JP3543400B2 - Method for producing organosilanols - Google Patents

Description

【０００８】
（式中、Ｒ¹ はそれぞれ炭素数１〜１０の一価炭化水素基又は炭素数１〜６の一価炭化水素基を有するトリオルガノシリルオキシ基を表し、Ｒ² はそれぞれ水素原子、炭素数１〜１０の一価炭化水素基又は炭素数１〜６の一価炭化水素基を有するトリオルガノシリルオキシ基を表し、Ｘは酸素原子又は炭素数１〜６の二価炭化水素基を表し、ａは０〜６の整数である。）
以下、本発明につき更に詳しく説明すると、本発明のオルガノシラノール類の製造方法において、その出発原料として使用するＳｉ−Ｈ結合含有有機ケイ素化合物は、下記一般式（１）で示されるものである。
【０００９】
【化３】

【００１０】
上式中、Ｒ¹ はそれぞれ炭素原子数１から１０までの一価炭化水素基、または炭素原子数１から６までの一価炭化水素基を有するトリオルガノシリルオキシ基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；ビニル基、アリル基、ブテニル基、ヘキセニル基、イソプロペニル基等のアルケニル基；フェニル基、トリル基、キシリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロエチル基、３，３，３−トリフルオロプロピル基等のハロゲン原子置換アルキル基；トリメチルシリルオキシ基、トリエチルシリルオキシ基、ｔ−ブチルジメチルシリルオキシ基、トリフェニルシリルオキシ基等が例示される。Ｒ² はそれぞれ水素原子、炭素原子数１から１０までの一価炭化水素基、または炭素原子数１から６までの一価炭化水素基を有するトリオルガノシリルオキシ基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；ビニル基、アリル基、ブテニル基、ヘキセニル基、イソプロペニル基等のアルケニル基；フェニル基、トリル基、キシリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロエチル基、３，３，３−トリフルオロプロピル基等のハロゲン原子置換アルキル基；トリメチルシリルオキシ基、トリエチルシリルオキシ基、ｔ−ブチルジメチルシリルオキシ基、トリフェニルシリルオキシ基等が例示される。Ｘは酸素原子、またはメチレン、フェニレン等の炭素原子数１から６までの二価炭化水素基である。ａは０または１から６の整数である。
【００１１】
本発明は、上記Ｓｉ−Ｈ結合含有有機ケイ素化合物を触媒の存在下に加水分解させるもので、これによりこの有機ケイ素化合物のＳｉ−Ｈ基がＳｉ−ＯＨ基に加水分解されたオルガノシラノールが得られるものである。
【００１２】
ここで、本発明においては、触媒として下記一般式（２）
Ｙ_b Ｚ_c Ｓｉ（ＯＲ³ ）_d （ＯＨ）_e Ｏ_{(4-b-c-d-e)/2} （２）
で示される硫黄原子及び窒素原子含有ケイ素樹脂とパラジウム化合物又はその錯化合物との反応により得られる触媒を使用する。なお、このケイ素樹脂としては、シリカとポリシルセスキオキサンがある。
【００１３】
この場合、式（２）のケイ素樹脂は、（ｉ）硫黄原子含有オルガノトリアルコキシシランと、（ii）窒素原子含有オルガノトリアルコキシシランと、および（iii）テトラアルコキシシランとを、Ｓｉ−Ｆ結合を有するフッ素含有ケイ素化合物もしくはフッ素塩化合物の存在下、水あるいは含水有機溶剤中で反応させて得ることができ、この硫黄原子および窒素原子含有ケイ素樹脂と、（iv）パラジウム化合物またはその錯化合物との反応により本発明の触媒を調製することができる。
【００１４】
ここで使用される硫黄原子含有オルガノトリアルコキシシラン（ｉ）は、一般式（４）
ＹＳｉ（ＯＲ³ ）₃ （４）
で示される。上式中、Ｙは１１個までの炭素原子を有し、かつ炭素、水素および適宜酸素よりなり、ケイ素−炭素結合を介してケイ素へ結合する一価の基であって、Ｙ中には少なくとも１個の硫黄原子を含む有機官能基があり、Ｒ³ は炭素原子数１から４までの一価炭化水素基である。ここで、Ｙとしては、Ｒ¹¹−Ｓｘ−Ｒ¹²−で表されるチオール又はチオエーテル官能基であることが好ましい。但し、Ｒ¹¹は水素原子、炭素数１〜４のアルキル基、炭素数２〜５のアルケニル基、炭素数６〜１０のアリール基又は−Ｒ¹³−Ｓｉ（ＯＲ¹⁴）₃基であり、Ｒ¹³は炭素数１〜１０の直鎖状又は分枝状のアルキレン基、Ｒ¹⁴は炭素数１〜４の一価炭化水素基である。また、ｘは１〜４の整数を示す。具体的は、以下の化合物が例示されるが、これらに限定されるものではない。
【００１５】
ＨＳ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
ＨＳ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＨＳ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
ＨＳ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＨＳ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
ＨＳ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＨＳ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
ＨＳ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＨＳＣＨ₂ Ｃ₆ Ｈ₄ （ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃
ＨＳＣＨ₂ Ｃ₆ Ｈ₄ （ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＣＨ₃ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
ＣＨ₃ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＣＨ₃ ＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
ＣＨ₃ ＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＣＨ₃ ＣＨ₂ ＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
ＣＨ₃ ＣＨ₂ ＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＣＨ₂ ＝ＣＨＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
ＣＨ₂ ＝ＣＨＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｃ₆ Ｈ₅ ＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
Ｃ₆ Ｈ₅ ＣＨ₂ Ｓ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｓ（（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ ）₂
Ｓ（（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ ）₂
Ｓ₄ （（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ ）₂
Ｓ₄ （（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ ）₂
Ｓ₄ （（ＣＨ₂ Ｃ₆ Ｈ₄ ＣＨ₂ ＣＨ₂ ）Ｓｉ（ＯＣＨ₃ ）₃ ）₂
Ｓ₄ （（ＣＨ₂ Ｃ₆ Ｈ₄ ＣＨ₂ ＣＨ₂ ）Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ ）₂
また、ここで使用される窒素原子含有オルガノトリアルコキシシラン（ii）は一般式（５）
ＺＳｉ（ＯＲ³ ）₃ （５）
で示される。上式中、Ｚは１１個までの炭素原子を有し、かつ炭素、水素および適宜酸素よりなり、ケイ素−炭素結合を介してケイ素へ結合する一価の基であって、Ｚ中に少なくとも１個の窒素原子を含む有機官能基があり、Ｒ³ は前記と同じである。ここで、Ｚとしては、Ｒ¹⁵Ｒ¹⁶Ｎ−Ｒ¹³−で表されるアミノ官能性基又はＮＣ−Ｒ¹³−で表されるシアノ官能性基であることが好ましい。但し、Ｒ¹⁵及びＲ¹⁶はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数２〜５のアルケニル基、炭素数６〜１０のアリール基、Ｒ¹⁵Ｒ¹⁶Ｎ−Ｒ¹⁷−基又は−Ｒ¹³−Ｓｉ（ＯＲ¹⁴）₃基である。なお、Ｒ¹³及びＲ¹⁴は上記と同様の意味を示す。具体的には、以下の化合物が例示されるが、これらに限定されるものではない。
【００１６】
Ｈ₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ＣＨ₂ ）ＨＮ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₆ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₈ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₃ ）₃
（Ｃ₆ Ｈ₅ ）₂ Ｎ（ＣＨ₂ ）₁₀Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₂ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₂ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₆ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₆ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₂ ＮＨＣＨ₂ Ｃ₆ Ｈ₄ （ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₂ ＮＨＣＨ₂ Ｃ₆ Ｈ₄ （ＣＨ₂）₂ Ｓｉ（ＯＣＨ₂ＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂ ）₂ ＮＨ（ＣＨ₂ ）₂ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
Ｈ₂ Ｎ（ＣＨ₂）₂ ＮＨ（ＣＨ₂）₂ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ＣＨ₃）₃
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ ＮＨ（ＣＨ₂ ）₂ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃
（ＣＨ₃ ＣＨ₂ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ ＮＨ（ＣＨ₂ ）₂ ＮＨ（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₅ Ｓｉ（ＯＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₅ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₇ Ｓｉ（ＯＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₇ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₉ Ｓｉ（ＯＣＨ₃ ）₃
ＮＣ（ＣＨ₂ ）₉ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃
また、ここで使用されるテトラアルコキシシラン（iii ）は一般式（６）
Ｓｉ（ＯＲ³ ）₄ （６）
で示される。上式中、Ｒ³ は前記と同じである。具体的には、以下の化合物が例示されるが、これらに限定されるものではない。
【００１７】
Ｓｉ（ＯＣＨ₃ ）₄ ，Ｓｉ（ＯＣ₂ Ｈ₅ ）₄ ，Ｓｉ（ＯＣ₃ Ｈ₇ ）₄ ，
Ｓｉ（ＯＣ₄ Ｈ₉ ）₄ ，Ｓｉ〔ＯＣ（＝ＣＨ₂ ）ＣＨ₃ 〕₄
上記硫黄原子含有オルガノトリアルコキシシランおよび窒素原子含有オルガノトリアルコキシシランとテトラアルコキシシランとの混合比は、目的生成物が固体となるように設定する。具体的には、硫黄原子含有オルガノトリアルコキシシランおよび窒素原子含有オルガノトリアルコキシシランとテトラアルコキシシランとのモル比が０．０１〜３の範囲が好ましく、０．１〜２の範囲が特に好ましい。このモル比が３より大きくなると目的物の性状が液体あるいはオイル状になってしまう場合があるので好ましくない。また、このモル比が０．０１未満になると硫黄原子および窒素原子によるパラジウム成分の固定化能が発現せず、好ましくない。
【００１８】
また、硫黄原子含有オルガノトリアルコキシシランと窒素原子含有オルガノトリアルコキシシランの混合比は、硫黄原子／窒素原子のモル比で１．５〜５の範囲、特には、２〜４の範囲になるのが好ましい。この比が１．５未満になるとパラジウム化合物またはその錯化合物と反応させ、触媒とした後、加水分解反応に用いるとパラジウム成分が脱落し、反応系を汚染してしまう場合が生じ、またこの比が５より大きくなると触媒を調製するために仕込んだパラジウム化合物またはその錯化合物の全てを固定化できない場合が生じる。
【００１９】
上記アルコキシシランの混合物は、分子中に少なくとも１個のＳｉ−Ｆ結合を有するフッ素含有ケイ素化合物もしくはフッ素塩化合物の存在下、水又は含水有機溶剤と反応させる。ここで用いられるフッ素含有ケイ素化合物としては、ＦＳｉ（ＯＣＨ₃ ）₃ 、ＦＳｉ（ＯＣＨ₂ −ＣＨ₃ ）₃ 、（ＮＨ₄ ）₂ ＳｉＦ₆ などが例示される。また、フッ素塩化合物としては、ＮａＦ、ＫＦ、（ＣＨ₃ ＣＨ₂ ＣＨ₂ ＣＨ₂ ）₄ ＮＦなどが例示される。
【００２０】
Ｓｉ−Ｆ結合を有するフッ素含有素ケイ素化合物もしくはフッ素塩化合物の使用量は、硫黄原子含有オルガノトリアルコキシシラン、窒素原子含有オルガノトリアルコキシシラン、およびテトラアルコキシシランの総和Ｓｉ／Ｆのモル比で１．０：０．０００１から１．０：２．０の範囲が好ましい。
【００２１】
これらアルコキシシランの混合物を上記フッ素含有ケイ素化合物もしくはフッ素塩化合物の存在下、水又は含水有機溶剤と反応させることにより、一般式（２）
Ｙ_b Ｚ_c Ｓｉ（ＯＲ³ ）_d （ＯＨ）_e Ｏ_{(4-b-c-d-e)/2} （２）
で示される硫黄原子および窒素原子含有ケイ素樹脂を得ることができる。上式中、Ｙ、Ｚ、およびＲ³ は前記と同じであり、ｂ，ｃ，ｄおよびｅは、０＜ｂ＜１，０＜ｃ＜０．５，ｃ＜ｂ，０＜ｂ＋ｃ＜１，０≦ｄ＜０．１，０＜ｅ＜１，０＜ｂ＋ｃ＋ｄ＋ｅ＜２を満足する正数である。
【００２２】
次に、上記硫黄原子および窒素原子含有ケイ素樹脂と、パラジウム化合物またはその錯化合物（iv）との反応による触媒の調製について述べる。まず、パラジウム化合物またはその錯化合物（iv）は、一般式（３）
ＰｄＬ_f （３）
で示される。上式中、Ｌはアミノ基またはメルカプト基により置換可能である少なくとも１個の配位子を表わし、ｆはＰｄの遊離価を満足するような数である。具体的には、以下の化合物が例示されるが、これらに限定されるものではない。
【００２３】
ＰｄＣｌ₂ ，ＰｄＢｒ₂ ，Ｐｄ（ＣＮ）₂ ，Ｐｄ（ＮＯ₃ ）₂ ，
Ｐｄ〔ＯＣ（＝Ｏ）ＣＨ₃ 〕₂ ，Ｐｄ（Ｃ₆ Ｈ₅ ＣＮ）₂ ，
Ｐｄ〔ＣＨ₃ Ｃ（＝Ｏ）ＣＨ＝Ｃ（−Ｏ）ＣＨ₃ 〕₂ ，
Ｐｄ（Ｈ₂ ＮＣＨ₂ ＣＨ₂ ＮＨ₂ ）Ｃｌ₂ ，
Ｐｄ₂ 〔Ｃ₆ Ｈ₅ ＣＨ＝ＣＨＣ（＝Ｏ）ＣＨ＝ＣＨＣ₆ Ｈ₅ 〕₃ ，
硫黄原子および窒素原子含有ケイ素樹脂と上記パラジウム化合物またはその錯化合物との反応は、通常環境温度から１００℃程度の範囲で行うことができる。好ましくは、６０〜７０℃の範囲である。また、この反応は無溶媒でも行うことができるが、適当な溶媒の存在下で行うことが好ましい。なかでも、テトラヒドロフラン、ジエチルエーテル、アセトン、酢酸エチル、ジメチルスルホキシド、ジメチルホルムアミド、メタノール、エタノール、イソプロパノール等の極性溶媒および／または水の中が好ましい。
【００２４】
硫黄原子および窒素原子含有ケイ素樹脂と上記パラジウム化合物またはその錯化合物との混合比は、硫黄原子および窒素原子含有ケイ素樹脂中の硫黄原子および窒素原子／パラジウム化合物またはその錯化合物中のパラジウム原子のモル比で２〜２００の範囲が好ましく、３〜１００がより好ましい。このモル比が２未満になると、パラジウム化合物またはその錯化合物の全てを固定化できない場合が生じ、また２００を超えるようになると、パラジウム成分の固定化はされるものの、パラジウム成分の触媒活性が極端に低下してしまう場合がある。
【００２５】
硫黄原子および窒素原子含有ケイ素樹脂と上記パラジウム化合物またはその錯化合物とを反応させた後、水素化ホウ素ナトリウム等の還元剤で生成物を還元してもよい。
【００２６】
硫黄原子および窒素原子含有ケイ素樹脂と上記パラジウム化合物またはその錯化合物とを反応させた後、生成した固体を濾過し、アルコールおよび水で洗浄した後、乾燥することによって、本発明のＳｉ−Ｈ結合含有有機ケイ素化合物の加水分解反応用触媒を得ることができる。
【００２７】
次に、本発明の上記触媒を用いたＳｉ−Ｈ結合含有有機ケイ素化合物の加水分解反応によるシラノール類の製造方法について述べる。この加水分解反応は上記式（１）のＳｉ−Ｈ結合を有する有機ケイ素化合物と理論等量以上の水とを上記触媒の存在下で反応させる。さらにこの反応は、通常環境温度から１００℃程度の範囲で行うことができる。好ましくは、４０〜７０℃の範囲である。また、この反応は無触媒でも行うことができるが、適当な溶媒の存在下で行うことが好ましい。なかでも、テトラヒドロフラン、ジエチルエーテル、アセトン、酢酸エチル、ジメチルスルホキシド、ジメチルホルムアミド等の非プロトン性極性溶媒が好ましい。また、この触媒は固体であるので、バッチ式あるいは連続式で上記反応を行なうことができる。バッチ式で反応を行なう場合、反応終了後は濾過等の分離操作により触媒を分離し、該触媒はそのまま次の反応にリサイクルすることができる。また、連続式で反応を行なう場合には、Ｓｉ−Ｈ結合含有有機ケイ素化合物、水、および溶媒の混合物をこの触媒床の上または中に通すことにより行なうことができる。なお、上記触媒の使用量は、特に制限されないが、パラジウム量として０．１〜２０００ｐｐｍであることが好ましい。
また、上記加水分解後は、常法に従い、触媒を濾別し、目的とするオルガノシラノールを減圧蒸留することにより単離することができる。この場合、本発明においては、この減圧蒸留時にシラノールが縮合することがなく、高収率で目的オルガノシラノールを得ることができる。また、濾別した触媒は繰り返して使用することができる。
【００２８】
【実施例】
以下、実施例と比較例を示し、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〕
〔硫黄原子および窒素原子含有ケイ素樹脂の調製〕攪拌装置付４つ口フラスコに、フッ化カリウム１．１６ｇ（０．０２モル）および水１６００．０ｇ（８８．８モル）を仕込み、室温にてメルカプトプロピルトリメトキシシラン１３１．３ｇ（０．６７モル）、γ−フェニルアミノプロピルトリメトキシシラン８４．２ｇ（０．３３モル）、およびテトラメトキシシラン１５２．０ｇ（１．００モル）の混合物を攪拌下、３分間で滴下した。室温下、２分間攪拌したところ、反応系は白色ゲル化した。さらに室温下、１時間攪拌後、生成した固体を濾別し、蒸留水、続いてアセトン洗浄した。次いで減圧乾燥し、溶媒を除去後、メルカプトプロピル基およびγ−フェニルアミノプロピル基含有ケイ素樹脂を２０２．４ｇ、収率９８％で得た。このメルカプトプロピル基およびγ−フェニルアミノプロピル基含有ケイ素樹脂中の硫黄分および窒素分は、それぞれ１０．１ｗｔ％、２．２ｗｔ％であった。
【００３０】
〔パラジウム含有触媒の調製〕攪拌装置付４つ口フラスコに、上記ケイ素樹脂３．７８ｇ、エタノール３０．０ｇ、および塩化パラジウム０．３ｇを仕込み、６０℃、６時間攪拌した。その後、水素化ホウ素ナトリウム０．０８ｇを添加し、さらに６０℃、１時間攪拌後、生成した固体を濾別し、アセトン、続いて蒸留水で洗浄した。次いで減圧乾燥し、溶媒を除去後、褐色固体状触媒を３．５０ｇ得た。この触媒中のパラジウム量の計算値および測定値は、いずれも４．６ｗｔ％であり、パラジウムは定量的に固定化されていた。
【００３１】
〔上記触媒を用いたシラノール合成反応〕攪拌装置付４つ口フラスコに、上記のようにして調製した触媒４．３ｇ、水８１．６ｇ（４．５３モル）、およびメチルエチルケトン１００２．７ｇを仕込み、６０℃にて１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン５０１．２ｇ（１．７８モル）を攪拌下、４．５時間で滴下した。滴下と共に水素ガスの発生がみられた。６０℃、６時間の攪拌後、ガスクロマトグラフィー／質量分析（以下、ＧＣ−ＭＳと略記する。）にて反応混合物を分析したところ、原料の１，１，１，３，５，７，７，７−オクタメチルテトラシロキサンは完全に消費され、目的生成物である１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン−３，５−ジオールが８７．４％生成していた。この反応混合物から触媒を濾別し、濾液を減圧下、濃縮した。濃縮物を減圧蒸留したところ、１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン−３，５−ジオールを９６〜９８℃／３５ｍｍＴｏｒｒの無色透明オイルの留分として得た。１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン−３，５−ジオールの単離収率は、７６．２％であり、純度は９８．５％であった。
【００３２】
〔実施例２〕
γ−フェニルアミノプロピルトリメトキシシランをγ−メチルアミノプロピルトリメトキシシラン６３．７ｇ（０．３３モル）に代えた以外は、実施例１の〔硫黄原子および窒素原子含有ケイ素樹脂の調製〕と同様な反応を行なったところ、メルカプトプロピル基およびγ−メチルアミノプロピル基含有ケイ素樹脂を１８３．０ｇ、収率９８％で得た。このメルカプトプロピル基およびγ−メチルアミノプロピル基含有ケイ素樹脂中の硫黄分および窒素分は、それぞれ１１．０ｗｔ％、２．４ｗｔ％であった。
【００３３】
攪拌装置付４つ口フラスコに、上記ケイ素樹脂４．０３ｇ、エタノール３０．８ｇ、および塩化パラジウム０．３０ｇを仕込み、６０℃、６時間攪拌した。その後、水素化ホウ素ナトリウム０．０９ｇを添加し、さら６０℃、１時間攪拌後、生成した固体を濾別し、アセトン、続いて蒸留水で洗浄した。次いで減圧乾燥し、溶媒を除去後、褐色固体状触媒を３．５８ｇ得た。この触媒中のパラジウム量の計算値および測定値は、いずれも４．３ｗｔ％であり、パラジウムは定量的に固定化されていた。
【００３４】
攪拌装置付４つ口フラスコに、上記のようにして調製した触媒０．３ｇ、水２．３ｇ（０．１３モル）、およびメチルエチルケトン３０．３ｇを仕込み、６０℃にて１，１，３，３−テトラメチルジシロキサン６．７ｇ（０．０５モル）を攪拌下、１時間で滴下した。滴下と共に水素ガスの発生がみられた。６０℃、３時間の攪拌後、ＧＣ−ＭＳにて反応混合物を分析したところ、原料の１，１，３，３−テトラメチルジシロキサンは完全に消費され、目的生成物である１，１，３，３−テトラメチルジシロキサン−１，３−ジオールは８５．４％生成していた。この反応混合物から触媒を濾別した後、濾液中のパラジウム量を測定したところ、０．１ｐｐｍ以下であった。なお、濾別した触媒をリサイクルし、同じ反応を同スケールで５回行なったが、１，１，３，３−テトラメチルジシロキサン−１，３−ジオールの収率は変わらず、触媒活性の低下はみられなかった。
【００３５】
〔実施例３〕
撹拌装置付４つ口フラスコに実施例１で調製したパラジウム含有ケイ素樹脂０．４ｇ、水２．４ｇ（０．１３モル）、およびメチルエチルケトン３５．３ｇを仕込み、６０℃にて１，４−ビス（ジメチルシリル）ベンゼン９．７ｇ（０．０５モル）を撹拌下、１時間で滴下した。滴下と共に水素ガスの発生がみられた。６０℃、４時間の撹拌後、ＧＣ−ＭＳにて反応混合物を分析したところ、原料の１，４−ビス（ジメチルシリル）ベンゼンは完全に消費され、目的生成物である１，４−ビス（ジメチルヒドロキシシリル）ベンゼンは、９２．６％生成していた。この反応混合物中から触媒を濾別した後、濾液中のパラジウム量を測定したところ、０．１ｐｐｍ以下であった。なお濾別した触媒をリサイクルし、同じ反応を同スケールで６回行なったが、１，４−ビス（ジメチルヒドロキシシリル）ベンゼンの収率は変わらず、触媒活性の低下はみられなかった。
【００３６】
〔比較例１〕
攪拌装置付４つ口フラスコに、あらかじめ水洗した５％パラジウム−カーボン３．３ｇ、水８１．２ｇ（４．５１モル）、およびメチルエチルケトン９９４．０ｇを仕込み、６０℃にて１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン５００．０ｇ（１．７７モル）を攪拌下、４．５時間で滴下した。滴下と共に水素ガスの発生がみられた。６０℃、６時間の攪拌後、ＧＣ−ＭＳにて反応混合物を分析したところ、原料の１，１，１，３，５，７，７，７−オクタメチルテトラシロキサンは完全に消費され、目的生成物である１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン−３，５−ジオールが７６．７％生成していた。この反応混合物から触媒を濾別し、濾液を減圧下、濃縮した。濃縮物を減圧蒸留したところ、１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン−３，５−ジオールを９６〜９８℃／３５ｍｍＴｏｒｒの無色透明オイルの留分として得た。１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン−３，５−ジオールの単離収率は、２７．２％であり、純度は９８．２％であった。なお、釜残をゲルパーミエーションクロマトグラフィー（以下、ＧＰＣと略記する。）にて分析したところ、平均分子量Ｍｗは２４００、分散度Ｍｗ／Ｍｎは１．２２の高分子量体のみであった。
【００３７】
〔比較例２〕
攪拌装置付４つ口フラスコに、あらかじめ水洗した５％パラジウム−カーボン０．１ｇ、水２．３ｇ（０．１３モル）、およびメチルエチルケトン３０．６ｇを仕込み、６０℃にて１，１，３，３−テトラメチルジシロキサン６．７ｇ（０．０５モル）を攪拌下、１時間で滴下した。滴下と共に水素ガスの発生がみられた。６０℃、３時間の攪拌後、ＧＣ−ＭＳにて反応混合物を分析したところ、原料の１，１，３，３−テトラメチルジシロキサンは完全に消費され、目的生成物である１，１，３，３−テトラメチルジシロキサン−１，３−ジオールは８０．４％生成していた。この反応混合物から触媒を濾別した後の濾液は薄褐色に着色しており、その濾液中のパラジウム量を測定したところ、１６．１ｐｐｍであった。
【００３８】
【発明の効果】
本発明のオルガノシラノールの製造方法は、上述した特定の固体支持体に化学的に結合した特定のパラジウム化合物もしくはその錯化合物からなる触媒の使用により、Ｓｉ−Ｈ結合を有する有機ケイ素化合物を加水分解することによって、反応系を該触媒成分で汚染することなしに、相当するオルガノシラノールを収率よく、かつ高純度に製造できるという特徴を有する。[0001]
[Industrial applications]
The present invention relates to a method for producing organosilanols by hydrolyzing an organosilicon compound having a Si—H bond.
[0002]
Problems to be solved by the prior art and the invention
It is well known that organosilanols useful as a plasticizer for silicone rubber and intermediates for synthesizing various silicone compounds can be obtained by a hydrolysis reaction of an organosilicon compound having a Si-H bond. It is more widely used in manufacturing than before. Several catalysts that promote this hydrolysis reaction are known, but carbon or alumina carrying a transition metal such as palladium, rhodium, and platinum is generally used. For example, triethylsilane (Et_ThreeSiH) is hydrolyzed in the presence of ruthenium-carbon to obtain triethylsilanol (Et)._ThreeThe reaction for obtaining SiOH) with a yield of 87% is Journal
of Organic Chemistry,31, 855 (1966).
[0003]
Hydrolysis of an organosilicon compound having a plurality of Si-H bonds by a similar method yields the corresponding polysilanol, but at a reduced yield. This is because the transition metal component is physically adsorbed on the carbon, so that some transition metal component is dropped into the reaction system, which promotes condensation between polysilanols having higher reactivity than monosilanol. That's why. In this case, condensation between polysilanols occurs even when the pH of the reaction system is adjusted with a pH buffer solution. In addition, when the polysilanol produced is purified by distillation from the reaction mixture, condensation between the polysilanol occurs due to a synergistic effect between the transition metal component dropped from the catalyst and heating, and the isolation yield is greatly reduced.
[0004]
The present invention solves the above-mentioned conventional problems and provides a method capable of producing a target organosilanol in high yield from an organosilicon compound having a Si-H bond even in the case of polysilanol. The purpose is to:
[0005]
Means and Action for Solving the Problems
The present inventors have conducted intensive studies in order to achieve the above object, and as a result, when hydrolyzing an organosilicon compound having a Si-H bond represented by the following general formula (1), the solid support is chemically bonded to the solid support. A catalyst comprising a bound specific palladium compound or a complex thereof, that is, the following general formula (2)
Y_bZ_cSi (OR^Three)_d(OH)_eO_{(4-bcde) / 2}        (2)
Wherein Y represents a sulfur atom-containing monovalent organic functional group having up to 11 carbon atoms and containing at least one sulfur atom, which is attached to the silicon atom via a silicon-carbon bond. , Z represents a nitrogen-containing monovalent organic functional group having up to 11 carbon atoms and containing at least one nitrogen atom, which is attached to the silicon atom via a silicon-carbon bond;^ThreeRepresents a monovalent hydrocarbon group having 1 to 4 carbon atoms, and b, c, d, and e are 0 <b <1, 0 <c <0.5, c <b, 0 <b + c <1, 0 ≦ It is a positive number satisfying d <0.1, 0 <e <1, 0 <b + c + d + e <2. )
And a silicon resin containing a sulfur atom and a nitrogen atom represented by the following general formula (3)
PdL_f                                                  (3)
(In the formula, L represents a ligand that can be substituted by an amino group or a mercapto group, and f is a number that satisfies the free value of Pd.)
It has been found that by using a catalyst obtained by the reaction with a palladium compound or a complex compound thereof represented by the formula (1), the corresponding organosilanol can be selectively obtained without contaminating the reaction system with the catalyst component. Further, when hydrolyzing an organosilicon compound having a plurality of Si-H bonds and purifying a highly reactive polysilanol generated from the reaction mixture by distillation, the palladium component does not fall off from the catalyst. The present inventors have found that polysilanol can be obtained with a higher isolation yield than the method, and have accomplished the present invention.
[0006]
Accordingly, the present invention provides a method for producing an organosilanol, which comprises hydrolyzing an organosilicon compound having a Si—H bond represented by the following general formula (1) in the presence of the catalyst.
[0007]
Embedded image

[0008]
(Where R¹Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or a triorganosilyloxy group having a monovalent hydrocarbon group having 1 to 6 carbon atoms,^TwoRepresents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a triorganosilyloxy group having a monovalent hydrocarbon group having 1 to 6 carbon atoms, respectively, and X represents an oxygen atom or a divalent group having 1 to 6 carbon atoms. A represents an integer of 0 to 6; )
Hereinafter, the present invention will be described in more detail. In the method for producing an organosilanol according to the present invention, the Si—H bond-containing organosilicon compound used as a starting material is represented by the following general formula (1).
[0009]
Embedded image

[0010]
In the above formula, R¹Is a monovalent hydrocarbon group having 1 to 10 carbon atoms or a triorganosilyloxy group having a monovalent hydrocarbon group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group Alkyl groups such as propyl, butyl, pentyl and hexyl groups; alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group and isopropenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; Aralkyl groups such as benzyl group and phenethyl group; halogen-substituted alkyl groups such as chloroethyl group and 3,3,3-trifluoropropyl group; trimethylsilyloxy group, triethylsilyloxy group, t-butyldimethylsilyloxy group and triphenyl Examples thereof include a silyloxy group. R^TwoIs a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a triorganosilyloxy group having a monovalent hydrocarbon group having 1 to 6 carbon atoms, and specifically, a methyl group Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group and hexyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group and isopropenyl group; phenyl group, tolyl group, xylyl group and the like Aryl group; aralkyl group such as benzyl group and phenethyl group; halogen atom-substituted alkyl group such as chloroethyl group and 3,3,3-trifluoropropyl group; trimethylsilyloxy group, triethylsilyloxy group and t-butyldimethylsilyloxy group And a triphenylsilyloxy group. X is an oxygen atom or a divalent hydrocarbon group having 1 to 6 carbon atoms such as methylene and phenylene. a is 0 or an integer of 1 to 6.
[0011]
The present invention hydrolyzes the Si—H bond-containing organosilicon compound in the presence of a catalyst, whereby an organosilanol in which the Si—H group of the organosilicon compound is hydrolyzed to a Si—OH group is obtained. It is something that can be done.
[0012]
Here, in the present invention, the following general formula (2) is used as the catalyst.
Y_bZ_cSi (OR^Three)_d(OH)_eO_{(4-bcde) / 2}        (2)
And a catalyst obtained by reacting a silicon resin containing a sulfur atom and a nitrogen atom represented by the formula with a palladium compound or a complex compound thereof. In addition, as this silicon resin, there are silica and polysilsesquioxane.
[0013]
In this case, the silicon resin of the formula (2) is obtained by forming (i) a sulfur atom-containing organotrialkoxysilane, (ii) a nitrogen atom-containing organotrialkoxysilane, and (iii) a tetraalkoxysilane into a Si—F bond. Can be obtained by reaction in water or a water-containing organic solvent in the presence of a fluorine-containing silicon compound or a fluorine salt compound having the following formula: (a) a sulfur atom- and nitrogen atom-containing silicon resin, and (iv) a palladium compound or a complex compound thereof. The catalyst of the present invention can be prepared by the reaction of
[0014]
The sulfur-containing organotrialkoxysilane (i) used here is represented by the general formula (4)
YSi (OR^Three)_Three                                        (4)
Indicated by In the above formula, Y is a monovalent group having up to 11 carbon atoms and consisting of carbon, hydrogen and optionally oxygen, which is bonded to silicon via a silicon-carbon bond, wherein Y has at least There is an organic functional group containing one sulfur atom,^ThreeIs a monovalent hydrocarbon group having 1 to 4 carbon atoms. Here, Y is R¹¹-Sx-R¹²It is preferably a thiol or thioether functional group represented by-. Where R¹¹Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or -R¹³-Si (OR¹⁴)_ThreeAnd R is¹³Is a linear or branched alkylene group having 1 to 10 carbon atoms, R¹⁴Is a monovalent hydrocarbon group having 1 to 4 carbon atoms. X represents an integer of 1 to 4. Specific examples include, but are not limited to, the following compounds.
[0015]
HS (CH_Two)_ThreeSi (OCH_Three)_Three
HS (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
HS (CH_Two)₆Si (OCH_Three)_Three
HS (CH_Two)₆Si (OCH_TwoCH_Three)_Three
HS (CH_Two)₈Si (OCH_Three)_Three
HS (CH_Two)₈Si (OCH_TwoCH_Three)_Three
HS (CH_Two)_TenSi (OCH_Three)_Three
HS (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
HSCH_TwoC₆H_Four(CH_Two)_TwoSi (OCH_Three)_Three
HSCH_TwoC₆H_Four(CH_Two)_TwoSi (OCH_TwoCH_Three)_Three
CH_ThreeS (CH_Two)_ThreeSi (OCH_Three)_Three
CH_ThreeS (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
CH_ThreeCH_TwoS (CH_Two)_ThreeSi (OCH_Three)_Three
CH_ThreeCH_TwoS (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
CH_ThreeCH_TwoCH_TwoS (CH_Two)_ThreeSi (OCH_Three)_Three
CH_ThreeCH_TwoCH_TwoS (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
CH_Two= CHCH_TwoS (CH_Two)_ThreeSi (OCH_Three)_Three
CH_Two= CHCH_TwoS (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
C₆H_FiveCH_TwoS (CH_Two)_ThreeSi (OCH_Three)_Three
C₆H_FiveCH_TwoS (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
S ((CH_Two)_ThreeSi (OCH_Three)_Three)_Two
S ((CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three)_Two
S_Four((CH_Two)_ThreeSi (OCH_Three)_Three)_Two
S_Four((CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three)_Two
S_Four((CH_TwoC₆H_FourCH_TwoCH_Two) Si (OCH_Three)_Three)_Two
S_Four((CH_TwoC₆H_FourCH_TwoCH_Two) Si (OCH_TwoCH_Three)_Three)_Two
The nitrogen-containing organotrialkoxysilane (ii) used herein is represented by the general formula (5)
ZSi (OR^Three)_Three                                        (5)
Indicated by In the above formula, Z is a monovalent group having up to 11 carbon atoms and consisting of carbon, hydrogen and optionally oxygen, bonded to silicon via a silicon-carbon bond, Organic functional groups containing nitrogen atoms, R^ThreeIs the same as above. Here, as Z, R¹⁵R¹⁶NR¹³An amino functional group represented by-or NC-R¹³It is preferably a cyano functional group represented by-. Where R¹⁵And R¹⁶Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms,¹⁵R¹⁶NR¹⁷-Group or -R¹³-Si (OR¹⁴)_ThreeGroup. Note that R¹³And R¹⁴Has the same meaning as described above. Specifically, the following compounds are exemplified, but not limited thereto.
[0016]
H_TwoN (CH_Two)_ThreeSi (OCH_Three)_Three
H_TwoN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
H_TwoN (CH_Two)₆Si (OCH_Three)_Three
H_TwoN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
H_TwoN (CH_Two)₈Si (OCH_Three)_Three
H_TwoN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
H_TwoN (CH_Two)_TenSi (OCH_Three)_Three
H_TwoN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_Three) HN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_Three) HN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_Three) HN (CH_Two)₆Si (OCH_Three)_Three
(CH_Three) HN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_Three) HN (CH_Two)₈Si (OCH_Three)_Three
(CH_Three) HN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_Three) HN (CH_Two)_TenSi (OCH_Three)_Three
(CH_Three) HN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)₆Si (OCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)₈Si (OCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)_TenSi (OCH_Three)_Three
(CH_ThreeCH_Two) HN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)₆Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)₈Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)_TenSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two) HN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)₆Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)₈Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)_TenSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two) HN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(C₆H_Five) HN (CH_Two)_ThreeSi (OCH_Three)_Three
(C₆H_Five) HN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(C₆H_Five) HN (CH_Two)₆Si (OCH_Three)_Three
(C₆H_Five) HN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(C₆H_Five) HN (CH_Two)₈Si (OCH_Three)_Three
(C₆H_Five) HN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(C₆H_Five) HN (CH_Two)_TenSi (OCH_Three)_Three
(C₆H_Five) HN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)_ThreeSi (OCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)₆Si (OCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)₈Si (OCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)_TenSi (OCH_Three)_Three
(C₆H_FiveCH_Two) HN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_Three)_TwoN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_Three)_TwoN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_Three)_TwoN (CH_Two)₆Si (OCH_Three)_Three
(CH_Three)_TwoN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_Three)_TwoN (CH_Two)₈Si (OCH_Three)_Three
(CH_Three)_TwoN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_Three)_TwoN (CH_Two)_TenSi (OCH_Three)_Three
(CH_Three)_TwoN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)₆Si (OCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)₈Si (OCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)_TenSi (OCH_Three)_Three
(CH_ThreeCH_Two)_TwoN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)₆Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)₈Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)_TenSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_Two)_TwoN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)₆Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)₈Si (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)_TenSi (OCH_Three)_Three
(CH_ThreeCH_TwoCH_TwoCH_Two)_TwoN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)_ThreeSi (OCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)₆Si (OCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)₆Si (OCH_TwoCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)₈Si (OCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)₈Si (OCH_TwoCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)_TenSi (OCH_Three)_Three
(C₆H_Five)_TwoN (CH_Two)_TenSi (OCH_TwoCH_Three)_Three
H_TwoN (CH_Two)_TwoNH (CH_Two)_ThreeSi (OCH_Three)_Three
H_TwoN (CH_Two)_TwoNH (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
H_TwoN (CH_Two)₆NH (CH_Two)_ThreeSi (OCH_Three)_Three
H_TwoN (CH_Two)₆NH (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
H_TwoN (CH_Two)_TwoNHCH_TwoC₆H_Four(CH_Two)_TwoSi (OCH_Three)_Three
H_TwoN (CH_Two)_TwoNHCH_TwoC₆H_Four(CH_Two)_TwoSi (OCH_TwoCH_Three)_Three
H_TwoN (CH_Two)_TwoNH (CH_Two)_TwoNH (CH_Two)_ThreeSi (OCH_Three)_Three
H_TwoN (CH_Two)_TwoNH (CH_Two)_TwoNH (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeO)_ThreeSi (CH_Two)_ThreeNH (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_TwoO)_ThreeSi (CH_Two)_ThreeNH (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
(CH_ThreeO)_ThreeSi (CH_Two)_ThreeNH (CH_Two)_TwoNH (CH_Two)_ThreeSi (OCH_Three)_Three
(CH_ThreeCH_TwoO)_ThreeSi (CH_Two)_ThreeNH (CH_Two)_TwoNH (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three
NC (CH_Two)_TwoSi (OCH_Three)_Three
NC (CH_Two)_TwoSi (OCH_TwoCH_Three)_Three
NC (CH_Two)_FiveSi (OCH_Three)_Three
NC (CH_Two)_FiveSi (OCH_TwoCH_Three)_Three
NC (CH_Two)₇Si (OCH_Three)_Three
NC (CH_Two)₇Si (OCH_TwoCH_Three)_Three
NC (CH_Two)₉Si (OCH_Three)_Three
NC (CH_Two)₉Si (OCH_TwoCH_Three)_Three
The tetraalkoxysilane (iii) used here is represented by the general formula (6)
Si (OR^Three)_Four                                          (6)
Indicated by In the above formula, R^ThreeIs the same as above. Specifically, the following compounds are exemplified, but not limited thereto.
[0017]
Si (OCH_Three)_Four, Si (OC_TwoH_Five)_Four, Si (OC_ThreeH₇)_Four,
Si (OC_FourH₉)_Four, Si [OC (= CH_Two) CH_Three]_Four
The mixing ratio between the above-mentioned organotrialkoxysilane containing a sulfur atom and the organotrialkoxysilane containing a nitrogen atom and tetraalkoxysilane is set so that the target product is solid. Specifically, the molar ratio of the sulfur-containing organotrialkoxysilane and the nitrogen-containing organotrialkoxysilane to the tetraalkoxysilane is preferably in the range of 0.01 to 3, and particularly preferably in the range of 0.1 to 2. If the molar ratio is more than 3, the properties of the target substance may become liquid or oily, which is not preferable. On the other hand, if the molar ratio is less than 0.01, the ability of immobilizing the palladium component by sulfur and nitrogen atoms is not exhibited, which is not preferable.
[0018]
The mixing ratio between the sulfur-containing organotrialkoxysilane and the nitrogen-containing organotrialkoxysilane is in the range of 1.5 to 5, particularly preferably in the range of 2 to 4 by the molar ratio of sulfur atom / nitrogen atom. Is preferred. If the ratio is less than 1.5, the catalyst reacts with a palladium compound or a complex compound thereof to form a catalyst, and if used in a hydrolysis reaction, the palladium component may fall off and contaminate the reaction system. If is more than 5, the palladium compound or its complex compound charged for preparing the catalyst may not be able to be immobilized.
[0019]
The mixture of the above alkoxysilanes is reacted with water or a water-containing organic solvent in the presence of a fluorine-containing silicon compound or fluorine salt compound having at least one Si-F bond in the molecule. As the fluorine-containing silicon compound used here, FSi (OCH_Three)_Three, FSi (OCH_Two-CH_Three)_Three, (NH_Four)_TwoSiF₆And the like. Examples of the fluorine salt compound include NaF, KF, (CH_ThreeCH_TwoCH_TwoCH_Two)_FourNF is exemplified.
[0020]
The amount of the fluorine-containing silicon compound or fluorine salt compound having a Si-F bond to be used is 1 mol per mole of the total Si / F of the sulfur-containing organotrialkoxysilane, the nitrogen-containing organotrialkoxysilane, and the tetraalkoxysilane. 0.0: 0.0001 to 1.0: 2.0.
[0021]
By reacting a mixture of these alkoxysilanes with water or a water-containing organic solvent in the presence of the above-mentioned fluorine-containing silicon compound or fluorine salt compound, the compound represented by the general formula (2)
Y_bZ_cSi (OR^Three)_d(OH)_eO_{(4-bcde) / 2}        (2)
Can be obtained. Where Y, Z, and R^ThreeIs the same as above, and b, c, d and e are 0 <b <1, 0 <c <0.5, c <b, 0 <b + c <1, 0 ≦ d <0.1, 0 < It is a positive number that satisfies e <1, 0 <b + c + d + e <2.
[0022]
Next, the preparation of a catalyst by the reaction of the above-described silicon resin containing a sulfur atom and a nitrogen atom with a palladium compound or its complex compound (iv) will be described. First, the palladium compound or its complex compound (iv) is represented by the general formula (3)
PdL_f                                                  (3)
Indicated by In the above formula, L represents at least one ligand which can be substituted by an amino group or a mercapto group, and f is a number satisfying the free value of Pd. Specifically, the following compounds are exemplified, but not limited thereto.
[0023]
PdCl_Two, PdBr_Two, Pd (CN)_Two, Pd (NO_Three)_Two,
Pd [OC (= O) CH_Three]_Two, Pd (C₆H_FiveCN)_Two,
Pd [CH_ThreeC (= O) CH = C (-O) CH_Three]_Two,
Pd (H_TwoNCH_TwoCH_TwoNH_Two) Cl_Two,
Pd_Two[C₆H_FiveCH = CHC (= O) CH = CHC₆H_Five]_Three,
The reaction of the silicon resin containing a sulfur atom and a nitrogen atom with the above-mentioned palladium compound or its complex compound can be carried out usually at a temperature in the range of ambient temperature to about 100 ° C. Preferably, it is in the range of 60 to 70 ° C. In addition, this reaction can be performed without a solvent, but is preferably performed in the presence of a suitable solvent. Among them, polar solvents such as tetrahydrofuran, diethyl ether, acetone, ethyl acetate, dimethylsulfoxide, dimethylformamide, methanol, ethanol, isopropanol and / or water are preferable.
[0024]
The mixing ratio of the silicon resin containing a sulfur atom and a nitrogen atom to the above palladium compound or a complex compound thereof is determined by the molar ratio of the sulfur atom and the nitrogen atom in the silicon resin containing a sulfur atom and a nitrogen atom to the palladium atom in the palladium compound or the complex compound. The ratio is preferably in the range of 2 to 200, more preferably 3 to 100. If the molar ratio is less than 2, the palladium compound or all of its complex compounds may not be able to be immobilized. If the molar ratio exceeds 200, the palladium component is immobilized, but the catalytic activity of the palladium component is extremely high. In some cases.
[0025]
After reacting the silicon resin containing a sulfur atom and a nitrogen atom with the above-mentioned palladium compound or its complex compound, the product may be reduced with a reducing agent such as sodium borohydride.
[0026]
After reacting the silicon resin containing a sulfur atom and a nitrogen atom with the above-mentioned palladium compound or its complex compound, the resulting solid is filtered, washed with alcohol and water, and then dried to obtain the Si—H bond of the present invention. A catalyst for a hydrolysis reaction of the contained organosilicon compound can be obtained.
[0027]
Next, a method for producing silanols by a hydrolysis reaction of a Si—H bond-containing organosilicon compound using the above catalyst of the present invention will be described. In this hydrolysis reaction, the organosilicon compound having a Si—H bond of the above formula (1) is reacted with a stoichiometric amount or more of water in the presence of the above catalyst. Further, this reaction can be carried out usually at a temperature in the range from the ambient temperature to about 100 ° C. Preferably, it is in the range of 40 to 70 ° C. This reaction can be carried out without a catalyst, but is preferably carried out in the presence of a suitable solvent. Of these, aprotic polar solvents such as tetrahydrofuran, diethyl ether, acetone, ethyl acetate, dimethylsulfoxide, and dimethylformamide are preferred. Further, since this catalyst is a solid, the above reaction can be performed in a batch system or a continuous system. When the reaction is performed in a batch system, after the reaction is completed, the catalyst is separated by a separation operation such as filtration, and the catalyst can be directly recycled to the next reaction. When the reaction is carried out in a continuous system, the reaction can be carried out by passing a mixture of an Si—H bond-containing organosilicon compound, water and a solvent over or through the catalyst bed. The amount of the catalyst used is not particularly limited, but is preferably 0.1 to 2000 ppm as palladium.
After the hydrolysis, the catalyst can be filtered off according to a conventional method, and the desired organosilanol can be isolated by distillation under reduced pressure. In this case, in the present invention, the desired organosilanol can be obtained in high yield without condensing silanol during the vacuum distillation. Further, the catalyst separated by filtration can be used repeatedly.
[0028]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
[0029]
[Example 1]
[Preparation of Silicon Resin Containing Sulfur Atom and Nitrogen Atom] In a four-necked flask equipped with a stirrer, 1.16 g (0.02 mol) of potassium fluoride and 1600.0 g (88.8 mol) of water were charged. A mixture of 131.3 g (0.67 mol) of mercaptopropyltrimethoxysilane, 84.2 g (0.33 mol) of γ-phenylaminopropyltrimethoxysilane, and 152.0 g (1.00 mol) of tetramethoxysilane was stirred. The solution was dropped for 3 minutes. After stirring at room temperature for 2 minutes, the reaction system became a white gel. After stirring at room temperature for 1 hour, the generated solid was separated by filtration and washed with distilled water and then with acetone. Next, the resultant was dried under reduced pressure, and after removing the solvent, 202.4 g of a silicon resin containing a mercaptopropyl group and a γ-phenylaminopropyl group was obtained at a yield of 98%. The sulfur content and the nitrogen content in the mercaptopropyl group- and γ-phenylaminopropyl group-containing silicon resin were 10.1 wt% and 2.2 wt%, respectively.
[0030]
[Preparation of palladium-containing catalyst] In a four-necked flask equipped with a stirrer, 3.78 g of the above silicon resin, 30.0 g of ethanol, and 0.3 g of palladium chloride were charged and stirred at 60 ° C for 6 hours. Thereafter, 0.08 g of sodium borohydride was added, and the mixture was further stirred at 60 ° C. for 1 hour, and the generated solid was separated by filtration and washed with acetone and subsequently with distilled water. Next, the resultant was dried under reduced pressure, and the solvent was removed, thereby obtaining 3.50 g of a brown solid catalyst. The calculated value and the measured value of the amount of palladium in this catalyst were both 4.6 wt%, and the palladium was fixed quantitatively.
[0031]
[Silanol synthesis reaction using the above catalyst] In a four-necked flask equipped with a stirrer, 4.3 g of the catalyst prepared as described above, 81.6 g (4.53 mol) of water, and 1002.7 g of methyl ethyl ketone were charged. At 60 ° C., 501.2 g (1.78 mol) of 1,1,1,3,5,7,7,7-octamethyltetrasiloxane was added dropwise with stirring over 4.5 hours. Hydrogen gas generation was observed with the dropwise addition. After stirring at 60 ° C. for 6 hours, the reaction mixture was analyzed by gas chromatography / mass spectrometry (hereinafter abbreviated as GC-MS), and the raw materials 1,1,1,3,5,7,7 were analyzed. , 7-Octamethyltetrasiloxane is completely consumed, and 87.4% of 1,1,1,3,5,7,7,7-octamethyltetrasiloxane-3,5-diol as a target product is produced. Was. The catalyst was filtered off from the reaction mixture, and the filtrate was concentrated under reduced pressure. When the concentrate was distilled under reduced pressure, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane-3,5-diol was obtained as a colorless transparent oil fraction at 96 to 98 ° C./35 mmTorr. Was. The isolation yield of 1,1,1,3,5,7,7,7,7-octamethyltetrasiloxane-3,5-diol was 76.2%, and the purity was 98.5%.
[0032]
[Example 2]
Same as [Preparation of sulfur atom- and nitrogen atom-containing silicon resin] in Example 1 except that 63.7 g (0.33 mol) of γ-methylaminopropyltrimethoxysilane was used instead of γ-phenylaminopropyltrimethoxysilane. As a result, 183.0 g of a silicon resin containing a mercaptopropyl group and a γ-methylaminopropyl group was obtained at a yield of 98%. The sulfur content and the nitrogen content in the mercaptopropyl group and γ-methylaminopropyl group-containing silicon resin were 11.0 wt% and 2.4 wt%, respectively.
[0033]
In a four-necked flask equipped with a stirrer, 4.03 g of the above silicon resin, 30.8 g of ethanol, and 0.30 g of palladium chloride were charged and stirred at 60 ° C. for 6 hours. Thereafter, 0.09 g of sodium borohydride was added, and the mixture was further stirred at 60 ° C. for 1 hour. Then, the generated solid was separated by filtration and washed with acetone and subsequently with distilled water. After drying under reduced pressure to remove the solvent, 3.58 g of a brown solid catalyst was obtained. The calculated value and the measured value of the amount of palladium in this catalyst were both 4.3 wt%, and the palladium was fixed quantitatively.
[0034]
In a four-necked flask equipped with a stirrer, 0.3 g of the catalyst prepared as described above, 2.3 g (0.13 mol) of water, and 30.3 g of methyl ethyl ketone were charged. 6.7 g (0.05 mol) of 3-tetramethyldisiloxane was added dropwise with stirring for 1 hour. Hydrogen gas generation was observed with the dropwise addition. After stirring at 60 ° C. for 3 hours, the reaction mixture was analyzed by GC-MS. As a result, the raw material 1,1,3,3-tetramethyldisiloxane was completely consumed, and the target product 1,1,1 85.4% of 3,3-tetramethyldisiloxane-1,3-diol was produced. After filtering off the catalyst from the reaction mixture, the amount of palladium in the filtrate was measured and found to be 0.1 ppm or less. The filtered catalyst was recycled, and the same reaction was carried out 5 times on the same scale. However, the yield of 1,1,3,3-tetramethyldisiloxane-1,3-diol was not changed, and the catalytic activity was not changed. No decrease was seen.
[0035]
[Example 3]
A 4-neck flask equipped with a stirrer was charged with 0.4 g of the palladium-containing silicon resin prepared in Example 1, 2.4 g (0.13 mol) of water, and 35.3 g of methyl ethyl ketone. 9.7 g (0.05 mol) of (dimethylsilyl) benzene was added dropwise with stirring for 1 hour. Hydrogen gas generation was observed with the dropwise addition. After stirring at 60 ° C. for 4 hours, the reaction mixture was analyzed by GC-MS. As a result, 1,4-bis (dimethylsilyl) benzene as the raw material was completely consumed, and the target product, 1,4-bis ( Dimethylhydroxysilyl) benzene was produced at 92.6%. After filtering off the catalyst from the reaction mixture, the amount of palladium in the filtrate was measured and found to be 0.1 ppm or less. The filtered catalyst was recycled, and the same reaction was carried out six times on the same scale. However, the yield of 1,4-bis (dimethylhydroxysilyl) benzene did not change, and no reduction in the catalytic activity was observed.
[0036]
[Comparative Example 1]
In a four-necked flask equipped with a stirrer, 3.3 g of 5% palladium-carbon previously washed with water, 81.2 g (4.51 mol) of water, and 994.0 g of methyl ethyl ketone were charged. 50,0 g (1.77 mol) of 3,5,7,7,7-octamethyltetrasiloxane was added dropwise over 4.5 hours while stirring. Hydrogen gas generation was observed with the dropwise addition. After stirring at 60 ° C. for 6 hours, the reaction mixture was analyzed by GC-MS. As a result, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane as a raw material was completely consumed. The product, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane-3,5-diol, was produced at 76.7%. The catalyst was filtered off from the reaction mixture, and the filtrate was concentrated under reduced pressure. When the concentrate was distilled under reduced pressure, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane-3,5-diol was obtained as a colorless transparent oil fraction at 96 to 98 ° C./35 mmTorr. Was. The isolated yield of 1,1,1,3,5,7,7,7,7-octamethyltetrasiloxane-3,5-diol was 27.2%, and the purity was 98.2%. When the residue was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC), it was found that only the high molecular weight product having an average molecular weight Mw of 2400 and a dispersity Mw / Mn of 1.22 was found.
[0037]
[Comparative Example 2]
In a four-necked flask equipped with a stirrer, 0.1 g of 5% palladium-carbon previously washed with water, 2.3 g (0.13 mol) of water, and 30.6 g of methyl ethyl ketone were charged. 6.7 g (0.05 mol) of 3-tetramethyldisiloxane was added dropwise with stirring for 1 hour. Hydrogen gas generation was observed with the dropwise addition. After stirring at 60 ° C. for 3 hours, the reaction mixture was analyzed by GC-MS. As a result, the raw material 1,1,3,3-tetramethyldisiloxane was completely consumed, and the target product 1,1,1 3,3-Tetramethyldisiloxane-1,3-diol was produced at 80.4%. The filtrate after filtering off the catalyst from the reaction mixture was colored light brown, and the amount of palladium in the filtrate was measured to be 16.1 ppm.
[0038]
【The invention's effect】
The method for producing an organosilanol of the present invention comprises hydrolyzing an organosilicon compound having a Si-H bond by using a catalyst comprising a specific palladium compound or a complex compound thereof chemically bonded to the specific solid support described above. By doing so, the corresponding organosilanol can be produced with high yield and high purity without contaminating the reaction system with the catalyst component.

Claims (3)

The following general formula (1)

(Wherein, R ¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or a triorganosilyloxy group having a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom and a carbon number, respectively) Represents a monoorganic hydrocarbon group having 1 to 10 monovalent hydrocarbon groups or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X represents an oxygen atom or a divalent hydrocarbon group having 1 to 6 carbon atoms, a is an integer of 0 to 6.)
An organosilicon compound having a Si—H bond represented by the following general formula (2)
^{_{Y b Z c Si (OR 3}} ) d (OH) e O (4-bcde) / 2 (2)
Wherein Y represents a sulfur atom-containing monovalent organic functional group having up to 11 carbon atoms and containing at least one sulfur atom, which is attached to the silicon atom via a silicon-carbon bond. , Z represents a nitrogen-containing monovalent organic functional group having up to 11 carbon atoms and containing at least one nitrogen atom, which is attached to the silicon atom via a silicon-carbon bond; ³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, and b, c, d, and e are 0 <b <1, 0 <c <0.5, c <b, 0 <b + c <1, 0 It is a positive number satisfying ≦ d <0.1, 0 <e <1, 0 <b + c + d + e <2.)
And a silicon resin containing a sulfur atom and a nitrogen atom represented by the following general formula (3)
PdL _f (3)
(In the formula, L represents a ligand that can be substituted with an amino group or a mercapto group, and f is a number that satisfies the free value of Pd.)
Method for producing organo silanols, characterized in that is hydrolyzed in the presence of O Ri resulting catalyst for the reaction of the in the palladium compound or a complex compound represented. The silicon resin containing a sulfur atom and a nitrogen atom is represented by the following general formula (4)
YSi (OR ³ ) ₃ (4)
(In the formula, Y and R ³ have the same meaning as described above.)
And a sulfur atom-containing organotrialkoxysilane represented by the following general formula (5)
Z Si (OR ³ ) ₃ (5)
(In the formula, Z and R ³ have the same meanings as described above.)
And a nitrogen-containing organotrialkoxysilane represented by the following general formula (6):
Si (OR ³ ) ₄ (6)
(Wherein, R ³ has the same meaning as described above.)
The method according to claim 1, which is obtained by reacting a tetraalkoxysilane represented by the formula (1) with water or a water-containing organic solvent in the presence of a fluorine-containing silicon compound or a fluorine salt compound having a Si-F bond. . 3. The method according to claim 1, wherein the molar ratio of the nitrogen atom and the sulfur atom to the palladium atom in the catalyst is 2 to 200.