JP2014031338A - Method of manufacturing high-purity (meth)acrylic silicone compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a (meth)acrylic silicone compound having high purity for an ophthalmic lens such as a contact lens.SOLUTION: A manufacturing method includes a process of producing a (meth)acrylic silicone compound of the formula (1) by reacting organohydrogenpolysiloxane and a (meth)acrylate compound of the formula (3), where Ris a hydrogen atom or a methyl group, a is 1 or 2, in the presence of an addition reaction catalyst, and the molar quantity of the (meth)acrylate compound is 1.4 times as large as the molar quality of organohydrogenpolysiloxane in the addition reaction.

Description

  The present invention relates to a method for producing a silicone compound for producing ophthalmic devices such as contact lenses, intraocular lenses, artificial corneas and the like. Specifically, a method for producing a silicone compound capable of providing a polymer suitable for an ophthalmic lens for the above ophthalmic device by copolymerizing with another hydrophilic monomer or by vinyl polymerization itself. About.

で表される３−［トリス（トリメチルシロキシ）シリル］プロピルメタクリレートが広く使用されている。しかしＴＲＩＳは、２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）のような親水性モノマーとの相溶性に劣るため、得られる共重合ポリマーは透明性を有しないという欠点があった。 As a monomer for ophthalmic lenses, known as TRIS, the following formula

3- [Tris (trimethylsiloxy) silyl] propyl methacrylate represented by the formula is widely used. However, since TRIS is inferior in compatibility with a hydrophilic monomer such as 2-hydroxyethyl methacrylate (HEMA), there is a drawback that the resulting copolymer does not have transparency.

ＳｉＧＭＡはＨＥＭＡのような親水性モノマーとの相溶性に優れるため、得られる共重合ポリマーは、比較的高酸素透過性で高い親水性であるという特徴を有する。しかし、該ＳｉＧＭＡと親水性モノマーとの共重合体ポリマーでは、長時間連続装用するには酸素透過性が不十分であった。従って、親水性モノマーと共重合してさらに高い酸素透過性を有するポリマーを提供できる（メタ）アクリルシリコーン化合物の開発が求められていた。 As another ophthalmic lens monomer, a silicone compound represented by the following formula, which is commonly known as SiGMA, is also known.

Since SiGMA is excellent in compatibility with a hydrophilic monomer such as HEMA, the resulting copolymer is characterized by relatively high oxygen permeability and high hydrophilicity. However, the copolymer polymer of SiGMA and hydrophilic monomer has insufficient oxygen permeability for continuous use for a long time. Therefore, development of a (meth) acryl silicone compound that can be copolymerized with a hydrophilic monomer to provide a polymer having higher oxygen permeability has been demanded.

［式中Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、およびＲ^５は炭素数１〜２０の直鎖もしくは分岐鎖のアルキル基または炭素数６〜１０のアリール基であり、Ｒ^６は水素、または炭素数１〜５の直鎖もしくは分岐鎖のアルキル基、または炭素数６〜１０のアリール基であり、ｎは１以上の整数であり、ｍは０もしくは１以上の整数であり、Ｘは炭素数が２〜２０の２価のアルキレン基であり、Ｙは−ＯＣＨ_２ＣＨ_２−、−ＯＣＨ（ＣＨ_３）ＣＨ_２−、または−ＯＣＨ_２ＣＨ（ＣＨ_３）−であり、ｐは３以上の整数である］
で表される（メタ）アクリルシリコーン化合物を記載している。 Patent Document 1 discloses the following formula (I)

[Wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ⁶ is hydrogen, Or a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, n is an integer of 1 or more, m is 0 or an integer of 1 or more, and X is A divalent alkylene group having 2 to 20 carbon atoms, Y is —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, or —OCH ₂ CH (CH ₃ ) —, and p is 3 It is an integer greater than]
The (meth) acryl silicone compound represented by these is described.

  Patent Document 1 describes a method for producing the (meth) acryl silicone compound by a dehydration condensation reaction between a polyorganosiloxane having a hydroxyl group at one end and a carboxylic acid having a polymerizable functional group. However, the (meth) acryl silicone compound obtained by the production method can be distributed in the degree of polymerization of silicone, and a high-purity (meth) acryl silicone compound cannot be obtained.

Patent Document 1 discloses that the (meth) acryl silicone compound is added to an organohydrogenpolysiloxane having a SiH group at one end and a polyether-containing (meth) acryl compound having a double bond at one end. A method of manufacturing is described. However, the Example of Patent Document 1 only describes a method for producing the (meth) acryl silicone compound by dehydration condensation reaction, and does not describe any production example by addition reaction. In the method described in Patent Document 1, the reaction between the (meth) acrylic group of the polyether-containing (meth) acrylic compound and the SiH group of the organohydrogenpolysiloxane also proceeds, and both ends of the (meth) acrylic compound are present. Since a compound introduced with organohydrogenpolysiloxane is produced, a high-purity (meth) acryl silicone compound cannot be obtained.

（ここでｍは３〜１０の整数のうちの一つ、ｎは１または２のうちの一つ、Ｒ¹は炭素数１〜４のアルキル基のうちの一つ、Ｒ^２は水素及びメチル基のうちの一つである）
で表される（メタ）アクリルシリコーン化合物が、親水性モノマーとの共重合性に優れ、酸素透過性の高い共重合体ポリマーを提供できることを見出し、上記式（ＩＩ）で表され特定のｍ、ｎ、Ｒ^１及びＲ^２を有する１種の化合物を高純度で有する（メタ）アクリルシリコーン化合物を製造する方法を開発した（特許文献２）。 The inventors have the following formula (II)

(Where m is one of integers from 3 to 10, n is one of 1 or 2, R ¹ is one of alkyl groups having 1 to 4 carbon atoms, R ² is hydrogen and methyl. One of the groups)
It is found that the (meth) acryl silicone compound represented by the formula (II) is excellent in copolymerization with a hydrophilic monomer and can provide a copolymer polymer having high oxygen permeability. A method for producing a (meth) acryl silicone compound having high purity of one compound having n, R ¹ and R ² has been developed (Patent Document 2).

JP 2001-55446 A Japanese Patent No. 4646152

  However, the method described in Patent Document 2 requires several steps, and further has a problem that a great amount of cost is required for purification of (meth) acrylic acid chloride after esterification. Therefore, there is a demand for a method capable of producing a (meth) acryl silicone compound represented by the above formula (II) and having a high purity at a low cost.

  In addition, when an organohydrogenpolysiloxane having a SiH group at one end and a polyether-containing (meth) acrylic compound having a double bond at one end are subjected to an addition reaction, in the prior art, a polyether-containing (meth) acrylic compound is used. Use in a small excess with respect to the organohydrogenpolysiloxane. However, in this method, the reaction between the (meth) acrylic group of the polyether-containing (meth) acrylic compound and the SiH group of the organohydrogenpolysiloxane also proceeds, and the organohydrogen is present at both ends of the (meth) acrylic compound. A compound introduced with polysiloxane is produced. Therefore, the target (meth) acryl silicone compound cannot be produced with high purity.

  In view of the above circumstances, an object of the present invention is to provide a method for producing a (meth) acryl silicone compound represented by the above formula (II) and having a high purity at a low cost.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor found that when an organohydrogenpolysiloxane having a SiH group at one end and allyloxy (ethoxy) ethyl (meth) acrylate are reacted in the presence of an addition reaction catalyst, allyloxy is reacted. By controlling the molar amount of (ethoxy) ethyl (meth) acrylate to be 1.4 times or more the molar amount of organohydrogenpolysiloxane, the addition reaction between the organohydrogenpolysiloxane and the (meth) acrylic group is suppressed. It has been found that the formation of a compound in which an organohydrogenpolysiloxane is addition-reacted to both ends (an allyl group and a (meth) acryl group) of the (meth) acrylate compound can be reduced.

（式中、Ｒ^１は炭素数１〜４のアルキル基であり、ｍは２〜９の整数である）
下記式（３）で表される（メタ）アクリレート化合物を

（式中、Ｒ^２は水素原子またはメチル基であり、ａは１または２である）
付加反応触媒存在下で反応させて、下記式（１）で表される（メタ）アクリルシリコーン化合物を生成する工程を含み、

（式中、Ｒ^１、Ｒ^２、ａ及びｍは上記の通りである）
上記付加反応において（メタ）アクリレート化合物のモル量がオルガノハイドロジェンポリシロキサンのモル量の１．４倍以上であることを特徴とする、製造方法を提供する。 That is, the present invention
A method for producing a high purity (meth) acryl silicone compound,
An organohydrogenpolysiloxane represented by the following formula (2):

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 2 to 9)
The (meth) acrylate compound represented by the following formula (3)

(Wherein R ² is a hydrogen atom or a methyl group, and a is 1 or 2)
Reacting in the presence of an addition reaction catalyst to produce a (meth) acryl silicone compound represented by the following formula (1):

(Wherein R ¹ , R ² , a and m are as described above)
In the above addition reaction, the molar amount of the (meth) acrylate compound is 1.4 times or more the molar amount of the organohydrogenpolysiloxane.

  Furthermore, this invention provides the polymer obtained by copolymerizing the high purity (meth) acryl silicone compound obtained with the said manufacturing method, and another monomer. The present invention also provides a polymer obtained by further vinyl polymerizing the high purity (meth) acryl silicone compound obtained by the above production method.

Since the production method of the present invention can reduce the formation of a compound in which an organohydrogenpolysiloxane is addition-reacted to both ends (allyl group and (meth) acryl group) of a (meth) acrylate compound, it has high purity. A (meth) acryl silicone compound can be provided. Furthermore, in the production method of the present invention, a high-purity (meth) acrylate compound can be obtained in one step. Moreover, since the solvent used for reaction and excess (meth) acrylate compound can be easily removed by heating under reduced pressure, the target compound can be easily produced. Therefore, the target high-purity (meth) acryl silicone compound can be produced very inexpensively and easily.

1 is a ¹ H-NMR chart of a (meth) acryl silicone compound obtained in Example 1. FIG. FIG. 2 is a ¹³ C-NMR chart of the (meth) acryl silicone compound obtained in Example 1.

上記式（１）中、Ｒ^１は炭素数１〜４のアルキル基であり、Ｒ^２は水素原子またはメチル基である。ｍは２〜９の整数、好ましくは３〜７の整数、最も好ましくは３である。ｍが上記下限値未満では得られるポリマーの酸素透過率が低くなるため好ましくない。また、ｍが上記上限値超では得られるポリマーの親水性が低くなるため好ましくない。ａは１または２の整数であり、好ましくは１である。ａが０であると親水性モノマーとの相溶性が悪くなるため好ましくない。また、aが上記値より大きいと原料である（メタ）アクリレート化合物の加熱・減圧下での除去が困難となるため好ましくない。 Hereinafter, the present invention will be described in detail.
The present invention is a method for producing a high purity (meth) acryl silicone compound, which is represented by the following general formula (1) and contains a high concentration of one compound having specific m, a, R ¹ and R ^2. is there.

The formula (1), ^{R 1} is an alkyl group having 1 to 4 carbon atoms, ^{R 2} is hydrogen atom or a methyl group. m is an integer of 2 to 9, preferably an integer of 3 to 7, and most preferably 3. If m is less than the above lower limit value, the oxygen permeability of the resulting polymer is low, such being undesirable. Further, if m exceeds the above upper limit value, the hydrophilicity of the resulting polymer is lowered, which is not preferable. a is an integer of 1 or 2, and is preferably 1. If a is 0, the compatibility with the hydrophilic monomer is deteriorated. Moreover, when a is larger than the above value, it is not preferable because it is difficult to remove the raw material (meth) acrylate compound under heating and reduced pressure.

（式中、Ｒ^１、Ｒ^２、ａ及びｍは上記の通りである） The high purity (meth) acryl silicone compound obtained by the method of the present invention is a compound having a structure represented by the following formula (4) in addition to the compound represented by the above formula (1) (hereinafter referred to as an isomer). It may contain.

(Wherein R ¹ , R ² , a and m are as described above)

In the present invention, “high purity” means one compound in which the (meth) acryl silicone compound obtained by the method of the present invention is represented by the above formula (1) and has specific m, a, R ¹ and R ² Is contained at a high concentration. In particular, the high-purity (meth) acryl silicone compound obtained by the method of the present invention may contain an isomer represented by the above formula (4), which is represented by the above formula (1) and has a specific m, a, R ¹ and one compound having ^{R 2} and the same m with the compound, a, one of the isomers having ^{R 1} and ^{R 2,} the sum as 95 wt% or more, containing preferably 96 wt% or more To do. The purity (mass%) of the (meth) acryl silicone compound is a value measured by gas chromatography (GC) analysis. In the high-purity (meth) acryl silicone compound obtained by the production method of the present invention, the content of the isomer is preferably less than 1% by mass, particularly 0.1 to 1% by mass, more particularly 0.4. It is -0.8 mass%. The smaller the isomer content, the better. When the high-purity (meth) acryl silicone compound contains the isomer, it may be used as a mixture without isolation, and can therefore be used as a mixture in the preparation of the polymer described below.

  The high-purity (meth) acryl silicone compound obtained by the production method of the present invention is characterized by a high Si content. In the high purity (meth) acryl silicone compound, the ratio of the organopolysiloxane residue to the total mass of the compounds represented by the above formulas (1) and (4) is 65 to 85% by mass, preferably 70 to 80% by mass. %. Thereby, a polymer with high oxygen permeability can be provided.

In the present invention, measurement by gas chromatography (GC) analysis may be performed under the following measurement conditions.
Measuring device: Agilent gas chromatograph (FID detector)
Capillary column: HP-5MS, J & W (0.25 mm x 30 m x 0.25 μm)
Temperature rising program: 50 ° C. (2 minutes) → 10 ° C./minute→300° C. (10 minutes)
Inlet temperature: 250 ° C
Detector temperature (FID): 300 ° C
Carrier gas: helium (1.0 mL / min)
Split ratio: 50: 1
Injection volume: 1 μL (hexane 10% solution)

（式中、Ｒ^１及びｍは上記の通りである）
下記式（３）で表される（メタ）アクリレート化合物を

（式中、Ｒ^２及びａは上記の通りである）
付加反応触媒存在下で反応させる工程を含む。 The production method of the present invention comprises an organohydrogenpolysiloxane represented by the following formula (2):

(Wherein R ¹ and m are as described above)
The (meth) acrylate compound represented by the following formula (3)

(Wherein R ² and a are as described above)
A step of reacting in the presence of an addition reaction catalyst.

  According to the present invention, in the above addition reaction, the molar amount of the (meth) acrylate compound is 1.4 times or more, preferably 1.5 to 2.5 times, more preferably 1.times. The molar amount of the organohydrogenpolysiloxane. It is characterized by being 6 to 1.8 times. If the molar amount of the (meth) acrylate compound relative to the molar amount of the organohydrogenpolysiloxane is less than the lower limit, an addition reaction between the organohydrogenpolysiloxane and the (meth) acryl group occurs, which is not preferable.

In the above formula (2), in particular, R ¹ is preferably a butyl group. The purity of the compound represented by the above formula (2) is 98% by mass or more, preferably 99% by mass or more as determined by the GC measurement described above.

In the above formula (3), in particular, a methacrylic compound in which R ² is a methyl group is preferably used because it has fewer side reactions than an acrylic compound in which R ² is H. The purity of the compound represented by the above formula (3) is 98% by mass or more, preferably 99% by mass or more by the above-described GC measurement.

The method for producing the compound represented by the above formula (3) is not particularly limited, and can be produced by a conventionally known method. For example, it can be suitably produced by a transesterification method. For example, by subjecting allyl glycol and methyl methacrylate to a transesterification reaction, allyloxyethyl methacrylate in which a = 1 in the above formula (3) can be produced.

  The addition reaction of the organohydrogenpolysiloxane and the (meth) acrylate compound is performed in the presence of an addition reaction catalyst. As the addition reaction catalyst, a catalyst generally used for the addition reaction can be used. For example, a noble metal catalyst such as a platinum group metal-based compound can be used, and examples thereof include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Of these, platinum-based catalysts are particularly preferably used. As the platinum catalyst, for example, chloroplatinic acid, an alcohol solution or aldehyde solution of chloroplatinic acid, a complex of chloroplatinic acid with various olefins or vinyl siloxane, and the like may be used. Among them, a chloroplatinic acid sodium bicarbonate neutralized-vinylsiloxane complex catalyst (calsted catalyst) solution can be preferably used.

  The amount of the addition reaction catalyst may be a catalytic amount. In particular, the metal equivalent is 1 to 10 ppm, preferably 2 to 5 ppm, based on the total amount of the organohydrogenpolysiloxane and the (meth) acrylate compound. If the amount of the addition reaction catalyst is small, the reaction speed is slow, and the reaction does not proceed. On the other hand, if the amount of the addition reaction catalyst is too large, side reactions are likely to occur and polymerization occurs, which is not preferable.

  For the above addition reaction, a reaction solvent may be used as necessary. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, methylcyclohexane and ethylcyclohexane, ether solvents such as dioxane, dibutyl ether and dimethoxyethane, ethyl acetate, Examples thereof include ester solvents such as butyl acetate, nitrile solvents such as acetonitrile and benzonitrile, and alcohol solvents such as ethanol and isopropyl alcohol. In particular, those having no active hydrogen such as methylcyclohexane, ethylcyclohexane, toluene, and xylene are preferably used. Ethanol, isopropyl alcohol and the like are not so preferable because they cause a dehydrogenation reaction between a hydroxyl group and SiH.

 Since the above addition reaction is exothermic, the reaction is carried out while dropping either the organohydrogenpolysiloxane or the (meth) acrylate compound rather than reacting the organohydrogenpolysiloxane with the (meth) acrylate compound at once. Is good. In particular, it is preferable to react with the (meth) acrylate compound while dropping the organohydrogenpolysiloxane. The dripping start temperature is 30 to 80 ° C., preferably 60 to 70 ° C. The aging temperature is preferably 70 to 80 ° C., and the aging time is preferably 1 to 4 hours. If the aging temperature is too high, side reactions such as polymerization occur, which is not preferable.

According to the production method of the present invention, it is possible to suppress the addition reaction of the organohydrogenpolysiloxane with the (meth) acryl group of the (meth) acrylate compound. Therefore, the production amount of a compound obtained by reacting organopolysiloxane with both the allyl group and the (meth) acryl group of the (meth) acrylate compound (hereinafter referred to as a both-end siloxane compound) can be reduced. Therefore, according to the method of the present invention, the content (mass%) of the both terminal siloxane compounds in the obtained high purity (meth) acryl silicone compound is less than 3 mass% as measured by gas chromatography, preferably It can be less than 2% by mass. Thereby, it becomes possible to provide the high purity (meth) acryl silicone compound mentioned above.

According to the production method of the present invention, the above-described high-purity (meth) acryl silicone compound can be obtained in one step, and further, the solvent used in the reaction and the excess (meth) acrylate compound are heated under reduced pressure. It can be easily removed. Therefore, the target high-purity (meth) acryl silicone compound can be produced very inexpensively and easily.

  The high purity (meth) acryl silicone compound of the present invention can form a polymer by vinyl polymerization alone. Moreover, it can also be copolymerized with another monomer, especially a hydrophilic monomer, and it can also be set as the polymer which forms a crosslinked structure. The hydrophilic monomer is not particularly limited as long as it is copolymerizable with the (meth) acryl silicone compound represented by the above formula (1). For example, a (meth) acryloyl group, a styryl group, an allyl group, Monomers having vinyl groups or other copolymerizable carbon-carbon unsaturated bonds can be used. Since the (meth) acryl silicone compound represented by the above formula (1) is excellent in compatibility with the hydrophilic monomer, it can provide a transparent copolymer.

Hydrophilic monomers include (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, vinyl benzoic acid, methyl (meth) acrylate, ethyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol mono Alkyl ether (meth) acrylate, both-terminal polymerizable group-containing siloxane macromer, trifluoroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, N, N-dimethylacrylamide N, N-diethylacrylamide, N-acryloylmorpholine, N-methyl (meth) acrylamide, N-vinylpyrrolidone, styrene, vinylpyridine, maleimide and the like. In addition, silicone compounds (such as bistrimethylsiloxymethylsilylpropylsilane monomer) containing a polymerizable group such as (meth) acryl, styryl, or (meth) acrylamide can also be used.

The (meth) acryl silicone compound represented by the above formula (1) has a polysiloxane moiety that is hydrophobic in the molecule. The polysiloxane moiety has an action of improving the oxygen permeability of the resulting polymer. In particular, since the (meth) acryl silicone compound represented by the formula (1) has a high Si group content, a polymer having high oxygen permeability can be provided. Moreover, since the (meth) acryl silicone compound represented by the above formula (1) also has a hydrophilic ether moiety in the molecule, it is possible to provide a polymer having high oxygen permeability and high hydrophilicity. it can. In addition, since the compound has a hydrophilic ether portion, the compatibility with the hydrophilic monomer is improved and the copolymerizability is high, so that the compound can be copolymerized with the hydrophilic monomer to provide a transparent polymer. .

The high-purity (meth) acryl silicone compound obtained by the method of the present invention contains one compound having a specific m, a, R ¹ and R ² represented by the above formula (1) at a high concentration. A transparent polymer can be provided by copolymerizing the high purity (meth) acryl silicone compound with a hydrophilic monomer or by vinyl polymerization alone. Furthermore, since the polymer has high oxygen permeability and high hydrophilicity, it can be suitably used for producing ophthalmic devices such as contact lenses, intraocular lenses, artificial corneas and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

In the following examples, NMR analysis ( ¹ H-NMR, ¹³ C-NMR) was performed using ECP500 (manufactured by JEOL Ltd.) and deuterated chloroform as a measurement solvent. Moreover, the measurement by gas chromatography was performed on condition of the following.
Measuring device: Agilent gas chromatograph (FID detector)
Capillary column: HP-5MS, J & W (0.25 mm x 30 m x 0.25 μm)
Temperature rising program: 50 ° C. (2 minutes) → 10 ° C./minute→300° C. (10 minutes)
Inlet temperature: 250 ° C
Detector temperature (FID): 300 ° C
Carrier gas: helium (1.0 mL / min)
Split ratio: 50: 1
Injection volume: 1 μL (hexane 10% solution)

（式中、Ｂｕはブチル基を意味する）
上記（メタ）アクリルシリコーン化合物の^１Ｈ−ＮＭＲスペクトルを図１に、^１３Ｃ−ＮＭＲスペクトルを図２に示す。また、得られた生成物の純度をガスクロマトグラフィーによる測定で算出したところ、該生成物は、上記式（５）で表される化合物と該化合物の異性体を合計として９６．０質量％有していた。尚、得られた生成物中、アリロキシエチルメタクリレートの両末端にオルガノポリシロキサンが導入された化合物の含有量（質量％）は１．８質量％であった。 [Example 1]
Synthesis of high-purity (meth) acryl silicone compound 136 g (0.8 mol) of allyloxyethyl methacrylate and 200 g of methylcyclohexane were charged into a 1 L flask equipped with a Dim funnel, a thermometer and a dropping funnel, and the temperature was raised to 65 ° C. 0.30 g of a toluene solution of a chloroplatinic acid alkali neutralized product-vinylsiloxane complex catalyst (platinum content: 0.5% by weight) was added, and 1-butyl-9-hydro-1,1,3 was added using a dropping funnel. 206 g (0.5 mol) (purity 99.7%) of 3,5,5,7,7,9,9-decamethylpentasiloxane was added dropwise over 1 hour. After dropping, the internal temperature rose to 75 ° C. The reaction mixture was aged at 80 ° C. for 4 hours and then confirmed by gas chromatography. As a result, the raw material 1-butyl-9-hydro-1,1,3,3,5,5,7,7, The 9,9-decamethylpentasiloxane peak disappeared and the reaction was complete. Methylcyclohexane and excess allyloxyethyl methacrylate were stripped under reduced pressure at an internal temperature of 110 ° C. to obtain 275 g of the product (yield 95%). When the structure of the obtained product was analyzed using ¹ H-NMR and ¹³ C-NMR, it was a (meth) acryl silicone compound represented by the following formula (5).

(In the formula, Bu means a butyl group)
FIG. 1 shows a ¹ H-NMR spectrum and FIG. 2 shows a ¹³ C-NMR spectrum of the (meth) acryl silicone compound. Further, when the purity of the obtained product was calculated by measurement by gas chromatography, the product was found to be 96.0% by mass in total of the compound represented by the above formula (5) and the isomers of the compound. Was. In addition, content (mass%) of the compound in which the organopolysiloxane was introduce | transduced into the both terminal of allyloxy ethyl methacrylate in the obtained product was 1.8 mass%.

[Comparative Example 1]
Allyloxyethyl methacrylate (102 g, 0.6 mol) and methylcyclohexane (200 g) were charged into a 1 L flask equipped with a Dim funnel, thermometer, and dropping funnel, and the temperature was raised to 65 ° C. 0.30 g of a toluene solution of a chloroplatinic acid alkali neutralized product-vinylsiloxane complex catalyst (platinum content: 0.5% by weight) was added, and 1-butyl-9-hydro-1,1,3 was added using a dropping funnel. 206 g (0.5 mol) (purity 99.7%) of 3,5,5,7,7,9,9-decamethylpentasiloxane was added dropwise over 1 hour. After dropping, the internal temperature rose to 75 ° C. The reaction mixture was aged at 80 ° C. for 4 hours, and then the reaction product was confirmed by gas chromatography. As a result, the starting material 1-butyl-9-hydro-1,1,3,3,5,5,7,7 , 9,9-decamethylpentasiloxane disappeared and the reaction was complete. Methylcyclohexane and excess allyloxyethyl methacrylate were stripped under reduced pressure at an internal temperature of 110 ° C. to obtain 262 g of product (yield 90%). When the structure of the obtained product was analyzed using ¹ H-NMR and ¹³ C-NMR, it was a (meth) acryl silicone compound represented by the above formula (5). Further, when the purity of the obtained product was calculated by measurement by gas chromatography, the product was found to contain 91.5% by mass in total of the compound represented by the above formula (5) and the isomers of the compound. Was. In addition, content (mass%) of the compound in which the organopolysiloxane was introduce | transduced into the both ends of allyloxy ethyl methacrylate in the obtained product was 5.3 mass%.

The production method of the present invention can provide a high-purity (meth) acryl silicone compound inexpensively and easily. In addition, since the compound obtained by the production method of the present invention can provide a polymer that is transparent, has high oxygen permeability, and is highly hydrophilic, ophthalmic devices such as contact lenses, intraocular lenses, It can be suitably used for producing artificial cornea and the like.

Claims (5)

A method for producing a high purity (meth) acryl silicone compound,
An organohydrogenpolysiloxane represented by the following formula (2):

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 2 to 9)
The (meth) acrylate compound represented by the following formula (3)

(Wherein R ² is a hydrogen atom or a methyl group, and a is 1 or 2)
Reacting in the presence of an addition reaction catalyst to produce a (meth) acryl silicone compound represented by the following formula (1):

(Wherein R ¹ , R ² , a and m are as described above)
In the above addition reaction, the molar amount of the (meth) acrylate compound is 1.4 times or more the molar amount of the organohydrogenpolysiloxane. The high purity (meth) acryl silicone compound obtained by the method according to claim 1 further contains a compound represented by the following formula (4) (hereinafter referred to as an isomer),

(Wherein R ¹ , R ² , a and m are as described above)
Said high purity (meth) acrylic silicone compounds, certain m is represented by the formula (1), a, the same m as one compound and the compound having the ^{R 1} and ^{R 2,} a, ^{R 1} and ^{R 2} The manufacturing method of Claim 1 which contains 95 mass% or more of the said 1 type of said isomer in total.   In the high purity (meth) acryl silicone compound obtained by the method according to claim 1 or 2, the formula is added to both the allyl group and the (meth) acryl group of the (meth) acrylate compound represented by the formula (3). The production method according to claim 1 or 2, wherein the content of the compound obtained by the reaction of the organohydrogenpolysiloxane represented by (2) is less than 3% by mass.   The polymer obtained by copolymerizing the high purity (meth) acryl silicone compound obtained by the method of any one of Claims 1-3, and another monomer.   The polymer obtained by vinyl-polymerizing the high purity (meth) acryl silicone compound obtained by the method of any one of Claims 1-3.

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