JP4433168B2 - Organoxysilane compounds having protected hydroxyl groups - Google Patents

Description

The present invention is a silane coupling agent, surface treating agent, about the organoxysilane compound having a hydroxyl group protected by a useful triorganosilyl group as a polymer modifier.

Alkoxysilane compounds having functional groups are widely used in silane coupling agents, surface treatment agents, polymer modifiers, and the like, such as amino groups, (meth) acryloxy groups, mercapto groups, epoxy groups, vinyl groups, etc. Examples include alkoxysilane compounds having a functional group. As one of the silane compounds having such a functional group, an alkoxysilane compound having a hydroxyl group can be considered. The alkoxysilane compound having a hydroxyl group is useful as a polymer modifier capable of introducing a hydroxyl group into a polymer, a silane coupling agent, or a surface treatment agent. However, a silane compound having a hydroxyl group cannot be present in a stable state because it causes an intermolecular reaction between the hydroxyl group and a silicon atom and becomes a polymer.
In addition, the following are mentioned as prior literature relevant to the present invention.

“ORGANOHALOSILANES Precursors to Silicone” (Netherlands), ELSEVIER PUBLISHING COMPANY, p. 350, 7th to 15th lines

The present invention has been made in view of the above circumstances, and an organoxysilane compound having a hydroxyl group protected by a triorganosilyl group that can be stably present and can exhibit the same effect as an organoxysilane compound having a hydroxyl group. The purpose is to provide goods .

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は炭素数１〜１０の１価炭化水素基、Ｒ⁵、Ｒ⁶は水素原子又はメチル基、Ａは炭素数１〜１０の直鎖又は分岐状の２価脂肪族炭化水素基、ａは０〜５の整数、ｎは０，１又は２である。）
で示されるオルガノキシシラン化合物が、化合物として安定に存在でき、また、シランカップリング剤、表面処理剤、高分子変性剤として用いた後で、脱保護することにより、容易に水酸基を生成することができ、水酸基を有するオルガノキシシラン化合物を用いたのと同等の効果が発現すること、特にアニオン重合末端変性剤として用いた場合、アニオン重合末端は保護された水酸基とは反応せず、選択的にオルガノキシシラン部位と反応するため、定量的にアニオン重合末端に保護された水酸基を導入することができ、その後脱保護することにより容易に水酸基変性ポリマーを製造できることを知見し、本発明を完成するに至ったものである。 As a result of intensive studies to achieve the above object, the present inventor has obtained the following general formula (1) in which a hydroxyl group is protected with a triorganosilyl group.

(In the formula, R ¹ , R ² , R ³ and R ⁴ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁵ and R ⁶ are hydrogen atoms or methyl groups, and A is a straight chain having 1 to 10 carbon atoms. Or a branched divalent aliphatic hydrocarbon group, a is an integer of 0 to 5, and n is 0, 1 or 2.)
The organoxysilane compound represented by can be stably present as a compound, and can easily generate a hydroxyl group by deprotection after being used as a silane coupling agent, surface treatment agent, or polymer modifier. It is possible to produce an effect equivalent to that of using an organoxysilane compound having a hydroxyl group. In particular, when used as an anionic polymerization terminal modifier, the anionic polymerization terminal does not react with a protected hydroxyl group and is selectively used. Since it reacts with the organoxysilane moiety, it can be quantitatively introduced into the hydroxyl group protected at the end of the anionic polymerization, and then it can be easily produced by deprotection to complete the present invention. It has come to be.

（式中、ａは０〜５の整数で、ａ＝０の場合、Ｒ ¹ Ｒ ² Ｒ ³ ＳｉＯ−はトリエチルシロキシ基、ｔ−ブチルジメチルシロキシ基、又はトリイソプロピルシロキシ基を示し、ａ＝１〜５の整数の場合、Ｒ ¹ 、Ｒ ² 、Ｒ ³ は炭素数１〜１０の１価炭化水素基を示し、Ｒ⁴は炭素数１〜１０の１価炭化水素基、Ｒ⁵、Ｒ⁶は水素原子又はメチル基、Ａは炭素数１〜１０の直鎖又は分岐状の２価脂肪族炭化水素基、ｎは０，１又は２である。）
で示されることを特徴とする保護された水酸基を有するオルガノキシシラン化合物。
［ＩＩ］Ｒ⁵、Ｒ⁶が共に水素原子、Ａが−Ａ’−ＣＨ₂ＣＨ₂−（Ａ’は炭素数１〜８の直鎖又は分岐状の２価脂肪族炭化水素基である。）、ａが０又は１であることを特徴とする［Ｉ］記載の保護された水酸基を有するオルガノキシシラン化合物。 Accordingly, the present invention provides the following organoxysilane compound.
[I] The following general formula (1)

( Wherein , a is an integer of 0 to 5, and when a = 0, R ¹ R ² R ³ SiO— represents a triethylsiloxy group, a t-butyldimethylsiloxy group, or a triisopropylsiloxy group, and a = 1 In the case of an integer of ˜5, R ¹ , R ² , R ³ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms , R ⁴ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ , R ⁶ Is a hydrogen atom or a methyl group, A is a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms , and n is 0, 1 or 2.)
An organoxysilane compound having a protected hydroxyl group, wherein
[II] R ⁵ and R ⁶ are both hydrogen atoms, A is —A′—CH ₂ CH ₂ — (A ′ is a linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. ), An organoxysilane compound having a protected hydroxyl group according to [I], wherein a is 0 or 1 .

  According to the present invention, an organoxysilane compound having a hydroxyl group protected with a triorganosilyl group can exist stably as a compound, and after being used for a silane coupling agent or polymer modification, a triorganosilyl group By deprotecting, effects equivalent to those obtained using an organoxysilane compound having a hydroxyl group can be exhibited.

（式中、ａは０〜５の整数で、ａ＝０の場合、Ｒ ¹ Ｒ ² Ｒ ³ ＳｉＯ−はトリエチルシロキシ基、ｔ−ブチルジメチルシロキシ基、又はトリイソプロピルシロキシ基を示し、ａ＝１〜５の整数の場合、Ｒ ¹ 、Ｒ ² 、Ｒ ³ は炭素数１〜１０の１価炭化水素基を示し、Ｒ⁴は炭素数１〜１０の１価炭化水素基、Ｒ⁵、Ｒ⁶は水素原子又はメチル基、Ａは炭素数１〜１０の直鎖又は分岐状の２価脂肪族炭化水素基、ｎは０，１又は２である。）
で示されるトリオルガノシリル基で保護された水酸基を有するオルガノキシシラン化合物である。 The organoxysilane compound of the present invention has the following general formula (1)

( Wherein , a is an integer of 0 to 5, and when a = 0, R ¹ R ² R ³ SiO— represents a triethylsiloxy group, a t-butyldimethylsiloxy group, or a triisopropylsiloxy group, and a = 1 In the case of an integer of ˜5, R ¹ , R ² , R ³ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms , R ⁴ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ , R ⁶ Is a hydrogen atom or a methyl group, A is a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms , and n is 0, 1 or 2.)
And an organoxysilane compound having a hydroxyl group protected by a triorganosilyl group.

  In this case, examples of the monovalent hydrocarbon group include a linear, branched, or cyclic alkyl group, an alkenyl group, an aryl group, and the like, and a linear or branched alkyl group is particularly preferable. The monovalent hydrocarbon group preferably has 1 to 6 carbon atoms. As said bivalent aliphatic hydrocarbon group, an alkylene group is preferable and it is more preferable that it is C1-C5.

Specific examples of the organoxysilane compound of the general formula (1) include the following alkoxysilane compounds : 6 -trimethylsiloxy- 4 -oxahexyltrimethoxysilane, 6-trimethylsiloxy- 4 -oxa Hexylmethyldimethoxysilane, 6-trimethylsiloxy- 4 -oxahexyldimethylmethoxysilane, 6-trimethylsiloxy- 4 -oxahexyltriethoxysilane, 6-trimethylsiloxy- 4 -oxahexylmethyldiethoxysilane, 6-trimethylsiloxy- 4 -oxahexyldimethylethoxysilane, triethylsiloxymethyltrimethoxysilane, triethylsiloxymethylmethyldimethoxysilane, triethylsiloxymethyldimethylmethoxysilane, triethylsiloxymethyl Rutriethoxysilane, triethylsiloxymethylmethyldiethoxysilane, triethylsiloxymethyldimethylethoxysilane, 2-triethylsiloxyethyltrimethoxysilane, 2-triethylsiloxyethylmethyldimethoxysilane, 2-triethylsiloxyethyldimethylmethoxysilane, 2-triethylsiloxy Ethyltriethoxysilane, 2-triethylsiloxyethylmethyldiethoxysilane, 2-triethylsiloxyethyldimethylethoxysilane, 3-triethylsiloxypropyltrimethoxysilane, 3-triethylsiloxypropylmethyldimethoxysilane, 3-triethylsiloxypropyldimethylmethoxysilane 3-triethylsiloxypropyltriethoxysilane, 3-triethylsiloxypropylmethyl Ethoxysilane, 3-triethylsiloxypropyldimethylethoxysilane, 4-triethylsiloxybutyltrimethoxysilane, 4-triethylsiloxybutylmethyldimethoxysilane, 4-triethylsiloxybutyldimethylmethoxysilane, 4-triethylsiloxybutyltriethoxysilane, 4- triethylsiloxy-butyl methyl diethoxy silane, 4-triethylsiloxy-butyldimethyl silane, 6- triethylsiloxy - 4 - oxa hexyltrimethoxysilane, 6-triethylsiloxy - 4 - oxa hexyl methyl dimethoxy silane, 6- triethylsiloxy - 4 - oxahexyl dimethyl silane, 6- triethylsiloxy - 4 - oxa hexyl triethoxysilane, 6-triethylsiloxy - 4 - Kisa hexyl methyl diethoxy silane, 6- triethylsiloxy - 4 - oxa hexyl dimethyl silane, t- butyl dimethylsiloxy methyltrimethoxysilane, t- butyl dimethylsiloxy methyl dimethoxysilane, t- butyl butyldimethylsiloxymethyl dimethyl silane, t-butyldimethylsiloxymethyltriethoxysilane, t-butyldimethylsiloxymethylmethyldiethoxysilane, t-butyldimethylsiloxymethyldimethylethoxysilane, 2- (t-butyldimethylsiloxy) ethyltrimethoxysilane, 2- (t- Butyldimethylsiloxy) ethylmethyldimethoxysilane, 2- (t-butyldimethylsiloxy) ethyldimethylmethoxysilane, 2- (t-butyldimethylsiloxy) ethyltrie Toxisilane, 2- (t-butyldimethylsiloxy) ethylmethyldiethoxysilane, 2- (t-butyldimethylsiloxy) ethyldimethylethoxysilane, 3- (t-butyldimethylsiloxy) propyltrimethoxysilane, 3- (t- Butyldimethylsiloxy) propylmethyldimethoxysilane, 3- (t-butyldimethylsiloxy) propyldimethylmethoxysilane, 3- (t-butyldimethylsiloxy) propyltriethoxysilane, 3- (t-butyldimethylsiloxy) propylmethyldiethoxy Silane, 3- (t-butyldimethylsiloxy) propyldimethylethoxysilane, 4- (t-butyldimethylsiloxy) butyltrimethoxysilane, 4- (t-butyldimethylsiloxy) butylmethyldimethoxysilane, 4- (t-butyl Rudimethylsiloxy) butyldimethylmethoxysilane, 4- (t-butyldimethylsiloxy) butyltriethoxysilane, 4- (t-butyldimethylsiloxy) butylmethyldiethoxysilane, 4- (t-butyldimethylsiloxy) butyldimethylethoxy silane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyltrimethoxysilane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyl methyl dimethoxy silane, 6- (t-butyl dimethylsiloxy) - 4 - oxahexyl dimethyl silane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyl triethoxysilane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyl methyl diethoxy silane, 6- (t-butyldimethyl siloxy) - 4 -Oxahexyldimethylethoxysilane, triisopropylsiloxymethyltrimethoxysilane, triisopropylsiloxymethylmethyldimethoxysilane, triisopropylsiloxymethyldimethylmethoxysilane, triisopropylsiloxymethyltriethoxysilane, triisopropylsiloxymethylmethyldiethoxysilane, triisopropyl Siloxymethyldimethylethoxysilane, 2-triisopropylsiloxyethyltrimethoxysilane, 2-triisopropylsiloxyethylmethyldimethoxysilane, 2-triisopropylsiloxyethyldimethylmethoxysilane, 2-triisopropylsiloxyethyltriethoxysilane, 2-triisopropyl Siloxyethylmethyldiethoxysilane, 2-triisopropylsiloxy Ethyldimethylethoxysilane, 3-triisopropylsiloxypropyltrimethoxysilane, 3-triisopropylsiloxypropylmethyldimethoxysilane, 3-triisopropylsiloxypropyldimethylmethoxysilane, 3-triisopropylsiloxypropyltriethoxysilane, 3-triisopropylsiloxy Propylmethyldiethoxysilane, 3-triisopropylsiloxypropyldimethylethoxysilane, 4-triisopropylsiloxybutyltrimethoxysilane, 4-triisopropylsiloxybutylmethyldimethoxysilane, 4-triisopropylsiloxybutyldimethylmethoxysilane, 4-triisopropyl Siloxybutyltriethoxysilane, 4-triisopropylsiloxybutylmethyldiethoxysilane, 4 Triisopropylsiloxy-butyldimethyl silane, 6- triisopropylsiloxy - 4 - oxa hexyltrimethoxysilane, 6-triisopropylsiloxy - 4 - oxa hexyl methyl dimethoxy silane, 6- triisopropylsiloxy - 4 - oxa hexyl dimethyl silane, 6-triisopropylsiloxy- 4 -oxahexyltriethoxysilane, 6-triisopropylsiloxy- 4 -oxahexylmethyldiethoxysilane, 6-triisopropylsiloxy- 4 -oxahexyldimethylethoxysilane, and the like.

Among these, from the viewpoint of the usefulness of the product and the ease of production, R ⁵ and R ^{6 in} the general formula (1) are both hydrogen atoms, and A is —A′—CH ₂ CH ₂ — (A ′). Is a straight-chain or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, preferably an alkylene group, and a compound in which a is 0 or 1, more specifically 6 -Trimethylsiloxy- 4 -oxahexyltrimethoxysilane, 6 -trimethylsiloxy- 4 -oxahexylmethyldimethoxysilane, 6-trimethylsiloxy- 4 -oxahexyldimethylmethoxysilane, 6-trimethylsiloxy- 4 -oxahexyltriethoxysilane 6-trimethylsiloxy- 4 -oxahexylmethyldiethoxysilane, 6-trimethylsiloxy- 4- oxahexyldimethylethoxysila 3-triethylsiloxypropyltrimethoxysilane, 3-triethylsiloxypropylmethyldimethoxysilane, 3-triethylsiloxypropyldimethylmethoxysilane, 3-triethylsiloxypropyltriethoxysilane, 3-triethylsiloxypropylmethyldiethoxysilane, 3- Triethylsiloxypropyldimethylethoxysilane, 6-triethylsiloxy- 4 -oxahexyltrimethoxysilane, 6-triethylsiloxy- 4 -oxahexylmethyldimethoxysilane, 6-triethylsiloxy- 4 -oxahexyldimethylmethoxysilane, 6-triethylsiloxy- 4 -oxa hexyl triethoxysilane, 6-triethylsiloxy 4 - oxahexyl methyl diethoxy silane, 6- triethylsiloxy 4 - Oki Hexyldimethylethoxysilane, 3- (t-butyldimethylsiloxy) propyltrimethoxysilane, 3- (t-butyldimethylsiloxy) propylmethyldimethoxysilane, 3- (t-butyldimethylsiloxy) propyldimethylmethoxysilane, 3- ( t-butyldimethylsiloxy) propyltriethoxysilane, 3- (t-butyldimethylsiloxy) propylmethyldiethoxysilane, 3- (t-butyldimethylsiloxy) propyldimethylethoxysilane, 6- (t-butyldimethylsiloxy)- 4 - oxa hexyltrimethoxysilane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyl methyl dimethoxy silane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyl dimethyl silane, 6- (t- Chill dimethylsiloxy) - 4 - oxa hexyl triethoxysilane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyl methyl diethoxy silane, 6- (t-butyl dimethylsiloxy) - 4 - oxa hexyl dimethyl silane, 3-triisopropylsiloxypropyltrimethoxysilane, 3-triisopropylsiloxypropylmethyldimethoxysilane, 3-triisopropylsiloxypropyldimethylmethoxysilane, 3-triisopropylsiloxypropyltriethoxysilane, 3-triisopropylsiloxypropylmethyldiethoxysilane , 3-triisopropylsiloxy dimethyl ethoxy silane, 6- triisopropylsiloxy - 4 - oxa hexyltrimethoxysilane, 6-triisopropyl Shi Carboxymethyl - 4 - oxa hexyl methyl dimethoxy silane, 6- triisopropylsiloxy - 4 - oxa hexyl dimethyl silane, 6- triisopropylsiloxy - 4 - oxa hexyl triethoxysilane, 6-triisopropylsiloxy - 4 - oxa hexyl methyl di Examples include ethoxysilane and 6-triisopropylsiloxy- 4 -oxahexyldimethylethoxysilane.

Moreover, the manufacturing method of the organoxysilane compound which has the protected hydroxyl group shown by the said General formula (1) in this invention is the following General formula (2), for example.
R ¹ R ² R ³ SiO— (CH ₂ CH ₂ O) _a —A′—CH═CH ₂ (2)
(In the formula, R ¹ , R ² , R ³ and A ′ are the same as above, and a is 0 or 1.)
And a compound having a double bond represented by the following general formula (3)
HSi (CH ₃ ) _n (OR ⁴ ) _3-n (3)
(Wherein R ⁴ and n are the same as above)
The method of making the hydrogen organoxysilane compound shown by these react with a platinum catalyst is illustrated.

The compound represented by the general formula (2) is, for example, the following general formula (4).
HO— (CH ₂ CH ₂ O) _a —A′—CH═CH ₂ (4)
(Wherein, a is 0 or 1)
And a compound represented by the following general formula (5)
R ¹ R ² R ³ SiCl (5)
(In the formula, R ¹ , R ² and R ³ are the same as above.)
It can manufacture by making it react with the chlorosilane compound shown by hydrochloric acid scavengers, such as an amine compound.

Specific examples of the compound represented by the general formula (2) include 6 -trimethylsiloxy- 4 -oxa-1-hexene, 3-triethylsiloxy-1-propene, and 6-triethylsiloxy- 4 -oxa-1. - hexene, 3- (t-butyl dimethyl siloxy) -1-propene, 6- (t-butyl dimethylsiloxy) - 4 - oxa-1-hexene, 3-triisopropylsiloxy-1-propene, 6- triisopropylsiloxy - 4 - oxa-1-hexene, and the like.

  Specific examples of the hydrogensilane compound represented by the general formula (3) used in the above reaction include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxy. Examples include silane and the like.

  The compounding ratio of the compound having a double bond represented by the general formula (2) and the hydrogensilane compound represented by the general formula (3) is not particularly limited. The range of 0.5 to 2 moles, particularly 0.8 to 1.2 moles of the hydrogen silane compound is preferred with respect to 1 mole of the compound having a bond.

  Specific examples of the platinum catalyst used in the above reaction include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and toluene of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex. Alternatively, xylene solution, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum and the like are exemplified.

  Although the usage-amount of a platinum catalyst is not specifically limited, From the point of reactivity and productivity, it is 0.000001 mol-0.01 mol with respect to 1 mol of compounds which have a double bond, Especially 0.00001 mol-0.001. A molar range is preferred.

  Although the reaction temperature of the said reaction is not specifically limited, 0 to 120 degreeC, Especially 20 to 100 degreeC is 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, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

（式中、Ｒ¹、Ｒ²、Ｒ³は炭素数１〜１０の１価炭化水素基、Ｒ⁵、Ｒ⁶は水素原子又はメチル基、Ａは炭素数１〜１０の直鎖又は分岐状の２価脂肪族炭化水素基、Ｘはハロゲン原子、ａは０〜５の整数、ｎは０，１又は２である。）
で示されるハロシラン化合物を、アルコールでアルコキシ化することにより製造することもできる。 In addition, the compound represented by the general formula (1) of the present invention is represented by the following general formula (6).

(In the formula, R ¹ , R ² and R ³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁵ and R ⁶ are hydrogen atoms or methyl groups, and A is linear or branched having 1 to 10 carbon atoms. A divalent aliphatic hydrocarbon group, X is a halogen atom, a is an integer of 0 to 5, and n is 0, 1 or 2.)
It can also be produced by alkoxylating a halosilane compound represented by

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵、Ｒ⁶、Ａは上記と同様であり、Ｙはハロゲン原子、ａは０〜５の整数である。）
で示されるグリニア試薬と、下記一般式（８）
Ｓｉ（ＣＨ₃）_n（ＯＲ⁴）_4-n （８）
（式中、Ｒ⁴、ｎは上記と同様である。）
で示されるシラン化合物との反応により製造することもできる。 Furthermore, the compound represented by the general formula (1) of the present invention is represented by the following general formula (7).

(Wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ and A are the same as above, Y is a halogen atom, and a is an integer of 0 to 5)
And the following general formula (8)
Si (CH ₃ ) _n (OR ⁴ ) _4-n (8)
(Wherein R ⁴ and n are the same as above)
It can also manufacture by reaction with the silane compound shown by these.

The obtained silane compound is useful as a silane coupling agent, a surface treatment agent for glass, a silicon wafer, and the like, and a polymer compound modifier. In this case, after being used for such applications, the triorganosilyl group (R ¹ R ² R ³ Si— group) is eliminated by a conventional method such as hydrolysis or alcoholysis, and until then, the triorganosilyl group The protected hydroxyl group can be deprotected to reveal the hydroxyl group.

Hereinafter, although a reference example and an example are shown and the present invention is explained concretely, the present invention is not restricted to the following example.

[ Reference Example 1]
Synthesis of 3-trimethylsiloxypropyltriethoxysilane In a flask equipped with a stirrer, reflux, dropping funnel and thermometer, 39.1 g (0.3 mol) of 3-trimethylsiloxy-1-propene, platinum-divinyltetramethyl 0.20 g of a toluene solution of a disiloxane complex (platinum content: 3 wt%) was charged and heated to 50 ° C. After the internal temperature was stabilized, 49.3 g (0.3 mol) of triethoxysilane was added dropwise over 2 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 62.5 g of a fraction having a boiling point of 89-90 ° C./0.4 kPa.
A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 279, 248, 193, 163, 135
¹ H-NMR spectrum (deuterated chloroform solvent)
A chart is shown in FIG.
IR spectrum is shown in the chart of FIG.
From the above results, it was confirmed that the obtained compound was 3-trimethylsiloxypropyltriethoxysilane.

[ Reference Example 2]
Synthesis of 3-trimethylsiloxypropylmethyldiethoxysilane In a flask equipped with a stirrer, reflux, dropping funnel and thermometer, 39.1 g (0.3 mol) of 3-trimethylsiloxy-1-propene, platinum-divinyltetra A toluene solution of a methyldisiloxane complex (platinum content 3 wt%) 0.20 g was charged and heated to 50 ° C. After the internal temperature was stabilized, 40.3 g (0.3 mol) of methyldiethoxysilane was added dropwise over 2 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 61.1 g of a fraction having a boiling point of 79-81 ° C./0.4 kPa.
A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 249, 207, 177, 163, 133
¹ H-NMR spectrum (deuterated chloroform solvent)
FIG. 3 shows a chart.
IR spectrum is shown in the chart of FIG.
From the above results, it was confirmed that the obtained compound was 3-trimethylsiloxypropylmethyldiethoxysilane.

[Example 1 ]
Synthesis of 3-t-butyldimethylsiloxy-1-propene In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 226.1 g (1.5 mol) of t-butyldimethylchlorosilane, 167.0 g of triethylamine ( 1.65 mol) and 500 ml of hexane were charged and heated to 50 ° C. After the internal temperature was stabilized, 95.9 g (1.65 mol) of allyl alcohol was added dropwise over 2 hours. After dropping, the temperature was raised and the mixture was stirred for 8 hours under reflux. After cooling the reaction solution to room temperature, 300 g of water was added to dissolve the resulting salt. The organic layer was dried over 20 g of sodium sulfate and distilled. 230.2 g of 3-t-butyldimethylsiloxy-1-propene was obtained as a fraction having a boiling point of 74-75 ° C./6.7 kPa (yield 89%).
Synthesis of 3- (t-butyldimethylsiloxy) propyltriethoxysilane Into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 51.7 g (0.3% of 3-t-butyldimethylsiloxy-1-propene) was added. Mol), 0.20 g of a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum content 3 wt%) was charged and heated to 50 ° C. After the internal temperature was stabilized, 49.3 g (0.3 mol) of triethoxysilane was added dropwise over 2 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 75.6 g of a fraction having a boiling point of 81-82 ° C./0.1 kPa.
A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 321, 279, 237, 193, 165, 135
¹ H-NMR spectrum (deuterated chloroform solvent)
FIG. 5 shows a chart.
IR spectrum is shown in the chart of FIG.
From the above results, it was confirmed that the obtained compound was 3- (t-butyldimethylsiloxy) propyltriethoxysilane.

[Example 2 ]
Synthesis of 3- (t-butyldimethylsiloxy) propylmethyldiethoxysilane Into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 51.7 g (0. 3 mol), 0.20 g of a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum content 3 wt%) was charged and heated to 50 ° C. After the internal temperature was stabilized, 40.3 g (0.3 mol) of methyldiethoxysilane was added dropwise over 2 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 71.9 g of a fraction having a boiling point of 85-86 ° C./0.15 kPa.
A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 291, 249, 207, 163, 133
¹ H-NMR spectrum (deuterated chloroform solvent)
FIG. 7 shows a chart.
IR spectrum is shown as a chart in FIG.
From the above results, it was confirmed that the obtained compound was 3- (t-butyldimethylsiloxy) propylmethyldiethoxysilane.

[Example 3 ]
Synthesis of 6-trimethylsiloxy- 4 -oxahexyltriethoxysilane Into a flask equipped with a stirrer, reflux, dropping funnel and thermometer, 34.9 g of 6-trimethylsiloxy- 4 -oxa-1-hexene (0.2% Mol), 0.13 g of a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum content 3 wt%) was charged and heated to 50 ° C. After the internal temperature was stabilized, 32.9 g (0.2 mol) of triethoxysilane was added dropwise over 2 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 48.1 g of a fraction having a boiling point of 84-90 ° C./0.010 kPa.
A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 205, 175, 163, 119, 73
¹ H-NMR spectrum (deuterated chloroform solvent)
FIG. 9 is a chart.
IR spectrum is shown in the chart of FIG.
From the above results, it was confirmed that the obtained compound was 6-trimethylsiloxy- 4 -oxahexyltriethoxysilane.

[Example 4 ]
Synthesis of 6-trimethylsiloxy- 4 -oxahexylmethyldiethoxysilane Into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 34.9 g of 6-trimethylsiloxy- 4 -oxa-1-hexene (0. 2 mol), 0.13 g of a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum content 3 wt%) was charged and heated to 50 ° C. After the internal temperature was stabilized, 26.9 g (0.2 mol) of methyldiethoxysilane was added dropwise over 2 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 45.1 g of a fraction having a boiling point of 74-78 ° C./0.013 kPa.
A mass spectrum, ¹ H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 221, 175, 145, 133, 73
¹ H-NMR spectrum (deuterated chloroform solvent)
FIG. 11 shows a chart.
IR spectrum is shown in the chart of FIG.
From the above results, it was confirmed that the obtained compound was 6-trimethylsiloxy- 4 -oxahexylmethyldiethoxysilane.

2 is a ¹ H-NMR spectrum of the compound of Reference Example 1. 3 is an IR spectrum of the compound of Reference Example 1. 2 is a ¹ H-NMR spectrum of the compound of Reference Example 2. 4 is an IR spectrum of the compound of Reference Example 2. 1 is a ¹ H-NMR spectrum of the compound of Example 1 . 2 is an IR spectrum of the compound of Example 1 . 2 is a ¹ H-NMR spectrum of the compound of Example 2 . 2 is an IR spectrum of the compound of Example 2 . 2 is a ¹ H-NMR spectrum of the compound of Example 3 . 4 is an IR spectrum of the compound of Example 3 . 2 is a ¹ H-NMR spectrum of the compound of Example 4 . 4 is an IR spectrum of the compound of Example 4 .

Claims (2)

The following general formula (1)

( Wherein , a is an integer of 0 to 5, and when a = 0, R ¹ R ² R ³ SiO— represents a triethylsiloxy group, a t-butyldimethylsiloxy group, or a triisopropylsiloxy group, and a = 1 In the case of an integer of ˜5, R ¹ , R ² , R ³ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms , R ⁴ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ , R ⁶ Is a hydrogen atom or a methyl group, A is a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms , and n is 0, 1 or 2.)
An organoxysilane compound having a protected hydroxyl group, wherein R ⁵ and R ⁶ are both hydrogen atoms, A is —A′—CH ₂ CH ₂ — (A ′ is a linear or branched divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms), a The organoxysilane compound having a protected hydroxyl group according to claim 1, wherein is 0 or 1.

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