JP2006282821A - Method for producing organic-modified silicone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an organic-modified silicone by which thickening and gelation at a purification step by heating and pressure-reducing after hydrosilylation step of a silane or siloxane containing an SiH group with an organic compound having an aliphatic unsaturated bond can be suppressed. <P>SOLUTION: The method for producing the organic-modified silicone by carrying out the purification step by heating and pressure reducing after the hydrosilylation step of (A) the silane or siloxane containing the SiH group with (B) the organic compound having an aliphatic unsaturated bond involves adding (C) a tetraalkylammonium hydroxide or a silanolate thereof, or an aminoalcohol to the reaction mixture before the purification step. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an organically modified silicone, and more particularly to a method for producing an organically modified silicone that can suppress thickening or gelation in a purification step by heating and decompression after a hydrosilylation reaction step.

  Organically modified silicones such as epoxy-modified silanes or siloxanes, polyether-modified silanes or siloxanes are used as resin modifiers, cosmetic raw materials and the like. Such an organically modified silicone is prepared by a hydrosilylation reaction between a SiH group-containing silane or siloxane and an epoxy compound or polyether having an aliphatic unsaturated bond. At that time, purification to remove unreacted raw materials and low-boiling substances such as a solvent used by heating under reduced pressure is performed, but there is a problem that the resulting organically modified silicone is thickened or gelled.

  For this reason, in order to suppress the thickening and gelation of the organically modified silicone in the purification step by heating and decompression after the hydrosilylation reaction step, benzothiazole is added before the purification step (see Patent Document 1) or It has been proposed to add a tertiary amine (see Patent Document 2).

However, even with these methods, it has not been possible to sufficiently suppress the thickening and gelation of the organically modified silicone in the purification step by heating and decompression after the hydrosilylation reaction step.
Japanese Patent Laid-Open No. 50-65596 JP-A-4-352793

  An object of the present invention is to produce an organically modified silicone capable of suppressing thickening or gelation in a purification step by heating and decompression after a hydrosilylation reaction step between a SiH group-containing silane or siloxane and an organic compound having an aliphatic unsaturated bond It is to provide a method.

  In the method for producing an organically modified silicone of the present invention, (A) SiH group-containing silane or siloxane and (B) a hydrosilylation reaction step between an organic compound having an aliphatic unsaturated bond and a purification step by heating under reduced pressure are performed. A method for producing a modified silicone, characterized in that (C) a tetraalkylammonium hydroxide or a silanolate thereof, or an amino alcohol is added to the reaction mixture before the purification step.

  The method for producing an organically modified silicone of the present invention can suppress thickening or gelation in a purification step by heating and decompression after a hydrosilylation reaction step between a SiH group-containing silane or siloxane and an organic compound having an aliphatic unsaturated bond. There is a feature.

  The silane or siloxane component (A) is characterized by containing a SiH group. (A) As component silane, organosilane such as trimethylsilane, dimethylethylsilane, dimethylisopropylsilane, dimethylphenylsilane; trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenyldimethoxysilane, etc. Examples of alkoxysilanes include halosilanes such as trichlorosilane, methyldichlorosilane, and phenyldichlorosilane.

  Examples of the component (A) siloxane include linear, partially branched linear, branched, cyclic, and dendritic siloxanes, and silicon atoms other than SiH groups. Examples of the bonding group include an alkyl group such as a methyl group, an ethyl group, and a propyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; an aralkyl group such as a benzyl group and a phenethyl group; a chloromethyl group, 3 -A substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond such as a halogenated alkyl group such as a chloropropyl group and a 3,3,3-trifluoropropyl group is exemplified. Examples of such siloxane include siloxanes represented by the following formula. In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and examples thereof are the same groups as described above. In the formula, m is an integer of 0 or more, n is an integer of 1 or more, p is an integer of 1 or more, q is an integer of 0 or more, and p + q is an integer of 3 or more. .

  The organic compound as the component (B) has an aliphatic unsaturated bond. Examples of the organic compound (B) include olefins having 16 or more carbon atoms, perfluoroalkyl group-containing olefins, aryl group-containing olefins, hydroxyl group-containing olefins, alkenyl group-containing epoxy compounds, and alkenyl group-containing polyters. Examples of such an organic compound of component (B) include compounds represented by the following formula. In the formula, x is an integer of 0 or more, y is an integer of 0 or more, and x + y is an integer of 1 or more.

ＣＨ₂＝ＣＨＣＨ₂ＯＨ

ＣＨ₂＝ＣＨＣＨ₂Ｏ(Ｃ₂Ｈ₄Ｏ)_x(Ｃ₃Ｈ₆Ｏ)_yＨ
ＣＨ₂＝ＣＨＣＨ₂Ｏ(Ｃ₂Ｈ₄Ｏ)_x(Ｃ₃Ｈ₆Ｏ)_yＣＨ₃

ＣＨ₂＝ＣＨＣＨ₂Ｏ(Ｃ₂Ｈ₄Ｏ)_x(Ｃ₃Ｈ₆Ｏ)_yＣＨ₂ＣＨ＝ＣＨ₂

CH ₂ = CH (CH ₂ ) ₁₃ CH ₃
CH ₂ = CH (CH ₂ ) ₁₄ CH ₃
CH ₂ = CH (CH ₂ ) ₁₅ CH ₃
CH ₂ = CH (CH ₂ ) ₁₆ CH ₃
CH ₂ = CHCH ₂ CF ₃
CH ₂ = CHCH ₂ C ₃ F ₇
CH ₂ = CHCH ₂ C ₄ F ₉

CH ₂ = CHCH ₂ OH

CH ₂ = CHCH ₂ O (C ₂ H ₄ O) _x (C ₃ H ₆ O) _y H
CH ₂ = CHCH ₂ O (C ₂ H ₄ O) _x (C ₃ H ₆ O) _y CH ₃

_{CH 2 = CHCH 2 O (C} 2 H 4 O) x (C 3 H 6 O) y CH 2 CH = CH 2

  As the organic compound (B), an alkenyl group-containing epoxy compound and an alkenyl group-containing polytel are preferable, and 4-vinyl-1,2-epoxycyclohexane is particularly preferable.

  The amount of component (B) added is generally such that the aliphatic unsaturated bond in component (B) falls within the range of 1 to 3 moles relative to the number of moles of SiH groups in component (A). It is preferable that the amount be in the range of 1 to 1.5 mol.

  The hydrosilylation reaction step of the component (A) and the component (B) can be performed in the presence of a hydrosilylation reaction catalyst at a temperature from room temperature to about 150 ° C, preferably from about 40 ° C to 120 ° C. Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, ruthenium-based catalysts, rhodium-based catalysts, palladium-based catalysts, osmium-based catalysts, and iridium-based catalysts. In particular, platinum-based catalysts are preferred because of their high catalytic activity. It is. Examples of the platinum-based catalyst include: chloroplatinic acid; metal platinum; a metal platinum supported on a carrier such as alumina, silica, carbon black, etc .; platinum vinylsiloxane complex, platinum phosphine complex, platinum phosphite complex And platinum alcoholate catalysts. The amount of the hydrosilylation catalyst added is preferably such that the metal atoms in the catalyst are about 0.0001 to 0.1% by mass with respect to the total mass of the raw materials.

  In this hydrosilylation reaction step, a solvent may be used as necessary. Usable solvents include ethers; ketones such as acetal and cyclohexanone; esters; phenols; alcohols such as ethanol and isopropyl alcohol; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; Hydrocarbon; dimethylpolysiloxane is exemplified.

  Completion of this hydrosilylation reaction step can be determined by determining the reaction rate of SiH groups in component (A). This reaction rate is preferably 90% or more, and particularly preferably 95% or more. Examples of the method for obtaining the reaction rate of the SiH group in the component (A) include a method in which a part of the reaction mixture is collected, an aqueous alcohol solution of KOH is added thereto, and the amount of hydrogen gas generated is measured. .

  In the production method of the present invention, (C) tetraalkylammonium hydroxide or its silanolate, or amino alcohol is added to the reaction mixture to suppress thickening or gelation in the subsequent purification step under heating and reduced pressure. Features. Examples of the (C) component tetraalkylammonium hydroxide include tetramethylammonium hydroxide and tetraethylammonium hydroxide. The tetraalkylammonium silanolate of component (C) is composed of the above tetraalkylammonium hydroxide and a cyclic siloxane such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, or a chain siloxane such as dimethylpolysiloxane and dimethylsiloxane oligomer. For example, it can be prepared by a method as disclosed in Japanese Patent Publication No. 46-210602. As the silanolate of component (C), tetramethylammonium silanolate is preferable. In addition, as the amino alcohol of component (C), ethanolamine, propanolamine, butanolamine, pentanolamine, N-methylethanolamine, N, N-dibutylethanolamine, N-methyldiethanolamine, N, N-diethylethanol Examples include amine, N, N-dimethylethanolamine, and N- (2-aminoethyl) -ethanolamine, and ethanolamine, propanolamine, and butanolamine are preferable.

  The amount of component (C) to be added is not particularly limited, but it is preferably at least 0.001 part by weight, particularly at least 0.01 part by weight based on 100 parts by weight of the reaction mixture or the reaction mixture and the solvent. It is preferable. (C) It is preferable to heat-mix the reaction mixture after addition of a component. Moreover, there is no limitation in the mixing time in that case, You may heat under reduced pressure as needed.

  Next, in the production method of the present invention, the organically modified silicone is purified by removing low boiling points such as unreacted raw materials and used solvents by distillation under heating and reduced pressure. This purification step can be performed by a conventionally known method.

  The production method of the organically modified silicone of the present invention will be described in detail with reference to Examples and Comparative Examples. The viscosity is a value at 25 ° C.

で表されるジメチルシロキサン・メチルハイドロジェンシロキサン共重合体３５７ｇ（ＳｉＨ基のモル数＝０.６９）、およびトルエン１５４ｇを仕込み、７０℃に加熱した。次に、１質量％−塩化白金酸のエタノール溶液を、反応原料の合計質量（４８０ｇ）に対し白金換算で３ｐｐｍとなるよう添加した後、式：

で表される４−ビニル−１,２−エポキシシクロヘキサン１２３ｇ（ビニル基のモル数＝０.９９）を温度が８５℃を超えないようにゆっくりと滴下した。なお、温度が７０℃以下とならないように必要に応じて温度調節を行った。滴下終了後、８０℃に加熱して１時間反応させた。反応混合物の一部を採取し、ＫＯＨのアルコール水溶液との反応による水素ガス発生量により、前記ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体中のＳｉＨ基の反応率が９９.６％であることを確認した。次いで、テトラメチルアンモニウムシラノレート（水酸化テトラメチルアンモニムとオクタメチルシクロテトラシロキサンとの反応物；水酸化テトラメチルアンモニウム換算で２質量％含有）２.９ｇ（反応原料および溶媒の合計１００質量部に対して０.６０質量部）を加え、１時間攪拌した後、減圧下、１２０〜１２５℃に加熱し、さらにこの温度で２時間攪拌した。次いで、反応混合物から未反応物等の低揮発成分を留去し、式：

で表される有機変性シリコーンを調製した。得られた有機変性シリコーンにゲル状物の発生は観察されず、ろ過後の有機変性シリコーンの粘度は４３０ｍｍ²／ｓであった。 [Example 1]
In a 1000 ml four-necked separable flask equipped with a thermometer, stirrer, nitrogen gas inlet, and condenser, the formula:

And a dimethylsiloxane / methylhydrogensiloxane copolymer 357 g (number of moles of SiH group = 0.69) and 154 g of toluene were charged and heated to 70 ° C. Next, after adding an ethanol solution of 1% by mass-chloroplatinic acid to 3 ppm in terms of platinum with respect to the total mass (480 g) of the reaction raw materials, the formula:

In this manner, 123 g of 4-vinyl-1,2-epoxycyclohexane represented by the formula (number of moles of vinyl group = 0.99) was slowly added dropwise so that the temperature did not exceed 85 ° C. In addition, temperature adjustment was performed as needed so that temperature might not become 70 degrees C or less. After completion of dropping, the mixture was heated to 80 ° C. and reacted for 1 hour. A portion of the reaction mixture was sampled, and the reaction rate of SiH groups in the dimethylsiloxane / methylhydrogensiloxane copolymer was 99.6% based on the amount of hydrogen gas generated by the reaction of KOH with an alcohol aqueous solution. confirmed. Next, 2.9 g of tetramethylammonium silanolate (reaction product of tetramethylammonium hydroxide and octamethylcyclotetrasiloxane; contained 2% by mass in terms of tetramethylammonium hydroxide) (total 100 parts by mass of reaction raw materials and solvent) 0.60 parts by mass) was added, and the mixture was stirred for 1 hour, then heated to 120 to 125 ° C. under reduced pressure, and further stirred at this temperature for 2 hours. Subsequently, low volatile components such as unreacted substances are distilled off from the reaction mixture, and the formula:

The organic modification silicone represented by these was prepared. Generation | occurrence | production of a gel-like thing was not observed in the obtained organic modified silicone, and the viscosity of the organic modified silicone after filtration was 430 mm < ² > / s.

[Example 2]
In Example 1, instead of tetramethylammonium silanolate, 0.3 g of butanolamine (0.06 parts by mass with respect to 100 parts by mass in total of the reaction raw materials and the solvent) was used. Modified silicone was prepared. Generation | occurrence | production of a gel-like thing was not observed in the obtained organic modified silicone, and the viscosity of the organic modified silicone after filtration was 460 mm < ² > / s.

[Comparative Example 1]
In Example 1, organic modification was performed in the same manner as in Example 1 except that 0.3 g of triethylamine (0.06 parts by mass with respect to a total of 100 parts by mass of the reaction raw materials and the solvent) was added instead of tetramethylammonium silanolate. Silicone was prepared. In this production method, a slight increase in viscosity was confirmed compared to when the low volatile component was distilled off. The viscosity of the organically modified silicone after filtration was 582 mm ² / s.

[Comparative Example 2]
An organically modified silicone was prepared in the same manner as in Example 1 except that tetramethylammonium silanolate was not added. In this manufacturing method, it was confirmed that the gel-like substance began to adhere around the thermometer from the time when the low-volatile component was distilled off. The viscosity of the organically modified silicone after filtration was 780 mm ² / s.

Since the method for producing an organically modified silicone of the present invention can suppress thickening or gelation in a purification step by heating and decompression after the hydrosilylation reaction step, production of various organically modified silicones such as epoxy-modified silicone and polyether-modified silicone Applicable to the method.

Claims (5)

(A) A method for producing an organically modified silicone comprising a hydrosilylation reaction step between a SiH group-containing silane or siloxane and (B) an organic compound having an aliphatic unsaturated bond, followed by a purification step by heating under reduced pressure. A method for producing an organically modified silicone, comprising adding (C) a tetraalkylammonium hydroxide or a silanolate thereof, or an amino alcohol to a reaction mixture before the step. The method for producing an organically modified silicone according to claim 1, wherein the component (B) is an alkenyl group-containing epoxy compound or an alkenyl group-containing polyether. 3. The method for producing an organically modified silicone according to claim 2, wherein the alkenyl group-containing epoxy compound as component (B) is 4-vinyl-1,2-epoxycyclohexane. The method for producing an organically modified silicone according to claim 1, wherein the component (C) is tetramethylammonium silanolate. The method for producing an organically modified silicone according to claim 1, wherein the component (C) is ethanolamine, propanolamine, or butanolamine.