JPH0665190A - Vinylbenzyl compound - Google Patents

Abstract

PURPOSE:To provide a new compound useful as a raw material for colorless transparent resin suitable for organic glass and giving a resin having excellent odorlessness in polishing, light-resistance, impact resistance, hard-coating suitability and dyeability and having low specific gravity, high refractive index and high Abbe number. CONSTITUTION:The compound of formula I {A is group of formula II [R<1> and R<2> are different kinds of alkylene or group of formula III ((k) and (k') are 0-2); X<1> to X<3> are O or S; (m) is 0-4; (n), (n'), (p) and (p') are 0 or 1]}, e.g. 1-(vinylbenzyloxy)-2(vinylbenzylthio)ethane. The compound can be produced e.g. by the dehydrohalogenation reaction of 1mol of a halogenomethylstyrene of formula IV (X<2> is halogen) with 0.2-1mol of a mercapto alcohol of formula V in the presence of a base (e.g. pyridine) in a solvent (e.g. THF) at 10-60 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent resin, particularly a monomer suitable as a raw material for manufacturing eyeglass lenses.
Particularly, a vinylbenzyl compound having a high refractive index, a high Abbe's number, a low specific gravity, excellent light resistance, impact resistance, hard coat property, dyeability, and suitable for producing a transparent resin having no bad odor during molding is provided. It is a thing.

[0002]

2. Description of the Related Art Conventionally, various investigations have been made on organic glass which replaces inorganic glass, but many drawbacks have not been obtained yet and those having sufficiently satisfactory properties have not yet been obtained. For example, a polymer obtained by polymerizing a monomer containing methyl methacrylate or diethylene glycol bis (allyl carbonate) as a main component is used as an optical material or a lens, but its refractive index is as low as about 1.50.

In recent years, various studies have been conducted to introduce a sulfur atom into the molecular structure in order to increase the refractive index. For example, JP-A-59-164501 discloses a distyrene compound having a sulfide structure, and JP-A-1-300201 and JP-A-1-309002 disclose a polyaddition of a vinyl compound and a polythiol compound. Resins made from the above are disclosed. The above vinyl compound has two vinylbenzylthio structures in one molecule, but the resin obtained by polyaddition of this vinyl compound does not have sufficient light resistance and has a strong sulfur odor during polishing of the resin. However, it is not practical because it has drawbacks such as

[0004]

Under the above-mentioned prior art, organic glass that can be suitably used for optical applications,
In other words, there is a strong demand for an organic glass having a high refractive index, a high Abbe number, a low specific gravity, excellent light resistance, impact resistance, hard coat property, and dyeability and having no bad odor during resin molding.

Therefore, the problem to be solved by the present invention is to provide a monomer which gives an organic glass excellent in the above various properties.

[0006]

Means for Solving the Problems As a result of intensive studies to overcome the above problems, the present inventors have found that a vinylbenzyl compound having both a vinylbenzyloxy structure and a vinylbenzylthio structure in one molecule is The inventors have found that the monomer is an excellent monomer having the above properties and completed the present invention.

That is, the present invention provides the following general formula (1)

[0008]

[Chemical 4]

[Where A is the general formula (2)

[0010]

[Chemical 5]

{Wherein R ¹ and R ² are the same or different alkylene groups or the general formula (3)

[0012]

[Chemical 6]

(Provided that k and k'are integers of 0 to 2), X ¹ , X ² and X ³ are oxygen atoms or sulfur atoms, and m is an integer of 0 to 4, n, n ',
p and p'are 0 or 1. }. ] It is a vinylbenzyl compound shown by these.

The alkylene group represented by R ¹ and R ² in the general formula (1) is not particularly limited, but since the refractive index decreases as the number of carbon atoms increases, the alkylene group has 2 to 6 carbon atoms,
In particular, it is preferable to select from 2 to 4. Specific examples of the alkylene group preferably used in the present invention include, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, butylene group, pentylene group, hexylene group, Examples thereof include a dimethylmethylene group.

Further, k and k'in the general formula (3) are 0 to 2
However, the larger the value, the lower the refractive index, so 0 or 1 is preferable. m may be in the range of 0 to 4, but when R ¹ and R ² of the general formula ( ² ) have the structure of the general formula (3), if m is too large, the hardness and light resistance of the resin may be increased. Therefore, the range of 0 to 2 is particularly preferable. Furthermore, the general formula (2)
Although n, n ', p and p'in the above are 0 or 1, it is more preferable that p and p'are 0 from the viewpoint of high refractive index.

When k, k ', m, n, n', p and p'are 0,-(CH ₂ ) _k -,-(CH ₂ )
^{_{k '-, - (X 1}} R 2) m -, - (X 2) n -, - (X 3)
_{n '-, - (CO (} X 2) n) p -, and - ((X ³⁾ _n C
O) _{p ′} − represents a bond.

The two vinylbenzyl groups contained in the compound of the present invention may be any of 2-vinylbenzyl group, 3-vinylbenzyl group and 4-vinylbenzyl group, but in the present invention, 3-vinylbenzyl group is preferable. Vinylbenzyl group or 4
It is preferably a vinylbenzyl group. In order to increase the refractive index of the resin obtained by polymerizing the compound of the present invention, in the above formula (1), when R ¹ and R ² are alkylene groups, X ¹ , X ² or X ³ is It is preferably a sulfur atom.

Specific examples of the vinylbenzyl compound used in the present invention are as follows. For example, 1-
(Vinylbenzyloxy) -2- (vinylbenzylthio) ethane, 2- (vinylbenzyloxyethyl) -2
′-(Vinylbenzylthioethyl) sulfide, 1-
(Vinylbenzyloxy) -3- (vinylbenzylthio) propane, 1- (vinylbenzyloxy) -4-
(Vinylbenzylthio) butane, 1- (vinylbenzyloxy) -2- (vinylbenzylthio) propane, 4-
Ether and sulfide compounds such as vinylbenzyloxy-1-vinylbenzylthiobenzene, 4-vinylbenzyloxymethyl-1-vinylbenzylthiomethylbenzene; 2-vinylbenzylthioglycolic acid vinylbenzyl, 3-vinylbenzylthiopropionic acid Vinylbenzyl, bis (vinylbenzyl) thiosuccinate, 4-
Thioheptanedioic acid vinylbenzyl vinylbenzyl thioester, bis (vinylbenzyl) terethiophthalate, 4
-Esters and thioesters such as vinylbenzyl vinylbenzothiobenzoate; 1- (vinylbenzylthiocarbonyloxy) -2- (vinylbenzyloxycarbonyloxy) ethane, 1- (vinylbenzylthiocarbonylthio) -2- (vinyl Benzyloxycarbonylthio) ethane, 1- (vinylbenzylthiocarbonylthio) -2- (vinylbenzyloxycarbonylthio)-
Examples thereof include carbonates such as 3-thiopentane, 1- (vinylbenzylthiocarbonyloxy) -4- (vinylbenzyloxycarbonyloxy) benzene, and thiocarbonates. Of the above compounds, ether and sulfide compounds can be preferably used.

The vinylbenzyl compound represented by the general formula (1) of the present invention can be identified and confirmed by the following means.

(A) By measuring the infrared absorption spectrum (IR), absorption based on the terminal double bond is observed at 1650 to 1620 cm ^-1 .

(A) ¹ H-nuclear magnetic resonance spectrum ( ¹ H-
The compound can be easily identified by measuring NMR). In particular, it can be identified by the characteristic absorption of the hydrogen atom of the vinylbenzyl group. That is, the peak based on the terminal vinyl group has a hydrogen atom of 4 at 5.0 to 6.0 ppm.
It is recognized as a doublet corresponding to 2 hydrogen atoms at 6.3 to 7.0 ppm, and a multiplet corresponding to 8 hydrogen atoms on the benzene ring at 7 to 8 ppm. A line is observed, and a peak corresponding to four hydrogen atoms of the benzyl group is observed as a single line at around 4 to 5 ppm. If other hydrogen atoms are present, a spectrum pattern corresponding to the bonding mode is shown.

(C) The respective weight% of carbon, hydrogen and sulfur was obtained by elemental analysis, and the weight% of each recognized element was further determined.
The weight percentage of oxygen can be calculated by subtracting the sum of the above from 100, and the composition formula of the compound can be determined.

The vinylbenzyl compound represented by the general formula (1) may be obtained by any method, but it is generally produced by the method described below.

(A) Method using halogenomethylstyrene By this method, a vinylbenzyl compound other than the compound having a carbonate bond or a thiocarbonate bond in the general formula (1) can be produced.

The following equation (4)

[0026]

[Chemical 7]

(However, X ² is a halogen atom.)
And a halogenomethylstyrene represented by the following formula (5)

[0028]

[Chemical 8]

{Wherein R ¹ and R ² are the same or different alkylene groups or the general formula (3)

[0030]

[Chemical 9]

(Provided that k and k'are integers of 0 to 2), X ¹ is an oxygen atom or a sulfur atom, m is an integer of 0 to 4, and p and p'are 0. Or 1
Is. } It is the method of making it react with mercapto alcohol. That is, the halogenomethylstyrene represented by the general formula (4) and the mercapto alcohol represented by the general formula (5) are dehydrohalogenated in the presence of a base to produce a vinylbenzyl compound of the general formula (1). can do.

The charging ratio of both raw materials is usually selected from the range of 0.2 to 1.0 mol of the compound represented by the general formula (5) with respect to 1 mol of the compound represented by the general formula (4). It is good, but it is particularly preferable to use it in the vicinity of 0.5 mol.

In this reaction, it is generally desirable to use a base for the purpose of promoting the reaction. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate and sodium hydride, and amines such as triethylamine, tripropylamine, pyridine and aniline. The amount of the base is represented by the general formula (5)
It is preferable to use 2 to 5 mol per 1 mol of the compound represented by.

This reaction can be carried out without a solvent, but it is common to use an organic solvent. Examples of the solvent preferably used as the solvent include aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as benzene, toluene, xylene, hexane, heptane and methylene chloride; diethyl ether, dioxane, tetrahydrofuran and the like. Ethers; N, N-dimethylformamide,
N, N-dialkylamides such as N, N-diethylformamide; dimethyl sulfoxide, water and the like.

When the solvent or base is used as an aqueous solution, tetrabutylammonium bromide or the like is used.
It is also preferable to use a phase transfer catalyst such as a primary ammonium salt in order to accelerate the reaction.

Further, the mercapto alcohol represented by the general formula (5) is previously reacted with a base to form a metal alkoxide or a metal thiolate, and then an etherification reaction is performed with the halogenomethylstyrene represented by the general formula (4). You can go.

The reaction temperature varies depending on the type of solvent,
Generally, 0 to 120 ° C is preferable, and 10 to 60 ° C is particularly preferable. The reaction time cannot be generally limited depending on the type of raw material, but is preferably 1 to 48 hours. The method for isolating the desired vinylbenzyl compound from the reaction mixture is not particularly limited, and a known method can be adopted.

(B) Method using hydroxymethylstyrene By this method, an ester bond in the general formula (1),
A vinylbenzyl compound having a thioester bond, a carbonate bond and a thiocarbonate bond can be produced.

The following equation (6)

[0040]

[Chemical 10]

Hydroxymethylstyrene represented by
Formula (7) below

[0042]

[Chemical 11]

Mercaptomethylstyrene represented by
Formula (8) below

[0044]

[Chemical 12]

{Wherein R ¹ and R ² are the same or different alkylene groups or the general formula (3)

[0046]

[Chemical 13]

(Provided that k and k'are integers of 0 to 2), X ¹ , X ² and X ³ are oxygen atoms or sulfur atoms, and m is an integer of 0 to 4, n and n '
Is 0 or 1 and X ³ and X ⁴ are halogen atoms. } It is the method of making it react with the compound shown by these. That is, by dehydrohalogenating the hydroxymethylstyrene of the general formula (6) and the mercaptomethylstyrene of the general formula (7) and the carboxylic acid halide or the carbonic acid halide of the general formula (8) in the presence of a base. The vinylbenzyl compound of the general formula (1) can be produced.

The charging ratio of the raw materials is usually the general formulas (6) and (7) with respect to 1 mol of the compound represented by the general formula (8).
The compound shown by 1 may be selected from the range of 0.1 to 1.0 mol, but it is particularly preferable to use each compound in the vicinity of 0.5 mol.

In this production method, it is desirable to use a base for the purpose of accelerating the reaction as in the production method (A), and it is common to carry out the reaction using an organic solvent. Furthermore, it is preferable to use a phase transfer catalyst.

Further, the hydroxymethylstyrene of the general formula (6) and the mercaptomethylstyrene of the general formula (7) and the carboxylic acid halide or the carbonic acid halide of the general formula (8) are dehydrohalogenated in the presence of a base. In this case, the three may be reacted at the same time, or the carboxylic acid halide or the carbonic acid halide of the general formula (8) and the hydroxymethylstyrene of the general formula (6) or the mercaptomethylstyrene of the general formula (7) may be reacted. It is also possible to react one of them and then to react the other.

Further, the hydroxymethylstyrene of the general formula (6) and the mercaptomethylstyrene of the general formula (7) may be previously reacted with a base to form a metal alkoxide and / or a metal thiolate, and then this reaction may be carried out. .

The reaction temperature varies depending on the type of solvent, but it is generally preferably -20 to 100 ° C, and particularly -20.
-50 degreeC is preferable. The reaction time cannot be generally limited depending on the type of raw material, but is preferably 1 to 24 hours. The method for isolating the desired vinylbenzyl compound from the reaction mixture is not particularly limited, and a known method can be adopted.

The vinylbenzyl compound represented by the general formula (1) of the present invention gives a polymer having a high refractive index, low dispersion, colorless and transparent, low specific gravity and no bad odor even when polished. The compound may be polymerized alone, or may be copolymerized with another copolymerizable monomer.

These copolymerizable monomers are selected according to the purpose and can be used without particular limitation. Examples of these monomers include unsaturated carboxylic acids such as methacrylic acid, maleic anhydride, and fumaric acid; methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol diester. Acrylate, diethylene glycol dimethacrylate, glycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2
-Acrylic acid and methacrylic acid ester compounds such as bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane and trifluoromethyl methacrylate; methylthiomethacrylate, methylthioacrylate, phenylthiomethacrylate, benzylthiomethacrylate, ethanedithioldithiomethacrylate Fumarate ester compounds such as monomethyl fumarate, diethyl fumarate and diphenyl fumarate; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallylma Rate, allyl cinnamate, allyl isocyanurate, diallyl chlorendate, diallyl hexaphthalate, diallyl car Sulfonate, allyl compounds such as allyl diglycol carbonate; styrene, divinylbenzene, chlorostyrene, alpha-methyl styrene, vinyl naphthalene, isopropenyl naphthalene, bromostyrene,
Aromatic vinyl compounds such as dibromostyrene; urethane (meth) acrylate or epoxy (meth) acrylate having two or more (meth) acryloyl groups in one molecule. These monomers may be used alone or in combination of two or more.

The type of these monomers may be selected according to the purpose, and the amount used may also be selected according to the purpose. These monomers are the vinylbenzyl compound of the general formula (1). It is preferably used in the range of 0 to 500 parts by weight with respect to 100 parts by weight.

Further, the vinylbenzyl compound of the present invention,
A polymer can also be obtained by polyaddition with a thiol compound having two or more mercapto groups in one molecule. Specific examples of thiol compounds that can be suitably used for this purpose are 1,2-ethanedithiol, 1,4-butanedithiol, di (2-mercaptoethyl) sulfide, ethylene glycol dithioglycolate, ethylene glycol dithioprote Pionate, 1,4-butanediol dithioglycolate, 1,4-benzenedithiol, di (2-
Thiol compound having two mercapto groups in one molecule such as mercaptoethyl) ether, 1,3-xylylenedithiol, 1,4-bis (2-mercaptoethyl) benzene, and 2-hydroxypropane-1,3-dithiol. ;
Mercapto in one molecule such as trithioglycerin, trimethylolpropane tris (thioglycolate), trimethylolpropane tris (thiopropionate), and 2- (2'-mercaptoethylthio) -1,3-dimercaptopropane Thiol compound having three groups; pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (thiopropionate), pentaerythritol tetramercaptan, tetrakis (2-mercaptoethylthiomethyl) methane, 5,5-
Bis (mercaptomethyl) -3,7-dithia-1,9-
Examples thereof include thiol compounds having four mercapto groups in one molecule such as nonanedithiol. These can be used alone or as a mixture of two or more kinds.

Of these, trimethylolpropane tris (thioglycolate), trimethylolpropane tris (thiopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis ( Thiopropionate), ethylene glycol dithioglycolate and the like are preferable. From the viewpoint of the refractive index of the obtained resin, 1,4-benzenedithiol, 1,4-bis (2-mercaptoethyl) benzene, 1,2-ethanedithiol, 2- (2'-mercaptoethylthio)- 1,
3-dimercaptopropane, pentaerythritol tetramercaptan, tetrakis (2-mercaptoethylthiomethyl) methane, 5,5- (bismercaptomethyl)
-3,7-Dithia-1,9-nonanedithiol and the like are preferable.

In the present invention, the vinylbenzyl compound and the thiol compound have a ratio of (number of vinyl groups of vinylbenzyl compound) / (number of mercapto groups of thiol compound) of 0.
It is preferable to mix them in a range of 5 to 20, preferably 1.0 to 10. When the total number of vinyl groups in the vinylbenzyl compound with respect to the total number of mercapto groups in the thiol compound is less than 0.5, the polymerization does not proceed sufficiently and the hardness of the resin obtained is insufficient, and the mercapto group in the polymer is insufficient. Remains, which is not preferable in terms of odor. On the other hand, if the above ratio exceeds 20, the amount of the thiol compound used is reduced and the impact resistance becomes insufficient, which is not preferable.

The method of polymerizing the vinylbenzyl compound of the present invention or a mixture of the vinylbenzyl compound and a monomer copolymerizable therewith (hereinafter, also simply referred to as a monomer) is not particularly limited, and a known cast polymerization method can be adopted. . The polymerization can be initiated by using radical polymerization initiators such as various peroxides and azo compounds, irradiation with ultraviolet rays, α rays, β rays, γ rays or the like, or a combination of both. To exemplify a typical polymerization method, between the molds held by the elastomer gasket or the spacer, the above-mentioned monomer containing a radical polymerization initiator is injected, and after curing in an air oven,
Cast-out polymerization is used.

The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples are benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide and lauroyl peroxide. , Acetylperoxide and other diacyl peroxides; t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate and other peroxyesters; Percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator used varies depending on the polymerization conditions, the type of the initiator, and the type and composition of the above-mentioned monomers, and cannot be unconditionally limited, but is generally 0.01 per 100 parts by weight of all the monomers. It is preferably used in the range of 10 to 10 parts by weight.

Among the polymerization conditions, the temperature particularly affects the properties of the obtained resin. Since this temperature condition is affected by the type and amount of initiator and the type of monomer, it cannot be unequivocally limited, but generally the polymerization is initiated at a relatively low temperature and the temperature is raised slowly. It is preferable to perform a so-called taper type two-stage polymerization in which the composition is cured at a high temperature at the end of the polymerization.

Since the polymerization time also depends on various factors like the temperature, it is preferable to determine the optimum time according to these conditions in advance, but generally, the conditions are set so that the polymerization is completed within 2 to 40 hours. Is preferred.

Cast polymerization can also be carried out by known photopolymerization using ultraviolet rays. In this case, benzoin as a photopolymerization initiator, benzoin methyl ether,
Benzoin butyl ether, benzophenol, acetophenone, 4,4'-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthone and the like can be mentioned. These photopolymerization initiators are generally used in the range of 0.001 to 5 parts by weight based on 100 parts by weight of all the monomers.

In the cast polymerization, a part or all of the vinylbenzyl compound-containing monomer of the present invention is preliminarily polymerized to prepare a liquid prepolymer, which can be copolymerized with this prepolymer as required. It is also possible to mix different monomers and carry out predetermined casting polymerization.

Of course, in the above-mentioned polymerization, a releasing agent, an ultraviolet absorber, an antioxidant, a coloring preventing agent, an antistatic agent, various stabilizers such as fluorescent dyes, dyes and pigments, and additives such as perfumes are necessary. It can be selected and used accordingly.

Further, the resin obtained by the above method may be subjected to the following treatments depending on its use.
That is, dyeing using a dye such as a disperse dye, a hard coating agent containing a silane coupling agent or a sol of an oxide such as silicon, zirconium, antimony, or aluminum as a main component, or a hard coating containing an organic polymer as a main component. Hard coating with chemicals, SiO ₂ , TiO ₂ , ZrO
It is also possible to perform processing such as antireflection treatment and antistatic treatment by vapor deposition of a thin film of a metal oxide such as ₂ or coating of a thin film of an organic polymer, and secondary treatment.

[0067]

EFFECTS OF THE INVENTION By polymerizing the vinylbenzyl compound of the present invention or a mixture of the vinylbenzyl compound and a monomer copolymerizable therewith, a colorless transparent resin having excellent odorlessness and light resistance during polishing and low specific gravity is obtained. Obtainable. Further, the resin obtained by the present invention has a high refractive index and a high Abbe number, and is excellent in impact resistance, hard coat property and dyeability.

Therefore, the resin obtained by the present invention is useful as an organic glass, and is most suitable for an optical lens such as a spectacle lens and an optical device lens, and is also suitable for an optical glass such as a prism, an optical disk substrate and an optical fiber. Can be used for

[0069]

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

Various properties of the resins obtained in the examples were measured by the following test methods.

(1) Refractive Index and Abbe Number The refractive index at 20 ° C. was measured using an Abbe refractometer manufactured by Atago Co. Bromonaphthalene or methylene iodide was used as the contact liquid.

(2) Appearance It was judged visually.

(3) Specific gravity Electronic specific gravity meter (ED-120T, manufactured by Mirage Trading Co., Ltd.)
Type).

(4) Light resistance After placing the sample in a long life xenon fade meter (FAC-25AX-HC type) manufactured by Suga Test Instruments Co., Ltd. and exposing it to xenon light for 100 hours, Suga Test Instruments Co., Ltd. The color difference meter (SM-4 type) was used to measure the YI of the sample, which was indicated by the increment ΔYI with respect to the initial YI.

(5) Impact resistance A 16 g steel ball was dropped from a height of 127 cm onto a sample plate having a thickness of 2 mm and a diameter of 65 mm, and the sample plate was evaluated as ◯ when it was not damaged and evaluated as x when it was damaged. did.

(6) Hard coat property A hard coat liquid (trade name: TS-56T, manufactured by Tokuyama Soda Co., Ltd.) was used to evaluate a sample that can be hard coated, and a sample that cannot be hard coated was evaluated as x. .

(7) Dyeability A disperse dye (trade name: Vista Brown, manufactured by Hattori Seiko Co., Ltd.) was dispersed in 2 g of 1 L of water and a sample was placed in the heated sample. What was not possible was evaluated by x.

(8) Odor Ball shaving machine (TOPCON ALE made by Tokyo Optical Machinery Co., Ltd.)
-60) was used to polish the sample. A sample having a bad odor was evaluated as 1, a sample having a bad odor was 2, a sample having a slight odor was 3, a sample having almost no odor was 4, and a sample having no odor was 5.

The compounds used in each Example and Comparative Example are as follows.

(A) Vinylbenzyl Compound VOSE: 1- (p-vinylbenzyloxy) -2-
(P-vinylbenzylthio) ethane

[0081]

[Chemical 14]

VOSS: 2- (p-vinylbenzyloxyethyl) -2 '-(p-vinylbenzylthioethyl)
Sulfide

[0083]

[Chemical 15]

VOSB: 4-p-vinylbenzyloxy-p-vinylbenzylthiobenzene

[0085]

[Chemical 16]

VOSP: 1- (p-vinylbenzyloxy) -2- (p-vinylbenzylthio) propane

[0087]

[Chemical 17]

VOSMB: 4-p-vinylbenzyloxymethyl-p-vinylbenzylthiomethylbenzene

[0089]

[Chemical 18]

VSTG: 2-p-vinylbenzyl thioglycolic acid p-vinylbenzyl

[0091]

[Chemical 19]

VTS: bis (p-vinylbenzyl) thiosuccinate

[0093]

[Chemical 20]

VTH: 4-thioheptanedioic acid p-vinylbenzyl p-vinylbenzyl thioester

[0095]

[Chemical 21]

VTP: Bis (p-vinylbenzyl) terethiophthalate

[0097]

[Chemical formula 22]

VBV: 4-p-vinylbenzyl 4-vinylbenzyl thiobenzoate

[0099]

[Chemical formula 23]

EGV: 1- (p-vinylbenzylthiocarbonyloxy) -2- (p-vinylbenzyloxycarbonyloxy) ethane

[0101]

[Chemical formula 24]

ETV: 1- (p-vinylbenzylthiocarbonylthio) -2- (p-vinylbenzyloxycarbonylthio) ethane

[0103]

[Chemical 25]

TETV: 1- (p-vinylbenzylthiocarbonylthio) -2- (p-vinylbenzyloxycarbonylthio) -3-thiopentane

[0105]

[Chemical formula 26]

PVBC: 1- (p-vinylbenzylthiocarbonyloxy) -4- (p-vinylbenzyloxycarbonyloxy) benzene

[0107]

[Chemical 27]

(B) Thiol compound PETG: pentaerythritol tetrakis (thioglycolate) PETM: pentaerythritol tetramercaptan METM: tetrakis (2-mercaptoethylthiomethyl) methane MTNT: 5,5-bis (mercaptomethyl) -3, 7
-Dithia-1,9-nonanedithiol

[0109]

[Chemical 28]

EGTG: ethylene glycol dithioglycolate (C) Other components St: styrene DVB: divinylbenzene BzMA: benzyl methacrylate HEMA: 2-hydroxyethyl methacrylate AIC: triallyl isocyanurate Example 1 p-chloromethylstyrene 76. 3 g (0.5 mol)
And 2-mercaptoethanol 19.5g (0.25mo
l) is dissolved in 200 ml of tetrahydrofuran and 20
% Aqueous sodium hydroxide solution (110 g) and tetrabutylammonium bromide (2 g) were added, and the mixture was heated with stirring at 60 ° C. for 5 hours. After completion of the reaction, dilute hydrochloric acid was added to neutralize, the mixture was extracted with methylene chloride, and washed twice with water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained oily substance was purified by column chromatography to give 1- (p-vinylbenzyloxy) -2- (p-vinylbenzylthio) ethane as a colorless and transparent oily substance.
6.5 g was obtained.

The IR spectrum of this product is shown in FIG. Absorption due to vinyl group is recognized at 1630 cm ^-1 . Further, the ¹ H-NMR (CDCl ₃ solution, tetramethylsilane standard, ppm) spectrum is shown in FIG. δ 2.6
Two peaks derived from methylene hydrogen (f) and (g) at 0 ppm and δ 3.55 ppm have binding constants of 6 respectively.
As a triple line of Hz, δ3.68 ppm and δ4.43 pp
2 derived from benzyl hydrogen (h) and (e) for m
Two peaks originating from hydrogen (a) and (l) at δ 5.16 ppm are double lines with a coupling constant of 10 Hz, and hydrogen (b) and (k) are at δ 5.67 ppm. 2) peaks derived from) have a coupling constant of 18 Hz.
Double line of hydrogen (c) and (j) at δ 6.67 ppm.
The two peaks derived from are coupling constants of 18 Hz and 10
With a quadruple line of Hz, eight peaks derived from the aromatic ring (i) are observed as multiplets near δ7 to 7.5 ppm.

[0112]

[Chemical 29]

The elemental analysis values (values in parentheses are calculated values) are C: 77.09% (77.38%) and H:
7.22% (7.14%), S: 10.54% (10.
33%), which was in good agreement with the calculated value.

Example 2 A vinylbenzyl compound was synthesized in the same manner as in Example 1 except that 2-mercaptoethanol was replaced with various mercapto alcohols or carboxylates. The physical properties of the obtained compound are shown in Table 1.

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

[Table 3]

Example 3 To 55 ml of toluene was added 6.7 g (0.05 mol) of p-hydroxymethylstyrene to 9.55 g (0.1 mol) of ethylene glycol dichloroformate, and the mixture was cooled to 0 ° C. Triethylamine (5.6 g, 0.055 mol) was added dropwise while maintaining the reaction temperature at 10 ° C or lower, and the mixture was stirred at 0 ° C for 2 hours. Furthermore, p-mercaptomethylstyrene 7.5
g (0.05 mol) was added, and triethylamine 5.6 g
(0.055 mol) was added dropwise while maintaining the reaction temperature at 10 ° C or lower. Then, it stirred at room temperature for 2 hours. After completion of the reaction, dilute hydrochloric acid was added to neutralize the mixture, and the toluene layer was separated.
It was washed with water once. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The oil obtained was purified using column chromatography, and 1- (p-vinylbenzylthiocarbonyloxy) -2- (p-vinylbenzyloxycarbonyloxy) ethane was obtained as a colorless transparent oil 11.2 g. Obtained.

In the IR spectrum of this product, absorption of carbonyl group was observed at 1710 and 1750 cm ^-1 . The ¹ H-NMR spectrum also supported this structure well.

Elemental analysis values (values in parentheses are calculated values) are C: 66.51% (66.31%) and H:
5.46% (5.56%), S: 8.32% (8.05)
%), Which was in good agreement with the calculated value.

Example 4 In the same manner as in Example 3, various carboxylic acid chlorides instead of ethylene glycol dichloroformate or
Vinyl benzyl compound was obtained using chloroformate. The physical properties of the obtained compound are shown in Table 2.

[0122]

[Table 4]

Example 4 To 100 parts by weight of the vinylbenzyl compound shown in Table 3, 1 part by weight of cumylperoxyoctate as a radical polymerization initiator was added and mixed well. This mixed solution was poured into a mold composed of a gasket made of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization was carried out using an air furnace, the temperature was gradually raised from 70 ° C to 120 ° C over 15 hours, and the temperature was maintained at 120 ° C for 2 hours. After the polymerization was completed, the mold was taken out of the air furnace, allowed to cool, and
The polymer was removed from the mold glass. The physical properties of the obtained polymer are shown in Table 3.

Comparative Example 1 In Example 4, the vinylbenzyl compound was replaced by 1,2
-Bis (vinylbenzylthio) ethane (hereinafter VBTE
(Abbreviated) was used in the same manner as in Example 4. The physical properties of the obtained polymer are also shown in Table 3.

[0125]

[Table 5]

Example 5 100 parts by weight of a mixture of a vinylbenzyl compound shown in Table 4 and a monomer copolymerizable therewith were added to a polymerization initiator t.
-Butylperoxy-2-ethylhexanoate (1 part by weight) was mixed and carried out in the same manner as in Example 4. Table 4 shows the physical properties of the obtained polymer.

[0127]

[Table 6]

Example 6 To 100 parts by weight of a mixture of a vinylbenzyl compound and a thiol compound shown in Table 5, 1 part by weight of t-butylperoxy-2-ethylhexanoate was added as a radical polymerization initiator. Mixed well. This mixed solution was poured into a mold composed of a gasket made of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed.
Polymerization was carried out using an air furnace, the temperature was gradually raised from 30 ° C to 90 ° C over 15 hours, and the temperature was maintained at 90 ° C for 2 hours. After completion of the polymerization, the mold was taken out of the air furnace, allowed to cool, and then the polymer was removed from the glass of the mold. Table 5 shows the physical properties of the obtained polymer.
It was shown to.

[0129]

[Table 7]

[Brief description of drawings]

FIG. 1 is a chart of an infrared absorption spectrum of the vinylbenzyl compound of the present invention obtained in Example 1.

FIG. 2 is a chart of ¹ H-nuclear magnetic resonance spectrum of the vinylbenzyl compound of the present invention obtained in Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 323/56 7419-4H 327/04 8619-4H 329/06 8619-4H 329/16 8619-4H C08F 12/34 MJY 7211-4J

Claims (1)

[Claims] 1. The following general formula (1): [However, A is the general formula (2) {Wherein R ¹ and R ² are the same or different alkylene groups or the general formula (3): (However, k and k ′ are integers of 0 to 2.)
X ¹ , X ² and X ³ are oxygen atoms or sulfur atoms, m is an integer of 0 to 4, and n, n ′, p and p ′ are 0 or 1. }. ] The vinyl benzyl compound shown by these.