JPH0547544B2 - - Google Patents

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 novel monomer for paints, inks, adhesives, rubber vulcanizing agents, photosensitive resins, crosslinking agents, etc. This invention relates to a dithiane compound and a method for producing the same. [Prior art] Optical materials that are currently widely used include:
There is a resin made by cast polymerization of diethylene glycol bisallyl carbonate. However, this resin has a refractive index ( _nD ) of 1.50, which is smaller than that of an inorganic lens, and in order to obtain the same optical properties as an inorganic lens, it is necessary to increase the center thickness, edge thickness, and curvature of the lens. Therefore, it is unavoidable that the overall thickness will be thicker. Various high refractive index resins have been proposed to improve this drawback. For example, high refractive index resins such as 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, a resin containing a large number of halogen atoms, such as phenyl methacrylate, in which a phenyl group is substituted with a halogen atom, has been proposed in JP-A-61-28901. However, these resins have problems of high specific gravity and poor weather resistance. Further, a composition for a high refractive index resin containing α-naphthyl methacrylate as a main component has been proposed in Japanese Patent Application Laid-Open No. 197711/1983. Although the resin obtained from this has a high refractive index, it is highly dispersible and has naphthyl groups, so it has poor weather resistance. [Problems to be Solved by the Invention] Under the above-mentioned prior art, resins that can be particularly suitably used for optical materials, that is, have various properties such as high refractive index, good transparency, weather resistance, and low specific gravity, have been developed. Resins with well-balanced properties are strongly desired. Therefore, the problems to be solved by the present invention are high refractive index and low dispersion, low specific gravity, transparency,
The object of the present invention is to provide a crosslinkable monomer that provides a resin that is excellent in hardness, weather resistance, etc., and can be polished. [Means for Solving the Problems] As a result of extensive research in order to solve the above problems, the present inventors have found that a polymer obtained by polymerizing a dithiane compound represented by the following general formula has the above-mentioned properties. The inventors discovered that the resin has excellent properties and completed the present invention. That is, the present invention is based on the general formula [] [However, R ₁ and R ₂ are hydrogen atoms or methyl groups, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, alkyl groups, respectively. group or alkylthio group, and X ₁ and X ₂ are each an oxygen atom or a sulfur atom. ] This is a dithiane compound represented by the following. In the general formula [], R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, alkyl groups or alkylthio groups, respectively.
As the above-mentioned halogen atoms, halogen atoms such as chlorine, bromine, and iodine are used, and chlorine atoms and bromine atoms are preferable from the viewpoint of increasing the refractive index and decreasing the specific gravity of the resulting resin. Further, the number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of the refractive index of the resulting resin, the number of carbon atoms is preferably 1 to 5, and a methyl group is particularly preferred. The number of carbon atoms in the alkylthio group is also not particularly limited, but from the viewpoint of the refractive index of the resulting resin, the number of carbon atoms is preferably 1 to 5, and a methylthio group or an ethylthio group is particularly preferred. In the general formula [], R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are preferably hydrogen atoms, halogen atoms or alkylthio groups from the viewpoint of the refractive index of the resulting resin. The number of halogen atoms and alkylthio groups contained in the dithiane compound of the present invention is:
From the viewpoint of the refractive index, specific gravity, and coloring of the resulting resin, the number is in the range of 0 to 4, respectively, and the total of both is 0.
It is preferable that it is in the range of ~4. Furthermore, in the general formula, X ₁ and X ₂ may be either oxygen atoms or sulfur atoms, but are preferably sulfur atoms in consideration of the refractive index of the resulting resin. The structure of the compound represented by the general formula [] 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 detected near 3150 to 2800 cm ^-1 , absorption based on terminal unsaturated hydrocarbon groups near 1650 to 1600 cm ^-1 , and When X ₁ or X ₂ is an oxygen atom, a characteristic absorption based on an ester bond is observed around 1725 cm ^-1 , and when X ₁ or X ₂ is a sulfur atom, a characteristic absorption based on a thioester bond is observed around 1665 cm ^-1 . be able to. (b) ¹ H-Nuclear Magnetic Resonance Spectrum ( ¹ H-NMR)
By measuring this, the bonding mode of the hydrogen atoms present in the compound of the present invention represented by the above general formula [] can be known, and the compound can be easily identified. In particular, in general formula [], if R ₁ or R ₂ is a methyl group, there will be a peak based on the proton of the methyl group around δ1.9ppm, and a peak based on the terminal vinylidene proton around δ5.7 and δ6.1ppm, respectively. A pattern unique to methacrylic acid esters is observed at a ratio of 3:3:1. Also, R ₁
Alternatively, when R ₂ is a hydrogen atom, six hydrogen atoms are observed at δ5.6 to 6.6 ppm in a pattern unique to acrylic esters. Furthermore, when R ₃ or R ₆ is a hydrogen atom, a peak is observed around δ6 ppm. Further, when R ₄ , R ₅ , R ₇ or R ₈ is a hydrogen atom, a pattern of peaks corresponding to the respective bonding states is exhibited around δ2.5 to δ4.5 ppm. moreover
When R ₃ to _{R 8} are alkyl groups, a normal alkyl proton peak of δ1 to 2 ppm is observed, and R ₃ to _{R 8}
When is an alkylthio group, a peak attributed to hydrogen on the carbon bonded to the sulfur atom is observed around δ3 to δ4.5 ppm. (c) The weight percent of oxygen can be calculated by determining the nuclear weight percent of carbon, hydrogen, sulfur, and halogen by elemental analysis and subtracting the sum of the recognized weight percent of each element from 100. Therefore, the compositional formula of the compound can be determined. The method for producing the compound represented by the general formula [] of the present invention is not particularly limited. Specific examples will be described in the Examples below, but a typical manufacturing method will be detailed as follows. General formula [] [However, X ₁ and X ₂ are each an oxygen atom or a sulfur atom, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, or alkyl groups, respectively. or an alkylthio group. ] A compound represented by the general formula [] [However, R ₉ is a hydrogen atom or a methyl group, and R ₁₀
is a hydroxyl group, a chlorine atom or an alkoxy group. ] It can be produced by an esterification reaction with the compound shown below. (a) Method using carboxylic acid A compound represented by the general formula [] and a carboxylic acid in which R ₁₀ is a hydroxyl group among the compounds represented by the general formula [] are subjected to dehydration condensation in the presence of an acid catalyst. The dithiane compound [] can be produced. Although the molar ratio of both raw materials may be appropriately determined as necessary, it is common to use an excess of one of the compounds. Moreover, if two types of carboxylic acids are added to the reaction system simultaneously or sequentially, an asymmetric dithiane compound can be produced. Examples of the acid used as a catalyst in this reaction include mineral acids such as hydrochloric acid and sulfuric acid, organic acids such as aromatic sulfonic acid, and Lewis acids such as boron fluoride etherate. Water is produced as a by-product in this reaction, but since the reaction is an equilibrium reaction, a Dean-Stark water separator is generally used, or a dehydrating agent such as anhydrous sodium sulfate or molecular sieve is added to the Soxhlet extractor. It is preferable to remove the solvent from the system by refluxing the solvent or by coexisting a dehydrating agent such as N,N'-dicyclohexylcarbodiimide in the reaction system. The solvent is preferably an aromatic hydrocarbon such as benzene or toluene, or a halogenated aliphatic hydrocarbon such as chloroform or dichloromethane. The reaction temperature varies depending on the type of solvent, but
Generally, 0°C to 120°C is preferred. The reaction time cannot be absolutely limited depending on the type of raw materials, but
It is particularly preferable to select from the range of 30 minutes to 20 hours, more preferably 1 hour to 6 hours. The method for isolating and purifying the target product, ie, the compound represented by the above general formula [], from the reaction system is not particularly limited, and any known method can be employed. (a) Method using carboxylic acid chloride A compound represented by the general formula [] and a carboxylic acid chloride in which R ₁₀ is a chlorine atom among the compounds represented by the general formula [] are dehydrochlorinated in the presence of a base. A dithiane compound of the general formula [] can be produced by the reaction. The molar ratio of the two raw materials to be charged may usually be selected from the range of (compound represented by general formula [])/(compound represented by general formula []) = 0.8 to 1.5,
It is particularly preferred to use preferably equal amounts. Moreover, if two or more types of carboxylic acid chlorides are added simultaneously or sequentially to the reaction system, an asymmetric dithiane compound can be produced. In this reaction, hydrogen chloride is produced as a by-product. Generally, in order to remove this 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. Examples of bases that are generally suitably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, tetramethylurea, sodium hydroxide, and sodium carbonate. The amount of base is carboxylic acid chloride 1
It is preferable to use 1.1 mol or more based on the mole. In the reaction in the present invention, it is generally preferable to use an organic solvent. Examples of solvents preferably used include aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, and ethylene chloride. : Ethers such as diethyl ether, dioxane, and tetrahydrofuran; N,N'-dimethylformamide, N,N-diethylformamide, etc.
-Dialkylamides; examples include dimethyl sulfoxide. The temperature in the reaction can be selected from a wide range, generally -20°C to 100°C, preferably 0°C.
You can choose from the range of ~50℃. The reaction time varies depending on the type of raw material, but is usually selected from the range of 5 minutes to 24 hours, preferably 1 to 4 hours. It is also preferable to stir the reaction mixture during the reaction. The method for isolating and purifying the target product, ie, the compound represented by the above general formula [], from the reaction system is not particularly limited, and any known method can be employed. (c) Method using carboxylic acid ester Using a compound represented by the general formula [] and a carboxylic acid ester in which R ₁₀ is an alkoxy group among the compounds represented by the general formula [],
The dithiane compound of the general formula [] can be produced by transesterification. In this reaction, it is preferable to use an acid or a base as a catalyst. Examples of acids suitably used as a catalyst include sulfuric acid, hydrochloric acid, and P-toluenesulfonic acid. Examples of the base include sodium hydroxide. , inorganic bases such as potassium hydroxide, sodium carbonate, and sodium hydrogen carbonate, and alkoxides such as sodium methoxide and potassium t-butoxide. In this reaction, alcohol (R ₉ OH) is produced. Since this reaction is an equilibrium reaction, it is preferable to remove this alcohol from the reaction system by a method such as distillation or azeotropy. For this reason, it is preferable to use a carboxylic acid ester as a raw material in which R ₉ has an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms. Moreover, if two types of carboxylic acid esters having different R ₁ and R ₂ are added simultaneously or sequentially to the reaction system, an asymmetric dithiane compound can be produced. This reaction is generally carried out without a solvent, but if the raw material is solid, it is preferable to use a solvent with a boiling point higher than that of the by-product alcohol. Examples of solvents that are preferably used include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene, or halogen-substituted aromatic hydrocarbons; N,N-
Examples include N,N-dialkylamides such as dimethylformamide and N,N-diethylformamide; dimethylsulfoxide and the like. The temperature in the reaction varies depending on the type of alcohol to be produced as a by-product, but is generally preferably a temperature at which the alcohol to be produced as a by-product is distilled off. The reaction time varies depending on the type of raw material, but is usually selected from the range of 30 minutes to 24 hours, preferably 2 hours to 8 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 above general formula [], from the reaction system is not particularly limited, and any known method can be employed. The compound represented by the above general formula [] of the present invention is useful as a crosslinkable monomer that provides a high refractive index resin that has a high refractive index, low dispersion, and low specific gravity, and has excellent transparency, hardness, weather resistance, etc. be. In addition, the compound is in a solid state at room temperature, and in order to maintain the refractive index and optical homogeneity of the resin obtained by polymerization, the compound is a radically polymerizable liquid unsaturated monomer with a homopolymer refractive index of 1560 or more. It is preferable to copolymerize with the polymer. Examples of such monomers include benzyl methacrylate, phenyl acrylate, bromophenyl methacrylate, bisphenol A dimethacrylate,
2,2',6,6'-tetrabromobisphenol A
Methacrylic esters and acrylic esters such as diacrylate and bisphenol S dimethacrylate; Styrenes such as styrene, chlorostyrene, bromostyrene, dibromostyrene, tribromostyrene, divinylbenzene, and vinylnaphthalene; diallyl phthalate, diallyl isophthalate , allyl compounds such as diallyl chlorendate, and mixtures thereof. When obtaining an optical material, especially a lens material, in the present invention, the composition ratio of the compound represented by the general formula [] of the present invention and the above radically polymerizable liquid unsaturated monomer is determined based on each monomer. Since there are suitable proportions depending on the type of
A range of 20 to 90% by weight is preferably used, more preferably a range of 30 to 80% by weight. The amount of the compound represented by the above general formula [] is
If it is less than 20% by weight, it will be difficult to obtain a high refractive index resin, which is the object of the present invention, and since crosslinking will not proceed sufficiently, impact resistance and heat resistance will 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 can be carried out by using radical polymerization initiators such as various peroxides and azo compounds, by irradiation with ultraviolet rays, α rays, β rays, γ rays, etc., or by a combination of both. To illustrate a typical polymerization method, between molds held by elastomer gaskets or spacers,
The above monomer composition containing a radical polymerization initiator may be injected, cured in an air oven, and then taken out. 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 peroxide such as oxide;
Peroxy esters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropylperoxycarbonate, di-2-
Ethylhexyl peroxide carbonate, di-
Percarbonates such as sec-butyl peroxycarbonate; azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator to be used varies depending on the polymerization conditions, the type of initiator, and the composition of the monomer composition, and cannot be absolutely limited, but it is generally 100 parts by weight of the monomer composition. for
It is suitable to use it in a range of 0.01 to 10 parts by weight, preferably 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 affected by the type and amount of the initiator and the type of monomer composition, so it cannot be absolutely limited, but in general, polymerization starts at a relatively low temperature and slowly progresses. It is preferable to carry out so-called tapered two-stage polymerization in which the temperature is raised and then the polymer is cured at a high temperature upon completion of polymerization. Like temperature, polymerization time also varies depending on various factors, so it is best to determine the optimal time according to these conditions in advance, but in general, conditions should be set so that polymerization is completed in 2 to 40 hours. It is preferable to choose. 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 optical 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 sols of oxides such as silicon, zirconium, antimony, and aluminum, and hard coatings mainly composed of organic polymers. We perform processing and secondary treatments such as hard coating treatment using agents, antireflection treatment and antistatic treatment by vapor deposition of thin films of metal oxides such as SiO ₂ , TiO ₂ , and ZrO, and coating of thin films of organic polymers. It is also possible. [Effects] The dithiane compound of the present invention has a high optical refractive index, low dispersion, low specific gravity, excellent transparency, hardness, weather resistance, etc., and is useful as a crosslinkable monomer that provides a resin that can be polished and beaded. . The optical refractive index resin obtained by copolymerizing this compound with a liquid unsaturated monomer is useful as an organic glass, and is suitable for optical lenses such as eyeglass lenses and optical equipment lenses. It can be suitably used for applications such as disk substrates and optical fibers. [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 identification and physical properties of the dithiane compound obtained in the present invention were carried out by the following analysis method. (1) IR spectrum Measured by the KBr method using IR-440 model manufactured by Shimadzu Corporation. (2) ¹ H-NMR spectrum Using PMX-60SI model (60 MHz) manufactured by JEOL Ltd., the sample was diluted with CDCl ₃ and measured using tetramethylsilane as an internal standard. (3) Elemental analysis Carbon and hydrogen were analyzed using a CHN coder MT-2 model manufactured by Yanagimoto Seisakusho Co., Ltd., and sulfur was measured using a flask combustion method. (4) Refractive index (N ²⁰ _D ) A dithiane compound was dissolved in a liquid unsaturated monomer using an Atsabe refractometer (Model 3T) manufactured by Atago Co., Ltd.
Obtained by extrapolation. Further, various physical properties of the high refractive index resins obtained in Examples were measured by the following test methods. (1) Refractive index (N ²⁰ _D ) Atsube number (ν) Using Atsube refractometer (Model 3T) manufactured by Atago Co., Ltd.
The refractive index and Atsube number at 20°C were measured.
Bromonaphthalin was used as the contact liquid. (2) Hardness (H _L ) Using a Rockwell hardness meter, the value on the L-scale was measured for a test piece with a thickness of 2 mm. (3) Appearance Judgment was made visually. (4) Weather resistance The sample was placed in a long-life xenon fade meter (FAC-25AX-HC model) manufactured by Suga Test Instruments Co., Ltd., and after being exposed to xenon light for 100 hours, the degree of coloration of the sample was visually observed. Those with a lower degree of coloring than polystyrene were evaluated as ○, those with the same degree of coloring were evaluated as △, and those with a higher degree of coloring were evaluated as ×. (5) Beaming property Topcon fully automatic beading machine manufactured by Tokyo Kogaku Kikai Co., Ltd.
Use the ALE-60 model to do the resin beading,
Those that were able to form a ball were evaluated as ○, and those that were impossible were evaluated as ×. Incidentally, liquid unsaturated monomers as copolymerization components used in the following examples are represented by the following symbols. However, the value in parentheses is the refractive index of the homopolymer. St: Styrene [1.590] ClSt: Chlorostyrene (mixture of o-form and m-form)
[1.610] BzMA: Benzyl methacrylate [1.568] Example 1 In a three-neck flask equipped with a stirrer, dropping funnel, and thermometer, 28 g of 1,4-dithiane-2,5-diol, 32 g of dry pyridine, and dry chloroform.
250ml was charged and cooled to 0°C. Next, 42.4 g of methacrylic acid chloride was added with stirring at 0-5°C. After stirring at 5° C. for 1 hour, the mixture was heated to room temperature and further stirred for 1 hour. water the reaction mixture
I poured it to 200ml. The organic layer was washed twice with dilute aqueous sodium hydroxide solution and then twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained solid was recrystallized from ethanol to obtain the desired 2,5-di(methacryloyloxy)-1,
46.3g of 4-dithiane was obtained. This stuff has a melting point of 105
It was colorless needle-like crystals with a temperature of ~107°C. IR of this thing
The chart is shown in Figure 2. Strong absorption was observed at 1725 cm ^-1 due to carbonyl group and at 1640 cm ^-1 due to terminal vinylidene group. Further, ¹ H-NMR (in CDCl ₃ solvent, based on tetramethylsilane, ppm) chart is shown in FIG.
Six hydrogens attributable to hydrogen (c) of the methyl group are a singlet at δ2.00, and two hydrogens attributable to hydrogen (e) or (f) at δ2.83 have a coupling constant of 14Hz and In a double doublet at 5Hz, two hydrogens attributed to hydrogen (e) or (f) at δ3.73 are attributed to hydrogen (a) at δ5.60 in a double doublet with coupling constants of 14Hz and 2Hz. The two hydrogens attributable to hydrogen (d) are a multiplet at δ5.85, and the two hydrogens attributable to hydrogen (b) at δ6.23 are a multiplet. Hydrogen was observed as multiplets. Also, elemental analysis values (( ) are calculated values.)
c = 49.90% (49.98%) H: 5.82% (5.59%)
S: 22.51 (22.24%), which agreed well with the calculated value. Also, by extrapolation using styrene, this 2,
The refractive index of 5-bis(methacryloyloxy)-1,4-dithiane was determined to be 1.542. Examples 2 to 7 Dithiane compounds were obtained in the same manner as in Example 1 using various raw materials. The properties of the obtained dithiane compound are shown in Table 1.

[Table] Example 8 30.4 g of 2,5-dihydroxy-1,4-dithiane, 51.6 g of acrylic acid, and 300 ml of toluene were placed in a three-neck flask equipped with a Dean-Stark separator equipped with a stirrer, thermometer, and condenser. , 3.0 g of cuprous chloride and 5.0 g of p-toluenesulfonic acid were charged. The mixture was heated to reflux with stirring, and the generated water was removed from the system. After reacting for 6 hours and cooling, insoluble materials were removed by filtration. The organic layer was washed with dilute aqueous sodium hydroxide solution, thoroughly washed with water, and then dried over anhydrous magnesium sulfate. The solid obtained by distilling off the solvent under reduced pressure was recrystallized from ethanol to obtain 41.5 g of 2,5-bis(acryloyloxy)-1,4-dithiane as colorless needle-like crystals. In the IR spectrum of this product, strong carbonyl group absorption was observed at 1730 cm ^-1 and absorption due to the terminal vinyl group was observed at 1640 cm ^-1 . In addition, ¹ H-NMR spectrum (in CDCl ₃ solvent,
Based on tetramethylsilane (ppm), two hydrogens attributable to hydrogen (e) or (f) in δ2.85 have a coupling constant of 14.
Hz and 5Hz double doublet, hydrogen at δ3.77
Two hydrogens attributable to (e) or (f) have a coupling constant of 14Hz
and 2Hz double doublet, hydrogen around δ5.8
The four hydrogens attributed to (a) and (d) are multiplets,
Two hydrogen atoms attributable to hydrogen (c) were observed as a multiplet at δ6.12, and two hydrogen atoms attributable to hydrogen (b) were observed as a multiplet at δ6.36. Also, elemental analysis values (( ) are calculated values.)
C: 45.88% (46.10%), H: 4.76% (4.65
%), S: 24.51% (24.63%), which was in good agreement with the calculated value. In addition, by extrapolation using styrene, this 2,5-
The refractive index of bis(acryloyloxy)1,4-dithiane was determined to be 1.545. Examples 9 to 11 Dithiane compounds were produced in the same manner as in Example 8 using various raw materials. The properties of the dithiane compound obtained are shown in Table 2.

[Table] Example 13 To 100 parts by weight of a mixture of 50 parts by weight of the dithiane compound produced in Examples 1 to 12 and 50 parts by weight of styrene, 1 part by weight of benzoyl peroxide as a radical polymerization initiator 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 furnace.
The temperature was gradually raised from 60°C to 130°C over 18 hours and maintained at 130°C for 2 hours. After polymerization,
The mold was removed from the air oven, and after cooling, the polymer was removed from the glass mold. Various physical properties of the obtained polymer were measured and shown in Table 3.

[Table] Example 14 The same procedure as in Example 13 was carried out except that the composition consisting of the dithiane compound and liquid unsaturated monomer shown in Table 4 was used. The physical properties of the obtained resin were measured and shown in Table 4.

【table】 [Brief explanation of the drawing]

1 and 2 are the ¹ H-nuclear resonance spectrum and infrared absorption spectrum of the compound of the present invention obtained in Example 1, respectively.

Claims (1)

[Claims] 1. The following formula [However, R ₁ and R ₂ are hydrogen atoms or methyl groups, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, alkyl groups, respectively. group or alkylthio group, and X ₁ and X ₂ are each an oxygen atom or a sulfur atom. ] A dithiane compound represented by 2 General formula [However, X ₁ and X ₂ are each an oxygen atom or a sulfur atom, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same or different hydrogen atoms, halogen atoms, or alkyl groups, respectively. or an alkylthio group. ] The compound represented by and the general formula [However, R ₉ is a hydrogen atom or a methyl group, and R ₁₀
is a hydroxyl group, a chlorine atom or an alkoxy group. ] The method for producing a dithiane compound according to claim 1, which comprises reacting the dithiane compound with a compound represented by the following.