JPH02268170A - Triazine compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The triazine compound of formula I (R<1> to R<3> are alkyl or aryl; at least one of R<1> to R<3> is group of formula II; R<4> and R<5> are H or alkyl; R<6> is group of formula III or formula IV; m is integer of >=0; R<7> is H or CH3; X<1> and X<2> are H, halogen or alkylthio; m is integer of >=0). EXAMPLE:2,4,6-Tris(m-ethenylbenzylthio)-triazine. USE:A monomer giving a resin having high refractive index, low specific gravity and excellent transparency, hardness, weather resistance, etc., and useful especially as an optical material. It can be used also as paint, ink, adhesive, vulcanization agent for rubber, photo-sensitive resin, crosslinking agent, etc. PREPARATION:The objective compound of formula I can be produced by reacting a compound of formula V (R<1> to R<3> are alkyl or aryl; at least one of R<1> to R<3> is group of formula VII; M<1> is H or alkali; n is integer of >=0) with a compound of formula W (X<3> is halogen; n<2> is integer of >=0).

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is particularly useful as a monomer for providing optical materials, and is also useful as a monomer for providing optical materials, as well as paints, inks, adhesives, rubber vulcanizing agents, photosensitive resins, This invention relates to a novel triazine compound useful as a crosslinking agent and a method for producing the same.

[Conventional technology]

Currently, as an optical material widely used, there is a resin made by cast polymerization of diethylene glycol pyruallyl carbonate. However, this resin has a refractive index (no) of 1.
50, which is smaller than inorganic lenses, and in order to obtain optical properties equivalent to inorganic lenses, it is necessary to increase the center thickness, edge thickness, and curvature of the lens, and avoid making it thick overall. I can't.

Various high refractive index resins have been proposed to improve this drawback. For example, high refractive index resins based on polycarbonate and polysulfone have been proposed. Although these resins have a high refractive index of about 1.60, they have problems such as low light transmittance, lack of optical homogeneity, and coloring.

For this reason, various crosslinkable high refractive index resins have been proposed.
For example, resins containing a large number of halogen atoms, such as phenyl methacrylate, in which phenyl groups are substituted with halogen atoms, have been proposed in JP-A-61-28901. However, these resins have large specific gravity and poor weather resistance.

In addition, a composition for a patent refractive index resin featuring α-naphthyl methacrylate has been proposed in Japanese Patent Application Laid-Open No. 197711/1983. Although the resin obtained from this has a high refractive index, it has poor weather resistance because it contains naphthyl groups.

[Problem to be solved by the invention]

Under the above-mentioned prior art, there is a strong demand for resins that can be used particularly suitably for optical materials, that is, resins that have well-balanced properties such as high refractive index, good transparency, weather resistance, and low specific gravity. It is rare.

Therefore, the problem to be solved by the present invention is to provide a monomer that provides a resin with a high refractive index, low specific gravity, and excellent transparency, hardness, weather resistance, etc.

[Means to solve the problem]

As a result of extensive research to solve the above problems, the present inventors have found that a polymer obtained by polymerizing a triazine compound represented by the following general formula is an excellent resin having the above properties. They discovered this and completed the present invention.

That is, the present invention The following formula (1) This is a triazine compound represented by

In the general formula (1), R1, R1, R3, R4 and R5
The number of carbon atoms in the alkyl group represented by is not particularly limited, but from the viewpoint of the refractive index of the resin obtained by polymerization, the number of carbon atoms is preferably 1 to 5. Examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and t-butyl group.

Further, the number of carbon atoms in the oryl group represented by R1, RZ and R3 is not particularly limited, but it is generally preferred that the number of carbon atoms is in the range of 6 to 10. Specific examples include phenyl group, tolyl group, xylyl group, benzyl group, and naphthyl group.

Further, in the general formula CI], the number of carbon atoms of the alkylthio groups represented by xl and X2 is not particularly limited, but from the viewpoint of refractive index, the number of carbon atoms is preferably 1 to 5. For example, methylthio group, ethylthio group, propylthio group, etc. can be mentioned.

In the general formula (I) of the present invention, the halogen atoms represented by XI and X2 are chlorine, bromine, and iodine, and chlorine and bromine are preferred from the viewpoint of weather resistance of the resulting resin. The number of halogen atoms contained in the triazine compound of the present invention is preferably in the range of 0 to 3 in order to obtain a resin with a high refractive index and low specific gravity.

m in the general formula (I) may be any integer greater than or equal to 0, but m is preferably 0 or 1 because if m becomes too large, the refractive index will be lowered.

Further, in the general formula (1), the larger n is, the more the content of sulfur atoms per molecule increases, and the refractive index of the resin obtained by polymerization increases. However, if n is made too large, a problem arises in that the compatibility of the compound of general formula (1) with the unsaturated monomer and the heat resistance are impaired. For this reason, it is preferable to select n from 0 to 4, particularly from 0 to 2.

Furthermore, does R6 in the general formula (1) reflect the refractive index?The structure of the triazine compound represented by the general formula (I) of the present invention can be confirmed by the following means.

(b) By measuring the infrared absorption spectrum (IR), absorption based on C-H bonds is observed near 3150 to 2800 cm-', absorption based on terminal unsaturated hydrocarbon groups is detected near 1650 to 1600 cm-', and Strong absorption of carbonyl groups based on thioester bonds can be observed nearby.

(o) 'H-Nuclear Magnetic Resonance Vector ('H-NMR
), it is possible to know the bonding mode of the hydrogen atoms present in the compound of the present invention represented by the general formula (I). 'H of the compound represented by the above general formula (1)
-NMR (δ, ppm; tetramethylsilane standard,
Figure 2 shows the 'H-NMR of 2,4,6-tris(m-ethynylbenzylthio)triazine as a representative example of the deuterated chloroform solvent. The analysis results are as follows.

That is, a singlet corresponding to two protons was observed at 4.2 ppm, and can be attributed to the methylene chain (C) of the benzyl group. A quartet corresponding to two protons was observed at 5.0 to 5.8 ppm, and can be attributed to methylene (a) of the ethynyl group. Also, 6.4~
7. A quartet corresponding to one proton was observed at opp-, which can be attributed to methine (bl) of the ethynyl group. Also, a multiplet corresponding to four protons was observed at 7.0 to 7.5 ppm. proton substituted with phenyl group (
d), (e), (f), (can be attributed to an illusion.

(c) The weight percent of carbon, hydrogen, nitrogen, sulfur, and halogen can be determined by elemental analysis, and the weight percent of oxygen can be calculated by subtracting the sum of the recognized weight percent of each element from 100. , thus the compositional formula of the compound can be determined.

The method for producing the compound represented by the general formula CI) of the present invention is not particularly limited. Specific examples will be described in detail in the Examples below, but a typical manufacturing method will be described as follows.

(i) General formula (II) With the compound shown by general formula ([[) A method of reacting with a compound shown in

(ii) general formula A compound represented by general formula A method of reacting with a compound shown in

(iii) general formula With the compound shown by General formula [■] A method of carrying out an esterification reaction with a compound represented by

By (i), (ii) and (iii) above -
A triazine compound represented by the general formula (1) can be obtained.

The general formula [■], (I), (IV), (V
), (VI) and [■] may be obtained by any method.

Specific examples of the reaction to obtain the compound represented by the general formula CI) are as follows.

fa) A compound represented by the general formula [■] and the general formula (I
ff) and a method for reacting the compound represented by the general formula (
A method of reacting a compound represented by IV) with a compound represented by general formula (V). These methods involve dehydrohalogenation or dehalogenation of alkali metal from the reaction system.

In the general formulas (II[) and (IV) which are raw materials, X″
As the halogen atom represented by and X4, a chlorine atom or a bromine atom is preferably employed. Furthermore, the general formula (n
), (III), (IV) and (V), n3+n4=
n, and n3+n4=n.

Although the molar ratio of the two compounds to be charged may be appropriately determined as necessary, it is common to use equimolar amounts. In addition, in the reaction, when Ml and Mz are hydrogen atoms, it is generally preferable to coexist a base as a hydrogen halide scavenger in the reaction system in order to remove hydrogen halide from the reaction system. The base used as the hydrogen halide scavenger is not particularly limited, and any known base can be used. Examples of bases that are generally suitably used include trialkylamines such as trimethylamine and triethylamine, pyridine, and tetramethylurea. It is also possible to react an alkali metal compound such as an alkali metal carbonate or an alkali metal hydroxide in the reaction system to form a thiolate and dehalogenate the alkali metal.

It is generally preferable to use an organic solvent in the reaction. Examples of solvents that are preferably used include alcohols such as ethanol and isopropyl alcohol, and N,N'-dialkylamides such as N,N'-dimethylformamide and N,N'-dimethylacetamide. can give.

The temperature in the reaction varies depending on the type of raw material and the type of solvent, but is generally preferably from 0°C to a temperature at which the solvent is refluxed. The reaction time also varies depending on the type of raw material, but it is usually sufficient to select from a range of 5 minutes to 40 hours, preferably 30 minutes to 24 hours. Further, it is preferable to stir the reaction mixture during the reaction.

The method for isolating and purifying the target product, ie, the compound represented by the general formula (I) from the reaction system, is not particularly limited, and any known method can be employed.

(b) Compound represented by general formula (Vl) and general formula (
A method of carrying out an esterification reaction with the compound shown in [2].

In other words, in the general formula [■]) (if s is a hydroxyl group, a dehydration reaction is carried out, if Xi is a chlorine atom, a dehydrochlorination reaction is carried out, and if Xi is an alkoxy group, a dealcoholization reaction is carried out. 0 Reaction conditions are for each method. In the case of a dehydration reaction, it is preferable to use an excess of one of the compounds and use an acid as a catalyst.The catalyst includes mineral acids such as sulfuric acid and hydrochloric acid, and organic acids such as aromatic sulfonic acids. Alternatively, a Lewis acid such as boron fluoride etherate may be mentioned.Also, since the reaction is an equilibrium reaction, it is preferable to remove water as a by-product.The method for removing water is not particularly limited.
A known method is employed.

The reaction temperature and reaction time vary depending on the type of raw materials and the type of solvent, and generally the reaction time is 30 minutes to 30 minutes at a temperature that refluxes the solvent.
The method for isolating and purifying the target product, that is, the compound represented by the general formula (I) from the reaction system, which is preferably 24 hours, is not particularly limited, and any known method can be employed.

In addition, in the case of dehydrochlorination reaction, the compounds are used in equimolar amounts,
In order to remove by-product hydrogen chloride from the reaction system, it is preferable to coexist a base as a hydrogen chloride scavenger in the reaction system.

The base used as the hydrogen chloride scavenger is not particularly limited, and any known base can be used. Commonly preferred bases include trialkylamines such as trimethylamine and triethylamine, pyridine, tetramethylurea, and sodium carbonate. Preferably, the reaction uses an organic solvent.

The reaction temperature and reaction time vary depending on the type of raw materials and the type of solvent, and are generally heated at -20 to 100°C for 5 minutes to 12 hours.
The method for isolating and purifying the compound represented by 1) is not particularly limited, and any known method can be employed.

In the case of dealcoholization reaction, it is preferable to use an excess of one of the compounds and to use an acid or a base as a catalyst. Examples of nucleic acid catalysts include sulfuric acid and p-toluenesulfonic acid, and examples of base catalysts include potassium. Examples include potassium alkoxides such as -t-butoxide.

In addition, since this reaction is an equilibrium reaction, it is preferable to remove the by-product alcohol from the reaction system.The reaction is generally carried out without a solvent, but if the raw material is solid, the boiling point is lower than that of the by-product alcohol. It is preferable to use a solvent with a high

The reaction temperature and reaction time vary depending on the type of raw materials and the type of alcohol by-produced, but generally it takes 30 minutes to 24 hours at the temperature at which alcohol is distilled off to obtain the desired product from the preferable 0 reaction system, that is, the general formula (1) above. The method for isolating and purifying the indicated compound is not particularly limited, and any known method can be employed.

The compound represented by the general formula [Natsu] of the present invention has a high refractive index and a low specific gravity, and is useful as a monomer that provides a resin with excellent transparency, hardness, weather resistance, etc.

When obtaining an optical material, particularly a lens material, using the triazine compound of the present invention, the general formula [! ] is the compound shown! Examples of polyfunctional unsaturated monomers which, when functional, are preferably copolymerized with radically copolymerizable polyfunctional unsaturated monomers, are as follows. In addition, acrylate and methacrylate are collectively referred to as (meth)acrylate, ethylene glycol (meth)acrylate, triethylene glycol di(meth)acrylate,
Di(meth) such as thioglycol di(meth)acrylate
Acrylates include divinylbenzene, 2.5-divinylpyridine, and the like. From the viewpoint of obtaining a polymer with a high refractive index, it is preferable to use a polyfunctional unsaturated monomer whose homopolymer has a refractive index of 1.55 or more. Specifically, bisphenol A1 bisphenol S, 2.2', 6.6'
-Tetrachlorobisphenol A, 2.2' 6.6
'-Tetrachlorobisphenol S, 2.2', 6゜6
'-Tetrabromobisphenol A or 2゜2',
6. Bisβ-methallyl carbonate, diacrylate or dimethacrylate of bisphenols such as 6'-tetrabromobisphenol S; tetrachlorophthalic acid bishydroxyethyl ester, tetrachloroisophthalic acid bishydroxyethyl ester, tetrachloroterephthalic acid bis Examples include bisβ-methallyl carbonate, diacrylate, or dimethacrylate such as hydroxyethyl ester, tetrabromophthalic acid bishydroxyethyl ester, or tetrabromoterephthalic acid bishydroxyethyl ester; divinylbenzene, 2.5 divinylpyridine, and the like.

Furthermore, from the viewpoint of reducing the specific gravity of the polymer, among the polyfunctional unsaturated monomers mentioned above, bisβ-methallyl carbonate, diacrylate or dimethacrylate of bisphenol A or bisphenol S; divinylbenzene; 2,5
-divinylpyridine and mixtures thereof are particularly useful.

On the other hand, it is okay to use an l-functional unsaturated monomer that can be radically copolymerized with the polyfunctional unsaturated monomer, and the mono-functional unsaturated monomer is a polymer with a high refractive index. From the viewpoint of obtaining the following properties, it is preferable to use a monomer whose homopolymer has a refractive index of 1.55 or more.

Specifically, the details are as follows. Phenyl (meth)acrylate, monochlorophenyl (meth)acrylate,
Dichlorophenyl (meth)acrylate, tribromophenyl (meth)acrylate, monobromophenyl (meth)acrylate, dibromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, monochlorophenoxyethyl (meth)acrylate ) acrylate, dichlorophenoxyethyl (meth)acrylate, trichlorophenoxyethyl (meth)acrylate, monobromophenoxyethyl (meth)acrylate, dibromophenoxyethyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, pentabromophenoxyethyl ( meth)acrylate, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dipromostyrene,
iodostyrene, methylstyrene, methoxystyrene,
Examples include 2-vinylthiophene, vinylnaphthalene, N-vinylcarbazole, benzyl (meth)acrylate, and ethylvinylbenzene.

Furthermore, from the viewpoint of reducing the specific gravity of the polymer, among the monofunctional unsaturated monomers mentioned above, phenyl (meth)acrylate, styrene, methylstyrene, methoxystyrene, vinylnaphthalene, benzyl (meth)acrylate, and ethylvinylbenzene are used. and mixtures thereof are particularly useful.

In the present invention, when obtaining an optical material, especially a lens material,
When the compound represented by the general formula (I) is a monofunctional compound, the composition ratio of the monomers is in the range of 30 to 90% by weight, particularly 40 to 80% by weight in the total monomers. It is preferable to use polyfunctional compounds, in which the proportion in the total monomers is 10 to 100% by weight, particularly 40 to 100% by weight.
It is preferable to use it in a range of % by weight.

On the other hand, when the compound represented by the general formula (1) is a monofunctional compound, the amount of the radical copolymerizable polyfunctional unsaturated monomer is 10 to 10% in proportion to the total monomers. 70
% by weight, particularly preferably 20 to 60% by weight, and in the case of a polyfunctional compound, 0 to 90% by weight in the total monomers.
, particularly preferably in the range of 0 to 60% by weight.

Furthermore, when the compound represented by the general formula (I) is a monofunctional compound, the amount of the monofunctional unsaturated monomer capable of radical copolymerization is 0 to 0 in proportion to the total monomers. It is preferably in the range of 40% by weight, particularly 0 to 20% by weight, and in the case of a polyfunctional compound, the proportion in the total monomers is preferably in the range of 0 to 90% by weight, particularly 0 to 60% by weight.

If the amount of the compound represented by the general formula (1) is less than 40% by weight, it will be difficult to obtain a polymer with a high refractive index, which is the object of the present invention.

On the other hand, when the amount of the polyfunctional component used is small, crosslinking does not proceed sufficiently, so that impact resistance and heat resistance tend to decrease.

The polymerization method for obtaining a high refractive index resin using the above-mentioned monomer composition is not particularly limited, and a known cast polymerization method can be employed. Polymerization initiation means include various peroxides, azo compounds, etc. This can be carried out by using a radical polymerization initiator, irradiation with ultraviolet rays, α rays, β rays, γ rays, etc., or a combination of both. To illustrate a typical polymerization method, the monomer composition containing a radical polymerization initiator is injected between molds held by an elastomer gasket or spacer, cured in an air oven, and then taken out. good.

The radical polymerization initiator is not particularly limited and any known one can be used, but representative examples include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide. diacyl peroxides such as oxides; peroxyesters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropylperoxybenzoate; carbonate, percarbonates such as 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 initiator, and the composition of the monomer composition, and is generally not limited to 100 parts by weight of the monomer composition. 0.01 to 1
It is suitable to use it in an amount of 0 parts by weight, preferably in a range of 0.01 to 5 parts by weight.

Among the polymerization conditions, temperature particularly affects the properties of the high refractive index resin obtained. This temperature condition is influenced by the type and amount of initiator and the type of monomer composition, so - although it cannot be generalized - polymerization is started at a relatively low temperature and the temperature is slowly increased. It is preferable to carry out so-called tapered two-stage polymerization, in which the polymers are gradually raised and then cured at high temperature at the end of the polymerization.

Like temperature, polymerization time also varies depending on various factors, so it is preferable to determine the optimal time according to these conditions in advance, but in general, conditions should be selected so that polymerization is completed in 2 to 40 hours. is preferred.

Of course, during the polymerization, various stabilizers and additives such as release agents, ultraviolet absorbers, antioxidants, color inhibitors, antistatic agents, fluorescent dyes, dyes, and pigments may be selected and used as necessary. You can.

Furthermore, the high refractive index resin obtained by the above method can be subjected to the following treatments depending on its use. In other words, dyeing using dyes such as disperse dyes, hard coating agents mainly composed of silane coupling agents and sol of oxides such as silicon, zirconia, antimony, and aluminum, and hard coatings mainly composed of organic polymers. Hard coating treatment with agent, Sin, , Ti1t, ZrO
Processing such as antireflection treatment, antistatic treatment, etc. by vapor deposition of a thin film of metal oxide, coating of a thin film of organic polymer, etc., and 2.
It is also possible to perform subsequent processing.

〔effect〕

The triazine compound of the present invention has a high refractive index and a small specific gravity,
It is useful as a monomer that provides resins with excellent transparency, hardness, weather resistance, etc. A high refractive index resin, which is a copolymer obtained by copolymerizing the compound and an unsaturated monomer, is useful as an organic glass, and is ideal for optical lenses such as eyeglass lenses and optical equipment lenses, for example. It can be suitably used for applications such as prisms, optical disk substrates, and optical fibers.

〔Example〕

EXAMPLES Hereinafter, in order to specifically explain the present invention, Examples will be given and explained, but the present invention is not limited to these Examples.

The physical properties of the triazine compounds and high refractive index resins obtained in Examples were measured by the following test methods.

(The refractive index at 20° C. was measured using a refractometer manufactured by Atsube with a refractive index of 11. Bromonaphthalene was used as the contact liquid.

Note that when the triazine compound is solid at room temperature, its refractive index was determined by dissolving it in a liquid unsaturated monomer and using an extrapolation method.

(2) Hardness Using a Rockwell hardness meter, the value on the L-scale was measured for a test piece with a thickness of 2 fl.

(3) Appearance Measured visually.

(4) Place the sample in a long-life xenon fade meter (FAC-25AX-IC type) manufactured by Weather Resistance Suga Test Instruments ■, and
After being exposed to xenon light for 0 hours, the degree of coloring of the sample was visually observed and evaluated as ○ if the degree of coloring was lower than that of polystyrene, △ if it was the same, and × if it was high.

The unsaturated monomers used in the following examples are represented by the following symbols. However, the value in brackets is the refractive index of the homopolymer.

St: Styrene 1.590 cist: Chlorostyrene (mixture of 0 and m forms) DV
B: PhMA: BzMA: CiBzMA divinylbenzene 1.6 Phenyl methacrylate benzyl methacrylate monochloropenzyl meth (0-form m-form mixture) 1.5 1.610 1.571 1.568 Acrylate Example 1 S-) Lyazine-2 ,4,6-1-lithiol 17.7
g (0.1 moj) was dissolved in N,N'-dimethylformamide 15ON1, m-chloromethylstyrene 4
7.3 g (0.31 mol) was added and placed in a water bath. Then 42.8 g of potassium carbonate (0.31 mo
The mixture was gradually added. After stirring for 1 hour, the reaction mixture was poured into 300 g of water. After extraction with 300ml of chloroform, the chloroform layer was washed once with 50ml of 2N hydrochloric acid and then twice with 50ml of water. The chloroform layer was dried over anhydrous magnesium sulfate, and the chloroform was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 28.5 g of a colorless viscous liquid.

The results of measuring the infrared spectrum of this material (using an IR spectrophotometer IR-440 manufactured by Shimadzu Corporation) are as shown in Figure 1, ranging from 3150 to 2800 cm-'
An absorption based on the C-H bond was shown at 1630 cm-', and an absorption based on the terminal unsaturated hydrocarbon group was shown at 1630 cm-'.

Its elemental analysis values are C68, 50%, H5, 17%, N8
．． 00%, 318.33% and composition formula Ct o H
* Calculated value for N S C68,53%, H5,18
%, N7.99%, and 318.30%.

Also 'H-NMR (JOEL JNM-PMX60SI
The measurement results with an NMR spectrometer (δ, I) pHi (tetramethylsilane standard, deuterated chloroform solvent) are shown in FIG. The analysis results are as follows.

That is, a singlet corresponding to 2 protons was observed at 4.2 ppm, and it can be attributed to methylene (C1) of the benzyl group.
A quartet corresponding to the individual parts was observed, and it can be attributed to the methylene (8) of the ethynyl group. Also, 6.4-7,0
A quartet corresponding to one proton was observed in ppm, and the kill was attributed to the ethynyl group (methine), 7.0
A multiplet corresponding to 4 protons was observed at ~7.5 ppm, and protons (d) and (el
, (f), (can be attributed to an illusion.

The above results revealed that the product was 2.4.6-)lis(m-ethynylbenzylthio)-triazine.

The yield was 54.3% (0,0543 moA') based on S'-triazine-2,4,6-dolithiol.

Furthermore, the refractive index was determined by extrapolation and was found to be n.

It was 1.653.

Example 2 17.7 g of S-) riazine-2,4,6) lithiol (
0,1++oj) to chloroform 150-, pyridine 2
6.1 g (0.33 moj) was added and placed in ice water. Next, 34.5 g of methacrylic acid chloride (0
, 33a+oj were gradually added. After stirring for 1 hour, the mixture was returned to room temperature and further stirred for 1 hour. The reaction mixture was poured into 200ml of water, and 150ml of chloroform was added. The chloroform layer was washed once with 50° of a 2N aqueous sodium hydroxide solution and then twice with 5° of water. The chloroform layer was dried over anhydrous magnesium sulfate, and the chloroform was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 16.2 g of a colorless viscous liquid.

When we measured the infrared spectrum of this product, we found that it was 3150
Absorption based on C-H bond at ~2800 cm-', 167
Absorption based on carbonyl group strong at 0 cm+-', 164
Absorption based on the terminal unsaturated hydrocarbon group was observed at 0 cm-'.

Its elemental analysis values are C47.25%, N3.97%, N1
1.03%, 525.22% and composition formula csHso
Calculated values for NS C47.23%, N3.96%, N
They were in good agreement with each other, 11.01% and 325.22%.

In addition, 'H-NMR (δ, pplI; tetramethylsilane standard, deuterium chloroform solvent) was measured and the result was 1.9.
A double line with a coupling constant of 2 Hz corresponding to 3 protons was observed in ppm, and can be attributed to the methyl group of the methacryloyl group.

2 equivalent to 2 protons in 5.6 to 6.1 ppm
A multiplet line was observed, which can be attributed to the methylene of the methacryloyl group.

The above results revealed that the product was 2.4.6-tris(methacryloylthio)-triazine.

The yield was 42.5% (0,0425 wof) based on S-triazine-2,4,6-dolithiol.

Furthermore, the refractive index was determined by extrapolation and was found to be n:.

It was 1,623.

Example 3 2.4.6-) 318 g of ribromotoriazine (0,1 s
o 1) to N,N'-dimethylacetamide 150-
46.5 g of p-mercaptomethylstyrene dissolved in
(0.31 mol) and 1.0 g of t-butylcatechol as a polymerization inhibitor were added. After refluxing and reacting for 3 hours, the reaction mixture was poured into 300 d of water. 300-
After extraction with chloroform, the chloroform layer was extracted with 2N-
It was washed once with 50 ml of aqueous sodium hydroxide solution, and then twice with 50 ml of water.

After drying the chloroform layer over anhydrous magnesium sulfate and distilling off the chloroform under reduced pressure, the residue was purified by silica gel column chromatography to obtain colorless solid 14.
3 g was obtained.

When we measured the infrared spectrum of this product, we found that it was 3150
Absorption based on C-H bond at ~2900 cm-', 164
Absorption based on the terminal unsaturated hydrocarbon group was observed at 0 cm''.

Its elemental analysis values are C68, 51%, N5.15%, N8
．． 01%, S 18.33% and composition formula C6°H?
Calculated values for NS C68,53%, N5.18%, N
The results showed good agreement of 7.99% and 318.30%.

In addition, when 'H-NMR (δ, pps; tetramethylsilane standard, deuterium chloroform solvent) was measured, 4
．． A singlet corresponding to two protons was observed at 3 pp-, which can be attributed to the methylene chain of the benzyl group.

A quartet corresponding to two protons was observed at 5.0 to 5.8 ppva, and can be attributed to the methylene of the ethynyl group. In addition, a quartet corresponding to one proton was observed at 6.4 to 7.099-, which can be attributed to methine in the ethynyl group, and a singlet corresponding to four protons was observed at 7.2-pp. This can be attributed to the proton substituted on the phenyl group.

The above results revealed that the product was 2.4.6-)lis(p-ethynylbenzylthio)-triazine.

The yield is 2.4.6-)27 for ribromotoriazine.
．． It was 2% (0,0272 soj!).

Furthermore, the refractive index was determined by extrapolation and was found to be n.

It was 1,655.

Example 4 The triazine compounds listed in Table 1 were synthesized by methods similar to those described in detail in Examples 1-3.

Table 1 also lists the properties, elemental analysis results, and refractive index of the synthesized triazine compounds.

It is abbreviated as

Example 5 Radical polymerization was performed on 100 parts by weight of a mixture of 60 parts by weight of 2,4.6-)lis(m-ethynylbenzylthio)-triazine synthesized in Example 1 and 40 parts by weight of styrene as an unsaturated monomer. t-Butylperoxy as initiator
1 part by weight of 2-ethylhexanate was added and mixed well. This mixed solution was poured into a mold consisting of a glass plate and a gasket made of ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization was carried out using an air oven at 30°C to 90°C for 18 hours, gradually increasing the temperature until 90°C.
It was kept at 0°C for 2 hours. After the polymerization was completed, the mold was taken out from the air oven, and after cooling, the polymer was removed from the glass mold.

The obtained polymer is colorless and transparent, and has a refractive index of 1.640,
The specific gravity was 1.17, the hardness was 114, and the weather resistance was also O.

Example 6 Same as Example 5 except that a mixture of 60 parts by weight of 2,4.6-)lis(methacryloylthio)-triazine synthesized in Example 2 and 40 parts by weight of styrene as an unsaturated monomer was used. carried out.

The obtained polymer is colorless and transparent, and has a refractive index of 1.618.
The specific gravity was 1.23, the hardness was 118, and the weather resistance was also 0.

Example 7 2,4.6-)lis(methynylbenzylthio)-triazine synthesized in Example 1 and the unsaturated it shown in Table 2
Example 5 was carried out in exactly the same manner as in Example 5, except that a mixture consisting of

The physical properties of the obtained polymer were measured and shown in Table 2.

Example 8 The same procedure as in Example 5 was carried out except that a mixture consisting of a triazine compound and an unsaturated monomer shown in Table 3 was used.

The physical properties of the obtained polymer were measured and shown in Table 3.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the compound of the present invention obtained in Example 1, and FIG. 2 is a 1H-nuclear magnetic resonance spectrum of the compound of the present invention obtained in Example 1.

Claims (4)

[Claims] (1) The following formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] [However, R^1, R^2 and R^3 are the same or different alkyl groups, aryl groups, or ▲ Mathematical formula , chemical formulas, tables, etc.▼ [However, R^4 and R^5 are the same or different types of hydrogen atoms or alkyl groups, respectively, and R^6 is, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, , R^7 is a hydrogen atom or a methyl group.) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X^1 and X^2 are the same or different hydrogen atoms, halogen atoms, or alkylthio groups, respectively. and m is an integer of 0 or more.) and n is an integer of 0 or more. ] Yes, at least one of these R^1 to R^3 is ▲There is a mathematical formula, chemical formula, table, etc.▼. ] A triazine compound represented by (2) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [However, R^1, R^2 and R^3 are the same or different alkyl groups, aryl groups, or ▲ mathematical formula , chemical formulas, tables, etc. ▼ [However, R^4 and R^5 are the same or different hydrogen atoms or alkyl groups, respectively, and M^1 is a hydrogen atom or an alkali metal, and n1 is an integer of 0 or more. be. ], and at least one of these R^1 to R^3 is ▲
There are mathematical formulas, chemical formulas, tables, etc.▼. ] Compounds represented by and general formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [III] [However, X^3 is a halogen atom, and R^4 and R^5 are the same or different, respectively. is a hydrogen atom or an alkyl group, and R^6 is: ▲There is a mathematical formula, chemical formula, table, etc.▼ (However, R^7 is a hydrogen atom or a methyl group.) Or ▲There is a mathematical formula, chemical formula, table, etc. ▼(However, X^1 and X^2 are the same or different hydrogen atoms, halogen atoms,
or an alkylthio group, and m is an integer of 0 or more. ), and n2 is an integer greater than or equal to 0. ] A method for producing a triazine compound according to claim (1), which comprises reacting with a compound represented by the following. (3) General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] [However, R^8, R^9 and R^1^0 are the same or different hydrogen atoms, alkylthio groups, Arylthio group or ▲ Numerical formula, chemical formula, table, etc.▼ [However, R^4 and R^5 are the same or different hydrogen atoms or alkyl groups, respectively, X^4 is a halogen atom, and n3 is It is an integer greater than or equal to 0. ], and at least one of these R^8 to R^1^0 is ▲There is a mathematical formula, chemical formula, table, etc.▼. ] The compound represented by the general formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [V] [However, M^2 is a hydrogen atom or an alkali metal, and R^4 and R^5 are They are hydrogen atoms or alkyl groups of the same or different types, respectively, and R^6 has ▲a mathematical formula, a chemical formula, a table, etc.▼ (However, R^7 is a hydrogen atom or a methyl group.) or ▲a mathematical formula, a chemical formula, There are tables, etc. ▼ (However, X^1 and X^2 are the same or different types of hydrogen atoms, halogen atoms,
or an alkylthio group, and m is an integer of 0 or more. ), and n4 is an integer greater than or equal to 0. ] A method for producing a triazine compound according to claim (1), which comprises reacting with a compound represented by the following. (4) General formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[VI] [However, R^1, R^2 and R^3 are the same or different alkyl groups, aryl groups, or ▲mathematical formula , chemical formulas, tables, etc.▼ [However, R^4 and R^5 are the same or different hydrogen atoms or alkyl groups, respectively, and n
is an integer greater than or equal to 0. ] At least one of these R^1 to R^3 is ▲There is a mathematical formula, chemical formula, table, etc.▼. ] Compounds and general formula [VII] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [VII] [However, X^5 is a hydroxyl group, chlorine atom, or alkoxy group, and R^7 is a hydrogen atom or a methyl group. It is. ] A method for producing a triazine compound according to claim (1), which comprises reacting with a compound represented by the following.