JP4395686B2 - Method for producing organosilicon compound - Google Patents

Description

（式中、Ｒ¹及びＲ²は炭素数１〜４の一価炭化水素基、Ｒ³は炭素数１〜１０の二価炭化水素基、Ｘはハロゲン原子、ｐは０，１又は２を示す。）
で表されるハロゲノアルキル基含有有機ケイ素化合物、下記一般式（３）
Ｙ−（Ｒ⁴Ｏ）_n−Ｒ⁴−ＯＨ （３）
（式中、Ｒ⁴は炭素数２〜１０の二価炭化水素基、Ｙはハロゲン原子、ｎは１〜１０を示す。）
で表される片末端ハロゲン基含有ヒドロキシアルキル（ポリ）アルキレンオキサイド化合物及び下記一般式（４）
Ｎａ₂Ｓ_q （４）
（式中、ｑは１〜４を示す。）
で表される無水硫化ソーダ又は無水多硫化ソーダと、場合により硫黄とを反応させることを特徴とする下記一般式（１）
【化４】

（式中、Ｒ ¹ 及びＲ ² は炭素数１〜４の一価炭化水素基、Ｒ ³ は炭素数１〜１０の二価炭化水素基、Ｒ ⁴ は炭素数２〜１０の二価炭化水素基、ｍは１〜１０、ｎは１〜１０、ｐは０，１又は２を示す。）
で表される有機ケイ素化合物の製造方法
を提供する。
【０００９】
以下、本発明につき更に詳しく説明すると、本発明の有機ケイ素化合物は、上述したように下記一般式（１）で表されるものである。
【化５】

【００１０】
上記式中、Ｒ¹及びＲ²は炭素数１〜４の一価炭化水素基を示し、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル、ｉ−ブチル、ｔ−ブチル基等のアルキル基などが挙げられ、これらの中でもメチル基、エチル基が好ましい。Ｒ³は炭素数１〜１０、好ましくは２〜６、特に好ましくは３の二価炭化水素基を示し、例えばメチレン基、エチレン基、プロピレン基、ｎ−ブチレン基、ｉ−ブチレン基、へキシレン基、デシレン基等のアルキレン基、フェニレン基等のアリーレン基、メチルフェニルエチレン基等のアラルキレン基などが挙げられる。Ｒ⁴は炭素数２〜１０、好ましくは２〜４、特に好ましくは２の二価炭化水素基を示し、例えばエチレン基、プロピレン基、ｎ−ブチレン基、ｉ−ブチレン基、へキシレン基、デシレン基等のアルキレン基、フェニレン基等のアリーレン基、更にアラルキレン基などが挙げられる。ｍは１〜１０、好ましくは２〜４の正数である。ｎは１〜１０、好ましくは１〜４、特に好ましくは１又は２、ｐは０，１又は２、好ましくは０又は１、特に好ましくは０を示す。このような一般式（１）で示される化合物としては、下記のものを代表例として例示することができる。
【００１１】
【化６】

【００１２】
なお、上述した化合物のＳは不均化反応等が生じるため、分布を持っており、実際はｍの異なる化合物の混合物として得られる。したがって、前述した一般式（１）におけるｍは、平均値としての値である。
【００１３】
このような有機ケイ素化合物は、上記したように、下記一般式（２）
【化７】

（式中、Ｒ¹，Ｒ²，Ｒ³及びｐは上記と同様の意味を示し、Ｘはハロゲン原子を示し、ハロゲン原子としては塩素、臭素が好ましい。）
で表されるハロゲノアルキル基含有有機ケイ素化合物と、下記一般式（３）
Ｙ−(Ｒ⁴Ｏ)_n−Ｒ⁴−Ｙ （３）
（式中、Ｒ⁴，ｎは上記と同様の意味を示し、Ｙはハロゲン原子を示し、ハロゲン原子としては塩素、臭素が好ましい。）
で表される片末端ハロゲン基含有ヒドロキシアルキル（ポリ）アルキレンオキサイド化合物と、下記一般式（４）
Ｎａ₂Ｓ_q （４）
（式中、ｑは１〜４を示す。）
で表される無水硫化ソーダ又は無水多硫化ソーダと、必要により硫黄とを反応させることにより、製造することができる。
【００１４】
この場合、上記一般式（２）の化合物としては、下記のものを代表例として例示することができる。
(ＣＨ₃Ｏ)₃Ｓｉ−(ＣＨ₂)₃−Ｃｌ
(ＣＨ₃ＣＨ₂Ｏ)₃Ｓｉ−(ＣＨ₂)₃−Ｃｌ
(ＣＨ₃Ｏ)₃Ｓｉ−(ＣＨ₂)₄−Ｃｌ
(ＣＨ₃Ｏ)₃Ｓｉ−(ＣＨ₂)₆−Ｂｒ
(ＣＨ₃Ｏ)₃Ｓｉ−(ＣＨ₂)₁₀−Ｂｒ
(ＣＨ₃Ｏ)₃Ｓｉ−ＣＨ₂ＣＨ(ＣＨ₃)ＣＨ₂−Ｃｌ
(ＣＨ₃ＣＨ₂Ｏ)₃Ｓｉ−ＣＨ₂ＣＨ(ＣＨ₃)ＣＨ₂−Ｃｌ
【００１５】
また、上記一般式（３）の化合物としては、下記のものを代表例として例示することができる。
Ｃｌ−ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＨ
Ｃｌ−(ＣＨ₂ＣＨ₂Ｏ)₂ＣＨ₂ＣＨ₂ＯＨ
Ｃｌ−(ＣＨ₂ＣＨ₂Ｏ)₃ＣＨ₂ＣＨ₂ＯＨ
Ｃｌ−(ＣＨ₂ＣＨ₂Ｏ)₁₀ＣＨ₂ＣＨ₂ＯＨ
Ｃｌ−(ＣＨ₂ＣＨ₂ＣＨ₂Ｏ)₂ＣＨ₂ＣＨ₂ＣＨ₂ＯＨ
Ｃｌ−(ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂Ｏ)₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＯＨ
Ｃｌ−(ＣＨ(ＣＨ₃)ＣＨ₂Ｏ)₂ＣＨ(ＣＨ₃)ＣＨ₂ＯＨ
【００１６】
更に、上記一般式（４）の化合物としては、Ｎａ₂Ｓ、Ｎａ₂Ｓ₂、Ｎａ₂Ｓ₃、Ｎａ₂Ｓ₄が挙げられる。
【００１７】
なお、この化合物（４）の無水硫化ソーダＮａ₂Ｓの製造方法としては、含水の硫化ソーダを脱水したものを使用してもよく、無水状態で硫化ソーダとソディウムアルコラートとを反応させたものを使用してもよく、更に金属ナトリウム又はカリウムと硫黄とを無水状態で反応させたものを使用してもよい。また、無水多硫化ソーダは、含水の多硫化ソーダを脱水したものを使用してもよく、前記した無水硫化ソーダと硫黄とを無水状態で反応させたものを使用してもよく、更に金属ナトリウム又はカリウムと硫黄とを無水状態で反応させたものを使用してもよい。
【００１８】
上記一般式（２）、（３）、（４）の化合物、及び場合により硫黄を反応させるに際し、溶媒の使用は任意であり、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレン等の炭化水素類、メタノール、エタノール等のアルコール類、ジブチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸エチル等のエステル類、ジメチルホルムアミド等のアミド類などが挙げられ、特にメタノール、エタノール等のアルコール類の使用が好ましい。
【００１９】
その際の反応温度は、０〜１５０℃程度であり、好ましくは５０〜１００℃程度である。反応時間は、硫化ソーダ又は多硫化ソーダが消失するまで行えばよいが、通常３０分〜２０時間程度である。
【００２０】
反応の方法は、任意であるが、例えば、一般式（４）で表される化合物と場合により硫黄及び溶媒を仕込み、一般式（２）及び（３）で表される化合物の混合物を滴下してもよく、一般式（２）で表される化合物を滴下後、一般式（３）で表される化合物を滴下してもよい。更に、一般式（２）及び（３）で表される化合物及び場合により硫黄及び溶媒を仕込み、一般式（４）で表される化合物を徐々に導入してもよい。
【００２１】
各成分の反応モル比は以下の通りである。
一般式（２）で表されるハロゲノアルキル基含有有機ケイ素化合物と一般式（３）で表される片末端ハロゲン基含有ヒドロキシアルキル（ポリ）アルキレンオキサイド化合物とのモル比は、一般式（２）の化合物／一般式（３）の化合物＝１／０．９〜１．１とするのが好ましく、一般式（２）で表されるハロゲノアルキル基含有有機ケイ素化合物及び一般式（３）で表される片末端ハロゲン基含有ヒドロキシアルキル（ポリ）アルキレンオキサイド化合物のハロゲン基と一般式（４）で表される無水硫化ソーダ又は無水多硫化ソーダのナトリウムとのモル比は、一般式（２）の化合物＋一般式（３）の化合物中のハロゲン／一般式（４）の化合物中のナトリウム＝１／０．９〜１．１とするのが好ましい。硫黄の添加量は任意であるが、少なくとも（ｍ−ｑ）モル添加すればよい。
【００２２】
なお、本発明の化合物は、下記一般式（５）
【化８】

（式中、Ｒ¹，Ｒ²，Ｒ³，ｍ，ｐは上記と同様の意味を示す。）
で表される化合物と下記一般式（６）
Ｘ−(Ｒ⁴Ｏ)_n−Ｒ⁴−ＯＨ （６）
（式中、Ｒ⁴，Ｘ，ｎは上記と同様の意味を示す。）
で表される化合物とから、あるいは、上述した下記一般式（２）
【００２３】
【化９】

（式中、Ｒ¹，Ｒ²，Ｒ³，ｐ，Ｘは上記と同様の意味を示す。）
で表される化合物と下記一般式（７）
Ｎａ−Ｓ_m−(Ｒ⁴Ｏ)_n−Ｒ⁴−ＯＨ （７）
（式中、Ｒ⁴，ｍ，ｎは上記と同様の意味を示す。）
で表される化合物とからも合成することが可能である。しかしながら、これらの方法は、本発明の化合物を高純度で合成することは可能であるが、この合成方法では原料コストが高くなる。
【００２４】
本発明の製造方法においては、下記一般式（８）
【化１０】

（式中、Ｒ¹，Ｒ²，Ｒ³，ｍ，ｐは上記と同様の意味を示す。）
で表される化合物及び下記一般式（９）
ＨＯ−Ｒ⁴−(ＯＲ⁴)_n−Ｓ_m−(Ｒ⁴Ｏ)_n−Ｒ⁴−ＯＨ （９）
（式中、Ｒ⁴，ｍ，ｎは上記と同様の意味を示す。）
で表される化合物を不純物として含有するものと推定されるが、この不純物を組成中に含有しても、本化合物をゴムや有機樹脂に添加あるいは無機フィラーに表面処理して使用する場合、何ら支障はない。
【００２５】
また、本化合物をゴムや有機樹脂に添加あるいは無機フィラーに表面処理して使用する場合、本化合物中のヒドロキシ基とアルコキシシリル基のアルコキシ基が交換し、分子内環化反応をした下記一般式（１０）の化合物や分子間反応した一般式（１１）の化合物が含まれていてもよい。
【００２６】
【化１１】

（式中、Ｒ¹，Ｒ²，Ｒ³，Ｒ⁴，ｐ，ｍ，ｎは上記と同様の意味を示し、ｔは正の整数を示す。）
【００２７】
本発明の式（１）の有機ケイ素化合物は、無機材料と有機材料との界面結合剤、有機樹脂やゴムの接着改良剤、プライマー組成物用成分等として有用である。
【００２８】
【実施例】
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００２９】
［実施例１］
窒素ガス導入管、温度計、ジムロート型コンデンサー及び滴下漏斗を備えた１リットルのセパラブルフラスコに、エタノール２５０ｇ、無水硫化ソーダ７８ｇ（１．０ｍｏｌ）、硫黄９６ｇ（３．０ｍｏｌ）を仕込み、７５℃にて３−クロロプロピルトリエトキシシラン２４０．５ｇ（１．０ｍｏｌ）及びジエチレングリコールモノクロライド１２４．５ｇ（１．０ｍｏｌ）の混合物を滴下した。この滴下には５０分を要した。滴下終了後、８時間熟成を続けた。その後、溶液を濾過した。
【００３０】
濾液をロータリーエバポレーターにて減圧濃縮して、褐色透明の液体２９５．１ｇを得た。このものの粘度は２５℃にて５８．６ｍｍ²／ｓ、屈折率は２５℃にて１．５１４０であった。このものの赤外線吸収スペクトル分析及び１Ｈ核磁気共鳴スペクトル分析を行った結果、下記平均組成式
(ＣＨ₃ＣＨ₂Ｏ)₃Ｓｉ(ＣＨ₂)₃-Ｓ₄-(ＣＨ₂)₂Ｏ(ＣＨ₂)₂ＯＨ
で表されるスルフィド基含有アルコキシシランであることが確認された。
【００３１】
［実施例２］
実施例１で使用したジエチレングリコールモノクロライドの代わりにトリエチレングリコールモノクロライド１６８．５ｇ（１．０ｍｏｌ）とした他は実施例１と同様に反応を行って、褐色透明の液体３２８．３ｇを得た。このものの赤外線吸収スペクトル分析及び、１Ｈ核磁気共鳴スペクトル分析を行った結果、下記平均組成式
(ＣＨ₃ＣＨ₂Ｏ)₃Ｓｉ(ＣＨ₂)₃-Ｓ₄-(ＣＨ₂)₂Ｏ(ＣＨ₂)₂Ｏ(ＣＨ₂)₂ＯＨ
で表されるスルフィド基含有アルコキシシランであることが確認された。
【００３２】
［実施例３］
実施例１で使用した３−クロロプロピルトリエトキシシランの代わりに３−クロロプロピルトリメトキシシラン１９８．５ｇ（１．０ｍｏｌ）とし、エタノールの代わりにメタノールとした他は実施例１と同様に反応を行って、褐色透明の液体２６８．５ｇを得た。このものの赤外線吸収スペクトル分析、及び１Ｈ核磁気共鳴スペクトル分析を行った結果、下記平均組成式
(ＣＨ₃Ｏ)₃Ｓｉ(ＣＨ₂)₃-Ｓ₄-(ＣＨ₂)₂Ｏ(ＣＨ₂)₂ＯＨ
で表されるスルフィド基含有アルコキシシランであることが確認された。
【００３３】
［実施例４］
実施例１で使用した硫黄の使用量を３２ｇ（１．０ｍｏｌ）とした他は実施例１と同様に反応を行って、褐色透明の液体２７２．１ｇを得た。このものの赤外線吸収スペクトル分析、及び１Ｈ核磁気共鳴スペクトル分析を行った結果、下記平均組成式
(ＣＨ₃ＣＨ₂Ｏ)₃Ｓｉ(ＣＨ₂)₃-Ｓ₂-(ＣＨ₂)₂Ｏ(ＣＨ₂)₂ＯＨ
で表されるスルフィド基含有アルコキシシランであることが確認された。
【００３４】
［実施例５］
実施例１で使用した無水硫化ソーダと硫黄の代わりに無水４硫化ソーダ１７４ｇ（１．０ｍｏｌ）とした他は実施例１と同様に反応を行って、褐色透明の液体２９７．８ｇを得た。このものの赤外線吸収スペクトル分析、及び１Ｈ核磁気共鳴スペクトル分析を行った結果、実施例１同様、下記平均組成式
(ＣＨ₃ＣＨ₂Ｏ)₃Ｓｉ(ＣＨ₂)₃-Ｓ₄-(ＣＨ₂)₂Ｏ(ＣＨ₂)₂ＯＨ
で表されるスルフィド基含有アルコキシシランであることが確認された。
【００３５】
［実施例６］
実施例１で使用した３−クロロプロピルトリエトキシシランの代わりに６−ブロモヘキシルトリメトキシシラン２８５ｇ（１．０ｍｏｌ）とした他は実施例１と同様に反応を行って、褐色透明の液体３０１．６ｇを得た。このものの赤外線吸収スペクトル分析、及び１Ｈ核磁気共鳴スペクトル分析を行った結果、下記平均組成式
(ＣＨ₃Ｏ)₃Ｓｉ(ＣＨ₂)₆-Ｓ₄-(ＣＨ₂)₂Ｏ(ＣＨ₂)₂Ｏ(ＣＨ₂)₂ＯＨ
で表されるスルフィド基含有アルコキシシランであることが確認された。
【００３６】
【発明の効果】
本発明の有機ケイ素化合物は、樹脂やゴムに添加し、無機材料とともに混練を行った場合でも分散性が良好で、成型前の樹脂やゴム組成物の粘度変化の少ない優れたものであり、界面結合剤、接着改良剤、プライマー組成物用成分等として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel organosilicon compound having an alkoxysilyl group at one end of a molecule and a hydroxyalkyl (poly) alkylene oxide group at the other end of the molecule, and further containing a polysulfide group in the molecule. It relates to a manufacturing method.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, compounds containing an alkoxysilyl group and a polysulfide group in the molecule are known. These compounds are used as an interfacial binder for inorganic materials such as silica, aluminum hydroxide, and talc and organic materials such as thermosetting resins, thermoplastic resins, and rubbers, adhesion improvers for organic resins and rubbers, primer compositions, etc. in use.
[0003]
Thus, the sulfide group-containing organosilicon compound is applied to a composite material composed of a resin or rubber and an inorganic material, but a conventionally known sulfide group-containing organosilicon compound is added to the resin or rubber. When kneading with an inorganic material, there is a problem that dispersibility is insufficient and the viscosity of the resin or rubber composition before molding may increase.
[0004]
The present invention aims to provide a method of manufacturing such a disadvantage, a novel organosilicon compound which solves the drawbacks.
[0005]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventor has found that a halogenoalkyl group-containing organosilicon compound represented by the following general formula (2) and a one-terminal halogen represented by the following general formula (3) By reacting a group-containing hydroxyalkyl (poly) alkylene oxide compound and anhydrous sodium sulfide or anhydrous polysulfide represented by the following general formula (4) with sulfur in some cases, it is represented by the following general formula (1). The organosilicon compound of the formula (1) has a good dispersibility even when added to a resin or rubber and kneaded with an inorganic material. It has been found that the viscosity of rubber and rubber can be stabilized and is effectively used in various applications such as an interfacial binder, and the present invention has been made.
[0006]
There is no known organosilicon compound having an alkoxysilyl group at one end of a molecule, a hydroxyalkyl (poly) alkylene oxide group at the other end, and a polysulfide group in the molecule as in the present invention. .
[0008]
Therefore, the present invention
[I] The following general formula (2)
[Chemical 3]

Wherein R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, and p is 0, 1 or 2. Show.)
A halogenoalkyl group-containing organosilicon compound represented by the following general formula (3):
Y— (R ⁴ O) _n —R ⁴ —OH (3)
(In the formula, R ⁴ is a divalent hydrocarbon group having 2 to 10 carbon atoms, Y is a halogen atom, and n is 1 to 10.)
A one-terminal halogen group-containing hydroxyalkyl (poly) alkylene oxide compound represented by the following general formula (4):
Na ₂ S _q (4)
(In the formula, q represents 1 to 4.)
An anhydrous sodium sulfide or an anhydrous sodium polysulfide represented by the following general formula (1):
[Formula 4]

(In the formula, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 2 to 10 carbon atoms. Group, m is 1 to 10, n is 1 to 10, and p is 0, 1 or 2.)
The manufacturing method of the organosilicon compound represented by these is provided.
[0009]
Hereinafter, the present invention will be described in more detail. As described above, the organosilicon compound of the present invention is represented by the following general formula (1).
[Chemical formula 5]

[0010]
In the above formula, R ¹ and R ² represent a monovalent hydrocarbon group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl, i-butyl, t -Alkyl groups, such as a butyl group, etc. are mentioned, Among these, a methyl group and an ethyl group are preferable. R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, particularly preferably 3 such as methylene group, ethylene group, propylene group, n-butylene group, i-butylene group, hexylene. Group, alkylene group such as decylene group, arylene group such as phenylene group, aralkylene group such as methylphenylethylene group, and the like. R ⁴ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to ⁴ carbon atoms, particularly preferably 2 carbon atoms, such as ethylene group, propylene group, n-butylene group, i-butylene group, hexylene group and decylene. And an alkylene group such as a group, an arylene group such as a phenylene group, and an aralkylene group. m is a positive number of 1 to 10, preferably 2 to 4. n represents 1 to 10, preferably 1 to 4, particularly preferably 1 or 2, and p represents 0, 1 or 2, preferably 0 or 1, particularly preferably 0. Examples of the compound represented by the general formula (1) include the following compounds as representative examples.
[0011]
[Chemical 6]

[0012]
In addition, since S of the above-mentioned compound has a disproportionation reaction or the like, it has a distribution and is actually obtained as a mixture of compounds having different m. Therefore, m in the general formula (1) described above is a value as an average value.
[0013]
Such an organosilicon compound has the following general formula (2) as described above.
[Chemical 7]

(In the formula, R ¹ , R ² , R ³ and p have the same meaning as described above, X represents a halogen atom, and chlorine and bromine are preferred as the halogen atom.)
And a halogenoalkyl group-containing organosilicon compound represented by the following general formula (3):
_{^{Y- (R 4 O) n -R}} 4 -Y (3)
(In the formula, R ⁴ and n have the same meanings as described above, Y represents a halogen atom, and the halogen atom is preferably chlorine or bromine.)
A one-terminal halogen group-containing hydroxyalkyl (poly) alkylene oxide compound represented by formula (4):
Na ₂ S _q (4)
(In the formula, q represents 1 to 4.)
It can manufacture by making the anhydrous sodium sulfide or anhydrous sodium polysulfide represented by these, and sulfur if necessary.
[0014]
In this case, as a compound of the said General formula (2), the following can be illustrated as a representative example.
(CH ₃ O) ₃ Si— (CH ₂ ) ₃ —Cl
(CH ₃ CH ₂ O) ₃ Si— (CH ₂ ) ₃ —Cl
(CH ₃ O) ₃ Si— (CH ₂ ) ₄ —Cl
(CH ₃ O) ₃ Si— (CH ₂ ) ₆ —Br
(CH ₃ O) ₃ Si— (CH ₂ ) ₁₀ —Br
_{(CH 3 O) 3 Si-} CH 2 CH (CH 3) CH 2 -Cl
_{(CH 3 CH 2 O) 3} Si-CH 2 CH (CH 3) CH 2 -Cl
[0015]
Moreover, as a compound of the said General formula (3), the following can be illustrated as a representative example.
Cl-CH ₂ CH ₂ OCH ₂ CH ₂ OH
_{Cl- (CH 2 CH 2 O)} 2 CH 2 CH 2 OH
_{Cl- (CH 2 CH 2 O)} 3 CH 2 CH 2 OH
_{Cl- (CH 2 CH 2 O)} 10 CH 2 CH 2 OH
_{Cl- (CH 2 CH 2 CH 2} O) 2 CH 2 CH 2 CH 2 OH
_{Cl- (CH 2 CH 2 CH 2} CH 2 O) 2 CH 2 CH 2 CH 2 CH 2 OH
_{Cl- (CH (CH 3) CH} 2 O) 2 CH (CH 3) CH 2 OH
[0016]
Furthermore, examples of the compound represented by the general formula (4) include Na ₂ S, Na ₂ S ₂ , Na ₂ S ₃ , and Na ₂ S ₄ .
[0017]
In addition, as a method for producing anhydrous sodium sulfide Na ₂ S of this compound (4), water-containing sodium sulfide dehydrated may be used, or a product obtained by reacting sodium sulfide and sodium alcoholate in an anhydrous state. It may be used, and further, metal sodium or potassium and sulfur reacted in an anhydrous state may be used. In addition, anhydrous sodium polysulfide may be obtained by dehydrating water-containing sodium polysulfide, or may be obtained by reacting the above-mentioned anhydrous sodium sulfide and sulfur in an anhydrous state. Alternatively, a product obtained by reacting potassium and sulfur in an anhydrous state may be used.
[0018]
In the reaction of the compounds of the above general formulas (2), (3) and (4), and optionally sulfur, the use of a solvent is optional, such as pentane, hexane, heptane, octane, benzene, toluene, xylene and the like. Hydrocarbons, alcohols such as methanol and ethanol, ethers such as dibutyl ether, tetrahydrofuran and dioxane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, amides such as dimethylformamide and the like In particular, the use of alcohols such as methanol and ethanol is preferred.
[0019]
The reaction temperature in that case is about 0-150 degreeC, Preferably it is about 50-100 degreeC. The reaction time may be carried out until sodium sulfide or sodium polysulfide disappears, but is usually about 30 minutes to 20 hours.
[0020]
The method of the reaction is arbitrary, but, for example, a compound represented by the general formula (4) and optionally sulfur and a solvent are charged, and a mixture of the compounds represented by the general formulas (2) and (3) is dropped. Alternatively, after the compound represented by the general formula (2) is dropped, the compound represented by the general formula (3) may be dropped. Further, the compound represented by the general formulas (2) and (3) and optionally sulfur and a solvent may be charged, and the compound represented by the general formula (4) may be gradually introduced.
[0021]
The reaction molar ratio of each component is as follows.
The molar ratio of the halogenoalkyl group-containing organosilicon compound represented by the general formula (2) to the one-terminal halogen group-containing hydroxyalkyl (poly) alkylene oxide compound represented by the general formula (3) is represented by the general formula (2). It is preferable that the compound of the general formula (3) = 1 / 0.9 to 1.1, and the halogenoalkyl group-containing organosilicon compound represented by the general formula (2) and the general formula (3) The molar ratio of the halogen group of the one-terminal halogen group-containing hydroxyalkyl (poly) alkylene oxide compound to the sodium of anhydrous sodium sulfide or anhydrous polysulfide represented by the general formula (4) Compound + halogen in compound of general formula (3) / sodium in compound of general formula (4) = 1 / 0.9 to 1.1 The amount of sulfur added is arbitrary, but at least (m-q) mol may be added.
[0022]
The compound of the present invention has the following general formula (5)
[Chemical 8]

(In the formula, R ¹ , R ² , R ³ , m, and p have the same meaning as described above.)
And a compound represented by the following general formula (6)
_{^{X- (R 4 O) n -R}} 4 -OH (6)
(In the formula, R ⁴ , X, and n have the same meaning as described above.)
Or a compound represented by the following general formula (2):
[0023]
[Chemical 9]

(In the formula, R ¹ , R ² , R ³ , p, and X have the same meaning as described above.)
And a compound represented by the following general formula (7)
^{_{Na-S m - (R 4}} O) n -R 4 -OH (7)
(In the formula, R ⁴ , m and n have the same meaning as described above.)
It is also possible to synthesize from the compound represented by However, these methods can synthesize the compound of the present invention with high purity, but this synthesis method increases the raw material cost.
[0024]
In the production method of the present invention, the following general formula (8)
[Chemical Formula 10]

(In the formula, R ¹ , R ² , R ³ , m, and p have the same meaning as described above.)
And a compound represented by the following general formula (9)
HO—R ⁴ — (OR ⁴ ) _n —S _m — (R ⁴ O) _n —R ⁴ —OH (9)
(In the formula, R ⁴ , m and n have the same meaning as described above.)
It is presumed that the compound represented by the formula (1) is contained as an impurity, but even if this impurity is contained in the composition, if the compound is used after being added to rubber or an organic resin or surface-treated to an inorganic filler There is no hindrance.
[0025]
In addition, when this compound is used by adding it to rubber or organic resin or surface treatment on an inorganic filler, the hydroxy group in this compound and the alkoxy group of alkoxysilyl group are exchanged, and the following general formula is obtained. The compound of (10) and the compound of the general formula (11) reacted between molecules may be contained.
[0026]
Embedded image

(In the formula, R ¹ , R ² , R ³ , R ⁴ , p, m, and n have the same meaning as described above, and t represents a positive integer.)
[0027]
The organosilicon compound of formula (1) of the present invention is useful as an interfacial binder between an inorganic material and an organic material, an organic resin or rubber adhesion improver, a primer composition component, and the like.
[0028]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0029]
[Example 1]
A 1 liter separable flask equipped with a nitrogen gas inlet tube, a thermometer, a Dimroth condenser and a dropping funnel was charged with 250 g of ethanol, 78 g (1.0 mol) of anhydrous sodium sulfide, and 96 g (3.0 mol) of sulfur at 75 ° C. A mixture of 240.5 g (1.0 mol) of 3-chloropropyltriethoxysilane and 124.5 g (1.0 mol) of diethylene glycol monochloride was added dropwise. This dripping took 50 minutes. After completion of the dropwise addition, aging was continued for 8 hours. The solution was then filtered.
[0030]
The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain 295.1 g of a brown transparent liquid. This had a viscosity of 58.6 mm ² / s at 25 ° C. and a refractive index of 1.5140 at 25 ° C. As a result of infrared absorption spectrum analysis and 1H nuclear magnetic resonance spectrum analysis of this product, the following average composition formula
_{(CH 3 CH 2 O) 3} Si (CH 2) 3 -S 4 - (CH 2) 2 O (CH 2) 2 OH
It was confirmed that it is a sulfide group-containing alkoxysilane represented by:
[0031]
[Example 2]
The reaction was carried out in the same manner as in Example 1 except that 168.5 g (1.0 mol) of triethylene glycol monochloride was used instead of diethylene glycol monochloride used in Example 1, to obtain 328.3 g of a brown transparent liquid. . As a result of infrared absorption spectrum analysis and 1H nuclear magnetic resonance spectrum analysis of this product, the following average composition formula
(CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ —S ₄ — (CH ₂ ) ₂ O (CH ₂ ) ₂ O (CH ₂ ) ₂ OH
It was confirmed that it is a sulfide group-containing alkoxysilane represented by:
[0032]
[Example 3]
The reaction was conducted in the same manner as in Example 1 except that 3-chloropropyltrimethoxysilane 198.5 g (1.0 mol) was used instead of 3-chloropropyltriethoxysilane used in Example 1, and methanol was used instead of ethanol. And 268.5 g of a brown transparent liquid was obtained. As a result of infrared absorption spectrum analysis and 1H nuclear magnetic resonance spectrum analysis of this product, the following average composition formula
(CH ₃ O) ₃ Si (CH ₂ ) ₃ —S ₄ — (CH ₂ ) ₂ O (CH ₂ ) ₂ OH
It was confirmed that it is a sulfide group-containing alkoxysilane represented by:
[0033]
[Example 4]
A reaction was carried out in the same manner as in Example 1 except that the amount of sulfur used in Example 1 was changed to 32 g (1.0 mol) to obtain 272.1 g of a brown transparent liquid. As a result of infrared absorption spectrum analysis and 1H nuclear magnetic resonance spectrum analysis of this product, the following average composition formula
(CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ -S _2- (CH ₂ ) ₂ O (CH ₂ ) ₂ OH
It was confirmed that it is a sulfide group-containing alkoxysilane represented by:
[0034]
[Example 5]
A reaction was carried out in the same manner as in Example 1 except that anhydrous sodium sulfide and 174 g (1.0 mol) of anhydrous sodium sulfide and sulfur used in Example 1 were used, to obtain 297.8 g of a brown transparent liquid. As a result of infrared absorption spectrum analysis and 1H nuclear magnetic resonance spectrum analysis of this product, as in Example 1, the following average composition formula
_{(CH 3 CH 2 O) 3} Si (CH 2) 3 -S 4 - (CH 2) 2 O (CH 2) 2 OH
It was confirmed that it is a sulfide group-containing alkoxysilane represented by:
[0035]
[Example 6]
The reaction was conducted in the same manner as in Example 1 except that 285 g (1.0 mol) of 6-bromohexyltrimethoxysilane was used instead of 3-chloropropyltriethoxysilane used in Example 1, and a brown transparent liquid 301. 6 g was obtained. As a result of infrared absorption spectrum analysis and 1H nuclear magnetic resonance spectrum analysis of this product, the following average composition formula
_{(CH 3 O) 3 Si (} CH 2) 6 -S 4 - (CH 2) 2 O (CH 2) 2 O (CH 2) 2 OH
It was confirmed that it is a sulfide group-containing alkoxysilane represented by:
[0036]
【The invention's effect】
The organosilicon compound of the present invention is excellent in dispersibility even when added to a resin or rubber and kneaded with an inorganic material, and is excellent in that there is little change in viscosity of the resin or rubber composition before molding. It is useful as a binder, adhesion improver, primer composition component, and the like.

Claims (1)

The following general formula (2)

Wherein R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, and p is 0, 1 or 2. Show.)
A halogenoalkyl group-containing organosilicon compound represented by the following general formula (3):
Y— (R ⁴ O) _n —R ⁴ —OH (3)
(In the formula, R ⁴ is a divalent hydrocarbon group having 2 to 10 carbon atoms, Y is a halogen atom, and n is 1 to 10.)
And a one-terminal halogen group-containing hydroxyalkyl (poly) alkylene oxide compound represented by the following general formula (4):
Na ₂ S _q (4)
(In the formula, q represents 1 to 4.)
An anhydrous sodium sulfide or anhydrous sodium polysulfide represented by the following general formula (1):

(In the formula, R ¹ and R ² are monovalent hydrocarbon groups having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 2 to 10 carbon atoms. Group, m is 1 to 10, n is 1 to 10, and p is 0, 1 or 2.)
The manufacturing method of the organosilicon compound represented by these .