JP2005170827A - Method for manufacturing silicone compound and silicone agent - Google Patents
Method for manufacturing silicone compound and silicone agent Download PDFInfo
- Publication number
- JP2005170827A JP2005170827A JP2003411704A JP2003411704A JP2005170827A JP 2005170827 A JP2005170827 A JP 2005170827A JP 2003411704 A JP2003411704 A JP 2003411704A JP 2003411704 A JP2003411704 A JP 2003411704A JP 2005170827 A JP2005170827 A JP 2005170827A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituent
- carbon atoms
- optionally substituted
- silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Silicon Polymers (AREA)
Abstract
Description
本発明は眼用レンズ用ポリマーに特に好適な、シリコーン化合物及びその製造方法に関しする。該製造方法により得られたシリコーン剤を用い、重合して得られるポリマーはコンタクトレンズ、眼内レンズ、人工角膜などの眼用レンズの原料として有用である。 The present invention relates to a silicone compound particularly suitable for an ophthalmic lens polymer and a method for producing the same. A polymer obtained by polymerization using the silicone agent obtained by the production method is useful as a raw material for ophthalmic lenses such as contact lenses, intraocular lenses, and artificial corneas.
従来、眼用レンズ用モノマーとして、ケイ素基を有する化合物が知られている。 Conventionally, compounds having a silicon group are known as monomers for ophthalmic lenses.
そのような化合物の一つとして、上記式（ｃ）または（ｃ’）で表される化合物が知られている（例えば、特許文献１）。この化合物は分子内に水酸基を有することから親水性モノマーとの相溶性が得やすいという特長を有するが、この化合物を重合して得られるポリマーをコンタクトレンズとして用いようとすると、眼にしみるという欠点があった。その原因の究明にコンタクトレンズをイソプロパノールで抽出し、その溶出物を調べたところ、下記式（ｄ） As one of such compounds, a compound represented by the above formula (c) or (c ′) is known (for example, Patent Document 1). Since this compound has a hydroxyl group in the molecule, it has a feature that it is easy to obtain compatibility with a hydrophilic monomer. However, when a polymer obtained by polymerizing this compound is used as a contact lens, it is a disadvantage that it is visible to the eyes. was there. To investigate the cause, the contact lens was extracted with isopropanol and the eluate was examined. The following formula (d)
で表される化合物が含まれていることが判った。この化合物（ｄ）は上記式（ｃ）または（ｃ’）を上記特許文献１記載の方法で合成したときに副生成物として含まれ、分子内に重合性置換基を有していないことから重合してもポリマー主鎖に結合されず、装用時にしみ出てきて装用感の悪化を招いているものと考えられる。
本発明は、副生成物（ｚ）の比率を抑えたシリコーン化合物（ａ）及び／または（ａ’）の製造方法を提供する。 The present invention provides a method for producing the silicone compound (a) and / or (a ′) with a reduced ratio of the by-product (z).
上記の目的を達成するために、本発明は下記の構成を有する。
（１） 下記一般式（ａ１）
In order to achieve the above object, the present invention has the following configuration.
(1) The following general formula (a1)
で表されるエポキシシランに、アクリル酸の金属塩またはメタクリル酸の金属塩存在下でアクリル酸またはメタクリル酸を反応させて下記一般式（ａ）及び／または（ａ’） Is reacted with acrylic acid or methacrylic acid in the presence of a metal salt of acrylic acid or a metal salt of methacrylic acid, and the following general formula (a) and / or (a ′):
で表されるシリコーン化合物を合成するに際し、反応系の水分率を２０００ｐｐｍ以下に維持して反応を行うことを特徴とするシリコーン化合物の製造方法。
（ここで、Ａはシロキサニル基を表す。Ｒ1は重合性基を有する炭素数１〜２０の置換基を表す。Ｒ2〜Ｒ4はそれぞれ独立に水素、置換されていてもよい炭素数１〜２０の置換基または−Ｘ−Ａを表す。Ｘは置換されていてもよい炭素数１〜２０の２価の置換基を表す。）
（２） 水分率が１重量％以下のアクリル酸もしくはメタクリル酸の金属塩を用いることを特徴とする上記（１）記載のシリコーン化合物の製造方法。
（３） 下記一般式（ａ）及び／または（ａ’）で示される化合物及び一般式（ｚ）で示される化合物を含み、
When the silicone compound represented by the formula (1) is synthesized, the reaction is carried out while maintaining the moisture content of the reaction system at 2000 ppm or less.
(Here, A represents a siloxanyl group. R 1 represents a substituent having 1 to 20 carbon atoms having a polymerizable group. R 2 to R 4 are each independently hydrogen and optionally substituted 1 carbon atom. Represents a substituent of -20 or -X-A. X represents an optionally substituted divalent substituent having 1 to 20 carbon atoms.)
(2) The method for producing a silicone compound according to the above (1), wherein a metal salt of acrylic acid or methacrylic acid having a moisture content of 1% by weight or less is used.
(3) including a compound represented by the following general formula (a) and / or (a ′) and a compound represented by the general formula (z),
一般式（ｚ）で表される成分の含有量が０．５重量％以下であることを特徴とするシリコーン剤。
（ここで、Ａはシロキサニル基を表す。Ｒ1は重合性基を有する炭素数１〜２０の置換基を表す。Ｒ2〜Ｒ4はそれぞれ独立に水素、置換されていてもよい炭素数１〜２０の置換基または−Ｘ−Ａを表す。Ｘは置換されていてもよい炭素数１〜２０の２価の置換基を表す。）
（４） シロキサニル基Ａが下記式（ｂ）
A silicone agent, wherein the content of the component represented by the general formula (z) is 0.5% by weight or less.
(Here, A represents a siloxanyl group. R 1 represents a substituent having 1 to 20 carbon atoms having a polymerizable group. R 2 to R 4 are each independently hydrogen and optionally substituted 1 carbon atom. Represents a substituent of -20 or -X-A. X represents an optionally substituted divalent substituent having 1 to 20 carbon atoms.)
(4) Siloxanyl group A is represented by the following formula (b)
で表されたものである上記（１）または（２）記載の製造方法により得られたシリコーン化合物。
［式（ｂ）中、Ａ1 〜Ａ11はそれぞれが互いに独立に水素、置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基のいずれかを表す。ｎは０〜２００の整数を表し、ａ、ｂ、ｃはそれぞれが互いに独立に０〜２０の整数を表す。ただしｎ＝ａ＝ｂ＝ｃ＝０の場合を除く。］
（５） シロキサニル基Ａがトリス（トリメチルシロキシ）シリル基、ビス（トリメチルシロキシ）メチルシリル基、トリメチルシロキシジメチルシリル基からなる群から選ばれた置換基である上記（３）記載のシリコーン剤。
A silicone compound obtained by the production method described in (1) or (2) above.
[In Formula (b), A 1 to A 11 are each independently hydrogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. Represents either. n represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where n = a = b = c = 0 is excluded. ]
(5) The silicone agent according to (3), wherein the siloxanyl group A is a substituent selected from the group consisting of a tris (trimethylsiloxy) silyl group, a bis (trimethylsiloxy) methylsilyl group, and a trimethylsiloxydimethylsilyl group.
本発明により、副生成物として生成し易い、コンタクトレンズとした時の刺激の原因と考えられる化合物（ｚ）等の化合物の生成が抑制されたシリコーン化合物（ａ）及び／または（ａ’）を得ることができる。 According to the present invention, a silicone compound (a) and / or (a ′) which is easily produced as a by-product and in which the production of a compound such as compound (z), which is considered to be a cause of irritation when a contact lens is formed, is suppressed. Can be obtained.
本発明は一般式（ａ１）の化合物を原料として一般式（ａ）及び／または（ａ’）の化合物を得る。 In the present invention, a compound of the general formula (a) and / or (a ′) is obtained from the compound of the general formula (a1) as a raw material.
一般式（ａ）及び／または（ａ’）において、Ｒ1は重合性基を有する炭素数１〜２０の置換基を表す。ここで重合性基とはラジカル重合可能な炭素−炭素二重結合を表す。Ｒ1で示されるカルボン酸であるＲ1−ＣＯＯ−の例としては、ビニロキシ酢酸基、アリロキシ酢酸基、（メタ）アクリル酸基、クロトン酸基、２−（メタ）アクリロイルプロパン酸基、３−（メタ）アクリロイルブタン酸基、４−ビニル安息香酸基などを挙げることができる。これらのうち、シリコーンモノマー（ａ）及び／または（ａ’）を合成する際に触媒として用いるカルボン酸塩を入手しやすいことから好ましいのはアクリル酸基およびメタクリル酸基である。Ｒ2〜Ｒ4はそれぞれ独立に水素、置換されていてもよい炭素数１〜２０の置換基または−Ｘ−Ａを表す。Ｘは置換されていてもよい炭素数１〜２０の２価の脂肪族または芳香族置換基を表す。Ａはシロキサニル基を表す。本明細書におけるシロキサニル基とは、少なくとも一つのＳｉ−Ｏ−Ｓｉ結合を有する基を表す。シロキサニル基としては下記式（ｂ）で表される置換基が原料の入手しやすさや合成の容易さの点で好ましく使用される。 In general formula (a) and / or (a ′), R 1 represents a substituent having 1 to 20 carbon atoms having a polymerizable group. Here, the polymerizable group represents a carbon-carbon double bond capable of radical polymerization. Examples of R 1 -COO- is a carboxylic acid represented by R 1, vinyloxy acetate group, allyloxy acetate group, (meth) acrylic acid, crotonic acid group, 2- (meth) acryloyl propane acid, 3- (Meth) acryloylbutanoic acid group, 4-vinylbenzoic acid group and the like can be mentioned. Among these, acrylic acid groups and methacrylic acid groups are preferable because carboxylate used as a catalyst when synthesizing the silicone monomer (a) and / or (a ′) is easily available. R 2 to R 4 each independently represent hydrogen, an optionally substituted substituent having 1 to 20 carbon atoms, or —X—A. X represents an optionally substituted divalent aliphatic or aromatic substituent having 1 to 20 carbon atoms. A represents a siloxanyl group. The siloxanyl group in this specification represents a group having at least one Si—O—Si bond. As the siloxanyl group, a substituent represented by the following formula (b) is preferably used in view of availability of raw materials and ease of synthesis.
［式（ｂ）中、Ａ1 〜Ａ11はそれぞれが互いに独立に水素、置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基のいずれかを表す。ｎは０〜２００の整数を表し、ａ、ｂ、ｃはそれぞれが互いに独立に０〜２０の整数を表す。ただしｎ＝ａ＝ｂ＝ｃ＝０の場合は除く。］
例えば、式（ｂ）のＡ1からＡ11としては、それぞれが独立に水素、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ヘキシル基、シクロヘキシル基、２−エチルヘキシル基、オクチル基などのアルキル基、フェニル基、ナフチル基などのアリール基を挙げることができる。これらの中で最も好ましいのはメチル基である。
[In Formula (b), A 1 to A 11 are each independently hydrogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. Represents either. n represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where n = a = b = c = 0 is excluded. ]
For example, A 1 to A 11 in formula (b) are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, hexyl. Groups, cyclohexyl groups, 2-ethylhexyl groups, alkyl groups such as octyl groups, and aryl groups such as phenyl groups and naphthyl groups. Of these, the most preferred is a methyl group.
式（ｂ）中、ｎは０〜２００の整数であるが、好ましくは０〜５０，さらに好ましくは０〜１０である。ａ、ｂ、ｃはそれぞれが互いに独立に０〜２０の整数であるが、好ましくはａ、ｂ、ｃがそれぞれ互いに独立に０〜５の整数である。ｎ＝０の場合、好ましいａ、ｂ、ｃの組み合わせはａ＝ｂ＝ｃ＝１、ａ＝ｂ＝１かつｃ＝０である。 In the formula (b), n is an integer of 0 to 200, preferably 0 to 50, more preferably 0 to 10. a, b and c are each independently an integer of 0 to 20, but preferably a, b and c are each independently an integer of 0 to 5. When n = 0, preferred combinations of a, b and c are a = b = c = 1, a = b = 1 and c = 0.
式（ｂ）で表される置換基の中で、工業的に比較的安価に入手できることから特に好適なものはトリス（トリメチルシロキシ）シリル基、ビス（トリメチルシロキシ）メチルシリル基、トリメチルシロキシジメチルシリル基、ポリジメチルシロキサン基、ポリメチルシロキサン基、ポリ−コ−メチルシロキサン−ジメチルシロキサン基などである。 Among the substituents represented by the formula (b), particularly preferred are tris (trimethylsiloxy) silyl group, bis (trimethylsiloxy) methylsilyl group, and trimethylsiloxydimethylsilyl group because they are industrially available at a relatively low cost. , Polydimethylsiloxane group, polymethylsiloxane group, poly-co-methylsiloxane-dimethylsiloxane group, and the like.
本発明のシリコーン化合物製造方法で使用するアクリル酸あるいはメタアクリル酸の量は、原料のエポキシシランに対して１〜５０当量が好ましく、エポキシシランを残存させないためには１．５〜４０当量がより好ましく、２〜３０当量加えるのが最も好ましい。 The amount of acrylic acid or methacrylic acid used in the method for producing a silicone compound of the present invention is preferably 1 to 50 equivalents relative to the raw material epoxy silane, and more preferably 1.5 to 40 equivalents in order not to leave the epoxy silane. Preferably, 2 to 30 equivalents are added most preferably.
本発明の製造方法では、アクリル酸若しくはメタアクリル酸の金属塩、好ましくはアルカリ金属塩、を触媒として用いる。この触媒の添加量は、原料のエポキシシランに対して０．００１〜５当量が好ましく、０．００５〜３当量がより好ましく、０．０１〜１当量が最も好ましい。 In the production method of the present invention, a metal salt of acrylic acid or methacrylic acid, preferably an alkali metal salt, is used as a catalyst. The amount of the catalyst added is preferably 0.001 to 5 equivalents, more preferably 0.005 to 3 equivalents, and most preferably 0.01 to 1 equivalents with respect to the raw material epoxysilane.
本発明のシリコーン化合物製造方法では合成反応中にシリコーン化合物が重合してしまうのを防ぐため重合禁止剤を加えてもよい。重合禁止剤の具体例としてはハイドロキノン、ハイドロキノンモノメチルエーテル、２，６−ジ−ｔ−ブチル−４−メチルフェノール、Ｎ−ニトロソフェニルヒドロキシルアミンアルミニウムなどを挙げることができる。また、重合禁止剤を用いる場合の添加量は（メタ）アクリル酸量に対して０．０００５〜５重量％が好ましく、０．００１〜３重量％がより好ましく、０．００５〜１重量％が最も好ましい。 In the method for producing a silicone compound of the present invention, a polymerization inhibitor may be added in order to prevent the silicone compound from being polymerized during the synthesis reaction. Specific examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, N-nitrosophenylhydroxylamine aluminum and the like. Moreover, 0.0005 to 5 weight% is preferable with respect to the amount of (meth) acrylic acid, when adding a polymerization inhibitor, 0.001 to 3 weight% is more preferable, 0.005 to 1 weight% is preferable. Most preferred.
本発明のシリコーン化合物製造方法における反応温度は低すぎると反応時間が長くなり過ぎ、高すぎると合成反応中にシリコーン化合物が重合してしまう危険性があることから、５０〜１８０℃が好ましく、６０〜１７０℃がより好ましく、７０〜１６０℃が最も好ましい。 If the reaction temperature in the method for producing a silicone compound of the present invention is too low, the reaction time becomes too long, and if it is too high, the silicone compound may be polymerized during the synthesis reaction. -170 degreeC is more preferable, and 70-160 degreeC is the most preferable.
本発明においては、一般式（ａ）及び／または（ａ’）の化合物を得る反応系において、反応系の水分率を２０００ｐｐｍ以下に保つことを特徴とする。２０００ｐｐｍ以下に保つことにより副反応生成物の生成を抑制することができ、コンタクトレンズとしたときには眼にしみにくい、より良好なレンズとすることができる。反応系の水分率として好ましくは、１５００ｐｐｍ以下、より好ましくは１０００ｐｐｍ以下である。 In the present invention, in the reaction system for obtaining the compound of the general formula (a) and / or (a ′), the water content of the reaction system is maintained at 2000 ppm or less. By maintaining it at 2000 ppm or less, it is possible to suppress the formation of side reaction products, and when using a contact lens, it is possible to obtain a better lens that is less likely to stain the eyes. The moisture content of the reaction system is preferably 1500 ppm or less, more preferably 1000 ppm or less.
反応系の水分率を２０００ｐｐｍ以下とするための方法については、例えば、本発明のシリコーン化合物製造方法で使用するエポキシシランおよびメタクリル酸は使用前に十分に脱水されていることが好ましい。脱水の方法は一般に液状の有機化合物を脱水する方法であればよく、その例としてはゼオライト、モレキュラーシーブ、硫酸ナトリウム、硫酸マグネシウムなどの乾燥剤を添加する方法や、トルエン等の溶媒と共沸するといった方法が挙げられる。 Regarding the method for setting the moisture content of the reaction system to 2000 ppm or less, for example, the epoxysilane and methacrylic acid used in the method for producing a silicone compound of the present invention are preferably sufficiently dehydrated before use. The method of dehydration is generally a method for dehydrating a liquid organic compound. Examples thereof include a method of adding a desiccant such as zeolite, molecular sieve, sodium sulfate or magnesium sulfate, or an azeotrope with a solvent such as toluene. The method is mentioned.
また、本発明の製造方法で用いられるアクリル酸若しくはメタアクリル酸の金属塩は使用前に十分に脱水を行う。脱水方法としては、一般に固体の脱水に用いられる方法が採用可能であり、その例としては真空乾燥機で減圧しながら加熱する方法や、デシケータ中で五酸化リン、濃硫酸、シリカゲル、塩化カルシウム等の脱水剤を共存させるといった方法が挙げられる。 The metal salt of acrylic acid or methacrylic acid used in the production method of the present invention is sufficiently dehydrated before use. As a dehydration method, a method generally used for solid dehydration can be employed. Examples thereof include a method of heating while reducing the pressure in a vacuum dryer, phosphorus pentoxide, concentrated sulfuric acid, silica gel, calcium chloride, etc. in a desiccator. The method of making a dehydrating agent coexist is mentioned.
また、本発明の製造方法においては、反応溶液への水分混入を防止するため、反応容器は反応前に十分乾燥して使用するのが好ましい。また、反応中に反応溶液が水分を吸収するのを防止するため、塩化カルシウム、シリカゲルなどの乾燥剤を充填した乾燥管を使用するのが好ましい。 In the production method of the present invention, it is preferable that the reaction vessel is sufficiently dried before the reaction in order to prevent moisture from being mixed into the reaction solution. In order to prevent the reaction solution from absorbing moisture during the reaction, it is preferable to use a drying tube filled with a desiccant such as calcium chloride or silica gel.
本発明のシリコーン化合物の製造方法により得られるシリコーン剤中に含まれる化合物（ｚ）（反応副生成物として得られる）の含有量は、原料のエポキシシラン（ａ１）が１重量％以下になるまで合成反応を行った時点で、０．７重量％以下になることが好ましく、該シリコーン化合物を重合して得られるポリマーを眼用レンズに用いるためには０．６重量％以下が好ましく、該ポリマーをソフトコンタクトレンズとして用いるためには０．５重量％以下が好ましい。 The content of the compound (z) (obtained as a reaction byproduct) contained in the silicone agent obtained by the method for producing a silicone compound of the present invention is such that the raw material epoxysilane (a1) is 1% by weight or less. When the synthesis reaction is performed, it is preferably 0.7% by weight or less, and in order to use a polymer obtained by polymerizing the silicone compound for an ophthalmic lens, 0.6% by weight or less is preferable. Is preferably 0.5% by weight or less for use as a soft contact lens.
本発明の製造方法により得られるシリコーン化合物を重合して得られるポリマーは、コンタクトレンズ、眼内レンズ、人工角膜などの眼用レンズとして特に好適である。 The polymer obtained by polymerizing the silicone compound obtained by the production method of the present invention is particularly suitable as an ophthalmic lens such as a contact lens, an intraocular lens, and an artificial cornea.
以下、実施例により本発明を具体的に説明するが、本発明はこれによって限定されるものではない。
測定方法
（１）ガスクロマトグラフ（ＧＣ）測定
ＧＣ測定は本体に島津製作所製ＧＣ−１８Ａ（ＦＩＤ検出器）、キャピラリーカラムにＪ＆Ｗ社ＤＢ−５（０．２５ｍｍ×３０ｍ×１μｍ）を用いた。キャリアガスはヘリウム（１３８ｋＰａ）、注入口温度２８０℃、検出器温度２８０℃、昇温プログラムは６０℃（５分）→１０℃／分→３２５℃（１９分）で測定した。サンプルは測定試料１００μＬをイソプロピルアルコール１ｍＬに溶解して調製し、１μＬ注入した。
（２）反応液および各原料の水分率測定
水分率測定は三菱化成工業製微量水分測定装置ＣＡ−０５型を用いて、カールフィッシャー法により行った。
（３）（メタ）アクリル酸アルカリ金属塩の水分率測定
真空乾燥機で４０℃、１６時間乾燥させ、下記式より水分率を計算した。
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
Measurement Method (1) Gas Chromatograph (GC) Measurement For GC measurement, GC-18A (FID detector) manufactured by Shimadzu Corporation was used for the main body, and J & W DB-5 (0.25 mm × 30 m × 1 μm) was used for the capillary column. The carrier gas was helium (138 kPa), the inlet temperature was 280 ° C., the detector temperature was 280 ° C., and the temperature raising program was 60 ° C. (5 minutes) → 10 ° C./minute→325° C. (19 minutes). A sample was prepared by dissolving 100 μL of a measurement sample in 1 mL of isopropyl alcohol, and 1 μL was injected.
(2) Moisture content measurement of reaction liquid and each raw material The moisture content measurement was performed by the Karl Fischer method using the trace moisture measuring device CA-05 type manufactured by Mitsubishi Chemical Industries.
(3) Moisture content measurement of (meth) acrylic acid alkali metal salt It dried at 40 degreeC and 16 hours with the vacuum dryer, and calculated the moisture content from the following formula.
水分率＝｛（乾燥前重量）−（乾燥後重量）｝／（乾燥前重量）
実施例１
３００ｍＬのナスフラスコに下式（ｃ１）
Moisture content = {(weight before drying) − (weight after drying)} / (weight before drying)
Example 1
In a 300 mL eggplant flask, the following formula (c1)
で表されるエポキシシラン１００ｇ（０．３ｍｏｌ）、メタクリル酸１０３．４ｇ（１．２ｍｏｌ）、メタクリル酸ナトリウム４．８ｇ（０．０５ｍｏｌ）、ｐ−メトキシフェノール５．５ｇ（０．０４ｍｏｌ）を加え、空気雰囲気下で１００℃に加熱して撹拌した。ＧＣでエポキシシラン（ｃ１）の面積％が０．１％以下になるのを確認した後、反応液を室温まで冷却した。反応液にヘキサン１５０ｍＬを加え、０．１Ｎ水酸化ナトリウム水溶液２５０ｍＬで３回、２．６％食塩水１７５ｍＬで３回洗浄し、有機層に硫酸ナトリウムを加えて乾燥し、ろ過してエバポレータで溶媒を留去した。得られた液体のＧＣを測定したところ、表１のような結果が得られた。 100 g (0.3 mol) of epoxysilane represented by the formula, 103.4 g (1.2 mol) of methacrylic acid, 4.8 g (0.05 mol) of sodium methacrylate, and 5.5 g (0.04 mol) of p-methoxyphenol were added. The mixture was heated and stirred at 100 ° C. in an air atmosphere. After confirming that the area percentage of the epoxysilane (c1) was 0.1% or less by GC, the reaction solution was cooled to room temperature. Add 150 mL of hexane to the reaction solution, wash 3 times with 250 mL of 0.1N aqueous sodium hydroxide solution and 3 times with 175 mL of 2.6% brine, dry the organic layer by adding sodium sulfate, filter and remove the solvent with an evaporator. Was distilled off. When GC of the obtained liquid was measured, the results shown in Table 1 were obtained.
実施例２
エポキシシランを下式（ｄ１）
Example 2
Epoxysilane is represented by the following formula (d1)
で表される化合物に、メタクリル酸量を表１に示す内容に変更した以外は実施例１と同様の方法で実験を行った。ＧＣ測定を行ったところ、表１のような結果が得られた。 The experiment was conducted in the same manner as in Example 1 except that the amount of methacrylic acid was changed to the content shown in Table 1 for the compound represented by When GC measurement was performed, the results shown in Table 1 were obtained.
実施例３
エポキシシラン、メタクリル酸量を表１に示す内容に変更した以外は実施例１と同様の方法で実験を行った。ＧＣ測定を行ったところ、表１のような結果が得られた。
Example 3
An experiment was performed in the same manner as in Example 1 except that the amounts of epoxysilane and methacrylic acid were changed to those shown in Table 1. When GC measurement was performed, the results shown in Table 1 were obtained.
実施例４
エポキシシラン、アクリル酸量を表１に示す内容に変更した以外は実施例１と同様の方法で実験を行った。ＧＣ測定を行ったところ、表１のような結果が得られた。
Example 4
An experiment was performed in the same manner as in Example 1 except that the amounts of epoxysilane and acrylic acid were changed to those shown in Table 1. When GC measurement was performed, the results shown in Table 1 were obtained.
比較例１
メタクリル酸量を表１に示す内容に変更した以外は実施例１と同様の方法で実験を行った。ＧＣ測定を行ったところ、表１のような結果が得られた。
Comparative Example 1
An experiment was performed in the same manner as in Example 1 except that the amount of methacrylic acid was changed to the contents shown in Table 1. When GC measurement was performed, the results shown in Table 1 were obtained.
Claims (5)
（ここで、Ａはシロキサニル基を表す。Ｒ1は重合性基を有する炭素数１〜２０の置換基を表す。Ｒ2〜Ｒ4はそれぞれ独立に水素、置換されていてもよい炭素数１〜２０の置換基または−Ｘ−Ａを表す。Ｘは置換されていてもよい炭素数１〜２０の２価の置換基を表す。） The following general formula (a1)
(Here, A represents a siloxanyl group. R 1 represents a substituent having 1 to 20 carbon atoms having a polymerizable group. R 2 to R 4 are each independently hydrogen and optionally substituted 1 carbon atom. Represents a substituent of -20 or -X-A. X represents an optionally substituted divalent substituent having 1 to 20 carbon atoms.)
（ここで、Ａはシロキサニル基を表す。Ｒ1は重合性基を有する炭素数１〜２０の置換基を表す。Ｒ2〜Ｒ4はそれぞれ独立に水素、置換されていてもよい炭素数１〜２０の置換基または−Ｘ−Ａを表す。Ｘは置換されていてもよい炭素数１〜２０の２価の置換基を表す。） Including a compound represented by the following general formula (a) and / or (a ′) and a compound represented by the general formula (z),
(Here, A represents a siloxanyl group. R 1 represents a substituent having 1 to 20 carbon atoms having a polymerizable group. R 2 to R 4 are each independently hydrogen and optionally substituted 1 carbon atom. Represents a substituent of -20 or -X-A. X represents an optionally substituted divalent substituent having 1 to 20 carbon atoms.)
［式（ｂ）中、Ａ1 〜Ａ11はそれぞれが互いに独立に水素、置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基のいずれかを表す。ｎは０〜２００の整数を表し、ａ、ｂ、ｃはそれぞれが互いに独立に０〜２０の整数を表す。ただしｎ＝ａ＝ｂ＝ｃ＝０の場合を除く。］ Siloxanyl group A is represented by the following formula (b)
[In Formula (b), A 1 to A 11 are each independently hydrogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. Represents either. n represents an integer of 0 to 200, and a, b, and c each independently represent an integer of 0 to 20. However, the case where n = a = b = c = 0 is excluded. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003411704A JP4507580B2 (en) | 2003-12-10 | 2003-12-10 | Method for producing silicone compound and silicone agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003411704A JP4507580B2 (en) | 2003-12-10 | 2003-12-10 | Method for producing silicone compound and silicone agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005170827A true JP2005170827A (en) | 2005-06-30 |
| JP4507580B2 JP4507580B2 (en) | 2010-07-21 |
Family
ID=34732368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003411704A Expired - Fee Related JP4507580B2 (en) | 2003-12-10 | 2003-12-10 | Method for producing silicone compound and silicone agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4507580B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005272459A (en) * | 2004-02-27 | 2005-10-06 | Toray Ind Inc | Silicone compound and its production method |
| WO2023062933A1 (en) | 2021-10-14 | 2023-04-20 | 信越化学工業株式会社 | Polysiloxane compound and method for producing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5622325A (en) * | 1979-07-31 | 1981-03-02 | Shin Etsu Chem Co Ltd | Production of polymerizable organopolysiloxane |
| JP2002234861A (en) * | 2001-02-09 | 2002-08-23 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl ester |
| JP2005170826A (en) * | 2003-12-10 | 2005-06-30 | Toray Ind Inc | Method of purifying silicone compound and silicone compound obtained therefrom |
-
2003
- 2003-12-10 JP JP2003411704A patent/JP4507580B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5622325A (en) * | 1979-07-31 | 1981-03-02 | Shin Etsu Chem Co Ltd | Production of polymerizable organopolysiloxane |
| JP2002234861A (en) * | 2001-02-09 | 2002-08-23 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl ester |
| JP2005170826A (en) * | 2003-12-10 | 2005-06-30 | Toray Ind Inc | Method of purifying silicone compound and silicone compound obtained therefrom |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005272459A (en) * | 2004-02-27 | 2005-10-06 | Toray Ind Inc | Silicone compound and its production method |
| WO2023062933A1 (en) | 2021-10-14 | 2023-04-20 | 信越化学工業株式会社 | Polysiloxane compound and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4507580B2 (en) | 2010-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5225964B2 (en) | Method for producing organophosphate compound | |
| JP5699931B2 (en) | Silicone monomer | |
| JP2011201880A (en) | Silicone monomer and raw material for ophthalmic lens | |
| JP4802569B2 (en) | Method for producing silicone monomer | |
| JP4826150B2 (en) | Method for producing silicone monomer | |
| JP2019167431A (en) | Acid group-containing polymerizable monomer having functional group having high relative dielectric constant | |
| JP4882241B2 (en) | Method for producing silicone compound | |
| CN105524102A (en) | Silicone compound having a radical-polymerizable group and a method for the preparation thereof | |
| JP4507580B2 (en) | Method for producing silicone compound and silicone agent | |
| JP4273885B2 (en) | Method for producing silicone monomer composition | |
| JP4617887B2 (en) | Vinyl group-containing compound and method for producing the same | |
| WO2010082659A1 (en) | Silicone monomer | |
| JP4400199B2 (en) | Method for purifying silicone compound and method for producing silicone agent | |
| JP2012017285A (en) | Silicone monomer, method of producing the same, monomer composition and polymer | |
| JP2004182724A (en) | Method for producing silicone monomer | |
| JP4720072B2 (en) | Method for purifying silicone agent and silicone agent | |
| JP5402934B2 (en) | Silicone monomer, its production method and use | |
| JP4645016B2 (en) | Method for producing silicone compound | |
| JP2007023246A (en) | New silicon-containing compound and method for producing the same | |
| JP5111837B2 (en) | Method for producing silicone monomer, method for producing intermediate thereof, and molded article thereof | |
| JP7324170B2 (en) | Method for producing silicone compound | |
| JP2006169140A (en) | Method for producing silicone compound and silicone agent | |
| JP2668495B2 (en) | Method for producing silicon-based powder material | |
| JP2020066578A (en) | Composition containing phosphate compound, and manufacturing method therefor | |
| WO2013098966A1 (en) | Silicone monomer and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061211 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090714 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090908 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091006 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091201 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100112 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100312 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100413 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100426 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4507580 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |