JP2008247868A - Cyclic thiocarbonate, method for producing the same, cured polymeric material, and optical material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material having a high refractive index which allows the easy control of a ring opening polymerization reaction. <P>SOLUTION: Disclosed is a cyclic thiocarbonate represented by formula (1), wherein X and Y each independently represents an oxygen atom or a sulfur atom, R<SP>1</SP>and R<SP>2</SP>each represents a 1-4C alkyl group, and R<SP>3</SP>and R<SP>4</SP>each represents a 1-8C alkylene chain, provided that each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>may contain a sulfur atom and may contain a cyclic structure. A polymerizable composition comprising the above cyclic thiocarbonate and, as an optional component, an organic compound having a functional group that reacts with the above cyclic thiocarbonate is also disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel cyclic thiocarbonate and a method for producing the same. Furthermore, the present invention relates to a polymerized cured product and an optical material using the cyclic thiocarbonate.

In recent years, plastic lenses have attracted attention as optical materials. A plastic lens is lighter and harder to break than a glass lens, and is easy to process such as dyeing and cutting. For example, polythioether, which is a ring-opening polymer of polyepisulfide described in Patent Document 1 and Patent Document 2, has a refractive index as high as 1.6 from the latter half to 1.7, and an Abbe number as high as 30 or more. Therefore, it contributes to thinning of optical lenses and prisms. However, it is known that polyepisulfide is difficult to control because of its high reactivity, and unexpected heat generation, smoke generation, and coloring occur during the ring-opening polymerization reaction in the production process.
JP-A-9-71580 Japanese Patent Laid-Open No. 9-110979

  An object of the present invention is to provide a high refractive index material that facilitates the control of the ring-opening polymerization reaction described above.

The present invention relates to the following matters.
[1] A cyclic thiocarbonate represented by the general formula (1).

（式中、Ｘ、Ｙはそれぞれ独立に酸素原子又は硫黄原子を表し、Ｒ^１、Ｒ^２は炭素数が１から４のアルキル基を表し、Ｒ^３、Ｒ^４は炭素数が１から８のアルキレン鎖を表す。ただし、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４の中に硫黄原子を含有していてもよく、環構造を含有していてもよい。）
［２］前記環状チオカーボネートと、任意成分として前記環状チオカーボネートと反応する官能基を有する有機化合物を含有することを特徴とする重合性組成物。
［３］任意成分がチオール化合物である、［２］記載の重合性組成物。
［４］［２］または［３］記載の重合性組成物を重合してなる重合硬化物。
［５］［４］記載の重合硬化物を含む光学材料。
［６］一般式（２）で表されるトリチオール化合物と一般式（３）で表されるジアリール（チオ）カーボネートを反応させ一般式（４）で表される化合物を得た後、一般式（４）で表される化合物を酸化反応することを特徴とする［１］記載の環状チオカーボネートの製造方法。（ただし、一般式（４）で表される化合物は単独で使用してもよく、複数で使用してもよい。）

(In the formula, X and Y each independently represent an oxygen atom or a sulfur atom, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ represent 1 to 8 carbon atoms. Represents an alkylene chain, provided that R ¹ , R ² , R ³ , R ⁴ may contain a sulfur atom or a ring structure.)
[2] A polymerizable composition comprising the cyclic thiocarbonate and an organic compound having a functional group that reacts with the cyclic thiocarbonate as an optional component.
[3] The polymerizable composition according to [2], wherein the optional component is a thiol compound.
[4] A polymerized cured product obtained by polymerizing the polymerizable composition according to [2] or [3].
[5] An optical material comprising the polymerized cured product according to [4].
[6] After reacting the trithiol compound represented by the general formula (2) with the diaryl (thio) carbonate represented by the general formula (3) to obtain the compound represented by the general formula (4), the general formula (4) The method for producing a cyclic thiocarbonate according to [1], wherein the compound represented by 4) is oxidized. (However, the compound represented by the general formula (4) may be used alone or in combination.)

（式中、Ｒは前記Ｒ^１又はＲ^２に相当し、Ｒ’は前記Ｒ^３またはＲ^４に相当する。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は前記と同様である。）

(In the formula, R corresponds to R ¹ or R ² and R ′ corresponds to R ³ or R ^4. R ¹ , R ² , R ³ and R ⁴ are the same as described above.)

（式中、Ａは前記Ｘ又はＹに相当する酸素原子又は硫黄原子を表し、Ａｒは芳香族置換基を表す。）

(In the formula, A represents an oxygen atom or a sulfur atom corresponding to X or Y, and Ar represents an aromatic substituent.)

（式中、Ｒ、Ｒ’、Ａは前記と同様である。）

(In the formula, R, R ′ and A are the same as described above.)

  The present invention provides a cyclic thiocarbonate which is a high refractive index polymerizable monomer that facilitates the control of the ring-opening polymerization reaction shown above and is useful as a raw material for a high refractive index material, a method for producing the same, and a polymerizable composition. be able to. Moreover, a polymerization hardened | cured material can be obtained by performing thermosetting using this polymeric composition. The polymerized cured product can be used for an optical material having a high refractive index, such as a plastic lens, a prism, an optical fiber, an information recording substrate, a colored filter, and an infrared absorption filter.

Hereinafter, the present invention will be described in detail. The cyclic thiocarbonate of the present invention is represented by the general formula (1), and X and Y each independently represent an oxygen atom or a sulfur atom. Among these, those in which X and Y are both oxygen atoms are preferable because the degree of coloring is low. R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ represent an alkylene chain having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. However, R ¹ , R ² , R ³ , R ⁴ may contain a sulfur atom or may contain a ring structure. The number of sulfur atoms is not particularly limited, but the ring structure is preferably an alicyclic structure.

  The cyclic thiocarbonate represented by the general formula (1) comprises a trithiol compound represented by the general formula (2) and a diaryl (thio) carbonate represented by the general formula (3) in the presence of a transesterification catalyst. It is produced by subjecting it to a transesterification reaction to obtain a compound represented by the general formula (4) and disulfiding it by an oxidation reaction. If the compounds represented by the general formula (4) are of the same type, a symmetrical cyclic thiocarbonate can be obtained. On the other hand, when an oxidation reaction is performed using a plurality of different types of compounds represented by the general formula (4), an asymmetric cyclic thiocarbonate can be obtained.

  Examples of the trithiol compound represented by the general formula (2) include 1,2,3-trimercaptopropane, 1,2,3-trimercaptobutane, 1,2,3-trimercaptopentane, 1,2,3-trimer. Mercaptohexane, 1,2,3-trimercaptoheptane, 1,2,4-trimercaptobutane, 1,2,5-trimercaptopentane, 1,2,6-trimercaptohexane, 1,2,7-tri Trithiols such as mercaptoheptane,

  Trithiols containing sulfur atoms such as 1,2,5-trimercapto-4-thiapentane, 1,2,9-trimercapto-4,7-thianonane, 1-mercaptomethyl-4- (2 ′, 3′-mercapto Trithiol containing a ring structure such as (propyl) cyclohexane, trithiol containing a sulfur atom such as 2-mercaptomethyl-5- (2 ′, 3′-mercaptopropyl) -1,4-dithiane and a ring structure, and the like.

  Examples of the diaryl (thio) carbonate represented by the general formula (3) include diphenyl carbonate and diphenyl thiocarbonate.

  The transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction. For example, basic compounds such as potassium carbonate, sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), quaternary ammonium salts (tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide); titanium tetrachloride, tetraalkoxy titanium ( Titanium compounds such as tetra-n-butoxy titanium and tetraisopropoxy titanium); tin compounds such as metal tin, tin hydroxide, dibutyltin dilaurate, dibutyltin oxide, butyltin tris (2-ethylhexanoate) It is done.

  Among transesterification catalysts, basic compounds such as potassium carbonate, sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), quaternary ammonium salts (tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide); and tetraalkoxy Titanium (tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.) is preferred.

  The amount of the transesterification catalyst used is 0.001 to 5% on a weight basis with respect to the total amount of the trithiol compound represented by the general formula (2) and the diaryl (thio) carbonate represented by the general formula (3). Preferably, it is used in the range of 0.01 to 2%, particularly preferably 0.05 to 1%.

  Since the high molecular weight compound is produced as a by-product when the reaction is carried out under a high temperature condition exceeding 150 ° C., the reaction temperature is such that the diaryl (thio) carbonate is dissolved in the trithiol compound. It is preferable to carry out the reaction at from C to 150C, more preferably from 20 to 120C, particularly from 20 to 100C. The reaction time is preferably 1 minute to 24 hours, more preferably 3 minutes to 10 hours, and particularly preferably 5 minutes to 5 hours. The pressure is not particularly limited as long as the desired product can be produced.

  It is preferable to deactivate the transesterification catalyst after completion of the transesterification reaction. As a method for inactivating the transesterification catalyst, neutralization may be performed by mixing an inorganic acid or an organic acid. Examples of the inorganic acid used for the neutralization reaction include sulfuric acid and the like, and examples of the organic acid include p-toluenesulfonic acid / monohydrate, methanesulfonic acid and the like. The amount of the inorganic acid or organic acid used is 1 to 3 times, preferably 1.05 to 2 times, more preferably 1.1 to 1.5 times on a molar basis with respect to the amount of the transesterification catalyst used. Is preferred.

  The reaction mixture after deactivating the catalyst is then dissolved in a solvent. Examples of the solvent include dichloromethane, chloroform, benzene, toluene, chlorobenzene, o-dichlorobenzene, etc. Among them, dichloromethane, chloroform and the like which are solvents having a low boiling point are particularly preferable.

The reaction mixture dissolved in the solvent is washed with the same volume of water. Thereafter, water is removed, and the solvent and aryl alcohol are removed by heating under reduced pressure. Finally, general formula (4) is obtained by performing distillation purification. Examples of the distillation purification method include vacuum distillation and thin film distillation. The temperature and pressure for distillation purification are 20 ° C. to 150 ° C. and 0.01 to 50 kPa, respectively.
The operating temperature from catalyst inactivation to distillation purification is preferably 20 to 150 ° C., preferably 20 to 120 ° C., more preferably 20 to 100 ° C. in consideration of high molecular weight due to side reactions.

The cyclic thiocarbonate represented by the general formula (1) can be produced by oxidizing the compound represented by the general formula (4) into a disulfide. At this time, it is preferably carried out in the presence of an oxidizing agent. The oxidizing agent is not particularly limited as long as it is a compound that promotes an oxidation reaction to disulfide. For example, sodium perchlorate, iodine, lead dioxide (PbO ₂ ), oxygen, copper sulfate, ferric chloride, potassium permanganate and the like can be mentioned. The oxidizing agent needs to be used at least 1 time on a molar basis with respect to the compound (4), more preferably 1.02 to 4 times, particularly preferably 1.05 to 2 times.

  In producing the cyclic thiocarbonate, the compound represented by the general formula (4) may be used singly or in plural kinds (at least two kinds). The use ratio in the case of using a plurality of types is appropriately selected according to the physical properties of the obtained optical material.

  The temperature condition of the oxidation reaction to disulfide is 20 to 150 ° C., more preferably 20 to 120 ° C., because a high molecular weight compound is produced as a by-product when the reaction is performed at a high temperature exceeding 150 ° C. In particular, the reaction is preferably performed at 20 ° C to 100 ° C. The time and pressure of the oxidation reaction are not particularly limited as long as the target product can be produced.

  The oxidation reaction can be performed in a solvent in which the raw material is dissolved and does not react with the raw material. Examples of the solvent include water; alcohol compounds such as methanol and ethanol; ketone compounds such as acetone and methyl ethyl ketone; ester compounds such as ethyl acetate and butyl acetate; ether compounds such as tetrahydrofuran and dioxane; chlorinated hydrocarbons such as chloroform and dichloromethane Examples thereof include polar compounds such as compounds, dimethylformamide, dimethylacetamide, acetonitonyl, and N-methylpyrrolidone.

  The obtained reaction mixture is dissolved in a solvent such as dichloromethane, chloroform, benzene, toluene, chlorobenzene and washed with the same volume of water 2 to 10 times, preferably 3 to 8 times. After separating the water, the cyclic thiocarbonate is isolated as a solid by removing the solvent. The removal temperature of the solvent is 20 to 150 ° C, preferably 20 to 120 ° C, particularly preferably 20 to 100 ° C. The pressure is not particularly limited as long as the solvent can be distilled off and the cyclic thiocarbonate is not distilled, but it is, for example, 0.01 to 50 kPa.

  After removal of the solvent, the cyclic thiocarbonate can be further washed with an insoluble solvent to obtain the desired purity. Examples of the insoluble solvent include heptane, hexane, chloroform, dichloromethane, dichloromethane-heptane (1: 1 (volume basis)), diisopropyl ether, methanol, ethanol, acetone, ethyl acetate, diethyl ether and the like. Particularly preferred are hexane, dichloromethane-heptane (1: 1 (volume basis)), diethyl ether and the like. The washing temperature is, for example, −40 to 50 ° C., particularly preferably −20 to 30 ° C. under a cold temperature.

The cyclic thiocarbonate obtained above becomes a polymerizable composition by containing an organic compound having a functional group that reacts with the cyclic thiocarbonate as an optional component.
The organic compound may be present alone or in a plurality of types as a resin modifier for adjusting the optical performance and mechanical performance of a polymerized cured product obtained by curing the polymerizable composition. .

  The organic compound having a functional group that reacts with cyclic thiocarbonate has at least one functional group that reacts with cyclic thiocarbonate, and a low molecular weight compound is particularly preferable. Specific examples include thiol compounds, amine compounds, allyl compounds, (meth) acrylate compounds, organic acids and anhydrides thereof, mercapto organic acids, mercaptoamines, and phenol compounds.

  Examples of the thiol compound having a functional group that reacts with cyclic thiocarbonate in the polymerizable composition include compounds having one or more SH groups. Usually, the number of SH groups is 8 or less, preferably 6 or less. Examples of such compounds include methyl mercaptan, ethyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1 , 6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 2,2-dimethyl-1,3 -Propanedithiol, 3-methyl-1,5-pentanedithiol, 2-methyl-1,8-octanedithiol, 1,4-cyclohexanedithiol, 1,4-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ) Ether, bis (2-mercaptoethyl) sulfide, bis 2-mercaptoethyl) disulfide, 2,5-bis (mercaptomethyl) -1,4-dioxane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,1,1-tris (mercaptomethyl) Ethane, 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, tetrakis (mercaptomethyl) methane, 3,3′-thiobis (propane-1,2-dithiol), 2,2′-thiobis (propane- 1,3-dithiol), pentaerythritol tetrakis (mercaptopropionate), aliphatic thiol compounds such as pentaerythritol tetrakis (mercaptoacetate); and benzyl mercaptan, thiophenol, 1,2-benzenedithiol, 1,3-benzene Dithiol, 1,4-benzenedithiol, 1, , 5-benzenetrithiol, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) ) Aromatic thiol compounds such as benzene and toluene-3,4-dithiol. Moreover, the compound (4) which is an intermediate at the time of manufacturing cyclic thiocarbonate can be mentioned as a thiol compound.

  Examples of the amine compound having a functional group that reacts with the cyclic thiocarbonate in the polymerizable composition include compounds having at least one amino group, such as ethylamine, n-propylamine, isopropylamine, and n-butylamine. , Sec-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, aminomethylbicycloheptane, cyclopentyl Amine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophor Primary aliphatic amine compounds such as diamine, bis (4-aminocyclohexyl) methane, 2,7-diaminofluorene; aniline, benzylamine, phenethylamine, meta (or para) xylylenediamine, 1,5-, 1,8 -Or a primary aromatic amine compound such as 2,3-diaminonaphthalene, 2,3-, 2,6-, or 3,4-diaminopyridine; diethylamine, dipropylamine, di-n-butylamine, di- sec-butylamine, dicyclohexylamine, di (2-ethylhexyl) amine, piperidine, pyrrolidine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1,1-di (4-piperidyl) Methane, 1,2- (4-piperidyl) ethane, 1,3- (4-piperidi) ) Secondary aliphatic amine compounds such as propane and 1,4-di (4-piperidyl) butane; and secondary aromatic amine compounds such as diphenylamine, dibenzylamine, N-methylbenzylamine and N-ethylbenzylamine Can be mentioned.

  Examples of the allyl compound having a functional group that reacts with cyclic thiocarbonate in the polymerizable composition include diallyl phthalate, diallyl terephthalate, diallyl carbonate, allylamine, diallylamine, and N-methylallylamine.

  Examples of the (meth) acrylate compound having a functional group that reacts with cyclic thiocarbonate in the polymerizable composition include benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and bisphenol A diester. (Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like can be mentioned.

  Examples of the organic acid having a functional group that reacts with the cyclic thiocarbonate compound and its anhydride in the polymerizable composition include thiodiglycolic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, and methylnorbornene acid. Anhydride, methylnalbornanoic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned.

  Examples of the mercapto organic acid having a functional group that reacts with the cyclic thiocarbonate compound in the polymerizable composition include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, and thiosalicylic acid. .

  Examples of the mercaptoamine having a functional group that reacts with the cyclic thiocarbonate compound in the polymerizable composition include aminoethyl mercaptan, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol.

  Examples of the phenol compound having a functional group that reacts with the cyclic thiocarbonate compound in the polymerizable composition include phenol, o-cresol, m-cresol, p-cresol, 3-methoxyphenol, catechol, resorcin, hydroquinone, and pyrogallol. Etc.

  Of the organic compounds having a functional group that reacts with the cyclic thiocarbonate compound in the polymerizable composition, a thiol compound, an amine compound, a mercaptoamine, and a phenol compound are preferable, and a thiol compound is particularly preferable in terms of refractive index. Among these compounds, the compound represented by the general formula (4) is particularly preferable, and an intermediate of cyclic thiocarbonate can be used as it is.

  The organic compound having a functional group that reacts with the cyclic thiocarbonate in the polymerizable composition is present in the range of 0 to 70% by weight, more preferably 0 to 60% by weight, and particularly 0 to 50% by weight. Can be made.

  The polymerizable composition of the present invention may be added with an internal mold release agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a paint, a filler, etc., as long as there is no problem depending on the purpose.

  The polymerized cured product of the present invention can be obtained by curing reaction of the polymerizable composition. In the curing reaction, the composition is stirred at 0 ° C. to 80 ° C. in the presence of a curing catalyst, then poured into a glass or metal mold, and 10 to 200 ° C. over 1 to 72 hours, particularly 20 ° C. to 150 ° C. It is preferable to carry out by heating while gradually raising the temperature. The catalyst may be appropriately used as necessary within a range in which the curing reaction can be controlled. The amount of the catalyst used is, for example, 10% by weight or less, more preferably 0.001 to 3% by weight, particularly preferably the polymerizable composition. May be 0.01 to 1% by weight.

  Examples of the catalyst used for the curing reaction include the same transesterification catalyst as in the production of compound (4). Examples thereof include potassium carbonate, sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), quaternary. Ammonium salt (tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide), 1,8-diazabicyclo [5.4.0] undecene-7, 1,4-diazabicyclo [2.2.2] octane, lithium diisopropylamide, sodium hydroxide And basic compounds such as

  The optical material containing the polymerized cured product obtained as described above can be widely used for high refractive index optical materials such as plastic lenses, prisms, optical fibers, information recording bases, colored filters, and infrared absorption filters.

[Production of cyclic thiocarbonate thiol]
In a glass reactor having an internal volume of 200 ml equipped with a stirrer and a thermometer, 24.04 g (0.171 mol) of 1,2,3-trimercaptopropane, 36.68 g (0.171 mol) of diphenyl carbonate and 28 wt. % Sodium methoxide-methanol solution (catalyst) 0.236 g (0.0012 mol) was charged, and the reaction was carried out for 10 minutes at 60 ° C. under normal pressure. Next, after adding 0.25 g (0.0025 mol) of sulfuric acid, the mixture was stirred for 1 hour under conditions of normal pressure and room temperature. The reaction solution was dissolved in 500 ml of dichloromethane, and extraction and washing operations were performed twice using 500 ml of saturated saline. Magnesium sulfate was added to the organic layer after the extraction operation for dehydration treatment, and dichloromethane as a solvent and phenol as a reaction product were removed under reduced pressure at 140 ° C. and 1 mmHg (133 Pa). After the purification treatment, 27.25 g (yield 95.6%) of a transparent liquid cyclic thiocarbonate thiol (A) was obtained.

The measurement result of ¹ H-NMR (in deuterated chloroform) of the obtained cyclic thiocarbonate thiol (A) is shown below.
¹ H-NMR: (300 MHz, CDCl ₃ ) 1.68-1.74 ppm (q, J = 1.0 Hz, SH), 2.97-3.04 ppm (m, J = 1.2, 2.2, _{CH 2 SH), 3.70-3.91ppm (m} , J = 1.2,2.2, - CH 2 CH (R) CH 2 SH), 4.04-4.13ppm (m, J = 1 .2,2.2, - _{CH CH} 2 SH)

The measurement results of mass spectrometry (DI-MS CI) of the obtained cyclic thiocarbonate thiol (A) are described below.
Mass found mass = 167 (Exact Mass = 166.97)

[Production of cyclic thiocarbonate]
In a glass reactor having an internal volume of 100 ml, 10.00 g (0.0601 mol) of cyclic thiocarbonate thiol (A) and 19.49 g (0.0721 mol) of ferric chloride hexahydrate were dissolved in 60 ml of methanol. The mixture was stirred for 1 hour under normal pressure and room temperature. The reaction solution was dissolved in 200 ml of dichloromethane and extracted and washed twice with 200 ml of saturated saline. Magnesium sulfate was added to the organic layer after the extraction operation for dehydration treatment, and dichloromethane as a solvent was removed under conditions of normal pressure and 80 ° C. The white powder after removal of the solvent was washed with dichloromethane-heptane (1: 1, v / v) to obtain 8.34 g (yield 84.1%) of cyclic thiocarbonate (B) as a white powder.

The measurement result of ¹ H-NMR (in heavy dimethyl sulfoxide) of the obtained cyclic thiocarbonate (B) is shown below.
¹ H-NMR: (300 MHz, CDCl ₃ ) 3.23-3.40 ppm (m, J = 1.5, 5.4, CH ₂ SS—), 3.75-4.04 ppm (m, J = 1) _{.5,5.4, CH 2 CH (R)} CH2SS -), 4.55-4.63ppm (m, J = 1.5,5.4, - CH CH 2 SS)

The mass spectrometry (LC / MS FAB) result of the obtained cyclic thiocarbonate compound (B) is described below.
Mass found mass = 331 (Exact Mass + H = 330.91)

[Production of polymerization cured product]
10 g (0.0303 mol) of cyclic thiocarbonate (B), 10 g (0.0601 mol) of cyclic thiocarbonate thiol (A) and 0.2 g of potassium carbonate were sufficiently stirred to obtain a polymerizable composition. Were cast into a mold sandwiched between silicon rubber spacers. After casting, the mixture was allowed to stand at room temperature (25 ° C.) for 2 hours, and then heated from 25 ° C. to 100 ° C. over 35 hours, and the resulting polymerized cured product was released. The reaction was mild, and no bubbles were observed in the resulting polymerized cured product. When the refractive index was measured with an Abbe refractometer (manufactured by Atago; MR-04), the following results were obtained. The refractive index (n _e ) represents the value when irradiated with e-line (λ = 546 nm) at 23 ° C., and the Abbe number (ν _e ) represents e-line (λ = 546 nm) and F ′ line ( (λ = 480 nm) and the refractive index (n _e , n _{F ′} , n _{C ′} ) when irradiated with the C ′ line (λ = 644 nm), were calculated by the following equation.
ν _e = ( _ne −1) / (n _{F ′} −n _{C ′} )
Refractive index (n _e ): 1.75, Abbe number (ν _e ): 31.0

  The cyclic thiocarbonate of the present invention is easy to control the ring-opening polymerization reaction, and since the polymerized cured product has a high refractive index and Abbe number, plastic lenses, prisms, optical fibers, information storage bases, colored filters, infrared absorption It can be used for optical materials such as filters, optical films, and adhesives.

Claims (6)

The cyclic thiocarbonate represented by the general formula (1).

(In the formula, X and Y each independently represent an oxygen atom or a sulfur atom, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ represent 1 to 8 carbon atoms. Represents an alkylene chain, provided that R ¹ , R ² , R ³ , R ⁴ may contain a sulfur atom or a ring structure.) A polymerizable composition comprising the cyclic thiocarbonate and an organic compound having a functional group that reacts with the cyclic thiocarbonate as an optional component. The polymerizable composition according to claim 2, wherein the optional component is a thiol compound. A polymerized cured product obtained by polymerizing the polymerizable composition according to claim 2. An optical material comprising the polymerized cured product according to claim 4. After reacting the trithiol compound represented by the general formula (2) and the diaryl (thio) carbonate represented by the general formula (3) to obtain the compound represented by the general formula (4), the general formula (4) The method for producing a cyclic thiocarbonate according to claim 1, wherein the compound represented is oxidized. (However, the compound represented by the general formula (4) may be used alone or in combination.)

(In the formula, R corresponds to R ¹ or R ² and R ′ corresponds to R ³ or R ^4. R ¹ , R ² , R ³ and R ⁴ are the same as described above.)

(In the formula, A represents an oxygen atom or a sulfur atom corresponding to X or Y, and Ar represents an aromatic substituent.)

(In the formula, R, R ′ and A are the same as described above.)