JP5564824B2 - Anthracene-9,10-diether compound, process for producing the same, and polymer thereof - Google Patents

Description

The present invention relates to an anthracene-9,10-diether compound useful as a high refractive index material, a production method thereof and a polymer thereof.

At present, plastic is actively used as a glass substitute material in the field of optical lenses. For example, polycarbonate and polymethyl methacrylate are well known. These plastic materials have lightness, safety, and design, but have a drawback that they are lower in refractive index than inorganic glass and easily become thick. Thus, in recent years, there has been an increasing demand for high refractive index plastic materials. In particular, high-refractive-index plastic materials have made significant progress in optical products, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, TFT prism lens sheets, aspheric lenses, optical disks, holograms, and optical fibers. Application studies to optical waveguides and the like have been actively conducted.

As a method for increasing the refractive index of an organic compound, it is already well known that it is useful to introduce a halogen atom (excluding fluorine) or a sulfur atom into the molecular structure. For example, a high refractive index polymer in which a halogen atom is introduced into a biphenyl skeleton using a high intrinsic refractive index of a halogen atom has been reported (Patent Document 1). However, due to halogenation, the light resistance is remarkably deteriorated and the specific gravity is high.
A monomer composition having a sulfur atom exhibiting a high intrinsic refractive index in addition to halogen has also been reported (Patent Document 2). However, although they have a high refractive index and excellent impact resistance, the light resistance of the obtained polymer is remarkably inferior, and unpleasant odor peculiar to sulfur has a problem.

On the other hand, a polymer of an acrylate compound having an aromatic skeleton is known to have a higher refractive index than a polymer of an alicyclic acrylate, and as a raw material for obtaining a polymer having a high refractive index, for example, phenyl There is a report example about a phenoxyethyl acrylate compound having a group (Patent Document 3). These acrylate compounds having an aromatic skeleton are light, excellent in transparency, and have a well-balanced high refractive index material (Patent Document 4, etc.). As an aromatic ring to be introduced, a biphenyl ring has a higher refractive index than a benzene ring. And also about the acrylate which has a naphthalene skeleton, there are some report examples as a high refractive index compound (patent documents 5 and 6). In addition, it is known that by introducing a ring having a higher degree of condensation or a polycyclic ring, a material having a higher refractive index can be obtained. Introduction of a fluorene skeleton or the like (Patent Document 7) or an anthracene skeleton (Patent Document 8) has been studied.

However, there are few reports on a polymerizable compound having an anthracene skeleton that is expected to have a higher refractive index and a polymer thereof. For example, 9-vinylanthracene has been proposed as an anthracene compound having a radically polymerizable group, but this compound does not undergo polymerization or copolymerization at all by a general radical polymerization method, or has a very low polymerization rate. . For this reason, an example of polymerization using a special metal salt catalyst such as an organoaluminum hydride has been reported (Patent Document 9).

On the other hand, examples of using an acrylate compound having an anthracene skeleton as a photopolymerization sensitizer have recently been reported (Patent Documents 10 and 11), but the document describes the effect as a photopolymerization sensitizer. However, there is no description regarding use as a polymer synthesis raw material having a high refractive index. Further, a compound in which an acrylate group is bonded to an anthracene skeleton via an ethylene oxide bond is disclosed, and it is shown that the polymer has a high refractive index (Patent Document 12). Thus, there is a demand for a polymer raw material having excellent coating film performance of the polymer to be produced.

JP 05-170702 A JP 2002-20433 A Special table 2003-144538 gazette JP 2003-064296 A JP 2001-276687 A JP 2008-81682 A JP 2004-083855 A JP 2006-312709 A Japanese Patent No. 02507889 JP 2007-99637 A JP 2007-204438 A JP 2009-40811 A

Accordingly, an object of the present invention is to provide a high refractive index acrylate compound having an anthracene skeleton and having radical polymerizability, and a polymer thereof.

In order to solve the above problems, the present inventor has intensively studied the structure and polymerizability of an anthracene compound having an acrylic group, and as a result, an anthracene-9,10-diether compound represented by the following general formula (1) is a polymerization initiator. The present invention has been completed by finding that it easily undergoes radical polymerization in the presence of the polymer and that the resulting polymer exhibits a high refractive index.

That is, the gist of the present invention is the gist of the following.

The first gist of the present invention resides in a novel anthracene-9,10-diether compound represented by the following general formula (1).

In the general formula (1), one of Z ¹ and Z ² represents a hydrogen atom, the other represents a (meth) acryloyl group, one of Z ³ and Z ⁴ represents a hydrogen atom, and the other represents (meth) Represents an acryloyl group, R ¹ represents a hydrogen atom or a methyl group, X and Y may be the same or different, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, Represents any of the arylthio groups

The second gist of the present invention is to produce an anthracene-9,10-diether compound represented by the above general formula (1), which comprises reacting an anthracene-9,10-diglycidyl ether compound with (meth) acrylic acid. Lies in the way.

The third aspect of the present invention is represented by the above general formula (1), which comprises using a quaternary onium salt as a catalyst when an anthracene-9,10-diglycidyl ether compound is reacted with (meth) acrylic acid. It exists in the manufacturing method of anthracene-9,10-diether compound.

The fourth gist of the present invention resides in a radical polymerizable composition containing an anthracene-9,10-diether compound represented by the general formula (1) and a radical polymerization initiator.

The fifth gist of the present invention resides in a polymer obtained by polymerizing an anthracene-9,10-diether compound represented by the general formula (1) in the presence of a radical polymerization initiator.

The sixth gist of the present invention is a polymer obtained by copolymerizing an anthracene-9,10-diether compound and a radical polymerizable monomer other than the anthracene-9,10-diether compound in the presence of a radical polymerization initiator. Exist.

The seventh gist of the present invention resides in the polymer described above, wherein the radical polymerization initiator is a thermal radical polymerization initiator.

The eighth gist of the present invention resides in the above polymer, wherein the radical polymerization initiator is a photo radical polymerization initiator.

A ninth aspect of the present invention resides in a high refractive index material containing the polymer described in the fifth aspect to the eighth aspect.

In the description of the present invention, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl.

The anthracene-9,10-diether compound of the present invention is a novel compound, which is easily polymerized in the presence of a radical polymerization initiator, and the polymer obtained by polymerization is industrially useful for showing a high refractive index. Compound.

The anthracene-9,10-diether compound of the present invention is a novel compound having the structure described in the following general formula (1). In the general formula (1), one of Z ¹ and Z ² represents a hydrogen atom. The other represents a (meth) acryloyl group, one of Z ³ and Z ⁴ represents a hydrogen atom, the other represents a (meth) acryloyl group, R ¹ represents a hydrogen atom or a methyl group, and X and Y are They may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

The anthracene-9,10-diether compound represented by the general formula (1) has the following isomers. That is, the case where Z ¹ and Z ³ are (meth) acryloyl groups and Z ² and Z ⁴ are hydrogen atoms is an anthracene-9,10-diether compound represented by the following general formula (2). .

In the general formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and the types of substituents represented by X and Y are the same as those in the general formula (1).

Further, a ^{Z 1} and ^{Z 4} is (meth) acryloyl group, if ^{Z 2} and ^{Z 3} is a hydrogen atom is 9,10 diether compound represented by the following general formula (3).

In the general formula (3), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and the types of substituents represented by X and Y are the same as in the general formula (1).

Furthermore, when Z ¹ and Z ³ are hydrogen atoms and Z ² and Z ⁴ are (meth) acryloyl groups, an anthracene-9,10-diether compound represented by the following general formula (4): is there.

In the general formula (4), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and the types of substituents represented by X and Y are the same as those in the general formula (1).

In the general formulas (1) to (4), the alkyl group represented by X or Y includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- Examples include butyl group, amyl group, 2-ethylhexyl group, 4-methylpentyl, 4-methyl-3-pentenyl group, and the halogen atom represented by X or Y is fluorine atom, chlorine atom, bromine atom, iodine Examples of the alkoxy group represented by X or Y include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and a hexyloxy group, and an aryloxy group represented by X or Y. Examples of the group include a phenoxy group, a p-tolyloxy group, an o-tolyloxy group, and naphthyloxy. The alkylthio group represented by X or Y includes a methylthio group, ethyl A thio group, a propylthio group, a butylthio group, a hexylthio group, etc. are mentioned. As the arylthio group represented by X or Y, a phenylthio group, an o-tolylthio group, an m-tolylthio group, a p-tolylthio group, a p-hydroxyphenyl group. A thio group etc. are mentioned.

Examples of the anthracene-9,10-diether compound represented by the general formula (1) include the following. That is, anthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether represented by the general formula (2), anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether Anthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyloxypropyl) ether represented by the general formula (3), anthracene-9- (3-methacryloyloxy) -2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, anthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether represented by the general formula (4) Anthracene-9,10-bis (3-hydroxy-2 Methacryloyloxypropyl) is ether.

Further, examples of the compound in which an anthracene skeleton of the anthracene-9,10-diether compound is substituted with an alkyl group include 2-methylanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2- Methyl anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-methylanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyl) Oxypropyl) ether, 2-methylanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-methylanthracene-9,10-bis ( 3-hydroxy-2-act Royloxypropyl) ether, 2-methylanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2-ethylanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) Ether, 2-ethylanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-ethylanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy 2-acryloyloxypropyl) ether, 2-ethylanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-ethylanthracene-9, 10-bis 3-hydroxy-2-acryloyloxypropyl) ether, 2-ethylanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2- (t-butyl) anthracene-9,10-bis ( 3-acryloyloxy-2-hydroxypropyl) ether, 2- (t-butyl) anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2- (t-butyl) anthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyloxypropyl) ether, 2- (t-butyl) anthracene-9- (3-methacryloyloxy-2-hydroxypropyl)- 10- (3-hydroxy-2-methacryloyloxyp (Lopyl) ether, 2- (t-butyl) anthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2- (t-butyl) anthracene-9,10-bis (3-hydroxy-) 2-methacryloyloxypropyl) ether, 2,6-dimethylanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2,6-dimethylanthracene-9,10-bis (3-methacryloyloxy) -2-hydroxypropyl) ether, 2,6-dimethylanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyloxypropyl) ether, 2,6-dimethylanthracene -9- (3-methacryloyloxy-2-hydro Cypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2,6-dimethylanthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2,6-dimethylanthracene- 9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether and the like can be mentioned.

Furthermore, examples of the compound in which the halogen atom is substituted on the anthracene skeleton of the anthracene-9,10-diether compound include 2-chloroanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2- Chloroanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-chloroanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyl) Oxypropyl) ether, 2-chloroanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-chloroanthracene-9,10-bis ( 3-hydroxy-2-a Liloyloxypropyl) ether, 2-chloroanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2-fluoroanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ) Ether, 2-fluoroanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-fluoroanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3- Hydroxy-2-acryloyloxypropyl) ether, 2-fluoroanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-fluoroanthracene-9 10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2-fluoroanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2-bromoanthracene-9,10-bis ( 3-acryloyloxy-2-hydroxypropyl) ether, 2-bromoanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-bromoanthracene-9- (3-acryloyloxy-2- Hydroxypropyl) -10- (3-hydroxy-2-acryloyloxypropyl) ether, 2-bromoanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) )ether, 2-bromoanthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2-bromoanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2,6- Dichloroanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2,6-dichloroanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2,6- Dichloroanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyloxypropyl) ether, 2,6-dichloroanthracene-9- (3-methacryloyloxy-2-hydroxy Propyl) -10- (3-hydro Cy-2-methacryloyloxypropyl) ether, 2,6-dichloroanthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2,6-dichloroanthracene-9,10-bis (3- Hydroxy-2-methacryloyloxypropyl) ether and the like.

Furthermore, examples of the compound in which an anthracene skeleton of the anthracene-9,10-diether compound is substituted with an alkoxy group include 2-methoxyanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2- Methoxyanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-methoxyanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyl) Oxypropyl) ether, 2-methoxyanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-methoxyanthracene-9,10-bis ( 3-hydroxy 2-acryloyloxypropyl) anthracene, 2-methoxyanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2-ethoxyanthracene-9,10-bis (3-acryloyloxy-2-) Hydroxypropyl) ether, 2-ethoxyanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-ethoxyanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- ( 3-hydroxy-2-acryloyloxypropyl) ether, 2-ethoxyanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-ethoxy Nthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2-ethoxyanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2-butoxyanthracene-9, 10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2-butoxyanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-butoxyanthracene-9- (3-acryloyl) Oxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyloxypropyl) ether, 2-butoxyanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2 -Methacryloyl Xylpropyl) ether, 2-butoxyanthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2-butoxyanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2,6-dimethoxyanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2,6-dimethoxyanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2,6-dimethoxyanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyloxypropyl) ether, 2,6-dimethoxyanthracene-9- (3-methacryloyloxy) -2-Hyd Xylpropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2,6-dimethoxyanthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2,6-dimethoxyanthracene- 9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether and the like can be mentioned.

Further, examples of the compound in which the anthracene skeleton of the anthracene-9,10-diether compound is substituted with an aryloxy group include 2-phenoxyanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2 -Phenoxyanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-phenoxyanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2- (Acryloyloxypropyl) ether, 2-phenoxyanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-phenoxyanthracene-9,10-bis 3-hydroxy-2-acryloyloxy propyl) ether, 2-phenoxy-9,10-bis (3-hydroxy-2-methacryloyloxy propyl) ether, and the like.

Further, examples of the compound in which the anthracene skeleton of the anthracene-9,10-diether compound is substituted with an alkylthio group include 2-methylthioanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2- Methylthioanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-methylthioanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-acryloyl) Oxypropyl) ether, 2-methylthioanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-methylthioanthracene-9,10-bis ( -Hydroxy-2-acryloyloxypropyl) ether, 2-methylthioanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, 2-ethylthioanthracene-9,10-bis (3-acryloyloxy) -2-hydroxypropyl) ether, 2-ethylthioanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-ethylthioanthracene-9- (3-acryloyloxy-2-hydroxypropyl) ) -10- (3-hydroxy-2-acryloyloxypropyl) ether, 2-ethylthioanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) A , 2-ethylthioanthracene-9,10-bis (3-hydroxy-2-acryloyloxypropyl) ether, 2-ethylthioanthracene-9,10-bis (3-hydroxy-2-methacryloyloxypropyl) ether, etc. Is mentioned.

Further, examples of the compound in which the anthracene skeleton of the anthracene-9,10-diether compound is substituted with an arylthio group include 2-phenylthioanthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, 2 -Phenylthioanthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, 2-phenylthioanthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (3-hydroxy- 2-acryloyloxypropyl) ether, 2-phenylthioanthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (3-hydroxy-2-methacryloyloxypropyl) ether, 2-phenylthioanthracene-9 , 1 - bis (3-hydroxy-2-acryloyloxy propyl) ether, 2-phenylthiomethyl-9,10-bis (3-hydroxy-2-methacryloyloxy propyl) ether, and the like.

Among the anthracene-9,10-diether compounds exemplified above, anthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether (compound of the following structural formula (5)), anthracene-9,10 -Bis (3-methacryloyloxy-2-hydroxypropyl) ether (compound of the following structural formula (6)) is preferable from the viewpoint of easy synthesis.

[Production method]
The anthracene-9,10-diether compound of the present invention represented by the general formula (1) is obtained by reacting a 9,10-dihydroxyanthracene compound with an epihalohydrin in the presence of a basic compound. A second reaction of the anthracene-9,10-diglycidyl ether compound represented by the first reaction, and an anthracene-9,10-diglycidyl ether compound obtained by the first reaction is further reacted with acrylic acid or methacrylic acid. It can be obtained from the reaction.

The 9,10-dihydroxyanthracene compound used as a raw material in the first reaction includes 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2-ethyl-9,10-dihydroxyanthracene, 2- (t -Butyl) -9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dimethoxyanthracene, 2-fluoro-9,10-dimethoxyanthracene, 2-bromo- 9,10-dimethoxyanthracene, 2,6-dichloro-9,10-dihydroxyanthracene, 2-methoxy-9,10-dihydroxyanthracene, 2-ethoxy-9,10-dihydroxyanthracene, 2-phenoxy-9,10- Dihydroxyanthracene, - methylthio-9,10-dihydroxy anthracene, 2-ethylthio-9,10-dihydroxy anthracene, 2-phenylthio-9,10-dihydroxy anthracene, and the like.

Examples of the epihalohydrin compound include epichlorohydrin, 2-methylepichlorohydrin, epibromohydrin, 2-methylepibromohydrin, and the like. The epihalohydrin compound is added in 2 mol times to 4 mol times with respect to the 9,10-dihydroxyanthracene compound. More preferably, it is added from 2.0 mole times to 2.4 mole times. If it is less than 2 mole times, unreacted 9,10-dihydroxyanthracene compound remains, which is not preferable. Moreover, when the addition amount of an epihalohydrin is excessive, for example, when adding more than 4 mol times, the purity of a product will fall and it is similarly not preferable.

Examples of the basic compound include organic bases such as trimethylamine, triethylamine, and pyridine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and sodium carbonate. The addition amount of the basic compound is desirably 2 to 3 times the molar amount of the 9,10-dihydroxyanthracene compound. The reaction is usually performed in the presence of a solvent. Solvents used include alcohol solvents such as water, methanol, ethanol, n-propyl alcohol, ethylene glycol and dimethoxyethanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, benzene, toluene, xylene and chlorobenzene. Aromatic solvents, halogen solvents such as dichloromethane, dichloroethane and dichloroethylene, ether solvents such as tetrahydrofuran and 1,4-dioxane, and amide solvents such as dimethylformamide and dimethylacetamide are used.

The reaction temperature is preferably 40 ° C. or higher and 120 ° C. or lower. If it is less than 40 ° C., the reaction is slow, and if it exceeds 120 ° C., by-products due to side reactions increase, which is not preferable. The reaction time depends on the reaction temperature, but is usually 0.5 to 2 hours.

In this way, anthracene-9,10-diether represented by the general formula (1) is obtained by a second reaction in which the anthracene-9,10-diglycidyl ether compound obtained in the first reaction is reacted with acrylic acid or methacrylic acid. Can be compounded.

The anthracene-9,10-diether compound represented by the general formula (1) of the present invention can be obtained by an addition reaction between an anthracene-9,10-diglycidyl ether compound and (meth) acrylic acid.

Generally, a basic catalyst is used in the addition reaction of a glycidyl compound and (meth) acrylic acid. As the catalyst used, for example, organic bases such as triethylamine and dibutylamine are known. JP-A-59-70642 discloses that a quaternary ammonium salt has a catalytic effect in the addition reaction of glycidylphenoxyphenyl ether and (meth) acrylic acid.

As a result of intensive studies on the effects of these catalysts in the addition reaction of (anthracene-9,10-diglycidyl ether compound used in this reaction with (meth) acrylic acid, from the viewpoint of both activity and selectivity, quaternary ammonium salts and quaternary salts are obtained. We found that phosphonium salts are suitable for this reaction. Examples of the quaternary ammonium salt include tetrabutylammonium bromide, tetraethylammonium bromide, benzyltrimethylammonium bromide, and benzyltriethylammonium bromide. Examples of the quaternary phosphonium salt include tributylmethylphosphonium iodide, tributyloctylphosphonium bromide, And tributylhexadecylphosphonium bromide.

The amount of the quaternary ammonium salt and / or quaternary phosonium salt used is preferably 0.5 mol% or more and 50 mol% or less with respect to the anthracene-9,10-diglycidyl ether compound. More preferably, it is 1 mol% or more and 20 mol% or less. If it is less than 0.5 mol%, the reaction rate is slow and it takes too much reaction time. If it exceeds 20 mol%, the purity of the product becomes low, which is not preferable.

Examples of the solvent used in the addition reaction of (meth) acrylic acid to the anthracene-9,10-diglycidyl ether compound include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, toluene, xylene, chlorobenzene, and the like. Various solvents such as aromatic solvents, ether solvents such as tetrahydrofuran and 1,4-dioxane are used.

The amount of (meth) acrylic acid added to the anthracene-9,10-diglycidyl ether compound is preferably 2 mol times or more and 10 mol times or less. More preferably, it is 2.1 mol times or more and 4 mol times or less. If it is less than 2 mol times, an unreacted anthracene-9,10-diglycidyl ether compound remains, and if it exceeds 4 mol times, a by-product tends to be formed, which is not preferable.

The reaction temperature is preferably 50 ° C to 150 ° C. More preferably, it is in the range of 70 ° C to 120 ° C. If it is less than 50 ° C., it takes too much reaction time, and if it exceeds 150 ° C., polymerization of (meth) acrylic acid proceeds, which is not preferable.

The reaction is preferably carried out in a nitrogen atmosphere. Under an air atmosphere, the reaction solution is easily colored, and the color tone of the product is deteriorated.

In the reaction, a polymerization inhibitor may be present in order to prevent polymerization of (meth) acrylic acid or the product. As the polymerization inhibitor, 4-methoxyphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) or the like is used. The addition amount of the polymerization inhibitor is preferably 0.05 to 5% by weight with respect to (meth) acrylic acid.

After completion of the reaction, an extraction solvent such as ethyl acetate is added and then washed with a saturated aqueous solution of sodium bicarbonate to remove excess (meth) acrylic acid. Next, after washing with water, the solvent is distilled off to obtain a high-purity target product as a mixture of three isomers of the general formulas (2) to (4).

Each of the obtained isomer mixtures can be isolated by recrystallization or separation and purification by silica gel column chromatography or the like. These structural isomers can be converted into a polymer by the polymerization reaction described later as a single compound that has been separated and purified, but can easily cause a polymerization reaction even in a mixture to obtain a polymer having a desired high refractive index. Can do.

The obtained compound was identified using an infrared spectrum, a mass spectrum, and a ¹ H-NMR spectrum, and it was confirmed that these compounds were anthracene-9,10-diether compounds represented by the general formula (1). .

[Polymerization reaction]
The anthracene-9,10-diether compound represented by the general formula (1) thus obtained has two acrylate groups which are polymerizable groups, and initiates radical polymerization such as thermal decomposition type, redox decomposition type, and photodecomposition type. In the presence or absence of the agent, polymerization can be performed by applying thermal energy, active energy rays such as ultraviolet rays, electron beams, microwaves, or mechanical energy. In addition, since it superposes | polymerizes rapidly to superpose | polymerize in presence of a radical polymerization initiator is preferable. These polymerization initiators are well known in the literature (for example, Takayuki Otsu, “Chemistry of Revised Polymer Synthesis”, Kagaku Dojin, 1979).

In the polymerization of the present invention, the anthracene-9,10-diether compound represented by the general formula (1) can be polymerized alone, but a normal radical polymerizable monomer other than the anthracene-9,10-diether compound is used. In addition, a copolymerizable photoradical polymerizable composition can be obtained. Examples of the radical polymerizable monomer include tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide. Examples of the acrylate include styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester. When these other radical polymerizable monomers are used, the anthracene-9 represented by the general formula (1) depends on the compatibility with the anthracene-9,10-diether compound represented by the general formula (1). , 10-diether compound is preferably used in the range of 0.1 to 90 parts by weight of other radical polymerizable monomer. Use of other radically polymerizable monomers in excess of 90 parts by weight is not preferable because performances such as heat resistance and refractive index of the polymer are lowered.

Examples of the radical polymerization initiator suitable for the polymerization of the anthracene-9,10-diether compound of the present invention include a thermal radical polymerization initiator and a photo radical polymerization initiator.

As the thermal radical polymerization initiator, either an organic peroxide or an azo compound can be used. Examples of the organic peroxide include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butyl peroxy-3.5-trimethylhexanoate, and t-butylperoxide. Peroxyesters such as oxyisopropyl carbonates, peroxyketals such as 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, diacyl peroxides such as lauroyl peroxide, etc. Can do. Examples of the initiator of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobi (cyclohexane-1- And azonitriles such as (carbonitrile).

The addition concentration of the thermal radical polymerization initiator is selected from a range of 0.1 to 10% by weight with respect to the total weight of the anthracene-9,10-diether compound and the radical polymerizable monomer used in combination as necessary. Is 1 to 3% by weight. If it is less than 0.1% by weight, the polymerization rate is slow, and if it is more than 10% by weight, the physical properties of the polymer are deteriorated.

Thermal radical polymerization carried out in the presence of a thermal radical polymerization initiator is usually carried out in the presence of a solvent, but it can also be carried out in a molten state. When a solvent is used, examples of the solvent include aromatic solvents such as toluene, xylene, t-butylbenzene, chlorobenzene, and chloronaphthalene, ether solvents such as tetrahydrofuran and 1,4-dioxane, cyclohexanone, and mail ethyl ketone. , Ketone solvents such as methyl isobutyl ketone, and amide solvents such as dimethylacetamide and dimethylformamide are used. The polymerization temperature is usually between 50 ° C and 150 ° C. When the temperature is lower than 50 ° C., the polymerization is too slow, which is not preferable, and when the temperature is higher than 150 ° C., the polymer is unfavorably colored. More preferably, it is in the range of 80 ° C to 120 ° C. When a solvent is used, as the polymerization proceeds, the polymer becomes insoluble and precipitates. The precipitate is filtered and dried to obtain a polymer obtained by polymerizing the anthracene-9,10-diether compound represented by the general formula (1). The polymer obtained does not melt even when heated to the melting point or higher of the anthracene-9,10-diether compound represented by the general formula (1) as a raw material, and is represented by the general formula (1). It can be confirmed that the polymer is a polymer because it does not dissolve in methanol, acetone, toluene, tetrahydrofuran, etc., which are good solvents for the anthracene-9,10-diether compound.

In the case of melting and polymerizing, after heating and melting above the melting point of the anthracene-9,10-diether compound represented by the general formula (1), a predetermined amount of thermal radical polymerization initiator is added. Continue heating in a nitrogen atmosphere. As time progresses, the melt polymerizes. The heating time is usually several minutes to several tens of minutes.

Moreover, the anthracene-9,10-diether compound represented by the general formula (1) can be polymerized by emitting active energy rays. Examples of active energy rays that can be used include visible light, UV light, and electron beams. First, polymerization by visible light and UV light will be described.

The anthracene-9,10-diether compound represented by the general formula (1) can be polymerized by light irradiation in the presence of a photoradical polymerization initiator.

Examples of the photo radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (eta ^{5-2,4-cyclopentadiene-1-yl)} bis (2,6-difluoro -3 (1H-pyrrol-1-yl) - phenyl) titanium, 2-isopropylthioxanthone, 2-t-butyl anthraquinone, and the like. Examples of actual industrial products include Irgacure 651, Irgacure 184, Darocure 1173, Irgacure 907, Irgacure 369, Darocure TPO, Irgacure 819, Irgacure 784, etc. manufactured by Ciba Specialty Chemicals (Irgacure and Darocure are registered by Ciba Specialty Chemicals) Trademark).

The addition concentration of the photo radical polymerization initiator used in the photo radical polymerization is based on the total weight of the anthracene-9,10-diether compound represented by the general formula (1) and the radical polymerizable monomer used in combination as necessary. In the range of 0.5 to 10% by weight, preferably 1 to 3% by weight. If it is less than 0.5% by weight, the polymerization rate is slow, and if it is more than 10% by weight, the physical properties of the polymer are deteriorated.

Examples of the lamp to be used include a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, a metal halide lamp, a fusion company H lamp, a D lamp, a V lamp, and a UV-LED, a blue LED, and the like. . The use of sunlight is also possible.

As a specific embodiment of radical photopolymerization, both polymerization in a solution state using a solvent and polymerization in a bulk state without using a solvent are possible. The solvent that can be used in the polymerization in the solution state using the former solvent is not particularly limited as long as it does not absorb the light to be irradiated and has no polymerization inhibiting effect. Among them, aromatic solvents such as toluene, xylene, t-butylbenzene, chlorobenzene, chloronaphthalene, halogenated carbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxane, etc. An ether solvent is preferably used. In the polymerization method in a solution state, the polymer becomes insoluble and precipitates with light irradiation. This is filtered and dried to obtain a polymer of an anthracene-9,10-diether compound represented by the general formula (1). The polymer obtained in this way does not melt even when heated above the melting point of the anthracene-9,10-diether compound represented by the general formula (1) of the raw material monomer. It does not dissolve at all in methanol, toluene, acetone, tetrahydrofuran, etc., which are good solvents for the anthracene-9,10-diether compound represented, and it can be confirmed from this that it is a polymer.

In addition, in the case of photopolymerization without using a solvent, there are a case where polymerization is performed in a lump according to a target shape and a case where polymerization is performed in a film form. When radical photopolymerization is performed in the form of a mass, it is obtained by heating to the melting point or higher of the anthracene-9,10-diether compound represented by the general formula (1) or by adding another radical polymerizable monomer. The mixture is heated and melted, a predetermined photoradical initiator is added and dissolved therein, and light irradiation is performed in a molten state.

It is also useful to make a radical polymerizable composition containing an anthracene-9,10-diether compound represented by the general formula (1) of the present invention and a radical polymerization initiator. By preparing a polymerizable composition prepared in advance, this radical polymerizable composition can be processed into an arbitrary shape, and then a polymer having a desired shape can be obtained by irradiation with thermal energy or active energy rays. In particular, it is useful when polymerized by processing into a film or the like in a molten state. Although polymerization using this radical polymerizable composition can be thermal radical polymerization, it is preferable to use photo radical polymerization so as not to cause unexpected polymerization due to heating when it is in a molten state.

The light source used for light irradiation is the same as the light source used in the solution state. As light is irradiated, the melt polymerizes. The light irradiation time is usually between several minutes and 10 minutes. The polymer obtained does not melt even when heated to the melting point or higher of the anthracene-9,10-diether compound represented by the general formula (1) of the raw material monomer, and the anthracene represented by the general formula (1) It can be confirmed that the polymer is a polymer because it does not dissolve in methanol, toluene, acetone, tetrahydrofuran, etc., which are good solvents for 9,10-diether compounds.

Next, in the case of photopolymerization without using a solvent, when polymerizing in a film form, for example, the following is performed. The film is prepared by, for example, preparing a radical polymerizable composition containing an anthracene-9,10-diether compound represented by the general formula (1) prepared as described above and a photoradical initiator, a polyester film, an aluminum foil, and a metal. The coating is performed on a substrate such as a plate using a bar coater to form a coating film having a thickness of about 10 to 200 microns. A polymerized film or sheet can be obtained by irradiating the coated material with light using the lamp described above. The obtained film or sheet does not melt even when heated above the melting point of the anthracene-9,10-diether compound represented by the general formula (1) of the raw material monomer, and is represented by the general formula (1). It can be confirmed that the polymer is a polymer because it does not dissolve in methanol, toluene, acetone, tetrahydrofuran, etc., which are good solvents for the anthracene-9,10-diether compound. Further, as a result of measuring the refractive index, a refractive index higher than that of the monomer was obtained, and it was shown that the film and the sheet were polymerized also in this respect.

It is also possible to use known techniques such as literature in these photopolymerizations (for example, Rad-Tech Research Group “Latest Trends in UV / EB Curing Technology” (CMC Publishing Co., Ltd., 2006)).

Polymerization by irradiation with an electron beam among active energy rays is also possible. In this case, the polymerization can be performed without using a radical polymerization initiator. For example, in the case of performing electron beam polymerization in a film state, the film is polymerized by electron beam irradiation at an acceleration voltage of 150 kV and a K value of 99 for 2 minutes. Can be obtained. The obtained film does not melt even when heated above the melting point of the anthracene-9,10-diether compound represented by the general formula (1) of the raw material monomer, and the anthracene represented by the general formula (1) It does not dissolve at all in the good solvent of -9,10-diether compound such as methanol, toluene, acetone, tetrahydrofuran, etc., and can be confirmed to be a polymer. As a result of measuring the refractive index, a refractive index higher than that of the monomer was obtained, indicating that the film was polymerized.

It is also possible to add additives other than the radical polymerization initiator before these polymerization operations. Additives such as polymerization inhibitors, antioxidants, light (ultraviolet) absorbers, light stabilizers, anti-aging agents, fire proofing agents, etc., to prevent the deterioration and deterioration of the polymer. Pigments, dyes, glossy materials, etc., plasticizers, slip agents, mold release agents, gelling agents, etc. for improving processability, flame retardants, antistatic agents, antibacterials, etc. Agents, deodorants, fragrances and the like.

In addition to exhibiting a high refractive index, the polymer produced in the present invention can be expected to have ultraviolet absorption, high hardness, high gloss rate, high hydrophobicity and the like from its structure. Moreover, since it has a hydroxyl group, the improvement of adhesiveness with a base material is also anticipated. Further, physical properties can be further improved by attaching an acetyl group or a trimethylsilyl group to the hydroxyl group or introducing various substituents into the polymer by polymer reaction after polymerization.

Applications of the polymer of the present invention include optical functional materials such as lenses, diffraction gratings, filters and reflectors, sealants, resists, insulating materials, electronic materials such as capacitor materials, energy-related materials such as capacitors and solar cells. Separation functional materials such as ion exchange resins, biomaterials such as dental materials, medical functional materials, high-strength materials, aviation such as adhesives, automobile materials, etc., paints, adhesives, etc., widely introduced in the literature (For example, the Polymer Materials / Technology Directory Editorial Committee “Polymer Materials / Technology Overview” (Industrial Technology Service Center, 2004), Optical Technology / Material Dictionary Editorial Committee “Optical Technology / Material Dictionary” (stock) Industrial Technology Service Center, 2006) In the field of optical materials, lenses can be made thinner as the refractive index becomes higher, and resist materials have higher resolution as the refractive index becomes higher. Fried, tend to high refractive index is required. Indicates what refractive index of the D line at room temperature is 1.55 or more, and wherein the high refractive index.

The present invention is illustrated by the following examples which are not intended to limit the scope of the invention. Unless otherwise noted, all parts and percentages are on a weight basis.

The product was confirmed by measurement using the following equipment.
(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Infrared (IR) spectrophotometer: Model IR-810 manufactured by JASCO Corporation
(3) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX FT NMR Spectrometer
(4) Mass spectrum: manufactured by Shimadzu Corporation, mass spectrometer, model GCMS-QP5000

<Synthesis of anthracene-9,10-diglycidyl ether by reaction of 9,10-anthracenediol with epichlorohydrin>
Under a nitrogen atmosphere, 345 g (3.73 mol) of epichlorohydrin and 100 ml of methanol were charged into a 2 L reactor equipped with a dropping funnel, a condenser, and a thermometer, and the temperature was raised to 50 ° C. To this was added 129 g (0.61 mol) of 9,10-anthracenediol and 614 g of an aqueous solution in which 50 g (1.25 mol) of caustic soda was dissolved over 3 hours, and then 2 hours. Pushed reaction. After separating the aqueous phase, the reaction solution is concentrated to distill off epichlorohydrin. 200 g of methyl isobutyl ketone was added as a solvent for the ring-closing reaction, an aqueous solution in which 6 g of caustic soda was dissolved in 18 g of water was added, and the mixture was heated at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was washed with water, cooled and the precipitated crystals were filtered and dried to obtain 128 g (0.40 mol) of pale yellow crystals 9,10-diglycidyloxyanthracene. The yield based on the starting 9,10-anthracenediol is 66 mol%.

Melting point: 133 ° C
IR (KBr, cm ⁻¹ ): 3020, 3000, 2920, 2860, 1430, 1380, 1330, 1156, 982, 908, 860, 768, 674.
¹ H-NMR (CDCl ₃ , 270 MHz): δ = 2.81 (dd, J ₁ = 6 Hz, J ₂ = 4 Hz, 2 H), 2.95 (dd, J ₁ = 6 Hz, J ₂ = 2.5 Hz, 2H), 3.50-3.62 (m, 2H), 4.08 (dd, J ₁ = 8 Hz, J ₂ = 2 Hz, 2 H), 4.43 (dd, J ₁ = 7 Hz, J ₂ = 2 Hz) , 2H), 7.42-7.56 (m, 4H), 8.24-8.38 (m, 4H).

<Reaction of anthracene-9,10-diglycidyl ether and methacrylic acid>
Under a nitrogen stream, 10.0 g (0.031 mol) of anthracene-9,10-diglycidyl ether obtained in the same manner as in Example 1 in a 300 ml three-necked flask equipped with a stirrer and a thermometer, 10.70 g (0 124 mol), 750 mg of tetrabutylammonium bromide as a catalyst, 4 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (hereinafter abbreviated as TEMPO) as a polymerization inhibitor, and methyl isobutyl ketone as a solvent 80 ml was added. The raw material composition was reacted at a reaction temperature of 110 ° C. for 3.5 hours. A part of the reaction solution was sampled and analyzed by liquid chromatography to confirm that the raw material anthracene-9,10-diglycidyl ether was completely consumed, and the reaction was completed. The reaction solution is cooled to room temperature, 30 ml of ethyl acetate is added as an extraction solvent, and the organic layer is washed with saturated aqueous sodium hydrogen carbonate to remove excess methacrylic acid. After washing with water, the solvent was distilled off under reduced pressure to obtain 15.2 g of a yellow solid.

When analyzed by liquid chromatography, three peaks, A1, B1, and C1, which were considered to be isomers of the anthracene-9,10-diether compound were detected. The combined purity of these three peaks was 94.1%. The composition of isomers was 4.0% for A1, 32.2% for B1, and 63.8% for C1.
Next, 15.2 g of the obtained crude product was recrystallized from a mixed solvent of 100 ml of methanol and 15 ml of water to obtain 3.1 g (0.0063 mol) of pale yellow crystals. The ratio of the isomers is 0.1% for A1, 4.9% for B1, and 95.0% for C1, and by ¹ H-NMR analysis, this C1 component is anthracene-9,10-bis (3- It was found to be methacryloyloxy-2-hydroxypropyl) ether. The yield of the isolated raw material based on the raw material anthracene-9,10-diglycidyl ether was 20 mol%.

Separation and purification of isomers A1, B1, and C1, physical properties, spectral data <Separation of isomer mixture by thin layer chromatographic plate>
About 120 mg of the above isomer mixture is taken and dissolved in a small amount of chloroform. This solution is applied to a uniform concentration along a straight line drawn on the bottom of a 20 cm square silica gel plate. By developing with ethyl acetate / n-hexane (volume ratio: 2/3), it was separated into three UV color bands. When these were analyzed by post-treatment, liquid chromatography and ¹ H-NMR, respectively, the color development band far from the origin was the dominant isomer C1, anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl). ) Ether, and the color development band in the middle is isomer B1, anthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (2-methacryloyloxy-3-hydroxypropyl) ether I understood that. The color development band closest to the origin was inferior isomer A1, although the amount was small and the spectrum could not be obtained, and was assumed to be anthracene-9,10-bis (2-methacryloyloxy-3-hydroxypropyl) ether.

<Physicochemical properties>
Anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether (isomer C1)
・ Light yellow solid
Melting point: 93.1-94.8 ° C
Mass spectrometry: (M ⁺ ) 494
IR (KBr, cm ⁻¹ ): 3420, 2960, 2930, 1725, 1638, 1620, 1460, 1380, 1350, 1295, 1160, 1100, 1060, 960, 760.
¹ H-NMR (CDCl ₃ , 270 MHz): δ = 8.22-8.31 (m, 4H), 7.42-7.52 (m, 4H), 6.19 (d, 2H), 5 .62 (d, 2H), 4.48-4.61 (m, 6H), 4.27 (d, 4H), 2.90 (d, 2H), 1.99 (s, 6H).

Anthracene-9- (3-methacryloyloxy-2-hydroxypropyl) -10- (2-methacryloyloxy-3-hydroxypropyl) ether (isomer B1)
-Light yellow liquid-Mass spectrometry: (M ⁺ ) 494
IR (KBr, cm ⁻¹ ): 3480, 3080, 2950, 2940, 1720, 1640, 1590, 1458, 1355, 1300, 1165, 1070, 940, 770.
¹ H-NMR (CDCl ₃ , 270 MHz): δ = 8.19-8.23 (m, 4H), 7.40-7.55 (m, 4H), 6.28 (s, 1H), 6 .19 (s, 1H), 5.70 (s, 1H), 5.63 (s, 1H), 5.43-5.63 (m, 1H), 4.34-4.62 (m, 5H) ), 4.32 (d, 2H), 4.18 (d, 2H), 2.04 (s, 3H), 1.99 (s, 3H).

Mixture of isomers: yellow-brown solid liquid chromatography mass spectrometry: the two peaks corresponding to the two isomers (B1, C1) separated and separated on a thin-layer chromatographic plate both showed 494 as M ⁺ However, the remaining one peak that was estimated to be anthracene-9-10-bis (2-methacryloyloxy-3-hydroxypropyl) ether of a small amount of isomer (A1) also shows the same M ⁺ , Confirmed correctness. The ¹ H-NMR and IR spectra of the mixture gave consistent results as a mixture of these isomers.

<Reaction of anthracene-9,10-diglycidyl ether and acrylic acid>
Under a nitrogen stream, 4.0 g (0.0124 mol) of anthracene-9,10-diglycidyl ether obtained in the same manner as in Example 1 in a 300 ml three-necked flask equipped with a stirrer and a thermometer, 2.24 g of acrylic acid (0 0.031 mol), tetrabutylammonium bromide 300 mg as a catalyst, TEMPO 2 mg as a polymerization inhibitor, and 40 ml of methyl isobutyl ketone as a solvent are added. This raw material composition was reacted at a reaction temperature of 105 ° C. for 6 hours. A part of the reaction solution is sampled and analyzed by liquid chromatography. The raw material anthracene-9,10-diglycidyl ether is completely consumed and the monoadduct of acrylic acid is almost disappeared. This was confirmed and the reaction was completed. The reaction solution is cooled to room temperature, 20 ml of ethyl acetate is added as an extraction solvent, and the organic layer is washed with saturated aqueous sodium hydrogen carbonate to remove excess acrylic acid. Next, after washing with water, the solvent was distilled off under reduced pressure to obtain 5.5 g of a pale yellow liquid.

Next, 5.5 g of the obtained crude product was recrystallized from 13 ml of methyl isobutyl ketone to obtain 0.88 g (0.0018 mol) of pale yellow crystals. The ratio of isomers was 0.3% for A2, 8.1% for B2, and 91.6% for C2. ¹ H-NMR analysis showed this to be the predominant isomer C2, anthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether. The yield of the isolated raw material based on the raw material anthracene-9,10-diglycidyl ether was 15 mol%.

Separation and purification of isomers (A2, B2, C2), physical properties, spectral data <Separation of isomer mixture by thin layer chromatographic plate>
Using the mother liquor after recrystallization, isomers were separated on a thin-layer chromatographic plate in the same manner as in Example 3. As a result of analysis, the color band far from the origin is C2 and is anthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether, and the color band closest to the origin is B2 and is a yellow viscous liquid. Of anthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (2-acryloyloxy-3-hydroxypropyl) ether. The color development band closest to the origin was inferior isomer A2 although the amount was small and the spectrum could not be taken, and it was estimated to be anthracene-9,10-bis (2-acryloyloxy-3-hydroxypropyl) ether.

<Physicochemical properties>
Anthracene-9,10-bis (3-acryloyloxy-2-hydroxypropyl) ether (isomer C2)
White crystals Melting point: 109.8-111.5 ° C
Mass spectrometry: (M ⁺ ) 466
IR (KBr, cm ⁻¹ ): 3420, 2940, 2870, 17221635, 1620, 1410, 1395, 1295, 1270, 1190, 1170, 1108, 1065, 805, 760.
¹ H-NMR (CDCl ₃ , 270 MHz): δ = 8.20-8.32 (m, 4H), 7.43-7.55 (m, 4H), 6.50 (d, 2H), 6 .22 (dd, 2H), 5.90 (d, 2H), 4.48-4.62 (m, 6H), 4.23 (d, 4H), 2.96 (bs, 1H).

Anthracene-9- (3-acryloyloxy-2-hydroxypropyl) -10- (2-acryloyloxy-3-hydroxypropyl) ether (isomer B2)
・ Yellow viscous liquid
Mass spectrometry: (M ⁺ ) 466
IR (neat, cm ⁻¹ ): 3460, 3080, 2950, 2890, 1730, 1640, 1625, 1415, 1360, 1300, 1280, 1200, 1070, 985, 810, 775.
· ¹ H-NMR spectrum _{(CDCl 3, 270MHz): 8.23-8.36} (m, 4H), 7.45-7.53 (m, 4H), 6.62-6.47 (m, 2H ), 6.14-6.34 (m, 2H), 5.88-6.00 (m, 2H), 5.48-5.59 (m, 1H) 4.50-4.62 (m, 3H), 4.36-4.50 (m, 2H), 4.16-4.28 (m, 4H), 2.90 (d, 1H).

Mixture of isomers: pale yellow liquid liquid chromatography mass spectrometry: The two peaks corresponding to the above two isomers separated and separated on a thin-layer chromatographic plate both showed 466 as M ⁺ , but a small amount of isomerism The remaining one peak (A2), which was assumed to be anthracene-9,10-bis (2-acryloyloxypropoxy-3-hydroxy) ether, was the same M ⁺ , confirming that this assumption was correct. . The ¹ H-NMR and IR spectra of the mixture gave consistent results as a mixture of these isomers.

<Thermal polymerization of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether>
1.0 g of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether synthesized and recrystallized in the same manner as in Example 3 was charged into a 50 ml eggplant flask, and 10 g of toluene was added. Then, 120 mg of azobisisobutyronitrile was added as a thermal polymerization initiator to prepare a polymerization solution. When the temperature of the reaction solution was heated to 100 ° C., it became cloudy after 3 minutes. The mixture was further heated for 10 minutes and cooled to obtain a white jelly-like product. After adding 30 ml of methanol to the reaction mixture and stirring sufficiently, the reaction solution was suction filtered and the filter residue was dried to obtain 0.85 g of a light yellow powder. The yield was 85%.

This pale yellow powder was heated to 95 ° C. or higher, which is the melting point of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, but did not melt at all, and anthracene-9,10- Since it does not dissolve in toluene, dichloromethane, or dimethylformamide, which are good solvents for bis (3-methacryloyloxy-2-hydroxypropyl) ether, the light yellow powder is anthracene-9,10-bis (3-methacryloyloxy- 2-hydroxypropyl) ether polymer was confirmed.

<Photopolymerization of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether>
Synthesis was performed in the same manner as in Example 3, and recrystallization was performed to 100 parts by weight of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether, and bis (η ⁵ − 2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (manufactured by Ciba Specialty, trade name: Irgacure 784) By adding parts by weight, a uniform radical photopolymerizable composition was obtained. This photo-radical polymerizable composition was applied to the surface of a polyester film (manufactured by Toray Industries Inc., trade name: Lumirror, film thickness 100 microns, Lumirror is a registered trademark of Toray Industries, Inc.) with a bar coater so as to have a film thickness of 300 microns. did. Next, irradiation was performed from 3 cm above using a blue LED (manufactured by Lumileds, center wavelength: 460 nm, 3 W) under a nitrogen atmosphere. A smooth film was obtained after 10 spectral irradiations.

This was heated on a hot plate to 95 ° C. or higher, which is the melting point of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether as a raw material monomer, but did not melt at all. Further, when the refractive index of this film was measured (measuring instrument: Elmer ER-7 MW-H), it was found to have a very high refractive index of 1.633 (n _D ).

<Photocopolymerization of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether and trimethylolpropane triacrylate>
Synthesis in the same manner as in Example 3 and recrystallization gave 30 parts by weight of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether and 70 parts by weight of trimethylolpropane triacrylate. As an initiator, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (manufactured by Ciba Specialty) , Trade name: Irgacure 784) was added to obtain a uniform radical photopolymerizable composition. This photoradical polymerizable composition was applied to the surface of a polyester film (trade name: Lumirror, film thickness: 100 microns) manufactured by Toray Co., Ltd. with a bar coater so as to have a film thickness of 300 microns. Subsequently, irradiation was performed from 3 cm above using a blue LED (manufactured by Lumileds, center wavelength: 460 nm, 3 W) under a nitrogen atmosphere. A smooth film was obtained after 10 spectral irradiations.

This was heated on a hot plate to 95 ° C. or higher, which is the melting point of anthracene-9,10-bis (3-methacryloyloxy-2-hydroxypropyl) ether as a raw material monomer, but did not melt at all. Moreover, when the refractive index of this film was measured (measuring instrument: Elmer ER-7 MW-H), 1.547 (n _D ) 0.027 higher than 1.520 of a photopolymer of trimethylolpropane triacrylate alone was obtained. there were.

From Example 6 and Example 7, it can be seen that the anthracene-9,10-diether compound of the present invention easily undergoes radical polymerization, and from Example 7, the polymer has a high refractive index. Further, from Example 8, the anthracene-9,10-diether compound of the present invention forms a copolymerizable composition with an existing radical polymerizable compound such as trimethylolpropane triacrylate, and the resulting polymer has a refractive index. It can be seen that there is an effect of increasing the rate.

Claims (6)

A radical polymerizable composition containing an anthracene-9,10-diether compound represented by the general formula (1) and a radical polymerization initiator.
(In General Formula (1), one of Z ¹ and Z ² represents a hydrogen atom, the other represents a (meth) acryloyl group, one of Z ³ and Z ⁴ represents a hydrogen atom, and the other represents (meta ) Represents an acryloyl group, R ¹ represents a hydrogen atom or a methyl group, X and Y may be the same or different, hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, alkylthio group Or any of arylthio groups.) A polymer obtained by polymerizing an anthracene-9,10-diether compound represented by the general formula (1) in the presence of a radical polymerization initiator.
(In General Formula (1), one of Z ¹ and Z ² represents a hydrogen atom, the other represents a (meth) acryloyl group, one of Z ³ and Z ⁴ represents a hydrogen atom, and the other represents (meta ) Represents an acryloyl group, R ¹ represents a hydrogen atom or a methyl group, X and Y may be the same or different, hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, alkylthio group Or any of arylthio groups.) Polymerization obtained by copolymerizing an anthracene-9,10-diether compound represented by the general formula (1) and another radical polymerizable monomer other than the anthracene-9,10-diether compound in the presence of a radical polymerization initiator. object.
(In General Formula (1), one of Z ¹ and Z ² represents a hydrogen atom, the other represents a (meth) acryloyl group, one of Z ³ and Z ⁴ represents a hydrogen atom, and the other represents (meta ) Represents an acryloyl group, R ¹ represents a hydrogen atom or a methyl group, X and Y may be the same or different, hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, alkylthio group Or any of arylthio groups.) The polymer according to claim 2 or 3 , wherein the radical polymerization initiator is a thermal radical polymerization initiator. The polymer according to claim 2 or 3 , wherein the radical polymerization initiator is a photo radical polymerization initiator. A high refractive index material comprising the polymer according to any one of claims 2 to 5 .