JP2008137918A - Method for producing silicone monomer, method for producing its intermediate and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a silicone compound, with which a silicone compound having excellent hydrolytic resistance and containing a three-dimensionally bulky substituent group and a silicone monomer are synthesized at high purity and a method for producing a silicone monomer using the production method and to obtain a molded article by copolymerizing the silicone monomer with another monomer and an ophthalmic lens composed of the molded article. <P>SOLUTION: A halosilane compound having a specific structure is reacted with a 3-glycidoxypropylalkoxysilane having a specific structure to give a specific silicone compound. The silicone compound is reacted with a base to give a specified silicone compound. The silicone compound is reacted with a carboxylic acid containing at least one radically polymerizable carbon-carbon double bond to give the silicone monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a silicone monomer, a method for producing a silicone compound as an intermediate thereof, and a molded article and an ophthalmic lens using the monomer. The molded body is suitable as an ophthalmic lens, and particularly suitable as a contact lens material.

At present, a siloxy group-containing monomer having high oxygen permeability is known as a raw material monomer for contact lens materials. Among them, a monomer having a hydroxyl group and a siloxy group in the monomer can impart hydrophilicity due to the hydroxyl group in addition to the high oxygen permeability described above. Therefore, such a monomer is excellent in compatibility with other hydrophilic monomers, and thus provides advantages such as moderate moisture content and reduction of dry feeling when worn for contact lenses containing such a monomer as a copolymerization component. be able to.
Depending on the copolymer composition of the contact lens, the physical properties of the lens may change due to hydrolysis. In order to improve these, development of a monomer having hydrolysis resistance is required.
Conventionally, a raw material monomer for contact lenses is produced via a silicone monomer intermediate represented by the formula (5 ′). As a method for producing the intermediate, a method by hydrosilylation shown in the following reaction formula (9) or a method by silanol exchange reaction shown in the following reaction formula (10) is known.

(Wherein R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} each independently represents a monovalent hydrocarbon group, R ^{5 ′} represents a C 1-4 alkyl group, and X represents a chlorine atom. , Bromine atom and iodine atom, n is an integer of 1-3.)

However, when the conventional method for producing a silicone monomer intermediate represented by the above formulas (9) and (10) is applied to a case where one of the substituents on silicon having a high hydrolysis resistance has 2 or more carbon atoms. Difficulties arise.
For example, in the hydrosilylation reaction of reaction formula (9), the silicon compound as a raw material is synthesized by a cohydrolysis reaction of the corresponding alkoxysilane and organohalosilane. When the number of carbon atoms is 2 or more, many compounds obtained by condensing alkoxysilanes as raw materials are obtained, and it is difficult to efficiently obtain a silicon compound as a raw material.

  Further, organosilanol is used in the silanol exchange reaction of Patent Document 1 represented by the reaction formula (10). Generally, organosilanol is synthesized by hydrolysis reaction of a corresponding organohalosilane. At that time, it is necessary to strictly adjust the pH in the system, and silanol is easy to dehydrate and condense. Therefore, it is difficult to obtain silanol efficiently especially when the substituent on silicon has 2 or more carbon atoms. It is.

  Thus, it was difficult to synthesize a compound having 2 or more carbon atoms on the silicon by a conventional method.

  On the other hand, a compound having no more than 2 carbon atoms as a substituent on silicon has a problem that its hydrolysis resistance is not sufficient.

  Further, in order to increase the functionality of contact lenses in the future, silicone monomers with higher hydrolysis resistance and contact lenses using them are required.

JP-A-4-74185

  An object of the present invention is to provide a method for producing a silicone compound and a silicone monomer using the same, which can synthesize a silicone compound and a silicone monomer having a sterically bulky substituent having excellent hydrolysis resistance and high purity. And a molded product obtained by copolymerizing the silicone monomer and another monomer, and an ophthalmic lens comprising the molded product.

  In the present invention, a compound represented by the following formula (1) and a compound represented by the following formula (2) are reacted in the presence of water to obtain a silicone compound represented by the following formula (3) and / or (4). Then, a method for producing a silicone compound is provided, in which the silicone compound represented by the following formula (3) and / or (4) is treated with a base to obtain the silicone compound represented by the following formula (5).

(In the above formulas (1) to (5), R ¹ , R ² , R ³ and R ⁴ are each independently selected from an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 1 to 7 carbon atoms and a phenyl group. , R ¹ , R ² , R ³ , at least one of which has 2 or more carbon atoms, R ⁵ is selected from an alkyl group having 1 to 4 carbon atoms, and X is selected from a chlorine atom, a bromine atom, and an iodine atom N is an integer of 1-3.)

  Moreover, this invention makes the silicone compound shown by the following formula (5) obtained by the method of the said invention and the compound shown by the following formula (6) react, and the following formula (7) and / or (8) The manufacturing method of the silicone monomer which obtains the silicone monomer shown by is provided.

(In the formula ^{(6) ~ (8),} R 1, R 2, R 3, R 4 and ^{R 5} are the above formula (1) ^R 1 in ^{~ (5), R 2,} R 3, R 4 and R ⁶ has the same meaning as R ^5, and R ⁶ is selected from organic groups having 2 to 20 carbon atoms having at least one carbon-carbon unsaturated double bond.

  Furthermore, this invention provides the molded object obtained by superposing | polymerizing the monomer mixture containing the silicone monomer obtained by the manufacturing method of the said invention. Furthermore, the present invention provides an ophthalmic lens comprising the molded article of the present invention.

  According to the production method of the present invention, a silicone compound having a substituent having a large steric hindrance that has been difficult to synthesize by a conventional method can be synthesized with high purity. The silicone compound obtained by this method is excellent in hydrolysis resistance and excellent in long-term stability. Therefore, the silicone monomer obtained by the present invention improves the hydrolysis resistance of the molded article obtained from the silicone monomer, particularly a contact lens. For this reason, even a copolymer with a monomer containing an ionic group is stable, and the lens physical properties hardly change for a long time.

  As described above, in the method for producing a silicone compound of the present invention, the compound represented by the above formula (1) and the compound represented by the above formula (2) are reacted in the presence of water to formula (3) and / or ( A silicone compound represented by 4) is obtained, and then the silicone compound represented by formula (3) and / or (4) is treated with a base to obtain a silicone compound represented by formula (5).

In the above formulas (1) to (5), R ¹ , R ² , R ³ and R ⁴ are each independently selected from an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 1 to 7 carbon atoms and a phenyl group, At least one of R ¹ , R ² and R ³ has 2 or more carbon atoms, R ⁵ is selected from an alkyl group having 1 to 4 carbon atoms, and X is selected from a chlorine atom, a bromine atom and an iodine atom. n is an integer of 1-3. In addition, when there are a plurality of groups represented by R ¹ , R ² , R ³ , R ⁴ or R ⁵ in each formula, the plurality of groups represented by the same symbol are also independent. .

In the method for producing a silicone compound of the present invention, the halosilane compound used as a raw material is represented by the above formula (1), and R ¹ , R ² and R ³ in the formula each independently have 1 carbon atom. A -7 alkyl group, an alkenyl group having 2 to 7 carbon atoms, and a phenyl group. For example, R ¹ , R ² , R ³ are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, benzyl group, A phenyl group, a tolyl group, a vinyl group, an allyl group and the like are exemplified, but since the present invention is effective particularly in the case of introducing a substituent having a large steric hindrance, at least one of R ¹ , R ² and R ³ is It is necessary to have 2 or more carbon atoms. When all of R ¹ , R ² and R ³ have 1 or less carbon atoms, it is difficult to obtain a molded article having high hydrolysis resistance. Examples of X, which is a halogen atom, include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable because of availability of raw materials.

  Specific examples of such halosilanes include allyldimethylchlorosilane, benzylchlorosilane, n-butyldimethylchlorosilane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, chlorodiisopropylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, chloro Examples include triethylsilane, chlorotrimethylsilane, chlorodiethylisopropylsilane, dimethylethylchlorosilane, dimethylisopropylchlorosilane, dimethyl-n-propylchlorosilane, diphenylmethylchlorosilane, triisopropylsilyl chloride, and triphenylsilyl chloride. These halosilanes can be used alone or in combination of two or more.

The 3-glycidoxypropylalkoxysilane, which is a raw material used simultaneously in the method for producing a silicone compound of the present invention, is represented by the above formula (2), wherein R ⁴ is a hydrogen atom, a carbon number. An alkyl group having 1-7, an alkenyl group having 2-7 carbon atoms, and a phenyl group; Specific examples of the alkyl group having 1 to 7 carbon atoms, the alkenyl group having 2 to 7 carbon atoms and the phenyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, cyclohexane Examples include propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenyl group, tolyl group, vinyl group, and allyl group.

R ⁵ in the formula is an alkyl group having 1 to 4 carbon atoms. For example, examples of R ⁵ include a methyl group, an ethyl group, a propyl group, and a butyl group. From the viewpoint of easy availability of raw materials and the reaction rate of cohydrolysis, a methyl group and an ethyl group are preferable. Groups are more preferred. Specific examples of such 3-glycidoxypropylalkoxysilane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Sidoxypropyldiethoxysilane, 3-glycidoxypropylmethoxysilane, 3-glycidoxypropylethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 3-glycid Xylpropylmethoxymethylsilane, 3-glycidoxypropylethoxymethylsilane, 3-glycidoxypropylmethoxydimethylsilane, 3-glycidoxypropylethoxydimethylsilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycid Xylpropyldiethylmethoxysilane, 3- Lysidoxypropylethylethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, 3-glycidoxypropyldimethoxypropylsilane, 3-glycidoxypropylmethoxypropylsilane, 3- Glycidoxypropylmethoxydipropylsilane, 3-glycidoxypropyldimethoxybutylsilane, 3-glycidoxypropylmethoxybutylsilane, 3-glycidoxypropylmethoxydibutylsilane, 3-glycidoxypropyldimethoxypentylsilane, 3 -Glycidoxypropylmethoxypentylsilane, 3-glycidoxypropylmethoxydipentylsilane, 3-glycidoxypropyldimethoxyhexylsilane, 3-glycidoxypropylmethoxyhexylsilane, 3-glycidoxypropylmethoxy Dihexylsilane, 3-glycidoxypropyldimethoxyheptylsilane, 3-glycidoxypropylmethoxyheptylsilane, 3-glycidoxypropylmethoxydiheptylsilane, 3-glycidoxypropyldimethoxyvinylsilane, 3-glycidoxypropylmethoxy Vinyl silane, 3-glycidoxypropylmethoxydivinylsilane, 3-glycidoxypropyldimethoxyallylsilane, 3-glycidoxypropylmethoxyallylsilane, 3-glycidoxypropylmethoxydiallylsilane, 3-glycidoxypropyldimethoxyphenylsilane, 3-glycidoxypropylmethoxyphenylsilane, 3-glycidoxypropylmethoxydiphenylsilane, 3-glycidoxypropyldimethoxytolylsilane, 3-glycidoxypropylmethoxytolylsilane, 3-glycidoxy Cypropylmethoxyditolylsilane, 3-glycidoxypropylmethoxymethylethylsilane, 3-glycidoxypropylmethoxymethylpropylsilane, 3-glycidoxypropylmethoxymethylbutylsilane, 3-glycidoxypropylmethoxymethylpentylsilane 3-glycidoxypropylmethoxymethylhexylsilane, 3-glycidoxypropylmethoxymethylheptylsilane, 3-glycidoxypropylmethoxymethylphenylsilane, 3-glycidoxypropylmethoxymethyltolylsilane, 3-glycidoxy Propylmethoxymethylvinylsilane, 3-glycidoxypropylmethoxymethylallylsilane, 3-glycidoxypropylmethoxyethylpropylsilane, 3-glycidoxypropylmethoxyethylbutylsilane, 3-glycidoxypropylmethoxy Ethylpentylsilane, 3-glycidoxypropylmethoxyethylhexylsilane, 3-glycidoxypropylmethoxyethylheptylsilane, 3-glycidoxypropylmethoxyethylphenylsilane, 3-glycidoxypropylmethoxyethyltolylsilane, 3-glycidylsilane Sidoxypropyl methoxyethyl vinyl silane, 3-glycidoxy propyl methoxyethyl allyl silane, 3-glycidoxy propyl methoxypropyl butyl silane, 3-glycidoxy propyl methoxypropyl pentyl silane, 3-glycidoxy propyl methoxypropyl hexyl silane, 3-glycidoxypropylmethoxypropyl heptylsilane, 3-glycidoxypropylmethoxypropylphenylsilane, 3-glycidoxypropylmethoxypropyltolylsilane, 3-glycidoxypropylmeth Shi propyl vinyl silane, 3-glycidoxypropyl-methoxypropyl allyl silane, and the like. These 3-glycidoxypropylalkoxysilanes can be used alone or in combination of two or more.

  In the formula (2), n represents the number of substituents on silicon, and 2 or 3 is preferable from the viewpoint of improving hydrolysis resistance, and 3 is more preferable.

  In the reaction in the presence of water in the present invention, the solvent to be used includes alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and ethers such as ethyl ether. Or a three-component system such as aromatic hydrocarbons such as toluene and xylene and distilled water. Although the density | concentration of the water in a solvent is not specifically limited, Usually, it is about 10 to 60 weight%. This reaction is preferably carried out by simultaneously dropping the compound represented by the above formula (1) and the compound represented by the above formula (2) while vigorously stirring the suspension solution. At the time of this dripping, the compound represented by the above formula (1) and the compound represented by the above formula (2) may be mixed well in advance, and the mixed solution may be dropped, or each may be dropped simultaneously. After the reaction, in order to remove hydrogen chloride generated in the system, it is washed with an alkaline aqueous solution such as saturated aqueous sodium hydrogen carbonate, dried over anhydrous sodium sulfate, etc., and purified to obtain the above formula (3) and / or (4). Can be obtained.

  This reaction proceeds in a wide temperature range, but is substantially carried out in a temperature range of -20 ° C to 60 ° C, preferably 0 ° C to 40 ° C. While the reaction time varies depending on the reaction conditions, it is usually carried out in the range of 1 hour to 10 hours.

  The ratio of the compound represented by the above formula (1) and the compound represented by the above formula (2) is represented by the above formula (1) with respect to the number of moles of the alkoxy group of the compound represented by the above formula (2). The stoichiometric amount (stoichiometric molar amount) to 10 times the molar amount (that is, 1 equivalent to 10 equivalents to 1 equivalent of the alkoxy group of the compound represented by (2)), preferably 2 times It is desirable to use a molar amount of 5 to 5 molar amounts (2 to 5 equivalents). If it is less than twice the theoretical molar amount, the co-hydrolysis reaction and the epoxide ring-opening reaction are insufficient, and it is difficult to obtain the desired product in high yield and high purity. On the other hand, if the molar amount exceeds 5 times, the compound represented by the above formula (1) is wasted, which is economically disadvantageous.

  In the treatment with the base carried out following the compound obtained above, the base used is an inorganic alkali metal salt such as sodium hydroxide, potassium hydroxide or potassium carbonate, or an organic alkali such as sodium methoxide or sodium ethoxide. Metal salts, tertiary alkylamines such as trimethylamine and triethylamine, aromatic amines such as pyridine and 4-dimethylaminopyridine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4 , 3,0] -5-nonene, heterocyclic amines such as 1,8-diazabicyclo [5,4,0] -7-undecene, etc. can be used. In view of production, it is desirable to use sodium hydroxide or potassium hydroxide. Note that one type of base can be used, or a plurality of types of bases can be used in combination.

  The molar amount of the base used in this reaction is equimolar or more, preferably 1.2 mol or more, more preferably 1.5 mol or more with respect to the compound represented by the above formula (3) and / or (4). desirable. The upper limit of the amount of the base used is not particularly limited, but is usually 10 mol or less with respect to 1 mol of the compound represented by the above formula (3) and / or (4). Solvents used simultaneously include alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, and ethyl ether. , Ethers such as tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, etc., distilled water, etc., can be used. You may mix and use. The reaction temperature is −78 ° C. to the boiling point of the solvent, preferably −20 ° C. to 40 ° C., more preferably 0 ° C. to room temperature. The reaction time depends on the reaction conditions, but is usually in the range of 1 hour to 48 hours.

  The treatment with the base of the present invention can be carried out by adding halohydroxypropoxypropylorganosiloxysilane to a solution containing the base. After the reaction, in order to remove inorganic or organic salts and excess base generated in the system, it is washed with an acid / alkaline aqueous solution and distilled water or the like, or the precipitate or crystals are filtered, and then dried over anhydrous sodium sulfate, By refine | purifying, the compound shown by the said Formula (5) can be obtained.

  In the present invention, the silicone compound represented by the above formula (5) obtained by the method for producing a silicone compound of the present invention is reacted with the compound represented by the above formula (6) to obtain the above formula (7) and / or The manufacturing method of the silicone monomer which obtains the silicone monomer shown by (8) is provided.

In the formula (6) to (8), wherein ^{(6) ~ (8),} R 1, R 2, R 3, R 4 and ^{R 5, R 1} in the formula (1) to (5) , R ² , R ³ , R ⁴ and R ^5, and R ⁶ is selected from C 2-20 organic groups having at least one carbon-carbon unsaturated double bond. )

  In the method for producing a silicone monomer of the present invention, the compound represented by the above formula (6) that is reacted with the silicone compound represented by the above formula (5) has at least one carbon-carbon double bond capable of radical polymerization. It is an organic group having 2 to 20 carbon atoms. Specific examples include vinyloxyacetic acid, allyloxyacetic acid, (meth) acrylic acid, crotonic acid, 2- (meth) acryloylpropanoic acid, 3- (meth) acryloylbutanoic acid, 4-vinylbenzoic acid and the like.

  In the reaction of the silicone compound represented by the formula (5) and the compound represented by the formula (6), it is not always necessary to use a solvent. When a solvent is used, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, ethyl Examples include ethers such as ether and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane. Solvent-free or aromatic hydrocarbons such as benzene and toluene are preferable.

  The above reaction is usually performed in a temperature range of 20 ° C to 40 ° C, preferably 60 ° C to 120 ° C. Although reaction time is not specifically limited, Usually, it is performed in the range of 4 hours-24 hours.

  In the production method of the silicone monomer of the present invention, the use ratio of the silicone compound represented by the formula (5) and the compound represented by the formula (6) is usually 1 with respect to 1 mol of the compound represented by the formula (5). It is desirable to use 10 mol to 10 mol, preferably 2 mol to 6 mol.

  The molded product of the present invention can be obtained by copolymerizing a monomer mixed solution composed of the above silicone monomer and another monomer. The polymerization reaction is performed in the presence of a radical initiator in the temperature range from room temperature to 80 ° C. As the radical initiator, any one of heat and photoinitiator can be used as long as it is used for vinyl polymerization. Examples of other monomers that can be used include ethylene glycol dimethacrylate, N, N-dimethylacrylamide, hydroxylethyl methacrylate, methacrylic acid, and N-vinylpyrrolidone. Further, the use ratio of the silicone monomer obtained by the method of the present invention and other monomers is not particularly limited, but usually the silicone monomer obtained by the method of the present invention is from 1 part by weight in the total monomer mixture. About 90 parts by weight.

A molded product can be obtained by polymerizing such a radical initiator-containing monomer mixture containing a silicone monomer in an arbitrary shape such as a sheet, a film, a rod, a button, or a disk. Further, in the case of an ophthalmic lens, the ophthalmic lens can be obtained by cutting the molded body or polymerizing it in a lens-shaped mold and machining it such as cutting and polishing.
Since the molded article of the present invention has excellent hydrolysis resistance and has both a hydrophilic group and a siloxy group, it can be suitably used for ophthalmic lenses, particularly contact lenses.

  Specific embodiments of the present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Example 1
Synthesis of silicone compounds

  While vigorously stirring 16.6 g of methanol cooled at 0 ° C, 16.7 g of hexane and 33.3 g of distilled water, 3-glycidyloxypropyldimethoxymethylsilane (25.16 g, 0.113 mol) and dimethylethylsilyl chloride (55.7 g, 0.454 mol) ) Were mixed and added dropwise over 1.5 hours. After dropping, the temperature was gradually raised from 0 ° C. to room temperature and stirred for 2 hours. The reaction was stopped, the aqueous layer was separated, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate (30 ml) and saturated brine (35 ml), and this operation was repeated once more and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and dried to obtain 44.35 g of a crude product.

  Purification by distillation gave a colorless transparent liquid (12.22 g, purity 83.8%) represented by the above formulas (11) and (12) as a mixture.

  Subsequently, potassium hydroxide (2.5 g, 43.9 mmol) / 50 wt% aqueous methanol solution (10 ml) cooled at 0 ° C. was mixed with the mixture represented by the above formulas (11) and (12) (9.32 g, 23.2 mmol) at a time. added. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 10 hours. About 50 ml of distilled water was added, the organic layer was separated, and the aqueous layer was extracted with ether (2 × 50 ml). The organic layer was washed with distilled water (3 × 50 ml) and saturated brine (2 × 50 ml), and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and vacuum drying was performed to obtain a crude product (7.8 g). Distillation under reduced pressure was performed to obtain a colorless transparent liquid (5.84 g, purity 89%) represented by the above formula (13). The purity of the compound was determined by gas chromatography.

Example 2
Synthesis of silicone compounds

  While stirring vigorously 24.9 g of methanol cooled at 0 ° C, 24.9 g of hexane and 50 g of distilled water, 3-glycidylyloxypropyltrimethoxysilane (33.1 g, 0.14 mol) and dimethylethylsilyl chloride (102.93 g, 0.84 mol) ) And mixed dropwise over 1 hour. After dropping, the mixture was further stirred at 0 ° C. for 2 hours, gradually warmed to room temperature and stirred for 1 hour. The reaction was stopped, the aqueous layer was separated, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate (50 ml) and saturated brine (50 ml). This operation was repeated once more and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and dried to obtain a crude product.

  Purification by distillation gave a colorless transparent liquid (23.53 g, purity 85%) represented by the above formulas (14) and (15) as a mixture.

  Subsequently, potassium hydroxide (3.0 g, 53.4 mmol) / 50 wt% aqueous methanol solution (8 ml) cooled at 0 ° C. was mixed with the mixture represented by the above formulas (14) and (15) (15.0 g, 23.3 mmol) at a time. added. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 18 hours. About 40 ml of distilled water was added, the organic layer was separated, and the aqueous layer was extracted with ether (50 ml × 2). The organic layer was washed with distilled water (100 ml × 3) and dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and vacuum drying was performed to obtain a crude product (11.94 g).

  A colorless transparent liquid (5.83 g, purity 85.8%) represented by the above formula (16) was obtained by distillation.

  The purity of the compound was determined by gas chromatography.

Example 3
Synthesis of silicone monomers

  p-Methoxyphenol (13.5 mg, 0.12 mmol), sodium methacrylate (0.4 g, 3.70 mmol), (4.5 g, 12.3 mmol) represented by the above formula (13) obtained in Example 1 and methacrylic acid (4.2 ml) , 49.4 mmol) was reacted at 100 ° C. for 8 hours.

  After cooling, the mixture was dissolved in 40 ml of ether, washed with 1N aqueous sodium hydroxide solution (5 × 20 ml) and saturated brine (2 × 20 ml), and dried over anhydrous sodium sulfate.

  After filtration, evaporation of the solvent, and vacuum drying, a crude product (5.06 g) was obtained, followed by purification by silica gel column chromatography. A colorless transparent liquid represented by the above formula (17) and / or (18) ( 2.92 g, yield 53%, purity 97.8%).

Example 4
Synthesis of silicone monomers

  p-Methoxyphenol (13.6 mg, 0.11 mmol), sodium methacrylate (0.37 g, 3.4 mmol), the compound represented by the above formula (16) obtained in Example 2 (5.12 g, 11.3 mmol) and methacrylic acid ( 3.84 ml, 45.2 mmol) was reacted at 100 ° C. for 9 hours.

  After cooling, it was dissolved in 20 ml of ether, washed with 1N aqueous sodium hydroxide solution (7 × 10 ml) and saturated brine (2 × 10 ml), and dried over anhydrous sodium sulfate.

  After filtration, evaporation of the solvent, and vacuum drying, a crude product (5.66 g) was obtained, and purified by silica gel column chromatography to obtain a colorless transparent liquid (3.49 g, 3.49 g, Yield 55%, purity 95.8%).

Example 5
Comparison of monomer hydrolyzability

  0.1 g of the compound represented by the above formula (17) and / or (18) obtained in Example 3 was added to a 20 mL screw tube with 2-propanol (3.90 g), acetic acid (0.24 g), distilled water (0.90 g). ) And 2,6-di-t-butyl-4-methylphenol (2 mg) were mixed well and sealed. The screw tube was treated at 80 ° C. for 168 hours. The change in the area of the target compound after 168 hours was measured with the area by gas chromatography at that time as 100% before the start of the treatment, and 100%.

Example 6
Comparison of monomer hydrolyzability

  The same test as in Example 5 was performed except that the compound represented by the above formula (19) and / or (20) was used instead of the above formula (17) and / or (18) in Example 5.

Example 7
Comparison of hydrolyzability of ophthalmic lenses

17.5% of a silicone compound containing the compound represented by the above formula (17) and / or (18) under a nitrogen atmosphere, 1.5% of ethylene glycol dimethacrylate, 15% of N, N-dimethylacrylamide, 12.58% of hydroxylethyl methacrylate, methacrylic acid After degassing a solution consisting of 0.8%, PVP K-90 2.5%, photoinitiator Irgacure 819 0.13%, 3,7-dimethyl-3-octanol 50%, put 100 μl each in mold, and light irradiation intensity 1.53 mW / cm Visible light was irradiated at ² and polymerization was performed at 50 ° C. for 30 minutes.

  After the polymerization, the ophthalmic lens obtained together with the mold was placed in isopropyl alcohol / ion exchange water = 70/30 and left for 30 minutes, and the peeled mold was removed. Subsequently, the ophthalmic lens was washed twice with isopropyl alcohol / ion exchange water = 70/30 for 30 minutes, then with ion exchange water for 30 minutes, and further with a packing solution (buffer solution containing boric acid: pH = about 7). Washed for minutes.

  Next, the ophthalmic lens filled with the packing solution was sealed in a screw tube and sterilized at 121 ° C. for 30 minutes in a steam sterilizer.

  After cooling, the sample that was allowed to stand for 24 hours or longer was cut into strips having a width of 5 mm and a length of 15 mm, and the elongation until the sample was broken with a tensile tester was measured.

  The samples treated with ion-exchanged water at 95 ° C. for 1 week, 2 weeks, and 4 weeks were measured for elongation in the same manner as described above, and the difference from the elongation of the untreated sample was compared in percentage.

Example 8
Comparison of hydrolyzability of ophthalmic lenses

  Example 7 was carried out in the same manner as Example 7 except that the compound represented by the above formula (19) and / or (20) was used in place of the compound represented by the above formula (17) and / or (18). It was.

Comparative Example 1
Synthesis of silicone compounds by conventional methods

  Dimethylethylsilyl chloride (24.53 g, 0.2 mol) and dimethoxymethylsilane (5.31 g, 0.05 mol) were mixed with 8.4 g of methanol cooled at 0 ° C., 8.3 g of hexane, and 16.7 g of distilled water and added dropwise over 1 hour. . After dropping, the mixture was further stirred at 0 ° C. for 2 hours, gradually warmed to room temperature and stirred overnight. After completion of the reaction, the mixture was washed with saturated aqueous sodium hydrogen carbonate (100 ml) and saturated brine (100 ml), and this operation was repeated once more, and the organic layer was dried over sodium sulfate. After filtration, the solvent was distilled off and distilled under normal pressure to obtain a colorless transparent liquid (9.95 g, bp 160-163 ° C., yield 79%).

  As a result of analyzing the crude product by gas chromatography, it was a mixture of several isomers and it was difficult to obtain only the target product represented by the above formula (21).

Comparative Example 2
Silanol synthesis

  Dimethylethylsilyl chloride (22.23 g, 0.181 mol), diethyl ether (110 ml) and 1% phenolphthalein ethanol solution (4 drops) are added to a 500 ml three-necked eggplant flask equipped with a thermometer and a dropping funnel, and saturated brine -Cooled with ice and added dropwise 0.5N-NaOH aqueous solution (about 360 ml) over 3 hours with vigorous stirring.

  After completion of the dropwise addition, the ether layer was separated, the aqueous layer was extracted with ether (3 × 20 ml), and the organic layers were combined and dried over potassium carbonate.

  After filtration and evaporation of the solvent, distillation was carried out under normal pressure, but the target product represented by the above formula (22) was not obtained, and only bis (dimethylethyl) disiloxane was obtained.

  From Comparative Examples 1 and 2, it was difficult to synthesize the silicone compound of the present invention using conventional techniques.

Comparative Example 3
Measurement of hydrolyzability of general-purpose silicone monomers

  The same test as in Example 5 was performed except that the compound represented by the above formula (23) and / or (24) was used instead of the above formula (17) and / or (18) in Example 5.

Comparative Example 4
Comparison of hydrolyzability of ophthalmic lenses

  Example 7 was carried out in the same manner as Example 7 except that the compound represented by the above formula (23) and / or (24) was used in place of the compound represented by the above formula (17) and / or (18). It was.

  The results of the monomer hydrolyzability comparison tests conducted in Examples 5 and 6 and Comparative Example 3 are shown in Table 1 below. Table 2 below shows the tensile test results of the hydrolyzability comparison of the ophthalmic lenses performed in Examples 7 and 8 and Comparative Example 4. The numerical values in Table 1 represent the area% of the monomer by gas chromatography, and the numerical values in Table 2 represent the difference from the untreated sample as a percentage (%).

  From Table 1, when Examples 5 and 6 and Comparative Example 3 in which silicon is substituted with a bulky siloxy group are compared, the hydrolysis resistance as a silicone monomer is improved. Furthermore, hydrolysis resistance improved as the substitution number of the siloxy group increased.

  Moreover, when the said monomer was polymerized from Table 2 and it was set as the ophthalmic lens, the change of elongation was small because hydrolysis resistance improved. Thus, according to this invention, it turned out that the molded object excellent in hydrolysis resistance can be obtained.

According to the production method of the present invention, it is possible to provide a silicone monomer and an intermediate having a sterically bulky substituent. The monomer obtained by this method and the ophthalmic lens obtained therefrom are excellent in hydrolysis resistance.

Claims (5)

A compound represented by the following formula (1) and a compound represented by the following formula (2) are reacted in the presence of water to obtain a silicone compound represented by the following formula (3) and / or (4). A method for producing a silicone compound, wherein a silicone compound represented by the following formula (5) is obtained by treating a silicone compound represented by the formula (3) and / or (4) with a base.

(In the formulas (1) to (5), R ¹ , R ² , R ³ and R ⁴ are each independently selected from an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 1 to 7 carbon atoms and a phenyl group, At least one of R ¹ , R ² and R ³ has 2 or more carbon atoms, R ⁵ is selected from an alkyl group having 1 to 4 carbon atoms, and X is selected from a chlorine atom, a bromine atom and an iodine atom. n is an integer of 1-3.)   When the compound represented by the above formula (1) and the compound represented by the above formula (2) are reacted in the presence of water, the above formula (2) is used with respect to 1 equivalent of the alkoxy group of the compound represented by the above formula (2). The method according to claim 1, wherein the compound represented by 1) is used in an amount of 2 to 5 equivalents. A silicone compound represented by the above formula (5) obtained by the method according to claim 1 or 2 is reacted with a compound represented by the following formula (6) to represent the following formula (7) and / or (8): A method for producing a silicone monomer to obtain a silicone monomer.

(In the formula ^{(6) ~ (8),} R 1, R 2, R 3, R 4 and ^{R 5} are the above formula (1) ^R 1 in ^{~ (5), R 2,} R 3, R 4 and R ⁶ has the same meaning as R ^5, and R ⁶ is selected from an organic group having 2 to 20 carbon atoms having at least one carbon-carbon unsaturated double bond.   The molded object obtained by superposing | polymerizing the monomer mixture containing the silicone monomer obtained by the manufacturing method of Claim 3. An ophthalmic lens comprising the molded article according to claim 4.