmol) was slowly added thereto, and after the addition, the reaction solution was heated to room temperature. After 16 hours, the reaction solution was diluted with ethyl acetate (80 mL) and the solution was washed with 0.1 M aqueous hydrochloric acid solution (100 mL). Sodium sulfate was added to the organic layer, dried, filtered, and then concentrated under reduced pressure. The residue after concentration was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane / dichloromethane = 50/50/3). The fractionation solution containing the target component is collected and concentrated under reduced pressure, and the residue is crystallized in a mixed solvent (ethyl acetate / hexane = 1/1) to collect the target diol represented by the following formula (4). Obtained at a rate of 74% (6.19 g; 20.1 mmol).

[Synthesis Example 3]
The diol (0.927 g; 3.00 mmol) represented by the above formula (4), N, N-dimethyl-4-aminopyridine (38.8 mg; 0.318 mmol), and triethylamine obtained in Synthesis Example 2 (1.20 mL; 11.9 mmol) was dissolved in dichloromethane (6.0 mL) under an argon atmosphere and the solution was cooled to 0 ° C. Methacryloyl chloride (0.90 mL; 9.3 mmol) was slowly added thereto, and after the addition, the reaction solution was heated to room temperature. After 4 hours, the reaction solution was diluted with diethyl ether (20 mL) and the solution was washed with 5% aqueous sodium hydrogen carbonate solution (40 mL). Sodium sulfate was added to the organic layer, dried, filtered, and then t-butylhydroquinone (BHQ, 9.3 mg; 0.056 mmol) was added to the solution as a polymerization inhibitor. After concentrating this solution under reduced pressure, BHQ (20.4 mg; 0.123 mmol) was further added to the residue. The mixture is dissolved in warm ethyl acetate, cooled to room temperature, and the desired dimethacrylate represented by the following formula (5) (hereinafter, may be referred to as "dimethacrylate (5)") is collected as white crystals. Obtained at a rate of 59% (0.782 g; 1.76 mmol).

[Example 1]
0.455 g (1.00 mmol) of dimethacrylate (5) and 2,2'-azobisisobutyronitrile (3.3 mg; 0.02 mmol) were placed in a 50 mL eggplant-shaped flask to create an argon atmosphere. 8.0 mL of 1,4-dioxane was added thereto with a syringe to dissolve it. Methyl methacrylate (MMA) (0.602 g; 6.01 mmol) was added thereto with a syringe, and the mixture was polymerized by heating and stirring at 60 ° C. for 20 hours. No gelation or precipitation of the system was observed during the polymerization, suggesting that the polymerization proceeded without a cross-linking reaction. After the reaction, the solution was added dropwise to 100 mL of methanol, and the precipitated solid was suction-filtered and vacuum-dried to obtain a cyclized copolymer (hereinafter referred to as "copolymer-1") as a white solid (0.866 g, 83% yield).

The molecular weight of the obtained copolymer-1 by GPC was Mn = 12,000 (g / mol), Mw = 57,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 4.75. Tg was 184 ° C.
¹ The molar ratio of the structural unit derived from dimethacrylate (5) and the structural unit derived from methyl methacrylate in the copolymer-1 analyzed by 1 H-NMR (measurement solvent: deuterated chloroform, room temperature) is 1: It was 5.2 (Fig. 1). Since the Tg of polymethylmethacrylate having the same molecular weight is about 100 ° C., it was recognized that the Tg can be increased by 80 ° C. or higher by copolymerizing the monomer (1) according to the present invention.
^{In 1} H-NMR, the obtained copolymer-1 was confirmed to have burned out of the signal corresponding to the carbon-carbon double bond, and the copolymer-1 was soluble in various organic solvents at around room temperature. From this, it was found that adjacent methacrylate groups were continuously incorporated into the main chain to form a cyclized copolymer. In general, the cross-linking reaction proceeds during copolymerization with a bifunctional monomer, which affects the melt-molding processability, whereas the copolymer obtained in this system, in which the cross-linking reaction does not occur, has a melt-molding processability. There is no problem.

[Synthesis Example 4]
Dimethyl sulfoxide (DMF) (80 mL) was added to the triol (9.51 g; 46.6 mmol) and imidazole (8.50 g; 125 mmol) represented by the above formula (3) obtained in Synthesis Example 1 under an argon atmosphere. ， Stirred at room temperature. The obtained solution was cooled in an ice bath, and a DMF solution (20 mL) of t-butyldimethylchlorosilane (TBDMS-Cl) (9.05 g; 60.0 mmol) was slowly added dropwise thereto. After completion of the dropping, the ice bath was removed and the solution was stirred at room temperature for 24 hours. 20 mL of 5% aqueous sodium hydrogen carbonate was added thereto, the mixture was transferred to a separating funnel, 300 mL of aqueous 5% aqueous sodium hydrogen carbonate was further added, and the mixture was extracted twice with 200 mL of ethyl acetate. The combined organic layer was dehydrated with magnesium sulfate and filtered. When the filtrate was concentrated under reduced pressure, an orange liquid was obtained. This was fractionated by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/1). Fractions containing the desired product are combined and concentrated under reduced pressure, and the obtained solid is recrystallized from a mixed solvent (hexane / ethyl acetate = 5/1) to obtain a diol represented by the following formula (6) as white crystals. It was obtained in a yield of 49% (7.25 g; 22.8 mmol).

[Synthesis Example 5]
Monosilyldiol (5.01 g; 16.0 mmol), N, N-dimethyl-4-aminopyridine (DMAP) (195 mg; 1) obtained in Synthesis Example 4 under an argon atmosphere. .60 mmol), and dichloromethane (32 mL) was added to triethylamine (TEA) (7.0 mL; 53 mmol). The resulting solution was cooled in an ice bath and methacryloyl chloride (4.8 mL; 48 mmol) was slowly added dropwise. After completion of the dropping, the ice bath was removed and the solution was stirred at room temperature for 4 hours. The reaction solution was concentrated under reduced pressure, dissolved in 200 mL of ethyl acetate, transferred to a separating funnel, 400 mL of 5% aqueous sodium hydrogen carbonate was added to separate the solution, and the mixture was further extracted with 200 mL of ethyl acetate. Magnesium sulfate was added to the combined organic layer, dehydrated, and filtered. T-Butylhydroquinone (9.3 mg; 0.056 mmol) was added to the filtrate, and the solution was concentrated under reduced pressure to obtain a yellow liquid. This was fractionated by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3/1), fractions containing the desired product were collected and concentrated under reduced pressure to obtain a yellow viscous liquid. This is allowed to stand at 3 ° C. for 2 weeks, and the precipitated transparent crystals are suction-filtered while being washed with cooled hexane to form dimethacrylate represented by the following formula (7) (hereinafter referred to as “dimethacrylate (7)”). (Sometimes referred to as) was obtained in a yield of 64% (4.67 g; 10.3 mmol).

[Example 2]
Dimethacrylate (0.455 g; 1.00 mmol) represented by the above formula (7) obtained in Synthesis Example 5 was placed in a 50 mL eggplant-shaped flask to create an argon atmosphere. To this, 5.3 mL of N-methylpyrrolidone (NMP) was added with a syringe to dissolve it. To this, 0.64 mL (0.60 g; 6.0 mmol) of methyl methacrylate (MMA) was added with a syringe. Next, 2,2'-azobisisobutyronitrile (AIBN) (33 mg; 0.20 mmol) was taken in a sample tube, and 10 mL of NMP was added to prepare an AIBN solution. 1 mL of this AIBN solution was taken, added to the above-mentioned monomer solution, and heated and stirred at 65 ° C. for 24 hours. After 24 hours, the reaction solution was added dropwise to 70 mL of methanol, and the precipitated solid was suction-filtered and vacuum-dried to obtain a cyclized copolymer (hereinafter referred to as "copolymer-2") as a white solid (0). .989 g, yield 87%).

The molecular weight of the obtained copolymer-2 by GPC was Mn = 31,000 (g / mol), Mw = 59,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 1.9. Tg was 146 ° C.
¹ The molar ratio of the structural unit derived from dimethacrylate (7) and the structural unit derived from methyl methacrylate in the copolymer-2 analyzed by 1 H-NMR (measurement solvent: deuterated chloroform, room temperature) is 1: It was 7.1.

[Example 3]
In a 50 mL eggplant-shaped flask, 0.699 g of the copolymer-2 produced in Example 2 (1.54 mmol of silyl groups) and _{0.599 g of tetrabutylammonium fluoride trihydrate (TBAF ・ 3H 2} O). Was added to adjust the reaction system to an argon atmosphere. A mixed solution of 5.0 mL of tetrahydrofuran (THF) and 0.20 mL of acetic acid (AcOH) was added to this system with a syringe, and deprotection was performed by stirring at room temperature for 60 hours. After 60 hours, this solution was added dropwise to 100 mL of methanol to reprecipitate, and suction filtration gave a white solid. The obtained white solid was vacuum dried for 1 day to obtain a desilylated copolymer (hereinafter referred to as "copolymer-3") (0.5874 g, yield 99%).

The molecular weight of the obtained copolymer-3 by GPC was Mn = 36,000 (g / mol), Mw = 64,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 1.8. Tg was 164 ° C.
¹ Molar ratio of structural units derived from dimethacrylate (7) in copolymer-3 to structural units derived from methyl methacrylate, analyzed by 1 H-NMR (measurement solvent: dimethyl sulfoxide-d _{6, room temperature).} Was 1: 6.1.

The reaction formulas of Example 2 and Example 3 are as follows.

[Example 4]
In Example 2, the same operation as in Example 2 was carried out except that the amount of MMA charged was 0.32 mL (0.30 g; 3.0 mmol), and the cyclized copolymer (hereinafter referred to as “copolymer-4”” was carried out. Was obtained as a white solid (0.734 g, yield 97%).

The molecular weight of the obtained copolymer-4 by GPC was Mn = 38,600 (g / mol), Mw = 78,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 2.0. Tg was 179 ° C.
¹ The molar ratio of the structural unit derived from dimethacrylate (7) and the structural unit derived from methyl methacrylate in the copolymer-4 analyzed by 1 H-NMR (measurement solvent: deuterated chloroform, room temperature) is 1: It was 3.0.

[Example 5]
In a 50 mL eggplant-shaped flask, 0.37 g of the copolymer-4 produced in Example 4 (1.54 mmol of silyl groups) and _{0.50 g of tetrabutylammonium fluoride trihydrate (TBAF ・ 3H 2} O). Was added to adjust the reaction system to an argon atmosphere. A mixed solution of 4.2 mL of tetrahydrofuran and 0.17 mL of acetic acid was added to this system with a syringe, and the mixture was stirred at room temperature for 60 hours for deprotection. After 60 hours, this solution was added dropwise to 100 mL of methanol to reprecipitate, and suction filtration gave a white solid. The obtained white solid was vacuum dried for 1 day to obtain a desilylated copolymer (hereinafter referred to as "copolymer-5") (0.3212 g, yield 97%).

The molecular weight of the obtained copolymer-5 by GPC was Mn = 44,000 (g / mol), Mw = 91,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 2.1. Tg was 204 ° C.
¹ Molar ratio of the structural unit derived from dimethacrylate (7) in the copolymer-5 and the structural unit derived from methyl methacrylate analyzed by 1 H-NMR (measurement solvent: dimethyl sulfoxide-d _{6, room temperature).} Was 1: 2.9.

[Synthesis Example 6]
Under an argon atmosphere, the triol (2.05 g; 10.0 mmol) represented by the above formula (3) and N, N-dimethyl-4-aminopyridine (DMAP) (17.0 mg; 0) obtained in Synthesis Example 1 Pyridine (50 mL) was added to (.139 mmol), and pivaloyl chloride (1.5 mL; 12 mmol) was slowly added dropwise thereto. After completion of the dropping, the solution was stirred at 80 ° C. for 20 hours. 20 mL of water was added thereto, the mixture was transferred to a separating funnel, 100 mL of dilute hydrochloric acid was further added, and the mixture was extracted twice with 50 mL of ethyl acetate. The combined organic layer was dehydrated with magnesium sulfate and filtered. When the filtrate was concentrated under reduced pressure, a white solid was obtained. This was fractionated by silica gel chromatography (developing solvent: hexane / ethyl acetate = 2/1). The fractions containing the desired product were combined, concentrated under reduced pressure, and vacuum dried to obtain a diol represented by the following formula (8) as a white solid in a yield of 80% (2.30 g; 7.97 mmol).

[Synthesis Example 7]
Monoesterdiol (4.39 g; 15.2 mmol), N, N-dimethyl-4-aminopyridine (DMAP) (190 mg; 1) obtained in Synthesis Example 6 under an argon atmosphere. .60 mmol), and dichloromethane (30 mL) was added to triethylamine (TEA) (8.4 mL; 60 mmol). The resulting solution was cooled in an ice bath and methacryloyl chloride (4.4 mL; 45 mmol) was slowly added dropwise. After completion of the dropping, the ice bath was removed and the solution was stirred at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, dissolved in 50 mL of ethyl acetate, transferred to a separating funnel, 250 mL of water was added to separate the liquid, and the mixture was further extracted with 200 mL of ethyl acetate. Magnesium sulfate was added to the combined organic layer, dehydrated, and filtered. The filtrate was concentrated under reduced pressure to give a white solid. This was fractionated by silica gel chromatography (developing solvent: hexane / ethyl acetate = 2/1), fractions containing the desired product were collected and concentrated under reduced pressure to obtain a white solid. When this solid was dissolved in 10 mL of ethyl acetate, 7 mL of hexane was added thereto, and the mixture was allowed to stand, dimethacrylate represented by the following formula (9) (hereinafter, may be referred to as "dimethacrylate (9)") was obtained. It was obtained as a colorless crystal in a yield of 60% (3.79 g; 8.94 mmol).

[Example 6]
Dimethacrylate (0.430 g; 1.01 mmol) and AIBN (26 mg; 0.16 mmol) represented by the above formula (9) obtained in Synthesis Example 7 were placed in a 100 mL eggplant-shaped flask to create an argon atmosphere. .. 1,4-Dioxane (50 mL) was added thereto with a syringe to prepare a solution. MMA (0.595 g; 5.9 mmol) was added thereto with a syringe, and the mixture was heated and stirred at 60 ° C. for 20 hours. When the reaction solution was added dropwise to 50 mL of methanol, a white solid was precipitated. The supernatant was removed by decantation, and the remaining white solid was vacuum dried to obtain a cyclized copolymer (hereinafter referred to as "copolymer-6") (0.459 g, yield 45%).

The molecular weight of the obtained copolymer-6 by GPC was Mn = 22,000 (g / mol), Mw = 30,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 1.4. Tg was 152 ° C.
¹ The molar ratio of the structural unit derived from dimethacrylate (9) and the structural unit derived from methyl methacrylate in the copolymer-6 analyzed by 1 H-NMR (measurement solvent: deuterated chloroform, room temperature) is 1: It was 5.0.

[Example 7]
Dimethacrylate (0.425 g; 1.00 mmol) and AIBN (17 mg, 0.10 mmol) represented by the above formula (9) obtained in Synthesis Example 7 were placed in a 100 mL eggplant-shaped flask to create an argon atmosphere. .. 1,4-Dioxane (31 mL) was added thereto with a syringe to prepare a solution. MMA (0.301 g, 3.0 mmol) was added thereto with a syringe, and the mixture was heated and stirred at 60 ° C. for 20 hours. The reaction solution was added dropwise to 20 mL of methanol, and the precipitated solid was suction-filtered and vacuum-dried to obtain a cyclized copolymer (hereinafter referred to as "copolymer-7") as a white solid (0.155 g, 21% yield).

The molecular weight of the obtained copolymer-7 by GPC was Mn = 15,000 (g / mol), Mw = 22,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 1.5. Tg was 175 ° C.
¹ The molar ratio of the structural unit derived from dimethacrylate (9) and the structural unit derived from methyl methacrylate in the copolymer-7 analyzed by 1 H-NMR (measurement solvent: deuterated chloroform, room temperature) is 1: It was 2.9.

[Synthesis Example 8]
Under an argon atmosphere, the triol (0.51 g; 2.5 mmol) represented by the above formula (3) and N, N-dimethyl-4-aminopyridine (DMAP) (3.1 mg; 0) obtained in Synthesis Example 1 Pyridine (12.5 mL) was added to .025 mmol), and cyclohexanecarbonyl chloride (0.41 mL; 3.0 mmol) was slowly added dropwise thereto. After completion of the dropping, the solution was stirred at 80 ° C. for 20 hours. 5 mL of water was added thereto, the mixture was transferred to a separating funnel, 30 mL of dilute hydrochloric acid was further added, and the mixture was extracted twice with 15 mL of ethyl acetate. The combined organic layer was dehydrated with magnesium sulfate and filtered. When the filtrate was concentrated under reduced pressure, a white solid was obtained. This was performed twice by silica gel chromatography (1st time: developing solvent: hexane / ethyl acetate / dichloromethane = 25/25/1, 2nd time: developing solvent: hexane / ethyl acetate = 3/1 → hexane / ethyl acetate / dichloromethane = Fractionation was performed according to 25/25/1). The fractions containing the desired product were combined, concentrated under reduced pressure, and vacuum dried to obtain a diol represented by the following formula (10) as a white solid in a yield of 76% (0.603 g; 1.92 mmol).

[Synthesis Example 9]
Under an argon atmosphere, the diol represented by the above formula (10) obtained in Synthesis Example 8 (0.316 g; 1.01 mmol), N, N-dimethyl-4-aminopyridine (DMAP) (13.0 mg; 0). .10 mmol) and TEA (0.56 mL; 4.0 mmol) with dichloromethane (2.0 mL). The resulting solution was cooled in an ice bath and methacryloyl chloride (0.30 mL; 3.1 mmol) was slowly added dropwise. After completion of the dropping, the ice bath was removed and the solution was stirred at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, dissolved in 5 mL of ethyl acetate, transferred to a separating funnel, 30 mL of water was added to separate the liquid, and the mixture was further extracted with 25 mL of ethyl acetate. Magnesium sulfate was added to the combined organic layer, dehydrated, and filtered. The filtrate was concentrated under reduced pressure to give a white solid. This was fractionated by silica gel chromatography (developing solvent: hexane / ethyl acetate = 2/1), fractions containing the desired product were collected and concentrated under reduced pressure to obtain a white solid 8. When this solid was dissolved in 0.5 mL of ethyl acetate, 2.1 mL of hexane was added thereto, and the mixture was allowed to stand, it may be referred to as dimethacrylate represented by the following formula (11) (hereinafter referred to as "dimethacrylate (11)"). (Yes) was obtained as colorless crystals in a yield of 49% (0.22 g; 0.49 mmol).

[Example 8]
Dimethacrylate (0.4518 g; 1.00 mmol) and AIBN (17 mg; 0.10 mmol) represented by the above formula (11) obtained in Synthesis Example 9 were placed in a 100 mL eggplant-shaped flask to create an argon atmosphere. .. 31 mL of 1,4-dioxane was added thereto with a syringe to dissolve it. MMA (0.306 g; 3.1 mmol) was added thereto with a syringe, and the mixture was heated and stirred at 60 ° C. for 20 hours. After 20 hours, the reaction solution was added dropwise to 20 mL of methanol, and the precipitated solid was suction-filtered and vacuum-dried to obtain a cyclized copolymer (hereinafter referred to as "copolymer-8") as a white solid (0). .4698 g, yield 61%).

The molecular weight of the obtained copolymer-8 by GPC was Mn = 12,000 (g / mol), Mw = 21,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 1.8. Tg was 170 ° C.
¹ The molar ratio of the structural unit derived from dimethacrylate (11) and the structural unit derived from methyl methacrylate in the copolymer-8 analyzed by 1 H-NMR (measurement solvent: deuterated chloroform, room temperature) is 1: 1. It was 2.2.

[Example 9]
Dimethacrylate (0.4510 g; 1.00 mmol) and AIBN (27 mg; 0.16 mmol) represented by the above formula (11) obtained in Synthesis Example 9 were placed in a 100 mL eggplant-shaped flask to create an argon atmosphere. .. 31 mL of 1,4-dioxane was added thereto with a syringe to dissolve it. MMA (0.607 g; 6.1 mmol) was added thereto with a syringe, and the mixture was heated and stirred at 60 ° C. for 20 hours. After 20 hours, the reaction solution was added dropwise to 20 mL of methanol, and the precipitated solid was suction-filtered and vacuum-dried to obtain a cyclized copolymer (hereinafter referred to as "copolymer-9") as a white solid (0). .6979 g, yield 64%).

The molecular weight of the obtained copolymer-9 by GPC was Mn = 12,000 (g / mol), Mw = 17,000 (g / mol), and the molecular weight distribution (Mw / Mn) = 1.4. Tg was 138 ° C.
¹ The molar ratio of the structural unit derived from dimethacrylate (11) and the structural unit derived from methyl methacrylate in the copolymer-9 analyzed by 1 H-NMR (measurement solvent: deuterated chloroform, room temperature) is 1: It was 4.6.

The copolymer of the present invention has excellent heat resistance and also excellent melt molding processability, and the molded product can be suitably used particularly for applications such as films, lenses, disks, and optical transmission materials. ..

Claims (12)

A copolymer of a monomer represented by the following formula (1) (hereinafter referred to as "monomer (1)") and a vinyl-based monomer different from the monomer (1).

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. Q ¹ is a trivalent group or 3 which may contain a hetero atom having 1 to 20 carbon atoms. It indicates a valence atom. Z indicates a non-polymerizable hydrocarbon group which may contain a hydrogen atom, a hydroxyl group, or a heteroatom having 1 to 20 carbon atoms.) The copolymer according to claim 1, wherein the monomer (1) is a compound represented by the following (2).

(In the formula (2), Q ² represents an atom of Group 14 of the periodic table. R ¹ , R ² , and Z are synonymous with those in the above formula (1). R ³ is a hydrogen atom or the number of carbon atoms. Indicates a hydrocarbon group that may contain 1 to 19 heteroatoms.) ^{The copolymer according to claim 2, wherein Q 2} is a carbon atom or a silicon atom in the formula (2). The copolymer according to claim 3, ^{wherein Q 2} is a carbon atom in the formula (2). The copolymer according to any one of claims 2 to 4, wherein ^{R 3} is a hydrogen atom or a methyl group in the formula (2). The copolymer according to any one of claims 1 to 5, wherein Z is represented by the following formula (X).
YO- (X)
(In formula (X), Y represents a hydrogen atom or a non-polymerizable hydrocarbon group that may contain a heteroatom having 1 to 20 carbon atoms.) In the formula (X), the non-polymerizable hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms is a hydrocarbon group (-R) or a hydrocarbon-substituted carbonyl group having 1 to 20 carbon atoms. (-C (= O) -R) , hydrocarbon-substituted oxycarbonyl group (-C (= O) -OR) , hydrocarbon tri-substituted silyl group (-Si (-R) ₃ ). The copolymer according to claim 6 (where R represents a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and an alkyl group having 4 to 15 carbon atoms. Three Rs of a hydrocarbon trisubstituted silyl group. May be the same or different.) The copolymer according to any one of claims 1 to 7, wherein the monomer (1) is derived from myo-inositol. The copolymer according to any one of claims 1 to 8, wherein the vinyl-based monomer is a (meth) acrylic acid ester. A copolymer containing a structural unit represented by the following formula (A) and a structural unit represented by the following formula (B), and the structural unit and formula represented by the formula (A) in the copolymer. A copolymer having a molar ratio of structural units represented by (B) of 1: 1 to 1: 1000.

(In formulas (A) and (B), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. Z is a hydrogen atom, a hydroxyl group, or a hetero with 1 to 20 carbon atoms. Indicates a non-polymerizable hydrocarbon group that may contain an atom.) The copolymer according to claim 10, wherein Z is represented by the following formula (X) in the formula (A).
YO- (X)
(In formula (X), Y represents a hydrogen atom or a non-polymerizable hydrocarbon group that may contain a heteroatom having 1 to 20 carbon atoms.) Wherein (A), a hydrocarbon group of non-polymerizable may contain a hetero atom having 1 to 20 carbon atoms, having 1 to 20 carbon atoms, a hydrocarbon group (-R), hydrocarbon substituted carbonyl group ( It is characterized by having -C (= O) -R) , a hydrocarbon-substituted oxycarbonyl group (-C (= O) -OR) , and a hydrocarbon trisubstituted silyl group (-Si (-R) ₃ ). The copolymer according to claim 11 (where R represents a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and an alkyl group having 4 to 15 carbon atoms. The three Rs of the hydrocarbon trisubstituted silyl group are It may be the same or different.)

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