JP5754272B2 - Carboxylic acid silyl ester compound having bulky substituent and method for producing the same - Google Patents

Description

  The present invention relates to a carboxylic acid silyl ester compound having a bulky substituent. This compound is useful as a surface coating composition additive, an additive such as a paint, and an additive for dental materials.

  Organosilicon compounds having two or more (meth) acryloxy groups are useful as surface coating composition additives, paint additives, and dental material additives. For example, Patent Document 1 (Japanese Patent Publication No. 49-7564) (Patent Publication) describes that methyltrimethacryloxysilane is useful as an additive in a coating composition for improving the surface properties of the plastic surface hardness and solvent resistance. In Non-Patent Document 1 (Dental Materials and Instruments, vol. 25, No. 4, 267-274 (2006)), silicon-containing dimethacrylate compounds such as dimethylsilyl dimethacrylate provide water repellency to dental composite resin There is a description that it is useful as an additive monomer for imparting.

Japanese Patent Publication No.49-7564

Dental materials and instruments, vol. 25, no. 4,267-274 (2006)

However, the compounds disclosed in Japanese Patent Publication No. 49-7564 (Patent Document 1), dental materials and instruments, vol. 25, no. 4, 267-274 (2006) (Non-Patent Document 1), after the coating or curing, the bond between the carboxyl group and the silicon atom undergoes a hydrolysis reaction over time, gradually imparted hardness, solvent resistance, Water repellency and the like are lost, and it is difficult to maintain the performance imparted for a long time.
The present invention has been made in view of the above circumstances. When used as a surface coating composition additive, an additive such as a paint, or a dental material, the carboxylic acid silyl ester compound capable of maintaining the imparted performance for a long period of time and its production It aims to provide a method.

  As a result of intensive studies to achieve the above object, the present inventors have used specific carboxylic acid silyl ester compounds as surface coating composition additives, paint additives, and dental material additives. Occasionally, it has been found that hardness, solvent resistance and water repellency can be imparted and the imparted performance can be maintained for a long period of time, and the present invention has been completed.

［式中、Ｒ¹、Ｒ²及びＲ³は水素原子又は炭素数１〜２０の非置換もしくは置換の１価炭化水素基であり、Ｒ ⁴ はイソプロピル基、ｓｅｃ−ブチル基、シクロペンチル基、シクロヘキシル基、ｔ−ブチル基、ｔ−アミル基、テキシル基、１−メチルシクロヘキシル基から選ばれる１価の２級又は３級炭化水素基、Ｒ⁵は炭素数３〜２０の分岐状のアルキル基又は環状のアルキル基、又は下記一般式（２）

（式中、Ｒ¹、Ｒ²及びＲ³は上記と同様である。）
で示される基である。］
で示される嵩高い置換基を有するカルボン酸シリルエステル化合物。
請求項２：
上記一般式（１）中のＲ⁴が、ｔ−ブチル基である請求項１記載の嵩高い置換基を有するカルボン酸シリルエステル化合物。
請求項３：
下記一般式（３）
Ｒ⁴Ｒ⁶ＳｉＸ₂ （３）
（式中、Ｒ⁴はイソプロピル基、ｓｅｃ−ブチル基、シクロペンチル基、シクロヘキシル基、ｔ−ブチル基、ｔ−アミル基、テキシル基、１−メチルシクロヘキシル基から選ばれる１価の２級又は３級炭化水素基、Ｒ⁶は炭素数３〜２０の分岐状のアルキル基又は環状のアルキル基、又はハロゲン原子、Ｘはハロゲン原子である。）
で示される嵩高い置換基を有するハロシラン化合物と、下記一般式（４）

（式中、Ｒ¹、Ｒ²及びＲ³は水素原子又は炭素数１〜２０の非置換もしくは置換の１価炭化水素基である。）
で示されるカルボン酸化合物を反応させることを特徴とする請求項１又は２記載の嵩高い置換基を有するカルボン酸シリルエステル化合物の製造方法。 Therefore, this invention provides the carboxylic acid silyl ester compound which has a bulky substituent shown below, and its manufacturing method.
Claim 1:
The following general formula (1)

Wherein R ¹ , R ² and R ³ are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is an isopropyl group, sec-butyl group, cyclopentyl group, cyclohexyl A monovalent secondary or tertiary hydrocarbon group selected from a group, a t-butyl group, a t-amyl group, a texyl group, and a 1-methylcyclohexyl group, R ⁵ is a branched alkyl group having 3 to 20 carbon atoms, or A cyclic alkyl group, or the following general formula (2)

(In the formula, R ¹ , R ² and R ³ are the same as above.)
It is group shown by these. ]
The carboxylic acid silyl ester compound which has a bulky substituent shown by these.
Claim 2 :
R ⁴ in general formula (1) is a carboxylic acid silyl ester compound having a bulky substituent group according to claim 1, wherein a t- butyl group.
Claim 3 :
The following general formula (3)
R ⁴ R ⁶ SiX ₂ (3)
(In the formula, R ⁴ is a monovalent secondary or tertiary selected from an isopropyl group, a sec-butyl group, a cyclopentyl group, a cyclohexyl group, a t-butyl group, a t-amyl group, a texyl group, and a 1-methylcyclohexyl group. (The hydrocarbon group, R ⁶ is a branched alkyl group having 3 to 20 carbon atoms or a cyclic alkyl group, or a halogen atom, and X is a halogen atom.)
A halosilane compound having a bulky substituent represented by the following general formula (4):

(Wherein, R ^1, R ² and R ³ Ru monovalent hydrocarbon radical der unsubstituted or substituted hydrogen atom or a C 1-20.)
The method for producing a carboxylic acid silyl ester compound having a bulky substituent according to claim 1 or 2, wherein the carboxylic acid compound represented by formula (1) is reacted.

  Carboxylic acid silyl ester compounds having bulky substituents provided by the present invention, when used as additives for surface coatings, additives such as paints, additives for dental materials, hardness, solvent resistance, Since water repellency can be imparted and the imparted performance can be maintained for a long period of time, it is useful as a surface coating composition additive, an additive such as a paint, and an additive for dental materials.

2 is a ¹ H-NMR spectrum of diacryloxy t-butylmethylsilane obtained in Reference Example 1. 2 is an IR spectrum of diacryloxy t-butylmethylsilane obtained in Reference Example 1. 1 is a ¹ H-NMR spectrum of triacryloxy t-butylsilane obtained in Example 1 . 2 is an IR spectrum of triacryloxy t-butylsilane obtained in Example 1 . 2 is a ¹ H-NMR spectrum of dimethacryloxy t-butylmethylsilane obtained in Reference Example 2 . 4 is an IR spectrum of dimethacryloxy t-butylmethylsilane obtained in Reference Example 2 . 2 is a ¹ H-NMR spectrum of dimethacryloxy t-butylpropylsilane obtained in Example 2. FIG. 2 is an IR spectrum of dimethacryloxy t-butylpropylsilane obtained in Example 2 . 2 is a ¹ H-NMR spectrum of diacryloxydiisopropylsilane obtained in Example 3 . 3 is an IR spectrum of diacryloxydiisopropylsilane obtained in Example 3 . 2 is a ¹ H-NMR spectrum of dimethacryloxydiisopropylsilane obtained in Example 4 . 4 is an IR spectrum of dimethacryloxydiisopropylsilane obtained in Example 4 . 2 is a ¹ H-NMR spectrum of diacryloxycyclohexylmethylsilane obtained in Reference Example 3 . 4 is an IR spectrum of diacryloxycyclohexylmethylsilane obtained in Reference Example 3 . 2 is a ¹ H-NMR spectrum of diacryloxydicyclopentylsilane obtained in Example 5 . 4 is an IR spectrum of diacryloxydicyclopentylsilane obtained in Example 5 .

［式中、Ｒ¹、Ｒ²及びＲ³は水素原子又は炭素数１〜２０の非置換もしくは置換の１価炭化水素基であり、Ｒ¹とＲ²又はＲ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、Ｒ⁴は炭素数３〜１０の１価の２級又は３級炭化水素基、Ｒ⁵は炭素数１〜２０の非置換もしくは置換の１価炭化水素基又は下記一般式（２）

（式中、Ｒ¹、Ｒ²及びＲ³は上記と同様である。）
で示される基である。］
で示される化合物である。 The carboxylic acid silyl ester compound having a bulky substituent of the present invention has the following general formula (1):

[Wherein R ¹ , R ² and R ³ are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² or R ² and R ³ are bonded to each other. And R ⁴ is a monovalent secondary or tertiary hydrocarbon group having 3 to 10 carbon atoms, and R ⁵ is unsubstituted or substituted having 1 to 20 carbon atoms. A monovalent hydrocarbon group or the following general formula (2)

(In the formula, R ¹ , R ² and R ³ are the same as above.)
It is group shown by these. ]
It is a compound shown by these.

Here, when R ¹ , R ² , R ³ are an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10, a linear, branched or cyclic alkyl group or alkenyl group. , Aryl group, aralkyl group and the like. Specifically, straight chain such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, etc. Branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, t-butyl group, t-amyl group, texyl group, 2-ethylhexyl group; cyclopentyl group, cyclohexyl group, 1-methyl Examples include cyclic alkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group, allyl group and propenyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and the like, and methyl group is particularly preferable. Moreover, a part or all of the hydrogen atoms of the hydrocarbon group may be substituted. Specific examples of the substituent include alkoxy groups such as a methoxy group, an ethoxy group, and an (iso) propoxy group; Groups consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; aryl groups having 6 to 18 carbon atoms such as cyano group, amino group, phenyl group and tolyl group; carbon numbers such as benzyl group and phenethyl group 7-18 aralkyl groups; an ester group, an ether group, an acyl group, a sulfide group, an alkylsilyl group, an alkoxysilyl group, and the like may be mentioned, and these may be used in combination. R ¹ and R ² and R ² and R ³ may be bonded to each other to form a ring having 3 to 20 carbon atoms, particularly an alicyclic ring, together with the carbon atom to which they are bonded. R ¹ , R ² and R ³ are particularly preferably a hydrogen atom or a methyl group.

R ⁴ is a monovalent secondary or tertiary hydrocarbon group having 3 to 10 carbon atoms, particularly 3 to 7 carbon atoms, specifically, an isopropyl group, a sec-butyl group, a cyclopentyl group, a cyclohexyl group, or a t-butyl group. , T-amyl group, texyl group, 1-methylcyclohexyl group and the like are exemplified, and t-butyl group and texyl group are particularly preferable.

When R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, the same groups as the above R ¹ , R ² and R ³ can be mentioned. R ⁵ is particularly preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, or a group represented by the above general formula (2).

  Specific examples of the compound represented by the above general formula (1) include diacryloxy t-butylmethylsilane, diacryloxy t-butylethylsilane, diacryloxy t-butylpropylsilane, diacryloxy t-butylisopropylsilane, diacryloxy t-butylbutylsilane. , Diacryloxy t-butylisobutylsilane, diacryloxy t-butylsec-butylsilane, diacryloxy t-butylcyclopentylsilane, diacryloxy t-butylcyclohexylsilane, diacryloxy t-butylphenylsilane, diacryloxy t-butylbenzylsilane, diacryloxydit-butylsilane, diacryloxy t-Amylmethylsilane, Diacryloxy t-Amylethylsilane, Diacryloxy t-Amylpropylsilane, Diacryl Xyl-t-amylisopropylsilane, diacryloxy-t-amylbutylsilane, diacryloxy-t-amylisobutylsilane, diacryloxy-t-amylsec-butylsilane, diacryloxy-t-amylcyclopentylsilane, diacryloxy-t-amylcyclohexylsilane, diacryloxy-t-amylphenylsilane, Diacryloxy t-amyl benzyl silane, diacryloxy t-amyl t-butyl silane, diacryloxy di t-amyl silane, diacryloxy texyl methyl silane, diacryloxy texyl ethyl silane, dia acryloxy hexyl propyl silane, diacryloxy texyl isopropyl Silane, diacryloxy texyl butyl silane, diacryloxy texyl isobutyl silane, diacryloxy texyl sec Butylsilane, diacryloxy cyclohexyl cyclopentyl silane, diacryloxy cyclohexyl cyclohexyl silane, diacryloxy texyl phenyl silane, diacryloxy hexyl benzyl silane, diacryloxy texyl t-butyl silane, diacryloxy texyl t- Amylsilane, Diacryloxyditexylsilane, Diacryloxy (1-methylcyclohexyl) methylsilane, Diacryloxy (1-methylcyclohexyl) ethylsilane, Diacryloxy (1-methylcyclohexyl) propylsilane, Diacryloxy (1-methylcyclohexyl) isopropylsilane, Diacryloxy (1 -Methylcyclohexyl) butylsilane, diacryloxy (1-methylcyclohexyl) isobutylsilane, diacryloxy (1-methylsilane) Cyclohexyl) sec-butylsilane, diacryloxy (1-methylcyclohexyl) cyclopentylsilane, diacryloxy (1-methylcyclohexyl) cyclohexylsilane, diacryloxy (1-methylcyclohexyl) phenylsilane, diacryloxy (1-methylcyclohexyl) benzylsilane, diacryloxy (1- Methylcyclohexyl) t-butylsilane, diacryloxy (1-methylcyclohexyl) t-amylsilane, diacryloxy (1-methylcyclohexyl) texylsilane, diacryloxydi (1-methylcyclohexyl) silane, triacryloxy t-butylsilane, triacryloxy t-amylsilane, Triacryloxy texylsilane, triacryloxy (1-methylcyclohexyl) silane, dimethyl Acryloxy t-butylmethylsilane, dimethacryloxy t-butylethylsilane, dimethacryloxy t-butylpropylsilane, dimethacryloxy t-butylisopropylsilane, dimethacryloxy t-butylbutylsilane, dimethacryloxy t-butylisobutylsilane, dimethacryloxy t-butylsec-butylsilane, Dimethacryloxy t-butylcyclopentylsilane, dimethacryloxy t-butylcyclohexylsilane, dimethacryloxy t-butylphenylsilane, dimethacryloxy t-butylbenzylsilane, dimethacryloxy di-t-butylsilane, dimethacryloxy t-amylmethylsilane, dimethacryloxy t-amylethylsilane, Dimethacryloxy t-amylpropylsilane, dimethacryloxy t-amylisotop Pyrsilane, dimethacryloxy t-amylbutylsilane, dimethacryloxy t-amylisobutylsilane, dimethacryloxy t-amyl sec-butylsilane, dimethacryloxy t-amylcyclopentylsilane, dimethacryloxy t-amylcyclohexylsilane, dimethacryloxy t-amylphenylsilane, dimethacryloxy t-amylbenzyl Silane, dimethacryloxy t-amyl t-butyl silane, dimethacryloxy di t-amyl silane, dimethacryloxy texyl methyl silane, dimethacryloxy texyl ethyl silane, dimethacryloxy texyl propyl silane, dimethacryloxy texyl isopropyl silane, Dimethacryloxy texyl butyl silane, dimethacryloxy texyl isobutyl silane, dimethacryloxy tex Sec-butyl silane, dimethacryloxy texylcyclopentyl silane, dimethacryloxy texyl cyclohexyl silane, dimethacryloxy texyl phenyl silane, dimethacryloxy texyl benzyl silane, dimethacryloxy texyl t-butyl silane, dimethacryloxy texyl Sil-t-amylsilane, dimethacryloxyditexylsilane, dimethacryloxy (1-methylcyclohexyl) methylsilane, dimethacryloxy (1-methylcyclohexyl) ethylsilane, dimethacryloxy (1-methylcyclohexyl) propylsilane, dimethacryloxy (1-methylcyclohexyl) isopropylsilane, Dimethacryloxy (1-methylcyclohexyl) butylsilane, dimethacryloxy (1-methylcyclohexyl) isobutyl Lan, dimethacryloxy (1-methylcyclohexyl) sec-butylsilane, dimethacryloxy (1-methylcyclohexyl) cyclopentylsilane, dimethacryloxy (1-methylcyclohexyl) cyclohexylsilane, dimethacryloxy (1-methylcyclohexyl) phenylsilane, dimethacryloxy (1-methylcyclohexyl) Benzylsilane, dimethacryloxy (1-methylcyclohexyl) t-butylsilane, dimethacryloxy (1-methylcyclohexyl) t-amylsilane, dimethacryloxy (1-methylcyclohexyl) texylsilane, dimethacryloxydi (1-methylcyclohexyl) silane, trimethacryloxyt -Butylsilane, trimethacryloxy t-amylsilane, trimethacryloxy texyl sila , Tri methacryloxy (1-methylcyclohexyl) silane, and the like. Among these, diacryloxy t-butylmethylsilane, diacryloxy t-butylethylsilane, diacryloxy t-butylpropylsilane, triacryloxy t-butylsilane, dimethacryloxy t-butylmethylsilane, dimethacryloxy t-butylethylsilane, dimethacryloxy t- Butylpropylsilane and trimethacryloxy t-butylsilane are preferred.

（式中、Ｒ¹、Ｒ²及びＲ³は水素原子又は炭素数１〜２０の非置換もしくは置換の１価炭化水素基であり、Ｒ¹とＲ²又はＲ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよい。）
で示されるカルボン酸化合物を反応させる方法が挙げられる。 Moreover, the manufacturing method of the compound shown by the said General formula (1) is the following general formula (3), for example.
R ⁴ R ⁶ SiX ₂ (3)
(Wherein R ⁴ is a monovalent secondary or tertiary hydrocarbon group having 3 to 10 carbon atoms, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, and X is (It is a halogen atom.)
A halosilane compound having a bulky substituent represented by the following general formula (4):

Wherein R ¹ , R ² and R ³ are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² or R ² and R ³ are bonded to each other. And may form a ring together with the carbon atom to which they are attached.)
The method of making the carboxylic acid compound shown by react is mentioned.

R ⁴ in the general formula (3) can be exemplified by those described above. When R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, the above R ¹ , R ² and the same groups as R ³ can be exemplified. Examples of the halogen atom for R ⁶ and X include a chlorine atom and a bromine atom.

  Specific examples of the halosilane compound having a bulky substituent represented by the general formula (3) include isopropylmethyldichlorosilane, isopropylethyldichlorosilane, isopropylpropyldichlorosilane, isopropylbutyldichlorosilane, isopropylisobutyldichlorosilane, and isopropylphenyl. Dichlorosilane, isopropylbenzyldichlorosilane, diisopropyldichlorosilane, sec-butylmethyldichlorosilane, sec-butylethyldichlorosilane, sec-butylpropyldichlorosilane, sec-butylbutyldichlorosilane, sec-butylisobutyldichlorosilane, sec-butyl Phenyldichlorosilane, sec-butylbenzyldichlorosilane, sec-butylisopropyldichlorosilane, dis c-Butyldichlorosilane, cyclopentylmethyldichlorosilane, cyclopentylethyldichlorosilane, cyclopentylpropyldichlorosilane, cyclopentylbutyldichlorosilane, cyclopentylisobutyldichlorosilane, cyclopentylphenyldichlorosilane, cyclopentylbenzyldichlorosilane, cyclopentylisopropyldichlorosilane, cyclopentyl sec-butyl Dichlorosilane, dicyclopentyldichlorosilane, cyclohexylmethyldichlorosilane, cyclohexylethyldichlorosilane, cyclohexylpropyldichlorosilane, cyclohexylbutyldichlorosilane, cyclohexylisobutyldichlorosilane, cyclohexylphenyldichlorosilane, cyclohexylbenzyldichlorosilane Cyclohexylisopropyldichlorosilane, cyclohexyl sec-butyldichlorosilane, cyclohexylcyclopentyldichlorosilane, dicyclohexyldichlorosilane, t-butylmethyldichlorosilane, t-butylethyldichlorosilane, t-butylpropyldichlorosilane, t-butylisopropyldichlorosilane, t-butylbutyldichlorosilane, t-butylisobutyldichlorosilane, t-butylsec-butyldichlorosilane, t-butylcyclopentyldichlorosilane, t-butylcyclohexyldichlorosilane, t-butylphenyldichlorosilane, t-butylbenzyldichlorosilane , Di-t-butyldichlorosilane, t-amylmethyldichlorosilane, t-amylethyldichlorosilane, t-amylpropyl Dichlorosilane, t-amylisopropyldichlorosilane, t-amylbutyldichlorosilane, t-amylisobutyldichlorosilane, t-amylsec-butyldichlorosilane, t-amylcyclopentyldichlorosilane, t-amylcyclohexyldichlorosilane, t-amyl Phenyldichlorosilane, t-amylbenzyldichlorosilane, t-amyl t-butyldichlorosilane, di-t-amyldichlorosilane, texylmethyldichlorosilane, texylethyldichlorosilane, texylpropyldichlorosilane, texylisopropyldichlorosilane , Texylbutyldichlorosilane, Texylisobutyldichlorosilane, Texyl sec-butyldichlorosilane, Texylcyclopentyldichlorosilane, Texylcyclohexyldi Lorosilane, Texylphenyldichlorosilane, Texylbenzyldichlorosilane, Texylt-butyldichlorosilane, Texylt-amyldichlorosilane, Ditexyldichlorosilane, (1-Methylcyclohexyl) methyldichlorosilane, (1-Methylcyclohexyl) ethyl Dichlorosilane, (1-methylcyclohexyl) propyldichlorosilane, (1-methylcyclohexyl) isopropyldichlorosilane, (1-methylcyclohexyl) butyldichlorosilane, (1-methylcyclohexyl) isobutyldichlorosilane, (1-methylcyclohexyl) sec -Butyldichlorosilane, (1-methylcyclohexyl) cyclopentyldichlorosilane, (1-methylcyclohexyl) cyclohexyldichlorosilane, (Lucyclohexyl) phenyldichlorosilane, (1-methylcyclohexyl) benzyldichlorosilane, (1-methylcyclohexyl) t-butyldichlorosilane, (1-methylcyclohexyl) t-amyldichlorosilane, (1-methylcyclohexyl) texyldichlorosilane , Di (1-methylcyclohexyl) dichlorosilane, isopropyltrichlorosilane, sec-butyltrichlorosilane, cyclopentyltrichlorosilane, cyclohexyltrichlorosilane, t-butyltrichlorosilane, t-amyltrichlorosilane, texyltrichlorosilane, (1-methyl) (Cyclohexyl) trichlorosilane and the like. Among these, t-butylmethyldichlorosilane, t-butylethyldichlorosilane, t-butylpropyldichlorosilane, and t-butyltrichlorosilane are particularly preferable.

In addition, R ¹ , R ² , and R ³ in the general formula (4) can be exemplified as described above, and specific examples of the carboxylic acid compound represented by the general formula (4) include acrylic acid, methacrylic acid, and crotonic acid. And cinnamic acid.

  Although the compounding ratio of the halosilane compound having a bulky substituent represented by the general formula (3) and the carboxylic acid compound represented by the general formula (4) is not particularly limited, from the viewpoint of reactivity and productivity, The carboxylic acid compound represented by the general formula (4) is added in an amount of 0.2 to 5 moles, particularly 0. It is preferable to use in the range of 5-2 mol.

  In the reaction between the halosilane compound having a bulky substituent and the carboxylic acid compound, hydrogen halide is by-produced, and the by-produced hydrogen halide may be trapped by adding a nitrogen-containing compound. Nitrogen-containing compounds include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, ethyldiisopropylamine, butylamine, dibutylamine , Tributylamine, hexylamine, 2-ethylhexylamine, octylamine, dioctylamine, trioctylamine, piperidine, N-methylpiperidine, morpholine, N-methylmorpholine, ethylenediamine, tetramethylethylenediamine, diethylenetriamine, aniline, N-methylaniline N-ethylaniline, N, N-dimethylaniline, N, N-diethylaniline, 1,8 Diazabicyclo [5.4.0] undecene-7 and the like.

  Although the compounding ratio of the halosilane compound having a bulky substituent represented by the general formula (3) and the nitrogen-containing compound is not particularly limited, it is bulky represented by the general formula (3) from the viewpoint of reactivity and productivity. The range of 0.1 to 15 mol, particularly 0.2 to 5 mol, of the nitrogen-containing compound is preferable with respect to 1 mol of the silicon-halogen atom bond of the halosilane compound having a substituent.

  Although the reaction temperature of the said reaction is not specifically limited, 0-200 degreeC, especially 20-150 degreeC is preferable, Reaction time is not specifically limited, However, 1-40 hours, Especially 1-20 hours are preferable.

  In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate. An aprotic polar solvent such as acetonitrile, N, N-dimethylformamide or N-methylpyrrolidone; a chlorinated hydrocarbon solvent such as dichloromethane or chloroform; These solvents may be used alone or in combination of two or more.

  From the reaction solution obtained as described above, the target product can be recovered by a usual method such as distillation.

  EXAMPLES Hereinafter, although an Example and an experiment example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[ Reference Example 1] Diacryloxy t-butylmethylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 43.0 g (0.25 mol) of t-butylmethyldichlorosilane and 55.6 g of triethylamine (0 .55 mol) and 150 ml of toluene were charged and heated to 40 ° C. After the internal temperature was stabilized, 37.9 g (0.53 mol) of acrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the produced salt was removed by filtration, the filtrate was distilled to obtain 38.1 g of a fraction having a boiling point of 74-76 ° C./0.2 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 242, 227, 185, 131, 55
¹ H-NMR spectrum (heavy benzene solvent)
A chart is shown in FIG.
IR spectrum FIG. 2 is a chart.
From the above results, it was confirmed that the obtained compound was diacryloxy t-butylmethylsilane.

[Example 1 ] Triacryloxy t-butylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 38.3 g (0.2 mol) of t-butyltrichlorosilane and 66.8 g of triethylamine (0. 66 mol) and 180 ml of toluene were charged and heated to 40 ° C. After the internal temperature was stabilized, 45.4 g (0.63 mol) of acrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the produced salt was removed by filtration, the filtrate was distilled to obtain 37.1 g of a fraction having a boiling point of 94-95 ° C./0.2 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 298, 241, 187, 133, 55
¹ H-NMR spectrum (heavy benzene solvent)
FIG. 3 shows a chart.
IR spectrum FIG. 4 is a chart.
From the above results, it was confirmed that the obtained compound was triacryloxy t-butylsilane.

Reference Example 2 Dimethacryloxy t-butylmethylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 34.4 g (0.2 mol) of t-butylmethyldichlorosilane and 44.5 g of triethylamine (0 .44 mol) and 120 ml of toluene were charged and heated to 40 ° C. After the internal temperature was stabilized, 36.2 g (0.42 mol) of methacrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the produced salt was removed by filtration, the filtrate was distilled to obtain 30.6 g of a fraction having a boiling point of 87-89 ° C./0.4 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 270, 255, 213, 69, 41
¹ H-NMR spectrum (heavy benzene solvent)
FIG. 5 shows a chart.
IR spectrum FIG. 6 is a chart.
From the above results, it was confirmed that the obtained compound was dimethacryloxy t-butylmethylsilane.

[Example 2 ] Dimethacryloxy t-butylpropylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 39.8 g (0.2 mol) of t-butylpropyldichlorosilane and 44.5 g of triethylamine (0 .44 mol) and 120 ml of toluene were charged and heated to 40 ° C. After the internal temperature was stabilized, 36.2 g (0.42 mol) of methacrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the produced salt was removed by filtration, the filtrate was distilled to obtain 37.8 g of a fraction having a boiling point of 129 ° C./0.6 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 298, 283, 241, 69, 41
¹ H-NMR spectrum (heavy benzene solvent)
FIG. 7 shows a chart.
IR spectrum FIG. 8 is a chart.
From the above results, it was confirmed that the obtained compound was dimethacryloxy t-butylpropylsilane.

[Example 3 ] Diacryloxydiisopropylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 37.0 g (0.2 mol) of diisopropyldichlorosilane and 44.5 g (0.44 mol) of triethylamine. 120 ml of toluene was charged and heated to 40 ° C. After the internal temperature was stabilized, 30.2 g (0.42 mol) of acrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the produced salt was removed by filtration, the filtrate was distilled to obtain 34.2 g of a fraction having a boiling point of 103 ° C./0.5 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 241, 213, 159, 77, 55
¹ H-NMR spectrum (heavy benzene solvent)
FIG. 9 is a chart.
IR spectrum FIG. 10 is a chart.
From the above results, it was confirmed that the obtained compound was diacryloxydiisopropylsilane.

[Example 4 ] Dimethacryloxydiisopropylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 37.0 g (0.2 mol) of diisopropyldichlorosilane and 44.5 g (0.44 mol) of triethylamine. 120 ml of toluene was charged and heated to 40 ° C. After the internal temperature was stabilized, 36.2 g (0.42 mol) of methacrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the generated salt was removed by filtration, the filtrate was distilled to obtain 36.0 g of a fraction having a boiling point of 85 ° C./0.4 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 284, 269, 241, 69, 41
¹ H-NMR spectrum (heavy benzene solvent)
FIG. 11 shows a chart.
IR spectrum FIG. 12 is a chart.
From the above results, it was confirmed that the obtained compound was dimethacryloxydiisopropylsilane.

[ Reference Example 3 ] Diacryloxycyclohexylmethylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 39.4 g (0.2 mol) of cyclohexylmethyldichlorosilane, 44.5 g of triethylamine (0.44) Mol) and 120 ml of toluene were charged and heated to 40 ° C. After the internal temperature was stabilized, 30.2 g (0.42 mol) of acrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the produced salt was removed by filtration, the filtrate was distilled to obtain 31.8 g of a fraction having a boiling point of 113 ° C./0.4 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 253, 185, 131, 77, 55
¹ H-NMR spectrum (heavy benzene solvent)
FIG. 13 shows a chart.
IR spectrum FIG. 14 is a chart.
From the above results, it was confirmed that the obtained compound was diacryloxycyclohexylmethylsilane.

[Example 5 ] Diacryloxydicyclopentylsilane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 47.4 g (0.2 mol) of dicyclopentyldichlorosilane and 44.5 g of triethylamine (0.44) Mol) and 120 ml of toluene were charged and heated to 40 ° C. After the internal temperature was stabilized, 30.2 g (0.42 mol) of acrylic acid was added dropwise over 1 hour, and the mixture was further stirred at that temperature for 2 hours. After the produced salt was removed by filtration, the filtrate was distilled to obtain 38.1 g of a fraction having a boiling point of 144 ° C./0.3 kPa.

A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 308, 239, 185, 167, 55
¹ H-NMR spectrum (heavy benzene solvent)
FIG. 15 is a chart.
IR spectrum FIG. 16 is a chart.
From the above results, it was confirmed that the obtained compound was diacryloxydicyclopentylsilane.

[Experimental Example 1] Comparison of hydrolyzability between dimethacryloxy t-butylmethylsilane and dimethacryloxydimethylsilane In a flask equipped with a stirrer, reflux condenser and thermometer, water 5 g, dimethacryloxy t-butylmethylsilane 0.54 g (0.002 mol), 0.46 g (0.002 mol) of dimethacryloxydimethylsilane and 5 g of heptane as an internal standard, stirred at room temperature, and progress of hydrolysis reaction of carboxylic acid silyl ester compound after 10 minutes The degree was quantified by gas chromatography analysis. As a result, dimethacryloxy t-butylmethylsilane was only 5% hydrolyzed, but all dimethacryloxydimethylsilane was hydrolyzed, and dimethacryloxy t-butylmethylsilane was compared to dimethacryloxydimethylsilane. It was found to be stable to hydrolysis.

Claims (3)

The following general formula (1)

Wherein R ¹ , R ² and R ³ are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is an isopropyl group, sec-butyl group, cyclopentyl group, cyclohexyl A monovalent secondary or tertiary hydrocarbon group selected from a group, a t-butyl group, a t-amyl group, a texyl group, and a 1-methylcyclohexyl group, R ⁵ is a branched alkyl group having 3 to 20 carbon atoms, or A cyclic alkyl group, or the following general formula (2)

(In the formula, R ¹ , R ² and R ³ are the same as above.)
It is group shown by these. ]
The carboxylic acid silyl ester compound which has a bulky substituent shown by these. R ⁴ in general formula (1) is a carboxylic acid silyl ester compound having a bulky substituent group according to claim 1, wherein a t- butyl group. The following general formula (3)
R ⁴ R ⁶ SiX ₂ (3)
(In the formula, R ⁴ is a monovalent secondary or tertiary selected from an isopropyl group, a sec-butyl group, a cyclopentyl group, a cyclohexyl group, a t-butyl group, a t-amyl group, a texyl group, and a 1-methylcyclohexyl group. (The hydrocarbon group, R ⁶ is a branched alkyl group having 3 to 20 carbon atoms or a cyclic alkyl group, or a halogen atom, and X is a halogen atom.)
A halosilane compound having a bulky substituent represented by the following general formula (4):

(Wherein, R ^1, R ² and R ³ Ru monovalent hydrocarbon radical der unsubstituted or substituted hydrogen atom or a C 1-20.)
The method for producing a carboxylic acid silyl ester compound having a bulky substituent according to claim 1 or 2, wherein the carboxylic acid compound represented by formula (1) is reacted.

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