JP6570064B2 - Process for producing 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane - Google Patents

Description

  The present invention relates to 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane suitable as a monomer for forming a resin (optical resin) constituting an optical member typified by an optical lens or an optical film. It relates to the manufacturing method.

  As optical members, resin materials are widely used because they can be reduced in size and weight, and are excellent in workability and productivity. In addition, with recent technological advancement, not only optical properties but also heat resistance There is also a need for excellent resin materials. In recent years, resin materials made from bisphenoxyethanolcyclododecanes with aromatic groups and cycloaliphatic groups in the molecule and a configuration called a cardo structure (for example, polycarbonate, polyester, polyacrylate, polyetherketone) Has been reported to have excellent transparency and heat resistance (for example, Patent Document 1). Further, the applicant of the present application has recently demanded a cured product of a glycidyl ether body obtained by reacting a bisphenoxyethanol having a cycloalkane skeleton, such as bisphenoxyethanol cyclododecanes, with an epihalohydrin in the advanced electronic device field. It has been found that it has excellent electrical characteristics such as a low dielectric constant and a low dielectric loss tangent in a high frequency region. However, almost no industrial production method for bisphenoxyethanol cyclododecanes is known, and development of an industrially superior production method has been demanded.

JP 2010-189629 A Japanese Patent Application No. 2015-178124

  The object of the present invention is to provide 1,1-bis- (4-hydroxyethoxy), which is known as a raw material monomer for polymers for forming optical resins and electronic materials, and whose production method is hardly known among bisphenoxyethanol cyclododecanes. An object of the present invention is to provide a method for industrially advantageously producing (-3-methylphenyl) cyclododecane.

  As a result of intensive studies to solve the above problems, the present inventors have used 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and ethylene carbonate as raw materials. It has been found that 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane can be advantageously produced industrially. Specifically, the following invention is included.

[1] Method for producing 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane by reacting 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane with ethylene carbonate .

[2] The 1,1-bis- described in [1], wherein the ethylene carbonate is used in an amount of 3.1 mol or more per 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane. A method for producing (4-hydroxyethoxy-3-methylphenyl) cyclododecane.

[3] [1] or [2], wherein the amount of ethylene carbonate used is 3.1 to 4.0 moles per mole of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane Of 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane.

  According to the present invention, high-purity 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane suitably used as a monomer for optical resins and electronic materials is industrially and highly yielded. It becomes possible to manufacture at a rate.

  In the present invention, 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and ethylene carbonate are reacted to produce 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane. It is characterized by obtaining. The target 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane is 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 2 mol of ethylene carbonate. In addition to this, a compound obtained by reacting 1 mol of ethylene carbonate with 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane as a side reaction product (hereinafter 1 mol addition) A compound obtained by reacting 3 mol of ethylene carbonate with 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (hereinafter sometimes referred to as 3 mol adduct). 4) ethylene carbonate per mole of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane. Or (sometimes hereinafter referred to 4 mol adduct) compounds reacted, (sometimes hereinafter referred to polymer) desired product compound obtained by polymerizing 2 moles or more carbonate bond, etc. is produced.

  1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane used in the present invention is an industrially available compound, but if necessary, in the presence of an acid, cyclododecanone, o-cresol, Can also be produced.

  The amount of ethylene carbonate used is, for example, 2 mol or more, preferably 3.1 mol or more, more preferably 3.1 mol to 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane. 4.0 moles are used. In the ethanolation reaction of phenolic hydroxyl groups of bisphenols using general ethylene carbonate, the physical properties of adducts of 3 mol or 4 mol or more are difficult to remove from the target product, whereas 1 mol adducts are phenolic. Since hydroxyl groups remain, it is easy to remove because of different physical properties. Use as much as 2 moles of ethylene carbonate for 1 mole of bisphenol as much as possible, and suppress the formation of 3 mole adducts and 4 moles or more adducts as much as possible. Things have been done. However, in the reaction with 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane of the present invention, if 3.1 mol or more is not used, 1 mol adduct does not decrease below a certain amount, Or since the increase rate of 3 mol adduct exceeded the decrease rate of 1 mol adduct, it turned out that a yield and quality may fall. Therefore, in order to obtain 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane with high yield and high purity, 1,1-bis- (4-hydroxy-3-methylphenyl) 3.1 mol or more of ethylene carbonate is used per 1 mol of cyclododecane. In addition, the amount of ethylene carbonate used is 4.0 mol or less with respect to 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane. Is easily suppressed.

  When carrying out this reaction, a solvent may or may not be used, but by reacting in the presence of an inert organic solvent, 1,1-bis- (4-hydroxyethoxy-3-methyl) is more efficiently obtained. Phenyl) cyclododecane is preferred because it is obtained. Examples of the inert organic solvent that can be used include aromatic hydrocarbons (eg, benzene, toluene, xylene, mesitylene, etc.), aliphatic hydrocarbons (eg, pentane, hexane, heptane, etc.), halogenated aromatic hydrocarbons (eg, chlorobenzene). , Dichlorobenzene, etc.), halogenated aliphatic hydrocarbons (eg, dichloromethane, 1,2-dichloroethane, etc.), ethers (eg, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl tertiary butyl ether, dioxane, cyclopentylmethyl) Ether, etc.), nitriles (eg acetonitrile, benzonitrile, etc.), amides (dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.) can be used A. Preferably, in a post-treatment step after the reaction, the organic layer containing 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane is washed directly with water without solvent substitution, Hydrophobic solvents are preferable because inorganic components used in the reaction can be removed, and toluene, xylene, and cyclopentyl methyl ether are particularly preferable. When the inert organic solvent is used, the amount used is 0.1 to 4 times by weight, preferably 0.5 to 1, times by weight of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane. 2 times the weight. When the amount of the solvent used is 0.1 weight times or more, stirring can be facilitated, so that a sufficient reaction rate can be obtained, and when the amount used is 4 weight times or less, the reaction accompanying dilution of the reaction system. It is possible to avoid a decrease in speed. Moreover, the inert organic solvent can also be used 1 type or in mixture of 2 or more types as needed.

  In this reaction, a catalyst is used if necessary. The catalyst used may be any of an alkali catalyst, an acid catalyst, and a quaternary ammonium salt, but an alkali catalyst is preferred from the viewpoint that the reaction proceeds rapidly and impurities are reduced. Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate and the like. Of these, potassium hydroxide, sodium hydroxide, and potassium carbonate are preferred. Examples of the acid catalyst include sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid and the like. Examples of the quaternary ammonium salt include benzyltriethylammonium chloride, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylammonium hydrogensulfate and the like. The catalysts may be used singly or, if necessary, the same type, or a mixture of two or more of an alkali catalyst and a quaternary ammonium salt, or an acid catalyst and a quaternary ammonium salt. The amount of the catalyst used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.15 mol, relative to 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane. is there. By using the catalyst in an amount of 0.01 mol or more with respect to 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane, a sufficient reaction rate can be obtained. By controlling the amount to 0.2 mol or less, generation of by-products such as multimers can be suppressed, and as a result, yield and purity can be improved and coloring can be reduced.

  The reaction temperature is usually 150 ° C. or lower, preferably 140 to 40 ° C., more preferably 130 to 70 ° C., particularly 120 to 90 ° C. By setting the reaction temperature to 150 ° C. or lower, it becomes possible to reduce the yield reduction and hue deterioration due to the increase of by-products, and by setting the reaction temperature to 40 ° C. or higher, a sufficient reaction rate can be obtained. It becomes possible. The reaction can be carried out in the air, but it is preferably carried out in an inert gas atmosphere such as nitrogen or argon from the viewpoint of safety and reduction of product coloring. The reaction can be followed by analytical means such as liquid chromatography.

  After the reaction, when the reaction mixture is in a slurry state, it is preferably washed with an alkaline aqueous solution and / or water in order to decompose and remove unreacted ethylene carbonate and polymer after adding a solvent and dissolving. Further, after appropriate post-treatment operations such as dehydration, filtration, adsorption treatment, etc., 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane is distilled, crystallized, and column chromatography. It can take out by the usual methods, such as. Further, the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane may be subjected to purification operations such as washing, adsorption, steam distillation, and recrystallization as needed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Hereinafter, in each Example and Reference Example, high performance liquid chromatography (HPLC) measurement was performed under the following measurement conditions, and the obtained area percentage values were defined as the residual rate, production rate, and HPLC purity of each component. (However, when the solvent used in the reaction is detected, it is the corrected surface percentage excluding the solvent peak.)
<HPLC measurement conditions>
Equipment: “LC-2010AHT” manufactured by Shimadzu Corporation
Column: “L-column ODS” manufactured by the Chemical Substance Evaluation Research Organization
(5μm, 4.6mmφ × 250mm)
Column temperature: 40 ° C
Detection wavelength: UV 254 nm
Mobile phase: liquid A = 30% methanol, liquid B = methanol mobile phase flow rate: 1.0 ml / min Mobile phase gradient: concentration of liquid B: 57% (0 minutes) → 57% (after 10 minutes) → 85% (20 After minutes) → 85% (after 30 minutes) → 100% (after 35 minutes) → 100% (after 55 minutes)

Example 1
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) .100 mol), 28.5 g (0.324 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate and 38 g of toluene were charged, the temperature was raised to 120 ° C., and the reaction was carried out at 120 ° C. for 16 hours. When the reaction solution was analyzed by HPLC, 1 mol of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane was found. The remaining amount of the adduct is 0.1% or less, the target 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane is 70.8%, and the 3 mol adduct is 4.9. %, And 19.3% polymer was produced. After concentrating the reaction mixture and distilling off toluene, the reaction mixture was diluted with 570 g of cyclopentyl methyl ether, diluted with 48 g of a 6% aqueous sodium hydroxide solution and stirred at 80 ° C. The coalescence was broken down. After the decomposition, stirring was stopped and the mixture was allowed to stand. Then, the aqueous layer was separated, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 40.3 g (yield 86.0%) of white crystals of methylphenyl) cyclododecane were obtained. The obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC. As a result, the HPLC purity was 97.0%, and the content of 3 mol adduct was 1.3%. there were.

(Example 2)
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) .100 mol), 28.5 g (0.324 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate and 38 g of cyclopentyl methyl ether were added, the temperature was raised to 115 ° C., and the reaction was carried out at 115 ° C. for 10 hours. When the reaction solution was analyzed by HPLC, 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane 0.2%, the remaining amount of 1 mol adduct was 1.6%, and the desired product 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was 67.6%, 3 mol adduct was 5.4%, and polymer was 17.4%. To this reaction mixture, 380 g of cyclopentyl methyl ether was added, 15 g of 29% sodium hydroxide aqueous solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand. Then, the aqueous layer was separated, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 41.8 g (yield 89.2%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 97.4%, and the content of 3 mol adduct was 1.8%. The content of 1 mol adduct was 0.5%.

(Example 3)
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) 100 mol), 30.8 g (0.350 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate, and 38 g of cyclopentyl methyl ether were heated to 115 ° C. and reacted at 115 ° C. for 6 hours. When the reaction solution was analyzed by HPLC, the amount of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 1 molar adduct was 0.1% or less, As a result, 77.0% of 1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was formed, 4.3% of a 3 mol adduct, and 14.4% of a polymer were formed. To this reaction mixture, 380 g of cyclopentyl methyl ether was added, 15 g of 29% sodium hydroxide aqueous solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand, and then the aqueous layer was separated and washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 42.3 g (yield 90.3%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 98.1%, and the content of 3 mol adduct was 1.3%. there were.

(Example 4)
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) 100 mol), 34.9 g (0.396 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate and 38 g of cyclopentyl methyl ether were added, the temperature was raised to 120 ° C., and the reaction was carried out at 120 ° C. for 7.5 hours. When the reaction solution was analyzed by HPLC, the amount of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 1 molar adduct was 0.1% or less, 66.5% of 1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was produced, 6.3% of a 3 mol adduct, and 19.0% of a polymer were produced. To this reaction mixture, 380 g of cyclopentyl methyl ether was added, 57 g of an 8% aqueous sodium hydroxide solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand. Then, the aqueous layer was separated, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 40.9 g (yield 87.3%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 97.1%, and the content of 3 mol adduct was 2.7%. there were.

(Example 5)
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) 100 mol), 37.0 g (0.420 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate and 38 g of cyclopentyl methyl ether were added, the temperature was raised to 115 ° C., and the reaction was carried out at 115 ° C. for 6 hours. When the reaction solution was analyzed by HPLC, the amount of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 1 molar adduct was 0.1% or less, As a result, 69.2% of 1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was produced, 10.6% of a 3 mol adduct, and 13.3% of a polymer were produced. To this reaction mixture, 380 g of cyclopentyl methyl ether was added, 57 g of an 8% aqueous sodium hydroxide solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand, and then the aqueous layer was separated and washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 39.0 g (yield 83.3%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 95.1%, and the content of 3 mol adduct was 4.7%. there were.

Example 6
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) 100 mol), 39.6 g (0.450 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate, and 38 g of cyclopentyl methyl ether, the temperature was raised to 115 ° C., and the reaction was carried out at 115 ° C. for 6 hours. When the reaction solution was analyzed by HPLC, the amount of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 1 molar adduct was 0.1% or less, 14.5% of 1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was produced, 11.5% of a 3 mol adduct, and 14.0% of a polymer. To this reaction mixture, 380 g of cyclopentyl methyl ether was added, 57 g of an 8% aqueous sodium hydroxide solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand. Then, the aqueous layer was separated, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 38.0 g (yield 81.1%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 94.8%, and the content of 3 mol adduct was 5.0%. there were.

(Example 7)
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) .100 mol), 44.0 g (0.500 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate and 38 g of cyclopentyl methyl ether were added, the temperature was raised to 115 ° C., and the reaction was carried out at 115 ° C. for 6 hours. When the reaction solution was analyzed by HPLC, the amount of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 1 molar adduct was 0.1% or less, 60.4% of 1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was produced, 16.2% of a 3 mol adduct, and 11.2% of a polymer were produced. To this reaction mixture, 380 g of cyclopentyl methyl ether was added, 57 g of an 8% aqueous sodium hydroxide solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand. Then, the aqueous layer was separated, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 36.1 g (yield 77.0%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 92.5%, and the content of 3 mol adduct was 6.9%. there were.

(Example 8)
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) 100 mol), 26.1 g (0.297 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate, and 38 g of toluene, the temperature was raised to 115 ° C., and the reaction was carried out at 115 ° C. for 28 hours. When the reaction solution was analyzed by HPLC, 0.5% of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and 16.5% of 1 mol adduct remained, and the target product 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was 62.0%, 3 mol adduct was 1.3%, and polymer was 14.1%. After concentrating the reaction mixture and distilling off toluene, 570 g of cyclopentyl methyl ether was added, and 48 g of a 6% aqueous sodium hydroxide solution was added, followed by stirring at 80 ° C. to decompose unreacted ethylene carbonate and polymer. did. After the decomposition, stirring was stopped and the mixture was allowed to stand. Then, the aqueous layer was separated, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 28.4 g (yield 60.6%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 96.0%, the content of the 3 molar adduct was 0.1%, The content of 1 mol adduct was 2.6%.

Example 9
To a glass reactor equipped with a stirrer, a cooler, and a thermometer, 38.1 g (0) of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) 100 mol), 22.0 g (0.250 mol) of ethylene carbonate, 1.9 g (0.014 mol) of potassium carbonate, and 38 g of cyclopentyl methyl ether, the temperature was raised to 115 ° C., and the reaction was carried out at 115 ° C. for 6 hours. When the reaction solution was analyzed by HPLC, 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane was found to be 0.1% or less, but 16.6% of 1 mol adduct remained. The target 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was 70.4%, the 3-mol adduct was 1.5%, and the polymer was 9.6. % Was produced. Therefore, in order to further reduce the 1 mol adduct, stirring was continued at the same temperature for 9 hours (15 hours in total). After the reaction, the reaction solution was analyzed by HPLC. As a result, the residual amount of 1-mol adduct of 1-bis- (4-hydroxy-3-methylphenyl) cyclododecane was 0.1% or less, 71.5% of 1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was formed, 19.4% of a 3 mol adduct, and 1.8% of a polymer were formed. To this reaction mixture, 380 g of cyclopentyl methyl ether was added, 57 g of an 8% aqueous sodium hydroxide solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand, and then the aqueous layer was separated and washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxy-3- 33.9 g (yield 72.4%) of white crystals of methylphenyl) cyclododecane were obtained. When the obtained 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane was analyzed by HPLC, the HPLC purity was 90.4%, and the 3-mol adduct was 8.3%. .

(Reference Example 1)
In a glass reactor equipped with a stirrer, a cooler, and a thermometer, 35.3 g (0.100 mol) of 1,1-bis- (4-hydroxyphenyl) cyclododecane (manufactured by Taoka Chemical Co., Ltd.) 19.4 g (0.220 mol) of ethylene carbonate, 1.8 g (0.013 mol) of potassium carbonate and 18 g of toluene were charged, the temperature was raised to 115 ° C., and the reaction was carried out at 115 ° C. for 17 hours. When the reaction solution was analyzed by HPLC, it was found that 1 mol of ethylene carbonate was added to 1,1-bis- (4-hydroxyphenyl) cyclododecane and 1,1-bis- (4-hydroxyphenyl) cyclododecane. The remaining amount is 0.1% or less, the target 1,1-bis- (4-hydroxyethoxyphenyl) cyclododecane is 93.3%, 1,1-bis- (4-hydroxyphenyl) cyclododecane 1 1.0% of the compound in which 3 mol of ethylene carbonate was added per mol and 4.0% of the polymer were produced. 124 g of toluene was added to the reaction mixture, 53 g of a 10% aqueous sodium hydroxide solution was further added, and the mixture was stirred at 80 ° C. to decompose unreacted ethylene carbonate and polymer. After the decomposition, stirring was stopped and the mixture was allowed to stand. Then, the aqueous layer was separated, and further washed with water until the washing water became neutral. After washing with water, the organic solvent phase is refluxed and dehydrated, and then cooled to 25 ° C. to precipitate crystals. The precipitated crystals are filtered and dried to obtain the desired 1,1-bis- (4-hydroxyethoxyphenyl) cyclohexane. 38.2 g (yield 86.7%) of white crystals of dodecane were obtained. The obtained 1,1-bis- (4-hydroxyethoxyphenyl) cyclododecane was analyzed by HPLC. The HPLC purity was 99.2% and 1,1-bis- (4-hydroxyphenyl) cyclododecane was 1 mol. On the other hand, the content of the compound in which 3 mol of ethylene carbonate was added was 0.1% or less.

Claims (2)

A process for producing 1,1-bis- (4-hydroxyethoxy-3-methylphenyl) cyclododecane by reacting 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane with ethylene carbonate, , the amount of ethylene carbonate and 1,1-bis - (4-hydroxy-3-methylphenyl) cyclododecane 1 mole is 3.1 mol or more 1,1-bis - (4-hydroxyethoxy-3- A process for producing methylphenyl) cyclododecane. The amount of ethylene carbonate and 1,1-bis - (4-hydroxy-3-methylphenyl) cyclododecane 1 mol 3.1 to 4.0 mol of claim 1, wherein the 1,1-bis - A method for producing (4-hydroxyethoxy-3-methylphenyl) cyclododecane.