JP2656109B2 - Triazine compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is particularly useful as a monomer for providing an optical material, and in addition, paints, inks, adhesives, rubber vulcanizing agents,
The present invention relates to a novel triazine compound useful as a photosensitive resin, a crosslinking agent, and the like, and a method for producing the same.

[Prior Art] Currently, as an optical material widely used, there is a resin obtained by casting polymerization of diethylene glycol virallyl carbonate. However, this resin has a refractive index (n ₀ ) of 1.50
In order to obtain optical characteristics that are smaller than inorganic lenses and equivalent to those of inorganic lenses, it is necessary to increase the center thickness, edge thickness, and curvature of the lens, and it is possible to avoid overall wall thickness. Absent.

Various high-refractive-index resins that have improved this disadvantage have been proposed. For example, polycarbonate and polysulfone-based high refractive index resins have been proposed. These resins have a refractive index of about
Although it is as high as 1.60, it has 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, Japanese Patent Application Laid-Open No. 61-28901 discloses a resin containing many halogen atoms such as phenyl methacrylate in which a phenyl group is substituted with a halogen atom. However, these resins have high specific gravity and poor weather resistance.

JP-A-60-197711 proposes a composition for a high refractive index resin containing α-naphthyl methacrylate as a main component. Although the resin obtained therefrom has a high refractive index, it has poor weather resistance due to having a naphthyl group.

[Problems to be solved by the invention]

Under the above-mentioned prior art, a resin that can be suitably used particularly for an optical material, that is, a resin in which various properties such as high refractive index, good transparency, weather resistance and low specific gravity are balanced is strongly desired. It is rare.

Accordingly, an object of the present invention is to provide a monomer which gives a resin having a high refractive index, a small specific gravity, and excellent transparency, hardness, weather resistance and the like.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve the above problems, and as a result, a polymer obtained by polymerizing a triazine compound represented by the following general formula is an excellent resin having the above properties. To complete the present invention.

That is, the present invention relates to the following formula [I] Is a triazine compound represented by the formula:

In the general formula (I), the alkyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ is not particularly limited to the number of carbon atoms,
The number of carbon atoms is 1 to 5 in view of the refractive index of the resin obtained by polymerization.
It is preferred that For example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, t-
A butyl group and the like can be mentioned.

The aryl group represented by R ¹ , R ² and R ³ is not particularly limited in the number of carbon atoms, but generally preferably has 6 to 10 carbon atoms. Specific examples include a phenyl group, a tolyl group, a xylyl group, a benzyl group, and a naphthyl group.

Further, in the general formula (I), the alkylthio group represented by X ¹ and X ² is not particularly limited to the number of carbon atoms,
The number of carbon atoms is preferably 1 to 5 from the viewpoint of the refractive index.
For example, a methylthio group, an ethylthio group, a propylthio group and the like can be mentioned.

In the general formula (I) of the present invention, the halogen atoms represented by X ¹ and X ² are chlorine, bromine and iodine halogen atoms, and chlorine and bromine atoms are preferred from the viewpoint of the weather resistance of the obtained 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 having a high refractive index and a low specific gravity.

M in the general formula [I] may be an integer of 0 or more, but if m is too large, the refractive index is lowered.
Is preferably 0 or 1.

In the general formula [I], as the value of n increases, the content of sulfur atoms per molecule increases, and the refractive index of the resin obtained by polymerization increases. However, when n is too large, there arises a problem that the compatibility of the compound of the general formula [I] with the unsaturated monomer and the heat resistance are impaired.
Therefore, it is preferable that n is selected from 0 to 4, particularly 0 to 2.

Further, R ⁶ in the general formula (I) is from the viewpoint of the refractive index. Is preferred.

The structure of the triazine compound represented by the general formula [I] of the present invention can be confirmed by the following means.

(A) By measuring the infrared absorption spectrum (IR), the absorption based on the C—H bond around 3150 to 2800 cm ⁻¹ ,
In the vicinity of 50 to 1600 cm ^-1, absorption based on the terminal unsaturated hydrocarbon group, and further R ⁶ In the case of ¹ , a strong absorption of a carbonyl group based on a thioester bond can be observed around 1665 cm ^-1 .

(B) ¹ H- can know the binding mode of the nuclear magnetic resonance spectrum ⁽¹ H-NMR) hydrogen atoms present in the compounds of the present invention represented by the general formula (I) by measuring. ¹ H-NMR of the compound represented by the general formula (I)
FIG. 2 shows ¹ H-NMR of 2,4,6-tris (m-ethenylbenzylthio) triazine as a representative example of (δ, ppm; tetramethylsilane reference, deuterated chloroform solvent). The analysis results are as follows.

That is, a singlet corresponding to two protons was observed at 4.2 ppm, which can be attributed to the methylene chain (c) of the benzyl group. A quartet corresponding to two protons is observed at 5.0 to 5.8 ppm, which can be attributed to the ethenyl group due to methylene (a). In addition, protons 1 to 6.4 to 7.0 ppm
A quartet corresponding to the individual is observed, which can be attributed to the ethenyl group due to methine (b). In addition, multiple lines corresponding to four protons were observed at 7.0 to 7.5 ppm, which can be attributed to protons (d), (e), (f), and (g) substituted with a phenyl group.

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

The method for producing the compound represented by the general formula [I] of the present invention is not particularly limited. A specific example will be described in detail in Examples below, but if a typical manufacturing method is described, it is as follows.

(I) General formula [II] And a compound represented by the general formula [III] A method of reacting with a compound represented by the formula:

(Ii) General formula (IV) And a compound represented by the general formula [V] A method of reacting with a compound represented by the formula:

(Iii) General formula [VI] And a compound represented by the general formula [VII] A method of subjecting a compound represented by the formula to an esterification reaction.

The triazine compound represented by the general formula [I] can be obtained by the above (i), (ii) and (iii).

The general formulas (II), (III), (IV),
As the compounds represented by [V], [VI] and [VII], those obtained by any method can be used.

Specific examples of the reaction for obtaining the compound represented by the general formula [I] are as follows.

(A) a compound represented by the general formula [II] and a compound represented by the general formula [II
A method of reacting a compound represented by the formula (I)
A method of reacting a compound represented by the general formula [V] with a compound represented by the general formula [V]. These methods are methods for dehydrohalogenating or dehalogenating alkali metal from the reaction system.

X ³ and X in the general formulas (III) and (IV) that are the raw materials
^{As the} halogen atom represented by ⁴ , a chlorine atom or a bromine atom is suitably employed. Further, the general formula (II),
In [III], [IV] and [V], n1 + n2 = n and n3 + n4 = n.

The molar ratio of both compounds to be charged may be appropriately determined as needed, but it is common to use equimolar amounts. or,
In the reaction, when M ¹ and M ² are hydrogen atoms, it is preferable to coexist a base as a hydrogen halide scavenger in the reaction system in order to generally remove hydrogen halide from the reaction system. The base as the hydrogen halide scavenger is not particularly limited, and a known base can be used. In general, bases that are preferably used include trialkylamines such as trimethylamine and triethylamine, pyridine, tetramethylurea and the like. Further, an alkali metal compound such as an alkali metal carbonate or an alkali metal hydroxide may be reacted in the reaction system to be converted into a thiolate to be dehalogenated.

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

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

The method for isolating and purifying the desired product from the reaction system, that is, the compound represented by the general formula [I], is not particularly limited.
A known method can be adopted.

(B) a compound represented by the general formula (VI) and a compound represented by the general formula [VI
A method of subjecting the compound represented by I] to an esterification reaction.
That is, when X ^{5 in the} general formula [VII] is a hydroxyl group, a dehydration reaction is performed, when X ⁵ is a chlorine atom, a dehydrochlorination reaction, and when X ⁵ is an alkoxy group, a dealcoholation reaction is performed. The reaction conditions vary depending on the method. In the case of a dehydration reaction, it is preferable to use one of the compounds in excess and use an acid as a catalyst. Examples of the catalyst include mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as aromatic sulfonic acid, and Lewis acids such as boron fluoride etherate. Since the reaction is an equilibrium reaction, it is preferable to remove by-produced water. The method for removing water is not particularly limited, and a known method is employed. The reaction temperature and reaction time are
Depending on the type of solvent, it is generally preferred that the solvent be refluxed at a temperature of 30 minutes to 24 hours. The method for isolating and purifying the target substance from the reaction system, that is, the compound represented by the general formula [I], is not particularly limited, and a known method can be employed.

In the case of a dehydrochlorination reaction, the compound is used in an equimolar amount, and it is preferable to use a base as a hydrogen chloride scavenger in the reaction system in order to remove by-produced hydrogen chloride from the reaction system.

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

The reaction temperature and the reaction time vary depending on the type of the raw material and the type of the solvent, and generally, it is preferably at −20 to 100 ° C. for 5 minutes to 12 hours. From the reaction system, the desired product, that is, the above-mentioned general formula (I)
The method for isolating and purifying the compound represented by is not particularly limited, and a known method can be employed.

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

Further, since the reaction is an equilibrium reaction, it is preferable to remove by-product alcohol out of the reaction system. The reaction is generally carried out without solvent, but when the raw material is a solid, it is preferable to use a solvent having a higher boiling point than the by-produced alcohol.

The reaction temperature and the reaction time vary depending on the type of the raw material and the type of the by-produced alcohol. Generally, the temperature at which the alcohol is distilled off is preferably 30 minutes to 24 hours. The method for isolating and purifying the target substance from the reaction system, that is, the compound represented by the general formula [I], is not particularly limited, and a known method can be employed.

The compound represented by the above general formula [I] of the present invention is useful as a monomer which gives a resin having a high refractive index, a small specific gravity, and excellent transparency, hardness, weather resistance and the like.

When an optical material, particularly a lens material, is obtained using the triazine compound of the present invention, when the compound represented by the general formula (I) is monofunctional, it is co-polymerized with a radically copolymerizable polyfunctional unsaturated monomer. Polymerization is preferred. Examples of the polyfunctional unsaturated monomer are as follows. In addition, acrylate and methacrylate are collectively referred to as (meth) acrylate. Di (meth) acrylates such as ethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, and thioglycol di (meth) acrylate; divinylbenzene, 2,5-divinylpyridine, and the like. From the viewpoint of obtaining a polymer having a high refractive index, it is preferable to use a polyfunctional unsaturated monomer having a homopolymer having a refractive index of 1.55 or more. Specifically, bisphenol A, bisphenol S, 2,2 ', 6,6'-tetrachlorobisphenol A, 2,2', 6,6'-tetrachlorobisphenol S, 2,2 ', 6,6' Bis-β-methallyl carbonate, diacrylate or dimethacrylate of bisphenols such as tetrabromobisphenol A or 2,2 ′, 6,6′-tetrabromobisphenol S; bishydroxyethyl tetrachlorophthalate, tetrachloroisophthalate Bis-β-methallyl carbonate such as acid bishydroxyethyl ester, tetrachloroterephthalic acid bishydroxyethyl ester, tetrabromophthalic acid bishydroxyethyl ester or tetrabromoterephthalic acid bishydroxyethyl ester;
Diacrylate or dimethacrylate; divinylbenzene, 2,5 divinylpyridine and the like.

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

On the other hand, a monofunctional unsaturated monomer capable of radical copolymerization may be used together with the polyfunctional unsaturated monomer. As the monofunctional unsaturated monomer, a monomer having a homopolymer having a refractive index of 1.55 or more is preferably used from the viewpoint of obtaining a polymer having a high refractive index.

The details are as follows. Phenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, monobromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, tribromophenyl (meth) acrylate,
Pentabromophenyl (meth) acrylate, monochlorophenoxyethyl (meth) acrylate, dichlorophenoxyethyl (meth) acrylate, trichlorophenoxyethyl (meth) acrylate, monobromophenoxyethyl (meth) acrylate, dibromophenoxyethyl (meth) acrylate, tri Bromophenoxyethyl (meth) acrylate, pentabromophenoxyethyl (meth) acrylate, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, iodostyrene, methylstyrene, methoxystyrene, 2-vinylthiophene, vinylnaphthalene, N-
Vinyl carbazole, benzyl (meth) acrylate,
Ethyl vinylbenzene and the like can be mentioned.

From the viewpoint of further reducing the specific gravity of the polymer, phenyl (meth) acrylate among the above monofunctional unsaturated monomers,
Styrene, methyl styrene, methoxy styrene, vinyl naphthalene, benzyl (meth) acrylate, ethyl vinyl benzene and mixtures thereof are particularly useful.

When an optical material, particularly a lens material, is obtained in the present invention, when the compound represented by the general formula [I] is a monofunctional compound, the proportion of the monomer in the monomer is 30 to 90. It is preferably used in the range of 40 to 80% by weight, and in the case of a polyfunctional compound, it is used in the range of 10 to 100% by weight, particularly 40 to 100% by weight in the total monomer. Is preferred.

On the other hand, when the compound represented by the general formula (I) is a monofunctional compound, the amount of the radically copolymerizable polyfunctional unsaturated monomer used is 10 to 10% of the total monomer. It is preferably 70% by weight, especially 20 to 60% by weight, and in the case of a polyfunctional compound, it is 0 to 90% by weight, particularly 0 to 90% by weight in the total monomers.
It is preferable in the range of 6060% by weight.

Furthermore, the amount of the monofunctional unsaturated monomer capable of being radically copolymerized is 0 to 40% by weight in the total monomer when the compound represented by the general formula [I] is a monofunctional compound. %, Preferably 0 to 20% by weight, and in the case of a polyfunctional compound, it is preferably 0 to 90% by weight, particularly preferably 0 to 60% by weight based on the total monomers.

When the amount of the compound represented by the general formula [I] is less than 40% by weight, it is difficult to obtain a polymer having 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, the cross-linking does not proceed sufficiently, so that the impact resistance and the heat resistance tend to be reduced.

The polymerization method for obtaining a high refractive index resin using the above monomer composition is not particularly limited, and a known casting polymerization method can be employed. Polymerization initiation means, use of various radical polymerization initiators such as peroxides and azo compounds, or ultraviolet, α-ray, β
Irradiation with gamma rays, gamma rays or the like or a combination of both can be performed. To illustrate a typical polymerization method, between the mold held by an elastomer gasket or a spacer, the monomer composition containing a radical polymerization initiator is injected, cured in an air furnace, and then removed. Good.

The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide. Diacyl peroxide such as oxide; peroxyester such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate and t-butylperoxybenzoate; diisopropylperoxy Percarbonates such as dicarbonate, di-2-ethylhexylperoxydicarbonate and di-sec-butylperoxydicarbonate; and azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator used varies depending on the polymerization conditions and the type of the initiator, the composition of the monomer composition, and cannot be unconditionally limited, but generally, based on 100 parts by weight of the monomer composition. It is preferably used in the range of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight.

Among the polymerization conditions, it particularly affects the properties of the high refractive index resin obtained at the temperature. Since this temperature condition is affected by the type and amount of the initiator and the type of the monomer composition, it cannot be unconditionally limited, but generally, the polymerization is started at a relatively low temperature and the temperature is slowly increased. It is preferable to perform a so-called tapered two-stage polymerization in which the polymerization is performed at a high temperature when the polymerization is completed. Since the polymerization time also varies depending on various factors like the temperature, it is preferable to determine an optimum time in advance according to these conditions, but in general, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

Of course, upon the polymerization, a release agent, an ultraviolet absorber, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, a dye,
Various stabilizers and additives such as pigments can be selected and used as needed.

Further, the high-refractive-index resin obtained by the above method can be subjected to the following treatment depending on its use. That is, dyeing using a dye such as a disperse dye, a silane coupling agent or silicon, zirconia, antimony, a hard coat agent mainly containing an oxide sol such as aluminum,
Anti-reflection treatment and charging by hard coating with a hard coating agent containing an organic polymer as a main component, deposition of a thin film of metal oxide such as SiO ₂ , TiO ₂ , ZrO, or coating of a thin film of an organic polymer Processing such as prevention processing and secondary processing can also be performed.

〔effect〕

The triazine compound of the present invention has a high refractive index and a small specific gravity, and is useful as a monomer that gives a resin excellent in transparency, hardness, weather resistance and the like. The high-refractive index resin, which is a copolymer obtained by copolymerization of the compound and the unsaturated monomer, is useful as an organic glass, for example, an eyeglass lens, and is most suitable as an optical lens such as an optical instrument lens, It can be suitably used for applications such as prisms, optical disk substrates, and optical fibers.

〔Example〕

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

Various properties of the triazine compound and the high refractive index resin obtained in the examples were measured by the following test methods.

(1) Refractive index The refractive index at 20 ° C. was measured using an Abbe refractometer. Bromonaphthalene was used as the contact liquid.

When the triazine compound is solid at room temperature, its refractive index was determined by dissolving in a liquid unsaturated monomer and extrapolating.

(2) Hardness Using a Rockwell hardness tester, the value on the L-scale was measured for a test piece having a thickness of 2 mm.

(3) Appearance It was measured visually.

(4) Weather resistance The sample was placed in a long life xenon fade meter (FAC-25AX-HC type) manufactured by Suga Test Instruments Co., Ltd., and after being exposed to xenon light for 100 hours, the degree of coloring of the sample was visually observed. ○, those that are less colored than polystyrene,
The equivalent was evaluated as Δ, and the higher was evaluated as ×.

The unsaturated monomers used in the following examples are represented by the following symbols. Here, [] indicates the refractive index of the homopolymer.

St: Styrene 1.590 ClSt: Chlorostyrene (mixture of o-form and m-form) 1.610 DVB: divinylbenzene 1.615 PhMA: phenyl methacrylate 1.571 BzMA: benzyl methacrylate 1.568 ClBzMA: monochlorobenzyl methacrylate (mixture of o-form and m-form) 1.582 Example 12 Preparation of 4,4,6-tris (m-ethenylbenzylthio) -triazine 17.7 g of S-triazine-2,4,6-trithiol (0.1 mol
l) was dissolved in 150 ml of N, N'-dimethylformamide,
-Chloromethylstyrene (47.3 g, 0.31 mol) was added and placed in a water bath. Then, 42.8 g (0.31 mol) of potassium carbonate was gradually added. After stirring for 1 hour, the reaction mixture was
Dried to 0ml. After extraction with 300 ml of chloroform, the chloroform layer was washed once with 50 ml of 2N hydrochloric acid, and then washed with 50 ml of water.
Washed twice with ml. After the chloroform layer was dried over anhydrous magnesium sulfate and chloroform was distilled off under reduced pressure, the residue was purified by silica gel chromatography to obtain 28.5 g of a colorless viscous liquid.

Infrared spectra (Shimadzu IR spectrometer photo meter IR-440 used) result of measurement of this compound is as shown in FIG. 1, absorption based on C-H bond in 3150～2800Cm ^-1, the 1630 cm ^-1 The absorption based on the terminal unsaturated hydrocarbon group was shown.

Its elemental analysis values were C68.50%, H5.17%, N8.00%, S18.
33% by calcd C68.53% for formula C ₁₀ H ₉ NS, H
5.18%, N7.99%, and S18.30% agreed well.

The measurement results of ¹ H-NMR (JOEL JNM-PMX60SI NMR-spectrometer (δ, ppm; based on tetramethylsilane, deuterated chloroform solvent) are shown in Fig. 2. The analysis results are as follows. is there.

That is, a singlet corresponding to two protons was observed at 4.2 ppm, which can be attributed to the benzyl group due to methylene (c). A quartet corresponding to two protons is observed at 5.0 to 5.8 ppm, which can be attributed to the ethenyl group due to methylene (a). In addition, a quartet corresponding to one proton is recognized at 6.4 to 7.0 ppm, which can be attributed to that of ethenyl group methine (b). A multiplet corresponding to four protons is recognized at 7.0 to 7.5 ppm. It can be attributed to the protons (d), (e), (f) and (g) substituted on the phenyl group.

The above results revealed that the product was 2,4,6-tris (m-ethenylbenzylthio) -triazine.

The yield was 54.3% (0.0543 mol) based on S'-triazine-2,4,6-trithiol.

Further, when the refractive index was determined by extrapolation method, ▲ n ²⁰ _D ▼ 1.6
53.

Example 2 Production of 2,4,6-tris (methacryloylthio) -triazine 17.7 g of S-triazine-2,4,6-trithiol (0.1 mol
l) was added to 150 ml of chloroform and 26.1 g (0.33 mol) of pyridine, and placed in ice water. Then, 34.5 g (0.33 mol) of methacrylic acid chloride was 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 200 ml of water, and 150 ml of chloroform was added. The chloroform layer was washed once with 50 ml of a 2N aqueous sodium hydroxide solution and then twice with 50 ml of water. After the chloroform layer was dried over anhydrous magnesium sulfate and chloroform was distilled off under reduced pressure, the residue was purified by silica gel chromatography to obtain 16.2 g of a colorless viscous liquid.

When the infrared spectrum of this product was measured,
2800 cm ^-1 to based on C-H bond absorption, absorption based on strong carbonyl group 1670 cm ^-1, absorption based on the unsaturated hydrocarbon group of the terminal to 1640 cm ^-1 was observed.

Its elemental analysis values were C47.25%, H3.97%, N11.03%, S2
Calcd for formula C ₅ H ₅ ONS a 5.22% C47.23
%, H3.96%, N11.01% and S25.22%.

When ¹ H-NMR (δ, ppm; based on tetramethylsilane, deuterated chloroform solvent) was measured, a doublet having a binding constant of 2H ₂ corresponding to three protons was found at 1.9 ppm,
This can be attributed to the methyl group of the methacryloyl group.

Two multiple lines corresponding to two protons were observed at 5.6 to 6.1 ppm, which can be attributed to the methacryloyl group due to methylene.

The above results revealed that the product was 2,4,6-tris (methacryloylthio) -triazine.

The yield was 42.5% (0.0425 mol) based on S-triazine-2,4,6-trithiol.

Further, when the refractive index was determined by extrapolation method, ▲ n ²⁰ _D ▼ 1.6
23.

Example 3 Preparation of 2,4,6-tris (p-ethenylbenzylthio) -triazine 318 g (0.1 mol) of 2,4,6-tribromotriazine was added to N, N '.
In 150 ml of dimethylacetamide, 46.5 g (0.31 mol) of p-mercaptomethylstyrene and 1.0 g of t-butylcatechol as a polymerization inhibitor were added. After reacting at reflux for 3 hours, the reaction mixture was poured into 300 ml of water. 300
After extraction with ml of chloroform, the chloroform layer was extracted with 2N-
Wash once with 50 ml of aqueous sodium hydroxide solution and then add 50 ml of water.
Washed twice with ml.

After the chloroform layer was dried over anhydrous magnesium sulfate and chloroform was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to give a colorless solid 14.3.
g was obtained.

When the infrared spectrum of this product was measured,
Absorption at 2900 cm ^-1 was due to C--H bonds, and absorption at 1640 cm ^-1 was due to an unsaturated hydrocarbon group at the end.

Its elemental analysis values were C68.51%, H5.15%, N8.01%, S18.
33% by calcd C68.53% for formula C ₁₀ H ₉ NS, H
5.18%, N7.99%, and S18.30% agreed well.

When ¹ H-NMR (δ, ppm; tetramethylsilane standard, deuterated chloroform solvent) was measured, a singlet corresponding to two protons was observed at 4.3 ppm, which could be attributed to that due to the methylene chain of the benzyl group. . A quartet corresponding to two protons is observed at 5.0 to 5.8 ppm, which can be attributed to the ethenyl group due to methylene. In addition, a quartet corresponding to one proton was recognized at 6.4 to 7.0 ppm, which can be attributed to the methine of the ethenyl group, and a singlet corresponding to four protons was recognized at 7.2 ppm, and the proton substituted with a phenyl group Can be attributed to

The above results revealed that the product was 2,4,6-tris (p-ethenylbenzylthio) -triazine.

The yield is 27.2% based on 2,4,6-tribromotriazine.
(0.0272 mol).

Further, when the refractive index was determined by extrapolation method, ▲ n ²⁰ _D ▼ 1.6
55.

Example 4 The triazine compounds described in Table 1 were synthesized in the same manner as described in detail in Examples 1 to 3. Table 1 also shows the properties of the synthesized triazine compound, the results of elemental analysis, and the refractive index.

Note that CH ₂ = CH- Abbreviated.

Example 5 Radical polymerization was conducted with respect to 100 parts by weight of a mixture of 60 parts by weight of 2,4,6-tris (m-ethenylbenzylthio) -triazine synthesized in Example 1 and 40 parts by weight of styrene as an unsaturated monomer. One part by weight of t-butylperoxy-2-ethylhexanate was added as an initiator and mixed well. This mixture was poured into a mold composed of a gasket composed of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out using an air furnace at 30 ° C. to 90 ° C. for 18 hours, gradually increasing the temperature, and maintaining the temperature at 90 ° C. for 2 hours. After the polymerization was completed, the mold was taken out of the air furnace, and after standing to cool, the polymer was removed from the glass of the mold.

The obtained polymer was colorless and transparent, had a refractive index of 1.640, a specific gravity of 1.17, a hardness of 114, and had no weather resistance.

Example 6 The same operation as in Example 5 was carried out except that a mixture of 2,4,6-tris (methacryloylthio) -triazine synthesized in Example 2 and 60 parts by weight of styrene as an unsaturated monomer was used. did.

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

Example 7 Except that a mixture of 2,4,6-tris (m-ethenylbenzylthio) -triazine synthesized in Example 1 and an unsaturated monomer shown in Table 2 was used, the same as Example 5 was used. The same was done.

 The physical properties of the obtained polymer are shown in Table 2 below.

Example 8 Example 8 was carried out in exactly the same manner as in Example 5, except that a mixture comprising a triazine compound and an unsaturated monomer shown in Table 3 was used.

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

[Brief description of the drawings]

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

Claims (4)

(57) [Claims] 1. The following formula [I] A triazine compound represented by the formula: 2. The general formula [II] And a compound represented by the general formula [III] The method for producing a triazine compound according to claim 1, wherein the compound is reacted with the compound represented by the formula (1). 3. A compound of the general formula (IV) And a compound represented by the general formula (V) The method for producing a triazine compound according to claim 1, wherein the compound is reacted with the compound represented by the formula (1). 4. A compound of the general formula (VI) And a compound represented by the general formula [VII] The method for producing a triazine compound according to claim 1, wherein the compound is reacted with the compound represented by the formula (1).