JP3700250B2 - Polyoxyalkylene triglyceryl ether compound, modified silicone compound, and production method thereof - Google Patents

Description

（ただし、式中、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴は水素原子、炭素数２〜２４のアシル基又は炭素数３〜１０の１−アルコキシアルキル基若しくは酸素に隣接する炭素がポリオキシアルキレン鎖に結合する環状エーテル基で、それらはたがいに同一でも異なっていてもよい。）
で表されるポリオキシアルキレントリグリセリルエーテル化合物、
（２）一般式［１］におけるＡ²Ｏが炭素数２〜４のオキシアルキレン基であり、かつその付加モル数ａ，ｂ，ｃ及びｄが１〜５０であるポリオキシアルキレントリグリセリルエーテル化合物、
（３）一般式［１］におけるＲ¹，Ｒ²，Ｒ³及びＲ⁴が水素原子であるポリオキシアルキレントリグリセリルエーテル化合物、
（４）一般式［１］におけるＺが、ＣＨ₂＝ＣＨＣＨ₂−、ＣＨ₂＝Ｃ(ＣＨ₃)ＣＨ₂−、ＣＨ₂＝ＣＨＣ(ＣＨ₃)₂−、ＣＨ₂＝Ｃ(ＣＨ₃)Ｃ(ＣＨ₃)₂−、ＣＨ₂＝ＣＨＣ(ＣＨ₃)₂ＣＨ₂−及びＣＨ₂＝Ｃ(ＣＨ₃)Ｃ(ＣＨ₃)₂ＣＨ₂−から選ばれた基であるポリオキシアルキレントリグリセリルエーテル化合物、
（５）式［２］
【化２７】

で表されるトリグリセリンに、一般式［３］
ＲＣＯＲ' …［３］
（ただし、式中、Ｒ及びＲ'はアルキル基で、それらはたがいに同一でも異なっていてもよい。）
で表されるケトン化合物を反応させて、一般式［４］
【化２８】

（ただし、式中、Ｒ及びＲ'はアルキル基で、それらはたがいに同一でも異なっていてもよい。）
で表される化合物を得、所望により１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加して、一般式［５］
【化２９】

（ただし、式中、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の付加モル数で０〜１００であり、Ｒ及びＲ'はアルキル基で、それらはたがいに同一でも異なっていてもよい。）
で表される化合物を得、一般式［６］
Ｚ−Ｘ …［６］
（ただし、式中、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ｘはハロゲン原子である。）
で表されるアルケニルハライドを反応し、一般式［７］
【化３０】

（ただし、式中、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の付加モル数で０〜１００であり、Ｒ及びＲ'はアルキル基で、それらはたがいに同一でも異なっていてもよい。）
で表される化合物を得、次いで酸を作用させて一般式［８］
【化３１】

（ただし、式中、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の付加モル数で０〜１００である。）
で表される化合物を得、さらに１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加させたのち、所望により末端水酸基をエステル化又はアセタール化することを特徴とする一般式［１］
【化３２】

（ただし、式中、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴は水素原子、炭素数２〜２４のアシル基又は炭素数３〜１０の１−アルコキシアルキル基若しくは酸素に隣接する炭素がポリオキシアルキレン鎖に結合する環状エーテル基で、それらはたがいに同一でも異なっていてもよい。）
で表されるポリオキシアルキレントリグリセリルエーテル化合物の製造方法、
（６）一般式［３］で表されるケトン化合物が、アセトン又はメチルエチルケトンであるポリオキシアルキレントリグリセリルエーテル化合物の製造方法、
（７）一般式［９］
【化３３】

［（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁶，Ｒ⁷及びＲ⁸のうち少なくとも１つは下記一般式［１０］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
【化３４】

（ただし、式中、Ｙは炭素数３〜１０の炭化水素基であり、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００である。）］
で表される変性シリコーン化合物、
（８）一般式［１１］
【化３５】

（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素原子で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
で表されるシリコーン化合物と、一般式［１２］
【化３６】

（ただし、式中、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基である。）
で表されるポリオキシアルキレントリグリセリルエーテル化合物とを反応することを特徴とする一般式［９］
【化３７】

［（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁶，Ｒ⁷及びＲ⁸のうち少なくとも１つは下記一般式［１０］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
【化３８】

（ただし、式中、Ｙは炭素数３〜１０の炭化水素基であり、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００である。）］
で表される変性シリコーン化合物の製造方法、
（９）一般式［１１］
【化３９】

（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素原子で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
で表されるシリコーン化合物と、一般式［１３］
【化４０】

（ただし、式中、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ｒ¹²，Ｒ¹³，Ｒ¹⁴及びＲ¹⁵は、炭素数２〜２４のアシル基又は炭素数３〜１０の１−アルコキシアルキル基若しくは酸素に隣接する炭素がポリオキシアルキレン鎖に結合する環状エーテル基で、それらはたがいに同一でも異なっていてもよい。）
で表されるポリオキシアルキレントリグリセリルエーテル化合物とを反応したのち、Ｒ¹²，Ｒ¹³，Ｒ¹⁴及びＲ¹⁵を脱離して水素原子とすることを特徴とする一般式［９］
【化４１】

［（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁶，Ｒ⁷及びＲ⁸のうち少なくとも１つは下記一般式［１０］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
【化４２】

（ただし、式中、Ｙは炭素数３〜１０の炭化水素基であり、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００である。）］
で表される変性シリコーン化合物の製造方法、
（１０）一般式［１１］
【化４３】

（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素原子で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
で表されるシリコーン化合物と、一般式［８］
【化４４】

（ただし、式中、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の付加モル数で０〜１００である。）
で表される化合物とを反応させて得られるシリコーン化合物に、１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加させることを特徴とする一般式［９］
【化４５】

［（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁶，Ｒ⁷及びＲ⁸のうち少なくとも１つは下記一般式［１０］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
【化４６】

（ただし、式中、Ｙは炭素数３〜１０の炭化水素基であり、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００である。）］
で表される変性シリコーン化合物の製造方法、及び、
（１１）一般式［１１］
【化４７】

（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
で表されるシリコーン化合物と、一般式［７］
【化４８】

（ただし、式中、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の付加モル数で０〜１００であり、Ｒ及びＲ'はアルキル基で、それらはたがいに同一でも異なっていてもよい。）
で表される化合物とを反応させたのち、アセタール基を加水分解することにより得られるシリコーン化合物に、１種又は２種以上の炭素数２〜８のアルキレンオキサイドを付加することを特徴とする一般式［９］
【化４９】

［（ただし、式中、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁶，Ｒ⁷及びＲ⁸のうち少なくとも１つは下記一般式［１０］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。）
【化５０】

（ただし、式中、Ｙは炭素数３〜１０の炭化水素基であり、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００である。）］
で表される変性シリコーン化合物の製造方法、
を提供するものである。
【０００６】
【発明の実施の形態】
本発明のポリオキシアルキレントリグリセリルエーテル化合物は、一般式［１］
【化５１】

で表される構造を有するものである。
一般式［１］において、Ａ¹Ｏ及びＡ²Ｏは、炭素数２〜８のオキシアルキレン基であり、このオキシアルキレン基におけるアルキレン基は直鎖状であってもよいし、分岐を有するものであってもよく、また、分岐に芳香環を有するものであってもよい。このようなオキシアルキレン基を導入するのに用いられる原料としては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、オキセタン、テトラヒドロフラン、スチレンオキシドなどを挙げることができるが、これらの中で、入手の容易さの点から炭素数２〜４のエチレンオキシド、プロピレンオキシド、ブチレンオキシド及びテトラヒドロフランを好適に使用することができる。
【０００７】
一般式［１］で表される化合物において、オキシアルキレン基は１種のみであってもよく、２種以上であってもよく、オキシアルキレン基が２種以上である場合、その付加の状態は、ブロック状、ランダム状のいずれであってもよい。また、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００である。オキシアルキレン基Ａ¹Ｏ及びＡ²Ｏの付加モル数は平均値を表し、例えば、Ａ¹Ｏの付加しない一般式［１］で表される化合物とＡ¹Ｏが１モル付加した一般式［１］で表される化合物の等モル混合物はｎの値が０.５となる。オキシアルキレン基Ａ¹Ｏ又はＡ²Ｏの付加モル数が１００を超えると、一般式［１］で表される化合物の粘度が高くなりすぎて製造及び取り扱いが困難になるおそれがある。製造及び取り扱いの容易さ、親水性親油性バランスなどから、Ａ¹Ｏの付加モル数は０〜５０であることが好ましく、Ａ²Ｏの付加モル数は１〜５０であることが好ましい。
【０００８】
一般式［１］において、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、例えば、ＣＨ₂＝ＣＨＣＨ₂−、ＣＨ₂＝Ｃ(ＣＨ₃)ＣＨ₂−、ＣＨ₂＝ＣＨＣ(ＣＨ₃)₂−、ＣＨ₂＝Ｃ(ＣＨ₃)Ｃ(ＣＨ₃)₂−、ＣＨ₂＝ＣＨＣ(ＣＨ₃)₂ＣＨ₂−、ＣＨ₂＝Ｃ(ＣＨ₃)Ｃ(ＣＨ₃)₂ＣＨ₂−などを挙げることができる。これらの中で、特にアリル基（ＣＨ₂＝ＣＨＣＨ₂−）及びメタリル基（ＣＨ₂＝Ｃ(ＣＨ₃)ＣＨ₂−）が好適である。一般式［１］において、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴は、水素原子、炭素数２〜２４のアシル基又は炭素数３〜１０の１−アルコキシアルキル基若しくは酸素に隣接する炭素がポリオキシアルキレン鎖に結合する環状エーテル基である。
【０００９】
炭素数２〜２４のアシル基は、脂肪族飽和アシル基、脂肪族不飽和アシル基、芳香族アシル基のいずれでもよく、脂肪族飽和アシル基としては、例えば、アセチル基、プロピオニル基、ブチリル基、バレリル基、オクタノイル基、デカノイル基、ラウロイル基、ミリストイル基、パルミトイル基、ステアロイル基などを、脂肪族不飽和アシル基としては、例えば、アクリロイル基、メタクリロイル基、クロトノイル基、オレオイル基などを、芳香族アシル基としては、例えば、ベンゾイル基、トルオイル基、フェニルアセチル基、シンナモイル基、ナフトイル基などを挙げることができる。
炭素数３〜１０の１−アルコキシアルキル基としては、例えば、１−メトキシエチル基、１−エトキシエチル基、１−プロポキシエチル基、１−ブトキシエチル基などを挙げることができる。また、酸素に隣接する炭素がポリオキシアルキレン鎖に結合する環状エーテル基としては、例えば、２−テトラヒドロフリル基、２−テトラヒドロピリル基などを挙げることができる。
【００１０】
本発明方法による一般式［１］で表されるポリオキシアルキレントリグリセリルエーテル化合物の製造について説明する。
まず、式［２］
【化５２】

で表されるトリグリセリンに、一般式［３］
ＲＣＯＲ' …［３］
で表されるケトン化合物を反応する。ただし、一般式［３］において、Ｒ及びＲ'はアルキル基であり、それらはたがいに同一でも異なっていてもよい。式［２］で表されるトリグリセリンに、一般式［３］で表されるケトン化合物を反応することにより、トリグリセリン両端の隣接する２個の水酸基を保護してなる、一般式［４］
【化５３】

で表されるジアセタール化合物を得る。
【００１１】
一般式［３］で表されるケトン化合物としては、例えば、アセトン、メチルエチルケトン、ジエチルケトン、メチルプロピルケトン、メチルイソプロピルケトン、メチルブチルケトン、メチルイソブチルケトン、ピナコロン、ジイソプロピルケトンなどを挙げることができるが、これらの中で、反応の容易さ及び後の工程での脱離の容易さなどの点から、アセトン及びメチルエチルケトンが好ましく、特にアセトンを好適に使用することができる。アセトンを用いた場合には、一般式［４］で表されるジアセタール化合物として、ジイソプロピリデントリグリセリンが得られる。ジイソプロピリデントリグリセリンは、工業薬品として市場より入手することも可能であり、市販のジイソプロピリデントリグリセリンを本発明のポリオキシアルキレントリグリセリルエーテル化合物の出発原料とすることができる。
【００１２】
次いで、一般式［４］で表されるジアセタール化合物に、所望により、１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加して、一般式［５］
【化５４】

で表される化合物を得る。一般式［５］において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の付加モル数で０〜１００であり、Ｒ及びＲ'はアルキル基で同一でも異なっていてもよい。アルキレンオキシドの付加反応は、通常アルカリ触媒を用い、６０〜２００℃、好ましくは８０〜１５０℃で行う。アルカリ触媒としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、ナトリウムエトキシド、金属ナトリウムなどを挙げることができるが、入手の容易さの点から、水酸化ナトリウム及び水酸化カリウム、ナトリウムメトキシドを好適に使用することができる。この反応に用いるアルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチレンオキシドなどを挙げることができるが、これらの中で、入手の容易さの点からエチレンオキシド、プロピレンオキシド及びブチレンオキシドを好適に使用することができる。
【００１３】
このようにして得られた一般式［５］で表される化合物に、一般式［６］
Ｚ−Ｘ …［６］
で表されるアルケニルハライドを反応させる。一般式［６］において、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ｘはハロゲン原子である。このようなアルケニルハライドとしては、例えば、ＣＨ₂＝ＣＨＣＨ₂Ｘ、ＣＨ₂＝Ｃ(ＣＨ₃)ＣＨ₂Ｘ、ＣＨ₂＝ＣＨＣ(ＣＨ₃)₂Ｘ、ＣＨ₂＝Ｃ(ＣＨ₃)Ｃ(ＣＨ₃)₂Ｘ、ＣＨ₂＝ＣＨＣ(ＣＨ₃)₂ＣＨ₂Ｘ、ＣＨ₂＝Ｃ(ＣＨ₃)Ｃ(ＣＨ₃)₂ＣＨ₂Ｘなどを挙げることができるが、これらの中でハロゲン化アリル（ＣＨ₂＝ＣＨＣＨ₂Ｘ）及びハロゲン化メタリル（ＣＨ₂＝Ｃ(ＣＨ₃)ＣＨ₂Ｘ）を特に好適に用いることができる。また、Ｘで示されるハロゲンとしては、例えば、塩素、臭素、ヨウ素を挙げることができ、これらの中で塩素が特に好適である。この反応は、通常、脱ハロゲン化水素剤の存在下、５０〜１５０℃、好ましくは７０〜１３０℃で行う。脱ハロゲン化水素剤としては、公知の塩基性化合物を用いることができる。
【００１４】
一般式［５］で表される化合物に、一般式［６］で表されるアルケニルハライドを反応させることにより、一般式［７］
【化５５】

で表される化合物を得る。一般式［７］において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の平均付加モル数で０〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ｒ及びＲ'はアルキル基で、それらはたがいに同一でも異なっていてもよい。
次に、このようにして得られた一般式［７］で表される化合物に酸を作用させて、保護基の脱離を行い、一般式［８］
【化５６】

で表される水酸基４個を有する化合物を得る。使用する酸としては、例えば、塩酸、リン酸、硫酸などの鉱酸や、酢酸、ｐ−トルエンスルホン酸などの有機酸を挙げることができる。これらの中で、後の処理などの点から、塩酸及びリン酸を好適に使用することができる。また、必要に応じて、一般式［７］で表される化合物と水の接触をよくするために、エタノール、イソプロピルアルコールなどのアルコールを同時に添加することができる。
【００１５】
さらに、この一般式［８］で表される化合物に、１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加して、一般式［１２］
【化５７】

で表されるポリオキシアルキレントリグリセリルエーテル化合物を得る。一般式［１２］において、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基である。すなわち、一般式［１２］で表される化合物は、一般式［１］において、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴がすべて水素原子である化合物である。
このアルキレンオキシドの付加反応は、通常アルカリ触媒を用いて行う。アルカリ触媒としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸カリウムなどを挙げることができるが、入手性の点から、水酸化ナトリウム、水酸化カリウム及びナトリウムメトキシドを好適に用いることができる。また、必要に応じて、アルキレンオキシドの付加反応を、塩化第二スズ、三フッ化ホウ素エーテラートなどのルイス酸触媒を使用し、−５０〜１００℃、好ましくは０〜７０℃で行うことができる。アルキレンオキシドとしては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、オキセタン、テトラヒドロフラン、スチレンオキシドなどを挙げることができるが、これらの中で、入手の容易さの点から炭素数２〜４のエチレンオキシド、プロピレンオキシド、ブチレンオキシド及びテトラヒドロフランを好適に使用することができる。
【００１６】
最後に、このようにして得られた一般式［１２］で表される化合物の水酸基を、所望によりエステル化又はアセタール化する。エステル化する場合は、炭素数２〜２４の脂肪酸又はこれらの反応性誘導体、例えば、酸無水物、酸ハライド、低級エステルなどを用ることができる。脂肪酸又はその反応性誘導体としては、アシル基として、一般式［１］のＲ¹，Ｒ²，Ｒ³及びＲ⁴の説明において例示した炭素数２〜２４のアシル基を有する化合物を用いることができる。エステル化によって、一般式［１］において、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴が炭素数２〜２４のアシル基である化合物を得ることができる。
アセタール化する場合は、炭素数３〜１０のビニルエーテル類、例えば、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、ジヒドロフラン、ジヒドロピランなどを用いることができる。アセタール化によって、一般式［１］において、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴が、炭素数３〜１０の１−アルコキシアルキル基又は酸素に隣接する炭素がポリオキシアルキレン鎖と結合する環状エーテル基である化合物を得ることができる。
【００１７】
次いで、本発明の変性シリコーン化合物について詳細に説明する。
本発明の変性シリコーン化合物は、一般式［９］
【化５８】

で表される構造を有する。一般式［９］において、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁶，Ｒ⁷及びＲ⁸のうち少なくとも１つは下記一般式［１０］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。
【化５９】

一般式［１０］において、Ｙは炭素数３〜１０の炭化水素基であり、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００である。
一般式［９］で表される化合物としては、（１）ｘ≧０かつｙ＝０であり、Ｒ⁶又はＲ⁸の一方が一般式［１０］で表される化合物、（２）ｘ≧０かつｙ＝０であり、Ｒ⁶及びＲ⁸の双方が一般式［１０］で表される化合物、（３）ｘ＝０かつｙ＞０であり、Ｒ⁷が一般式［１０］で表される化合物、（４）ｘ＞０かつｙ＞０であり、Ｒ⁷が一般式［１０］で表される化合物などを挙げることができ、用途に応じてポリオキシアルキレン鎖との組み合わせを考慮して適当な化合物を選択することができる。
【００１８】
一般式［９］において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基であり、このようなオキシアルキレン基としては、例えば、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシトリメチレン基、オキシテトラメチレン基、オキシスチレン基などを挙げることができる。
一般式［９］において、Ａ²Ｏは炭素数２〜８のオキシアルキレン基であり、このようなオキシアルキレン基としては、例えば、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシトリメチレン基、オキシテトラメチレン基、オキシスチレン基などを挙げることができる。
一般式［９］において、ｘとｙの合計は０〜８００であり、好ましくは１〜４００である。ｘとｙの合計が８００を超えると、一般式［９］で表される化合物の粘度が高くなり、取り扱いが困難となるおそれがある。また、一般式［１０］において、ｎは０〜１００であり、好ましくは０〜５０である。ｎが１００を超えると、一般式［９］で表される化合物の粘度が高くなり、取り扱いが困難となるおそれがある。一般式［１０］において、ａ，ｂ，ｃ及びｄは１〜１００であり、好ましくは１〜２０である。ａ，ｂ，ｃ及びｄが１００を超えると、一般式［９］で表される化合物の粘度が高くなり、取り扱いが困難となるおそれがある。
【００１９】
以下に、一般式［９］で表される変性シリコーン化合物の製造方法について述べる。一般式［１０］で表される水酸基４個を有するポリオキシアルキレン誘導体基を有する変性シリコーン化合物は、先に述べた一般式［７］で表される化合物を原料として、以下に述べる経路［１］〜［４］を経ることにより製造することができる。
経路［１］
一般式［７］で表される化合物に酸を作用させて、アセタール基の分解を行い、一般式［８］
【化６０】

で表される化合物を得る。一般式［８］において、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基である。この際用いられる酸としては、塩酸、リン酸、硫酸など鉱酸や、酢酸、ｐ−トルエンスルホン酸など有機酸などを挙げることができるが、後の処理などの点から、塩酸及びリン酸を好適に使用することができる。必要に応じて一般式［７］で表される化合物と水との接触をよくするために、エタノール、イソプロピルアルコールなどのアルコールを添加することができる。
さらに、この一般式［８］で表される化合物に、１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加して、一般式［１２］
【化６１】

で表されるポリオキシアルキレントリグリセリルエーテル化合物を得る。一般式［１２］において、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基である。すなわち、一般式［１２］で表される化合物は、一般式［１］において、Ｒ¹，Ｒ²，Ｒ³及びＲ⁴がすべて水素原子である化合物である。
【００２０】
このアルキレンオキシドの付加反応は、通常アルカリ触媒を用いて、好ましくは６０〜２００℃、より好ましくは８０〜１５０℃で行う。アルカリ触媒としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシドなどを挙げることができるが、入手の容易さの点から、水酸化ナトリウム、水酸化カリウム及びナトリウムメトキシドを好適に用いることができる。また、必要に応じて、アルキレンオキシドの付加反応を、塩化第二スズ、三フッ化ホウ素エーテラートなどのルイス酸触媒を使用し、−５０〜１００℃、好ましくは０〜７０℃で行うことができる。アルキレンオキシドとしては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、オキセタン、テトラヒドロフラン、スチレンオキシドなどを挙げることができるが、これらの中で、入手の容易さの点から炭素数２〜４のエチレンオキシド、プロピレンオキシド、ブチレンオキシド及びテトラヒドロフランを好適に使用することができる。
【００２１】
このようにして得られた一般式［１２］で表されるポリオキシアルキレントリグリセリルエーテル化合物と、一般式［１１］
【化６２】

で表されるシリコーン化合物とを触媒の存在下に付加反応させ、目的とする変性シリコーン化合物を得る。一般式［１１］において、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素原子で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。
一般式［１２］で表されるポリオキシアルキレントリグリセリルエーテル化合物の二重結合と、一般式［１１］で表されるシリコーン化合物のシリリジン基の反応に用いる触媒としては、ニッケル、ルテニウム、ロジウム、パラジウム、イリジウム、白金などの第ＶIII族遷移金属又はそれらの化合物が挙げられるが、塩化白金酸が入手しやすく、また、そのアルコール溶液が均一系触媒であるため、取り扱いが容易であり好ましい。この二重結合とシリリジン基との反応の際、水酸基とシリリジン基の脱水素反応を防止するために、酢酸カリウムなどのバッファー剤を系内に添加するなどの公知の方法を用いることが好ましい。また、この反応には、必要に応じて溶剤を使用してもよく、使用しなくてもよい。用いる溶剤としては、付加反応を阻害しないものであれば特に制限はなく、例えば、四塩化炭素、トルエン、キシレン、ヘキサン、オクタン、ジブチルエーテル、ジオキサン、テトラヒドロフラン、酢酸エチル、酢酸ブチル、メチルエチルケトンなどを挙げることができる。なお、エタノール、イソプロパノール、ｎ−ブタノールなどのアルコール溶剤も使用することができるが、この場合にはシリリジン基と水酸基との脱水素反応を防止又は抑制するために酢酸カリウムなどのバッファー剤を使用することが好ましい。この反応は通常、７０〜１２０℃で０.５〜３０時間行うことで完結する。反応終了後、触媒及び溶剤を除去することにより、目的とする一般式［９］で表される本発明の変性シリコーン化合物を得ることができる。
【００２２】
経路［２］
ポリオキシアルキレントリグリセリルエーテル化合物の水酸基と、シリコーン化合物のシリリジン基の脱水素反応を防止するために、一般式［１２］で表されるポリオキシアルキレントリグリセリルエーテル化合物の水酸基に対して保護基を導入し、一般式［１３］
【化６３】

で表されるポリオキシアルキレントリグリセリルエーテル化合物を得る。一般式［１３］において、Ａ¹Ｏ及びＡ²Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、ａ，ｂ，ｃ及びｄはオキシアルキレン基Ａ²Ｏの付加モル数で１〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基であり、Ｒ¹²，Ｒ¹³，Ｒ¹⁴及びＲ¹⁵は水酸基の保護基であり、炭素数２〜２４のアシル基又は炭素数３〜１０の１−アルコキシアルキル基若しくは酸素に隣接する炭素がポリオキシアルキレン鎖と結合する環状エーテル基で、それらはたがいに同一でも異なっていてもよい。
【００２３】
水酸基のエステル化による保護には、酸ハロゲン化物又は酸無水物を好適に用いることができ、水酸基のアセタール化による保護にはビニルエーテル類を好適に用いることができる。酸ハロゲン化物及び酸無水物としては、酢酸、酪酸、プロピオン酸などの酸ハロゲン化物及び酸無水物を挙げることができるが、これらの中で、入手及び脱アシル化反応の容易さなどから塩化アセチル及び無水酢酸を好適に使用することができる。また、ビニルエーテル類としては、メチルビニルエーテル、エチルビニルエーテル、ジヒドロフラン、ジヒドロピランなどを挙げることができるが、これらの中で、入手の容易さや副反応が少ないなどの理由から、ジヒドロフラン及びジヒドロピランを好適に使用することができる。
引き続き、このようにして得られた一般式［１３］で表されるポリオキシアルキレントリグリセリルエーテル化合物と、一般式［１１］で表されるシリコーン化合物とを白金触媒どの存在下に付加反応させ、さらにＲ¹²，Ｒ¹³，Ｒ¹⁴及びＲ¹⁵を脱離してポリオキシアルキレン鎖の末端を水酸基とすることにより、一般式［９］で表される本発明の変性シリコーン化合物を得る。
【００２４】
経路［３］
一般式［１１］
【化６４】

で表されるシリコーン化合物と、一般式［８］
【化６５】

で表されるポリオキシアルキレントリグリセリルエーテル化合物を、白金触媒などの存在下に付加反応させ、一般式［１４］
【化６６】

で表されるシリコーン化合物を得る。一般式［１１］及び一般式［１４］において、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素原子で、それ以外はメチル基又はフェニル基であり、Ｒ¹⁶，Ｒ¹⁷及びＲ¹⁸のうち少なくとも１つは下記一般式［１５］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。また、一般式［８］において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基である。
【００２５】
一般式［１５］
【化６７】

において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、Ｙは炭素数３〜１０の炭化水素基である。
さらに、この一般式［１４］で表されるシリコーン化合物に、１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加して、目的とする一般式［９］で表される本発明の変性シリコーン化合物を得る。
この反応においては、通常、シロキサン結合の分解を防ぐため、塩化第二スズ、三フッ化ホウ素テトラエーテラートなどのルイス酸触媒などを使用することが好ましい。この反応に用いられるアルキレンオキシドとしては、前記のアルキレンオキシドを用いることができる。
【００２６】
経路［４］
一般式［１１］
【化６８】

で表されるシリコーン化合物と、一般式［７］
【化６９】

で表される化合物を、白金触媒などの存在下に付加反応させ、一般式［１６］
【化７０】

で表されるシリコーン化合物を得る。一般式［１１］及び一般式［１６］において、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素原子で、それ以外はメチル基又はフェニル基であり、Ｒ¹⁹，Ｒ²⁰及びＲ²¹のうち少なくとも１つは下記一般式［１７］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。また、一般式［７］において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基である。
【００２７】
一般式［１７］
【化７１】

において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基の平均付加モル数で０〜１００であり、Ｙは炭素数３〜１０の炭化水素基であり、Ｒ及びＲ'はアルキル基で、それらはたがいに同一でも異なっていてもよい。
次いで、一般式［１６］で表される化合物に酸を作用させて、アセタール基の分解を行い、一般式［１４］
【化７２】

で表されるシリコーン化合物を得る。一般式［１１］及び一般式［１４］において、Ｒ⁵はメチル基又はフェニル基であり、Ｒ⁹，Ｒ¹⁰及びＲ¹¹のうち少なくとも１つは水素原子で、それ以外はメチル基又はフェニル基であり、Ｒ¹⁶，Ｒ¹⁷及びＲ¹⁸のうち少なくとも１つは下記一般式［１５］で表される基で、それ以外はメチル基又はフェニル基であり、ｘ及びｙは繰り返し単位の数であり、ｘとｙの合計は０〜８００である。また、一般式［８］において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、Ｚは末端に二重結合を有する炭素数３〜１０の炭化水素基である。
【００２８】
一般式［１５］
【化７３】

において、Ａ¹Ｏは炭素数２〜８のオキシアルキレン基で、１種でも２種以上でもよく、２種以上の場合はブロック状付加でもランダム状付加でもよく、ｎはオキシアルキレン基Ａ¹Ｏの付加モル数で０〜１００であり、Ｙは炭素数３〜１０の炭化水素基である。
さらに、この一般式［１４］で表されるシリコーン化合物に、１種又は２種以上の炭素数２〜８のアルキレンオキシドを付加して、目的とする一般式［９］で表される本発明の変性シリコーン化合物を得る。
この反応においては、通常、シロキサン結合の分解を防ぐため、塩化第二スズ、三フッ化ホウ素テトラエーテラートなどのルイス酸触媒などを使用することが好ましい。この反応に用いられるアルキレンオキシドとしては、前記のアルキレンオキシドを用いることができる。
【００２９】
【実施例】
以下に、実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。
なお、実施例中に示される化学式において、ＥＯはオキシエチレン基を、ＰＯはオキシプロピレン基を、ＢＯはオキシブチレン基を、ＴＭＯはオキシテトラメチレン基を表し、［ ／ ］はオキシアルキレン基の付加状態がランダム状であることを表す。
また、実施例において、水酸基価はＪＩＳ Ｋ ００７０（１９９２）により、不飽和度はＪＩＳ Ｋ １５５７ ６.７（１９７０）により測定した。
実施例１〜１８において、ＧＰＣ分析は次の条件で行い、重量平均分子量を求めた。
カラム：ＳＨＯＤＥＸ ＫＦ−８０１，ＫＦ−８０３，ＫＦ−８０４
展開溶媒：テトラヒドロフラン
流速：１.０ml／min
カラム温度：４０℃
実施例１９〜３３において、ＧＰＣ分析は次の条件で行い、重量平均分子量を求めた。
カラム：ＰＬゲル５μｍミックスＤ×３本
展開溶媒：酢酸エチル
流速：１.０ml／min
カラム温度：４０℃
製造例１（トリグリセリルモノアリルエーテルの製造）
温度計、窒素ガス吹き込み管、かき混ぜ装置を付した１０リットル容量のステンレス製耐圧反応容器に、ジイソプロピリデントリグリセリン［化合物(Ａ)、ＤＩＴＧ］３,８４５ｇ（１２モル）と水酸化カリウム１,３４６ｇ（２４モル）をとり、反応系内を窒素ガスで置換した。昇温して系内の温度を７５〜８５℃に保持しながら、ボンベに予め計量した塩化アリル１,１０２ｇ（１４.４モル）を１時間で滴下して反応した。滴下終了後１１５〜１２５℃に昇温して４時間熟成した。熟成後、７５〜８５℃に冷却し、３〜５mmHgの減圧下、窒素ガス吹き込みながら、過剰の塩化アリルを留去した。さらにこの反応液の一部をとり、酢酸でpHを７.０に調整し、１００℃、１００mmHg以下で１時間脱水を行い、８０℃に冷却後、析出した塩をろ別して分析用の試料を得た。この化合物を化合物(Ｂ)とする。化合物(Ｂ)の分析値は、水酸基価１０.０mgKOH／ｇ、不飽和度２.７０meq／ｇであった。
また、ＩＲにより化合物(Ｂ)を分析した。

さらに、反応液に１重量％の希塩酸を加え、pH１.０に調整し、７５〜８５℃で３時間加水分解したのち、炭酸ナトリウムを加えてpH７.０になるまで中和し、脱水ろ過して淡黄色液状のトリグリセリルモノアリルエーテル［化合物(Ｃ)］２,９２６ｇを得た（収率８７％）。化合物(Ｃ)の分析値は、水酸基価８１０mgKOH／ｇ、不飽和度３.５４meq／ｇであった。
また、ＩＲにより化合物(Ｃ)を分析した。

化合物(Ａ)、化合物(Ｂ)及び化合物(Ｃ)の構造を次に示す。
【化７４】

実施例１（ポリオキシアルキレントリグリセリルエーテル化合物の合成）
温度計、窒素ガス吹き込み管、かき混ぜ装置を付した５リットル容量のステンレス製耐圧反応容器に、製造例１で製造したトリグリセリルモノアリルエーテル［化合物(Ｃ)］２８０ｇ（１モル）と水酸化カリウム２.４ｇをはかり取り、溶解し、反応系内を窒素ガスで置換した。昇温して８５〜９５℃に保持し、エチレンオキシド５２７ｇ（１２.０モル）を滴下して反応した。滴下終了後、８５〜９５℃でさらに２時間熟成した。熟成終了後、窒素ガスを吹き込みながら、３〜５mmHgの減圧下で未反応の残存エチレンオキシドを留去した。反応液を１重量％の希塩酸で中和し、その後脱水、ろ過して、淡黄色液状のポリエーテル化合物(１−Ｃ)７７４ｇを得た（収率９６％）。化合物(１−Ｃ)の分析値は、水酸基価２８６mgKOH／ｇ、不飽和度１.２２meq／ｇであった。ＧＰＣ分析による重量平均分子量は７８０であった。
また、ＩＲにより化合物(１−Ｃ)を分析した。

これらの結果より、化合物(１−Ｃ)の構造は、式［１−Ｃ］であると推定した。
【化７５】

実施例２（ポリオキシアルキレントリグリセリルエーテルの合成）
実施例１と同様にして、反応容器に製造例１で製造したトリグリセリルモノアリルエーテル２８０ｇ（１モル）と水酸化カリウム３.６ｇをはかり取り、実施例１のエチレンオキシド５２７ｇの代わりに、エチレンオキシド９２４ｇ（２１.０モル）を用いて反応して、液状淡黄色のポリエーテル化合物(２−Ｃ)１,１５６ｇを得た（収率９６％）。化合物(２−Ｃ)の分析値は、水酸基価１９２mgKOH／ｇ、不飽和度０.８５meq／ｇであった。ＧＰＣ分析による重量平均分子量は９８０であった。
また、ＩＲにより化合物(２−Ｃ)を分析した。

これらの結果より、化合物(２−Ｃ)の構造は、式［２−Ｃ］であると推定した。
【化７６】

実施例３（ポリオキシアルキレントリグリセリルエーテルの合成）
実施例１と同様にして、反応容器に製造例１で製造したトリグリセリルモノアリルエーテル２８０ｇ（１モル）と水酸化カリウム８.６５ｇをはかり取り、実施例１のエチレンオキシド５２７ｇの代わりに、エチレンオキシド１,８８３ｇ（４２.８モル）を用いて反応して、液状淡黄色のポリエーテル化合物(３−Ｃ)２,０４５ｇを得た（収率９６％）。化合物(３−Ｃ)の分析値は、水酸基価１０９mgKOH／ｇ、不飽和度０.４６meq／ｇであった。ＧＰＣ分析による重量平均分子量は２,０２０であった。
また、ＩＲにより化合物(３−Ｃ)を分析した。

これらの結果より、化合物(３−Ｃ)の構造は、式［３−Ｃ］であると推定した。
【化７７】

実施例４（ポリオキシアルキレントリグリセリルエーテル化合物の合成）
実施例１と同様にして、製造例１で製造したトリグリセリルモノアリルエーテル２８０ｇ（１モル）と水酸化カリウム１６.２ｇをはかり取り、実施例１のエチレンオキシド５２７ｇの代わりに、エチレンオキシド３,７６６ｇ（８５.６モル）を用いて反応して、液状淡黄色のポリエーテル化合物(４−Ｃ)３,８４４ｇを得た（収率９５％）。化合物(４−Ｃ)の分析値は、水酸基価５８.１mgKOH／ｇ、不飽和度０.２４meq／ｇであった。ＧＰＣ分析による重量平均分子量は３,８００であった。
また、ＩＲにより化合物(４−Ｃ)を分析した。

これらの結果より、化合物(４−Ｃ)の構造は、式［４−Ｃ］であると推定した。
【化７８】

実施例５（ポリオキシアルキレントリグリセリルエーテル化合物の合成）
実施例１と同様にして、反応容器に製造例１で製造したトリグリセリルモノアリルエーテル２８０ｇ（１モル）と水酸化カリウム２.１ｇをはかり取り、実施例１のエチレンオキシド５２７ｇの代わりに、予め混合したエチレンオキシド１７４ｇ（４.０モル）とプロピレンオキシド２３０ｇ（３.９７モル）を用いて反応して、液状淡黄色のポリエーテル化合物(５−Ｃ)６５７ｇを得た（収率９６％）。化合物(５−Ｃ)の分析値は、水酸基価３４０mgKOH／ｇ、不飽和度１.４０meq／ｇであった。ＧＰＣ分析による重量平均分子量は６５０であった。
また、ＩＲにより化合物(５−Ｃ)を分析した。

これらの結果より、化合物(５−Ｃ)の構造は、式［５−Ｃ］であると推定した。
【化７９】

実施例６（ポリオキシアルキレントリグリセリルエーテル化合物の合成）
実施例１と同様にして、反応容器に製造例１で製造したトリグリセリルモノアリルエーテル２８０ｇ（１モル）と水酸化カリウム２.４ｇをはかり取り、実施例１のエチレンオキシド５２７ｇの代わりに、予め混合したエチレンオキシド３３４ｇ（７.５８モル）とブチレンオキシド１８２ｇ（２.５３モル）を用いて反応して、液状淡黄色のポリエーテル化合物(６−Ｃ)７３１ｇを得た（収率９０％）。化合物(６−Ｃ)の分析値は、水酸基価３１１mgKOH／ｇ、不飽和度１.３５meq／ｇであった。ＧＰＣ分析による重量平均分子量は７４０であった。
また、ＩＲにより化合物(６−Ｃ)を分析した。

これらの結果より、化合物(６−Ｃ)の構造は、式［６−Ｃ］であると推定した。
【化８０】

実施例７（ポリオキシアルキレントリグリセリルエーテル化合物の合成）
実施例１と同様にして、反応容器に製造例１で製造したトリグリセリルモノアリルエーテル２８０ｇ（１モル）と水酸化カリウム２.８４ｇをはかり取り、実施例１のエチレンオキシド５２７ｇの代わりに、プロピレンオキシド６６７ｇ（１１.５モル）を用いて反応して、液状淡黄色のポリエーテル化合物(７−Ｃ)８９０ｇを得た（収率９４％）。化合物(７−Ｃ)の分析値は、水酸基価２６０mgKOH／ｇ、不飽和度１.１０meq／ｇであった。ＧＰＣ分析による重量平均分子量は８６０であった。
また、ＩＲにより化合物(７−Ｃ)を分析した。

これらの結果より、化合物(７−Ｃ)の構造は、式［７−Ｃ］であると推定した。
【化８１】

実施例８（ポリオキシアルキレントリグリセリルエーテル化合物の合成）
実施例１と同様にして、反応容器に製造例１で製造したトリグリセリルモノアリルエーテル２８０ｇ（１モル）と水酸化カリウム４.４ｇをはかり取り、反応系内を窒素ガスで置換した。昇温して８５〜９５℃に保持し、プロピレンオキシド９５７ｇ（１６.５モル）を滴下して反応し、さらに２時間熟成した。次いで、エチレンオキシド２４２ｇ（５.５モル）を滴下して反応した。滴下終了後、同温度でさらに２時間熟成した。熟成終了後、窒素ガスを吹き込みながら、３〜５mmHgの減圧下で未反応の残存プロピレンオキシド及びエチレンオキシドを留去した。反応液を１重量％の希塩酸で中和し、その後脱水、ろ過して、淡黄色液状のポリエーテル化合物(８−Ｃ)１,４０５ｇを得た（収率９５％）。化合物(８−Ｃ)の分析値は、水酸基価１６５mgKOH／ｇ、不飽和度０.７０meq／ｇであった。ＧＰＣ分析による重量平均分子量は１,３８０であった。
また、ＩＲにより化合物(８−Ｃ)を分析した。

これらの結果より、化合物(８−Ｃ)の構造は、式［８−Ｃ］であると推定した。
【化８２】

実施例９（ポリオキシアルキレントリグリセリルエーテル化合物の合成）
実施例１と同様に、反応容器に製造例１で製造したトリグリセリンモノアリルエーテル２８０ｇ（１モル）と三フッ化ホウ素ジエチルエーテル１６.４ｇとテトラヒドロフラン９００ｇ（１２.５モル）をはかりとり、反応系内を窒素置換した。昇温して５５〜６５℃に保持し、エチレンオキシド４６２ｇ（１０.５モル）滴下して反応した。滴下終了後、同温度でさらに２時間反応を続けた。その後、反応液を５重量％炭酸ナトリウム水溶液で中和し、３〜５mmHgの減圧下、窒素を吹き込みながら未反応の残存エチレンオキシド、テトラヒドロフランを留去した。その後、脱水、ろ過して淡黄色の液状のポリエーテル化合物(９−Ｃ)１,４４０ｇを得た（収率８８％）。化合物(９−Ｃ)の分析値は、水酸基価１５４mgKOH／ｇ、不飽和度０.６７meq／ｇであった。ＧＰＣ分析による重量平均分子量は１,４５０であった。
また、ＩＲにより化合物(９−Ｃ)を分析した。

これらの結果より、化合物(９−Ｃ)の構造は、式［９−Ｃ］であると推定した。
【化８３】

製造例２（トリグリセリルモノメタリルエーテルの製造）
温度計、窒素ガス吹き込み管、かき混ぜ装置を付した２リットル容量のステンレス製耐圧反応容器に、ジイソプロピリデントリグリセリン［化合物(Ａ)、ＤＩＴＧ］６４１ｇ（２モル）と水酸化カリウム２２４ｇ（４モル）をとり、反応系内を窒素ガスで置換した。昇温して系内の温度を７５〜８５℃に保持しながら、ボンベに予め計量した塩化メタリル２１７ｇ（２.４モル）を１時間で滴下して反応した。滴下終了後１１５〜１２５℃に昇温して４時間熟成した。熟成後、７５〜８５℃に冷却し、３〜５mmHgの減圧下、窒素ガス吹き込みながら、過剰の塩化メタリルを留去した。さらにこの反応液の一部をとり、酢酸でpHを７.０に調整し、１００℃、１００mmHg以下で１時間脱水を行い、８０℃冷却後、析出した塩をろ別して分析用の試料を得た。この化合物(Ｄ)の分析値は、水酸基価３６.１mgKOH／ｇ、不飽和度２.５０meq／ｇであった。
さらに、反応液に１重量％の希塩酸を加え、pH１.０に調整し、７５〜８５℃で３時間加水分解したのち、炭酸ナトリウムを加えてpH７.０になるまで中和し、脱水ろ過して淡黄色液状のトリグリセリルモノメタリルエーテル［化合物(Ｅ)］６１０ｇを得た（収率８８％）。
化合物(Ｅ)の分析値は、水酸基価７８３mgKOH／ｇ、不飽和度３.１６meq／ｇであった。また、ＩＲにより化合物(Ｅ)を分析した。

これらの結果より、化合物(Ｅ)の構造は、式［Ｅ］であることが確かめられた。
【化８４】

実施例１０
実施例１と同様にして、反応容器に製造例２で製造したトリグリセリルモノメタリルエーテル２９４ｇ（１モル）と水酸化ナトリウム１.６ｇをはかり取り、反応系内を窒素ガスで置換した。昇温して８５〜９５℃に保持し、予め計量したエチレンオキシド２３５.７ｇ（５.３６モル）を滴下して反応した。滴下終了後、８５〜９５℃でさらに２時間熟成した。熟成終了後、窒素ガスを吹き込みながら、３〜５mmHgの減圧下で未反応の残存エチレンオキシドを留去した。反応液を１重量％希塩酸で中和し、その後脱水、ろ過して、淡黄色液状のポリエーテル化合物(１０−Ｅ)５０３ｇを得た（収率９５％）。化合物(１０−Ｅ)の分析値は、水酸基価４４０mgKOH／ｇ、不飽和度１.９０meq／ｇであった。ＧＰＣ分析による重量平均分子量は５１０であった。
また、ＩＲにより化合物(１０−Ｅ)を分析した。

これらの結果より、化合物(１０−Ｅ)の構造は、式［１０−Ｅ］であると推定した。
【化８５】

実施例１〜１０の仕込み条件及びアルキレンオキシドの付加状態を第１表に、分析値を第２表に示す。
【００３０】
【表１】

【００３１】
［注］アルキレンオキシド仕込み量は、原料の化合物(Ｃ)２８０ｇ（１モル）、化合物(Ｅ)２９４ｇ（１モル）に対する量である。表中、ＥＯはエチレンオキシドを、ＰＯはプロピレンオキシドを、ＢＯはブチレンオキシドを、ＴＨＦはテトラヒドロフランを表す。
【００３２】
【表２】

【００３３】
［注］表中の分子量は、測定した水酸基価より計算で求めた。
実施例１１
温度計、窒素ガス吹き込み管、かき混ぜ装置を付した５リットル容量のステンレス製耐圧反応容器に、ジイソプロピリデントリグリセリン［化合物(Ａ)］９６０ｇ（３.０モル）と水酸化カリウム４.６ｇをはかり取り、溶解し、反応系内を窒素ガスで置換した。昇温して８５〜９５℃に保持し、１０kg／cm²以下の条件でエチレンオキシド１,３４６ｇ（３０.６モル）を５時間滴下して反応した。滴下終了後、８５〜９５℃でさらに２時間熟成した。熟成終了後、窒素ガスを吹き込みながら、３〜５mmHgの減圧下で未反応の残存エチレンオキシドを留去した。
次に反応容器を６０℃まで冷却して水酸化カリウム５８９.１ｇ（１０.５モル）をとり、反応系内を窒素ガスで置換した。昇温して系内の温度を７５〜８５℃に保持しながら、ボンベに予め計量した塩化アリル３４４.３ｇ（４.５モル）を１時間で滴下して反応した。滴下終了後１１５〜１２５℃に昇温して４時間熟成した。熟成後、７５〜８５℃に冷却し、３〜５mmHgの減圧下、窒素ガス吹き込みながら、過剰の塩化アリルを留去した。次に６０℃まで冷却後、この反応液の一部をとり、酢酸でpHを７.０に調整し、１００℃、１００mmHg以下で１時間脱水を行い、８０℃に冷却して析出した塩をろ別して化合物(１１−Ｂ)を得た。化合物(１１−Ｂ)の分析値は、水酸基価０.３mgKOH／ｇ、不飽和度１.２４meq／ｇであった。
これらの結果より、化合物(１１−Ｂ)の構造は、式［１１−Ｂ］であると推定した。
【化８６】

さらに、反応液に１重量％の希塩酸を加え、pHを１.０に調整し、７５〜８５℃で３時間加水分解したのち、２０重量％炭酸ナトリウム水溶液でpHを６〜７の範囲に調整し、１００℃、１００mmHg以下、１時間で生成したアセトンを水と共に留去し、次に８０℃に冷却し、析出した塩をろ別して淡黄色液状の化合物(１１−Ｃ１)１,９６０ｇを得た。化合物(１１−Ｃ１)の分析値は、水酸基価３１０mgKOH／ｇ、不飽和度１.３８meq／ｇであった。これらの結果より、化合物(１１−Ｃ１)の構造は、式［１１−Ｃ１］であると推定した。
【化８７】

引き続き、反応容器に、化合物(１１−Ｃ１)１,０８６ｇ（１.５モル）と水酸化カリウム４.０ｇをはかり取り、溶解し、反応系内を窒素ガスで置換した。昇温して８５〜９５℃に保持し、１０kg／cm²以下の条件でプロピレンオキシド９１３.５ｇ（１５.８モル）を４時間滴下して反応した。滴下終了後、８５〜９５℃でさらに２時間熟成した。熟成終了後、窒素ガスを吹き込みながら、３〜５mmHgの減圧下で未反応の残存プロピレンオキシドを留去した。次に６０℃まで冷却後、反応液を１重量％の希塩酸でpHを６.０に調整し、１００℃、１００mmHg以下で１時間脱水を行った。その後８０℃に冷却し、析出した塩をろ別して、淡黄色液状の化合物(１１−Ｃ２)１,８９４ｇを得た（収率９５％）。化合物(１１−Ｃ２)の分析値は、水酸基価１７１mgKOH／ｇ、不飽和度０.７６meq／ｇであった。ＧＰＣ分析より、数平均分子量は１,３０９であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１１−Ｃ２)の構造は、式［１１−Ｃ２］であると推定した。
【化８８】

実施例１２
実施例１１と同様にして、反応容器にジイソプロピリデントリグリセリン［化合物(Ａ)］１,１２０ｇ（３.５モル）と水酸化カリウム４.３ｇをはかり取り、プロピレンオキシド１,０３５ｇ（１７.９モル）を用いて４時間反応し、さらに水酸化ナトリウム４９０ｇ（１２.３モル）、塩化アリル４０１.６ｇ（５.３モル）を用いてアリル基を導入し、次いでアセタール基を希塩酸で加水分解したのち精製を行い、液状淡黄色の化合物(１２−Ｃ１)１,８００ｇを得た。化合物(１２−Ｃ１)の分析値は、水酸基価３９２mgKOH／ｇ、不飽和度１.７４meq／ｇであった。これらの結果より、化合物(１２−Ｃ１)の構造は、式［１２−Ｃ１］であると推定した。
【化８９】

次に、反応容器に化合物(１２−Ｃ１)１,１４５ｇ（２モル）とナトリウムメトキシド８.３ｇをはかり取り、エチレンオキシド６０９.８ｇ（１３.９モル）とブチレンオキシド３３２.６ｇ（４.６モル）の混合物を用いて５時間反応し、淡黄色液状の化合物(１２−Ｃ２)１,９５７ｇを得た（収率９４％）。化合物(１２−Ｃ２)の分析値は、水酸基価２２０mgKOH／ｇ、不飽和度０.９７meq／ｇであった。ＧＰＣ分析より、数平均分子量は１,０２４であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１２−Ｃ２)の構造は、式［１２−Ｃ２］であると推定した。
【化９０】

実施例１３
実施例１１と同様にして、反応容器にジイソプロピリデントリグリセリン［化合物(Ａ)］８００ｇ（２.５モル）と水酸化ナトリウム９.６ｇをはかり取り、プロピレンオキシド１５９５ｇ（２７.５モル）を用いて８時間反応し、さらに水酸化カリウム５６１ｇ（１０モル）、塩化アリル２８６.９ｇ（３.８モル）を用いてアリル基を導入し、次いでアセタール基を希塩酸で加水分解したのち精製を行い、液状淡黄色の化合物(１３−Ｃ１)１,９５０ｇを得た。化合物(１３−Ｃ１)の分析値は、水酸基価２６０mgKOH／ｇ、不飽和度１.１５meq／ｇであった。
これらの結果より、化合物(１３−Ｃ１)の構造は、式［１３−Ｃ１］であると推定した。
【化９１】

次に、反応容器に化合物(１３−Ｃ１)８６３ｇ（１モル）と水酸化ナトリウム６.１ｇをはかり取り、プロピレンオキシド９５７ｇ（１６.５モル）を８時間反応し、熟成後さらに続けてエチレンオキシド２３１ｇ（５.３モル）を４時間反応し、淡黄色液状の化合物(１３−Ｃ２)１,９０５ｇを得た（収率９３％）。化合物(１３−Ｃ２)の分析値は、水酸基価１１５mgKOH／ｇ、不飽和度０.５０meq／ｇであった。ＧＰＣ分析より、数平均分子量は１,９６２であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１３−Ｃ２)の構造は、式［１３−Ｃ２］であると推定した。
【化９２】

実施例１４
実施例１１と同様にして、反応容器にジイソプロピリデントリグリセリン［化合物(Ａ)］３２０ｇ（１モル）とナトリウムメトキシド１６.９ｇをはかり取り、プロピレンオキシド２,０８８ｇ（３６モル）を用いて１５時間反応し、さらに水酸化カリウム３３６.６ｇ（６モル）、塩化アリル１３０.１ｇ（１.７モル）を用いてアリル基を導入し、次いでアセタール基を希塩酸で加水分解したのち精製を行い、液状淡黄色の化合物(１４−Ｃ１)１,８４０ｇを得た。化合物(１４−Ｃ１)の分析値は、水酸基価１１２mgKOH／ｇ、不飽和度０.４８meq／ｇであった。これらの結果より、化合物(１４−Ｃ１)の構造は、式［１４−Ｃ１］であると推定した。
【化９３】

次に、反応容器に化合物(１−Ｃ)１,００２ｇ（０.５モル）とナトリウムメトキシド４.４ｇをはかり取り、エチレンオキシド４６２ｇ（１０.５モル）を８時間反応し、淡黄色液状の化合物(１４−Ｃ２)１,４１０ｇを得た（収率９６％）。化合物(１４−Ｃ２)の分析値は、水酸基価７７.２mgKOH／ｇ、不飽和度０.３３meq／ｇであった。ＧＰＣ分析より、数平均分子量は２,９１５であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１４−Ｃ２)の構造は、式［１４−Ｃ２］であると推定した。
【化９４】

実施例１５
実施例１１と同様にして、反応容器にジイソプロピリデントリグリセリン［化合物(Ａ)］４８０ｇ（１.５モル）とナトリウムメトキシド８.４ｇをはかり取り、エチレンオキシド６９３ｇ（１５.８モル）とプロピレンオキシド９１３.５ｇ（１５.８モル）の混合物を用いて８時間反応し、さらに水酸化ナトリウム２７０ｇ（６.８モル）、塩化アリル１８３.６ｇ（２.４モル）を用いてアリル基を導入し、次いでアセタール基を希塩酸で加水分解したのち精製を行い、液状淡黄色の化合物(１５−Ｃ１)１,７８０ｇを得た。化合物(１５−Ｃ１)の分析値は、水酸基価１７２mgKOH／ｇ、不飽和度０.７６meq／ｇであった。
これらの結果より、化合物(１５−Ｃ１)の構造は、式［１５−Ｃ１］であると推定した。
【化９５】

次に、反応容器に化合物(１５−Ｃ１)１,３０５ｇ（１モル）と水酸化カリウム５.７ｇをはかり取り、プロピレンオキシド６０９ｇ（１０.５モル）を５時間反応し、淡黄色液状の化合物(１５−Ｃ２)１,８１４ｇを得た（収率９５％）。化合物(１５−Ｃ２)の分析値は、水酸基価１１９mgKOH／ｇ、不飽和度０.５２meq／ｇであった。ＧＰＣ分析より、数平均分子量は１,８９４であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１５−Ｃ２)の構造は、式［１５−Ｃ２］であると推定した。
【化９６】

実施例１６
実施例１１と同様にして、反応容器にジイソプロピリデントリグリセリン［化合物(Ａ)］３２０ｇ（１モル）と水酸化カリウム１２.８ｇをはかり取り、エチレンオキシド９６８ｇ（２２モル）とプロピレンオキシド１,２７６ｇ（２２モル）の混合物を用いて１２時間反応し、さらに水酸化ナトリウム２４０ｇ（６モル）、塩化アリル１３７.７ｇ（１.８モル）を用いてアリル基を導入し、次いでアセタール基を希塩酸で加水分解したのち精製を行い、液状淡黄色の化合物(１６−Ｃ１)２,１３０ｇを得た。化合物(１６−Ｃ１)の分析値は、水酸基価９６.５mgKOH／ｇ、不飽和度０.４２meq／ｇであった。
これらの結果より、化合物(１６−Ｃ１)の構造は、式［１６−Ｃ１］であると推定した。
【化９７】

次に、反応容器に化合物(１６−Ｃ１)１,１６３ｇ（０.５モル）と水酸化カリウム４.９ｇをはかり取り、エチレンオキシド４６２ｇ（１０.５モル）を７時間反応し、淡黄色液状の化合物(１６−Ｃ２)１,５５７ｇを得た（収率９６％）。化合物(１６−Ｃ２)の分析値は、水酸基価７０.０mgＫＯＨ／ｇ、不飽和度０.３０meq／ｇであった。ＧＰＣ分析より、数平均分子量は３,２０２であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１６−Ｃ２)の構造は、式［１６−Ｃ２］であると推定した。
【化９８】

実施例１７
実施例１１と同様にして、反応容器にジイソプロピリデントリグリセリン［化合物(Ａ)］８００ｇ（２.５モル）と水酸化ナトリウム６.９ｇをはかり取り、エチレンオキシド５５０ｇ（１２.５モル）を用いて３時間反応し、熟成後さらに続けてブチレンオキシド９４５ｇ（１３.１モル）を５時間反応し、さらに水酸化カリウム５６１ｇ（１０モル）、塩化アリル２８６.９ｇ（３.８モル）を用いてアリル基を導入し、次いでアセタール基を希塩酸で加水分解したのち精製を行い、液状淡黄色の化合物(１７−Ｃ１)１,９５０ｇを得た。化合物(１７−Ｃ１)の分析値は、水酸基価２６２mgKOH／ｇ、不飽和度１.１４meq／ｇであった。
これらの結果より、化合物(１７−Ｃ１)の構造は、式［１７−Ｃ１］であると推定した。
【化９９】

次に、反応容器に化合物(１７−Ｃ１)１,２８５ｇ（１.５モル）と水酸化ナトリウム３.７ｇをはかり取り、エチレンオキシド２４２.４ｇ（５.５モル）とプロピレンオキシド３１９.５（５.５モル）の混合物を５時間反応し、淡黄色液状の化合物(１７−Ｃ２)１,７７８ｇを得た（収率９６％）。化合物(１７−Ｃ２)の分析値は、水酸基価１８１mgKOH／ｇ、不飽和度０.８０meq／ｇであった。ＧＰＣ分析より、数平均分子量は１,２４５であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１７−Ｃ２)の構造は、式［１７−Ｃ２］であると推定した。
【化１００】

実施例１８
実施例１１と同様にして、反応容器にジイソプロピリデントリグリセリン［化合物(Ａ)］１,１２０ｇ（３.５モル）と水酸化ナトリウム５.４ｇをはかり取り、プロピレンオキシド１,０３５ｇ（１７.９モル）を用いて５時間反応し、さらに水酸化カリウム６８７.２ｇ（１２.３モル）、塩化メタリル４７５.１ｇ（５.３モル）を用いてメタリル基を導入し、次いでアセタール基を希塩酸で加水分解したのち精製を行い、液状淡黄色の化合物(１８−Ｅ１)１,８４０ｇを得た。化合物(１８−Ｅ１)の分析値は、水酸基価３８３mgKOH／ｇ、不飽和度１.７０meq／ｇであった。
これらの結果より、化合物(１８−Ｅ１)の構造は、式［１８−Ｅ１］であると推定した。
【化１０１】

次に、反応容器に化合物(１８−Ｅ１)１,１７２ｇ（２モル）と水酸化ナトリウム３.２ｇをはかり取り、エチレンオキシド４４８.８ｇ（１０.２モル）を４時間反応し、淡黄色液状の化合物(１８−Ｅ２)１,５４４ｇを得た（収率９５％）。化合物(１８−Ｅ２)の分析値は、水酸基価２７９mgKOH／ｇ、不飽和度１.２３meq／ｇであった。ＧＰＣ分析より、数平均分子量は８０９であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１８−Ｅ２)の構造は、式［１８−Ｅ２］であると推定した。
【化１０２】

実施例１１〜１８の一般式［１］におけるＡ¹Ｏ部分のアルキレンオキシド付加、アルケニル化、脱アセタール化までの反応の仕込条件、アルキレンオキシドの付加状態及び分析値を第３表に、一般式［１］におけるＡ²Ｏ部分のアルキレンオキシド付加反応の仕込条件、アルキレンオキシドの付加状態及び分析値を第４表に示した。
【００３４】
【表３】

【００３５】
【表４】

【００３６】
実施例１９〜２６に使用したポリオキシアルキレントリグリセリルエーテル化合物の記号、構造式及び物性を第５表に、シリコーン化合物の記号、構造式及び物性を第６表に示す。
【００３７】
【表５】

【００３８】
【表６】

【００３９】
【表７】

【００４０】
【表８】

【００４１】
【表９】

【００４２】
【表１０】

【００４３】
実施例１９（経路１による変性シリコーンの合成）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した５００ミリリットル４ツ口フラスコに、化合物(２−Ｃ)２３５.０ｇ、シリコーン化合物(Ｓ−１)４４.５ｇ、トルエン５６.０ｇ及び酢酸カリウム０.２０ｇを投入し、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を滴下し、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて減圧条件下で揮発分を留去し、引き続き吸着剤をろ別することにより目的の変性シリコーン化合物(１９−１ＣＳ)２６３.０ｇを得た（収率９４％）。得られた化合物の分析値は、水酸基価１６１mgKOH／ｇ、不飽和度０.００meq／ｇであった。ＧＰＣ分析より、重量平均分子量は１,４００であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(１９−１ＣＳ)の構造は、式［１９−１ＣＳ］であると推定した。
【化１０３】

実施例２０（経路１による変性シリコーンの合成）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した５００ミリリットル４ツ口フラスコに、化合物(５−Ｃ)１４３.０ｇ、シリコーン化合物(Ｓ−２)７３.０ｇ、トルエン４３.０ｇ及び酢酸カリウム０.２０ｇを投入し、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を滴下し、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて減圧条件下で揮発分を留去し、引き続き吸着剤をろ別することにより目的の変性シリコーン化合物(２０−１ＣＳ)１７７ｇを得た（収率８２％）。得られた化合物の分析値は、水酸基２２５mgKOH／ｇ、不飽和度０.００meq／ｇであった。
ＧＰＣ分析より、重量平均分子量は２０,５００であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(２０−１ＣＳ)の構造は、式［２０−１ＣＳ］であると推定した。
【化１０４】

実施例２１（経路１による変性シリコーンの合成）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した５００ミリリットル４ツ口フラスコに、化合物(６−Ｃ)１１１.０ｇ、シリコーン化合物(Ｓ−３)１６６.８ｇ、トルエン５６.０ｇ及び酢酸カリウム０.２０ｇを投入し、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を滴下し、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて減圧条件下で揮発分を留去し、引き続き吸着剤をろ別することにより目的の変性シリコーン化合物(２１−１ＣＳ)２５５.０ｇを得た（収率９２％）。得られた化合物の分析値は水酸基１２４mgKOH／ｇ、不飽和度０.０１meq／ｇであった。
ＧＰＣ分析より、重量平均分子量は１,８００であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(２１−１ＣＳ)の構造は、式［２１−１ＣＳ］であると推定した。
【化１０５】

実施例２２
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した５００ミリリットル４ツ口フラスコに、化合物(７−Ｃ)１８２.０ｇ、シリコーン化合物(Ｓ−４)８７.６ｇ、トルエン５４.０ｇ及び酢酸カリウム０.２０ｇを投入し、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を滴下し、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて減圧条件下で揮発分を留去し、引き続き吸着剤をろ別することにより目的の変性シリコーン化合物(２２−１ＣＳ)２４３.１ｇを得た（収率９０％）。得られた化合物の分析値は、水酸基１７５mgKOH／ｇ、不飽和度０.００meq／ｇであった。
ＧＰＣ分析より、重量平均分子量は２,６００であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(２２−１ＣＳ)の構造は、式［２２−１ＣＳ］であると推定した。
【化１０６】

製造例３（経路２による変性シリコーン化合物の合成−水酸基の保護）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した５００ミリリットル４ツ口フラスコに化合物(８−Ｃ)３００ｇ、無水酢酸９４.６ｇ、酢酸ナトリウム０.１５ｇを投入し、１００±５℃で４時間反応を行った。反応後、１０重量％水酸化ナトリウム水溶液を用いて系内に発生した酢酸を中和した。液の静置により分離した酢酸ナトリウム水溶液を除去し、残った液に窒素を導入しながら脱水後、ろ過を行った。この結果、水酸基の保護された化合物(８−ＣＰ)３２０.３ｇが得られた（収率８１％）。得られた化合物の分析値は、水酸基価０.９mgKOH／ｇ、不飽和度０.６２meq／ｇであった。
製造例４（経路２による変性シリコーン化合物の合成−水酸基の保護）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した５００ミリリットル４ツ口フラスコに、化合物(１０−Ｅ)３００ｇ、ジヒドロピラン２１７.７ｇ、ｐ−トルエンスルホン酸１.０ｇを投入し、４０±５℃で１２時間反応を行った。反応終了後、反応液に酸吸着剤［キョーワード３００、協和化学工業(株)製］を入れ、窒素を導入しながら未反応のジヒドロピランを留去し、ろ過を行った。その結果、水酸基の保護された化合物(１０−ＥＰ)４７３.１ｇが得られた（収率９１％）。得られた化合物の分析値は、水酸基価１.０mgKOH／ｇ、不飽和度１.１５meq／ｇであった。
実施例２３（経路２による変性シリコーン化合物の合成）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した１リットル４ツ口フラスコに、製造例３で合成した化合物(８−ＣＰ)２４２.０ｇ、シリコーン化合物(Ｓ−５)１２１.７ｇ、トルエン７３.０ｇ及び酢酸カリウム０.２０ｇ、を投入し、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を滴下し、８０℃で８時間反応を行った。反応終了後、窒素を吹き込みながら減圧条件下で揮発分を留去した。引き続き、メタノール１００.０ｇ、５重量％塩酸３０.０ｇを投入し、１００℃で１０時間、エステルの加水分解を行った。反応終了後、炭酸ナトリウムを用いて中和し、酸吸着剤［キョーワード３００、協和化学工業(株)製］２０ｇを加え、窒素を吹き込みながら減圧条件下で揮発分を留去し、吸着剤をろ別することにより目的の変性シリコーン化合物(２３−２ＣＳ)２７０.８ｇを得た（収率７４％）。得られた化合物の分析値は、水酸基価１０３mgKOH／ｇ、不飽和度０.０１meq／ｇであった。
ＧＰＣ分析より、重量平均分子量は４３,４００であった。また、赤外吸収スペクトル分析を行った。

これらの結果により化合物(２３−２ＣＳ)の構造は、式［２３−２ＣＳ］であると推定した。
【化１０７】

実施例２４
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した１リットル４ツ口フラスコに、製造例６で製造した化合物(２４−ＥＰ)３００.０ｇ、シリコーン化合物(Ｓ−６)２２.１ｇ、トルエン６５.０ｇ及び酢酸カリウム０.２０ｇ、を投入し、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を滴下し、８０℃で８時間反応を行った。引き続き、メタノール１５０ｇ、ｐ−トルエンスルホン酸０.５０ｇを投入し、４０℃で８時間、アセタール交換反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］２０ｇを加え、窒素を吹き込みながら減圧条件下で揮発分を留去し、吸着剤をろ別することにより目的の変性シリコーン化合物(２４−２ＣＳ)１７２.４ｇ（収率５４％）を得た。得られた化合物の分析値は、水酸基価３９２mgKOH／ｇ、不飽和度０.００meq／ｇであった。
ＧＰＣ分析より、重量平均分子量は２３,０００であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(２４−２ＣＳ)の構造は、式［２４−２ＣＳ］であると推定した。
【化１０８】

製造例５（経路３による変性シリコーン化合物の合成−トリグリセリン誘導体変性シリコーンの合成）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した１リットル４ツ口フラスコに、化合物(Ｃ)２２６.０ｇ、シリコーン化合物(Ｓ−１)１７８.０ｇ、トルエン４００ｇ及び酢酸カリウム０.３０ｇを投入した。窒素雰囲気下で７０℃まで昇温し、かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を滴下し、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］２０ｇを加え、１時間撹拌を行ってから吸着剤をろ別した。引き続き減圧条件下で揮発分を留去することにより変性シリコーン化合物(ＣＳ−１)２９９.０ｇを得た（収率７４％）。得られた化合物の分析値は、水酸基４５３mgKOH／ｇ、不飽和度０.０２meq／ｇであった。
実施例２５（経路３による変性シリコーン化合物の合成−トリグリセリン誘導体変性シリコーン化合物のエチレンオキシド付加物の合成）
温度計、窒素ガス吹き込み管、かき混ぜ装置を付した１リットル容量のステンレス製耐圧反応容器に、製造例５で合成したトリグリセリン誘導体変性シリコーン化合物(ＣＳ−１)１００ｇと三フッ化ホウ素ジエチルエーテル０.６ｇをはかり取り、反応系内を窒素ガスで置換した。昇温して５５〜６５℃に保持し、エチレンオキシド１５８ｇ（３.６モル）を滴下して反応した。滴下終了後、５５〜６５℃でさらに２時間反応を続けた。その後、反応液を５重量％炭酸ナトリウム水溶液で中和し、減圧下、窒素を吹き込みながら未反応の残存エチレンオキシドを留去した。その後、脱水、ろ過して淡黄色液状の変性シリコーン化合物(２５−３ＣＳ)２１７ｇを得た（収率８４％）。得られた化合物の分析値は、水酸基価１８７mgKOH／ｇ、不飽和度０.００meq／ｇであった。
ＧＰＣ分析より、重量平均分子量は１,２００であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(２５−３ＣＳ)の構造は、式［２５−３ＣＳ］であると推定した。
【化１０９】

製造例６（経路４による変性シリコーン化合物の合成−トリグリセリン誘導体変性シリコーン化合物の合成）
温度計、窒素ガス吹き込み管、冷却管、かき混ぜ装置を付した１リットル４ツ口フラスコに、化合物(Ｂ)１０９.０ｇ、シリコーン化合物(Ｓ−３)３３３.７ｇ、トルエン９０.０ｇ及び酢酸カリウム０.３０ｇを投入した。窒素雰囲気下で７０℃まで昇温し、かき混ぜながら系に塩化白金酸イソプロピルアルコール溶液（白金換算２０ppm）を投入し、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］２０ｇを加えて１時間撹拌し、吸着剤をろ別したのち、引き続き減圧条件下で揮発分を留去することにより化合物(ＢＳ−３)３９８.７ｇを得た（収率９０％）。得られた化合物の分析値は、水酸基２.５mgKOH／ｇ、不飽和度０.０２meq／ｇであった。
さらに、反応液３００ｇにメタノール１００ｇ、１重量％の希塩酸５０ｇを加え、７５〜８５℃で３時間加水分解したのち、炭酸ナトリウム水溶液を加えて中和し、窒素を吹き込みながら脱水後、トルエン２０ｇを投入し、ろ過を行った。引き続き減圧条件下で揮発分を留去することにより淡黄色液状の変性シリコーン化合物(ＣＳ−３)１９８.１ｇを得た（収率６６％）。得られた化合物の分析値は、水酸基価１５７mgKOH／ｇ、不飽和度０.０１meq／ｇであった。
実施例２６（経路４による変性シリコーン化合物の合成−トリグリセリン誘導体変性シリコーン化合物のエチキレンオキシド付加物の合成）
温度計、窒素ガス吹き込み管、かき混ぜ装置を付した１リットル容量のステンレス製耐圧反応容器に、製造例８で製造したトリグリセリン誘導体変性シリコーン化合物(ＣＳ−３)１４３ｇ及び三フッ化ホウ素ジエチルエーテル０.６ｇをはかり取り、反応系内を窒素ガスで置換した。昇温して５５〜６５℃に保持し、エチレンオキシド１５６ｇ（４.０モル）を滴下して反応した。滴下終了後、５５〜６５℃でさらに２時間反応を続けた。その後、反応液を５重量％炭酸ナトリウム水溶液で中和し、減圧下、窒素を吹き込みながら未反応の残存エチレンオキシドを留去した。その後、脱水、ろ過して淡黄色液状の変性シリコーン化合物(２６−４ＣＳ)を１２４.３ｇ得た（収率８２％）。得られた化合物の分析値は、水酸基価７９.０mgKOH／ｇ、不飽和度０.００meq／ｇであった。
ＧＰＣ分析より、重量平均分子量は２,８５０であった。また、赤外吸収スペクトル分析を行った。

これらの結果より、化合物(２６−４ＣＳ)の構造は、式［２６−４ＣＳ］であると推定した。
【化１１０】

【００４４】
実施例２７〜３３に使用したポリオキシアルキレントリグリセリルエーテル化合物の構造式及び物性を第７表に、シリコーン化合物の構造式及び物性を第８表に示す。
【００４５】
【表１１】

【００４６】
【表１２】

【００４７】
【表１３】

【００４８】
【表１４】

【００４９】
【表１５】

【００５０】
実施例２７
撹拌装置、温度計、冷却管、滴下漏斗及び窒素導入管を取り付けた１リットル４ツ口フラスコに、ポリオキシアルキレントリグリセリルエーテル化合物(１４−Ｃ２)３０３.０ｇ（０.１モル）、シリリジン基含有シリコーン化合物(Ｓ−７)１１１.２ｇ（０.１モル）、トルエン２０７.１ｇ及び酢酸カリウム０.２５ｇを仕込み、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら７０℃に保持した系に、最終的に系内の触媒濃度が１０ppmとなるように塩化白金酸の２−プロパノール溶液を１時間かけて滴下した。滴下終了後、８０℃で５時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて窒素ガスを吹き込みながらトルエンなどを減圧留去し、続いて吸着剤、酢酸カリウムをろ別することにより変性シリコーン化合物(２７−１Ｃ２Ｓ)３８４.０ｇを得た（収率９３％）。
得られた化合物の水酸基価は５５.７mgKOH／ｇ、不飽和度は０.００meq／ｇ、重量平均分子量は４,０９０であった。また、赤外吸収スペクトル分析を行った。

出発原料、反応条件、分析値より、化合物(２７−１Ｃ２Ｓ)の構造は、式［２７−１Ｃ２Ｓ］であると推定した。
【化１１１】

実施例２８
撹拌装置、温度計、冷却管、滴下漏斗、及び窒素導入管を取り付けた５００ミリリットル４ツ口フラスコに、ポリオキシアルキレントリグリセリルエーテル化合物(１７−Ｃ２)１２５.０ｇ（０.１モル）、シリリジン基含有シリコーン化合物(Ｓ−５)８１.０ｇ（０.００５モル）、トルエン２０６.０ｇ及び酢酸カリウム０.３０ｇを仕込み、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら７０℃に保持した系に、最終的に系内の触媒濃度が２０ppmとなるように塩化白金酸の２−プロパノール溶液を１時間かけて滴下した。滴下終了後、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて窒素ガスを吹き込みながらトルエンなどを減圧留去し、続いて吸着剤、酢酸カリウムをろ別することにより変性シリコーン化合物(２８−１Ｃ２Ｓ)１８２.５ｇを得た（収率８９％）。
得られた化合物の水酸基価は１１２mgKOH／ｇ、不飽和度は０.００meq／ｇ、重量平均分子量は３９,５５０であった。また、赤外吸収スペクトル分析を行った。

出発原料、反応条件、分析値より、変性シリコーン化合物(２８−１Ｃ２Ｓ)の構造は、式［２８−１Ｃ２Ｓ］であると推定した。
【化１１２】

実施例２９
撹拌装置、温度計、冷却管、滴下漏斗及び窒素導入管を取り付けた２リットル４ツ口フラスコに、ポリオキシアルキレントリグリセリルエーテル化合物(１２−Ｃ２)４１２.４ｇ（０.４モル）、シリリジン基含有シリコーン化合物(Ｓ−６)２５.７ｇ（０.０１モル）、トルエン４３８.１ｇ及び酢酸カリウム０.７０ｇを仕込み、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら７０℃に保持した系に、最終的に系内の触媒濃度が２０ppmとなるように塩化白金酸の２−プロパノール溶液を１時間かけて滴下した。滴下終了後、８０℃で１２時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］３０ｇを加えて窒素ガスを吹き込みながらトルエンなどを減圧留去し、続いて吸着剤、酢酸カリウムをろ別することにより変性シリコーン化合物(２９−１Ｃ２Ｓ)３８５.４ｇを得た（収率８８％）。
得られた化合物の水酸基価は２０５mgKOH／ｇ、不飽和度は０.０１meq／ｇ、重量平均分子量は４２,１３０であった。また、赤外吸収スペクトル分析を行った。

出発原料、反応条件、分析値より、化合物(２９−１Ｃ２Ｓ)の構造は、式［２９−１Ｃ２Ｓ］であると推定した。
【化１１３】

実施例３０
撹拌装置、温度計、冷却管、滴下漏斗及び窒素導入管を取り付けた５００ミリリットル４ツ口フラスコに、ポリオキシアルキレントリグリセリルエーテル化合物(１１−Ｃ２)２６３.２ｇ（０.２モル）、シリリジン基含有シリコーン化合物(Ｓ−１)４４.５ｇ（０.２モル）、トルエン７６.９ｇ及び酢酸カリウム０.１５ｇを仕込み、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら７０℃に保持した系に、最終的に系内の触媒濃度が１０ppmとなるように塩化白金酸の２−プロパノール溶液を１時間かけて滴下した。滴下終了後、８０℃で５時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて窒素ガスを吹き込みながらトルエンなどを減圧留去し、続いて吸着剤、酢酸カリウムをろ別することにより変性シリコーン化合物(３０−１Ｃ２Ｓ)２９１.７ｇを得た（収率９５％）。
得られた化合物の水酸基価は１４８mgKOH／ｇ、不飽和度は０.００meq／ｇ、重量平均分子量は１,５２０であった。また、赤外吸収スペクトル分析を行った。

出発原料、反応条件、分析値より、化合物(３０−１Ｃ２Ｓ)の構造は、式［３０−１Ｃ２Ｓ］であると推定した。
【化１１４】

実施例３１
撹拌装置、温度計、冷却管、滴下漏斗及び窒素導入管を取り付けた１リットル４ツ口フラスコに、ポリオキシアルキレントリグリセリルエーテル化合物(１３−Ｃ２)２００.０ｇ（０.１モル）、シリリジン基含有シリコーン化合物式(Ｓ−５)８１.０ｇ（０.００５モル）、トルエン２８１.０ｇ及び酢酸カリウム０.５０ｇを仕込み、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら７０℃に保持した系に、最終的に系内の触媒濃度が２０ppmとなるように塩化白金酸の２−プロパノール溶液を１時間かけて滴下した。滴下終了後、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］２０ｇを加えて窒素ガスを吹き込みながらトルエンなどを減圧留去し、続いて吸着剤、酢酸カリウムをろ別することにより変性シリコーン化合物(３１−１Ｃ２Ｓ)２４０.５ｇを得た（収率８６％）。
得られた化合物の水酸基価は７９.９mgKOH／ｇ、不飽和度は０.００meq／ｇ、重量平均分子量は５３,４３０であった。また、赤外吸収スペクトル分析を行った。

出発原料、反応条件、分析値より、化合物(３１−１Ｃ２Ｓ)の構造は、式［３１−１Ｃ２Ｓ］であると推定した。
【化１１５】

実施例３２
撹拌装置、温度計、冷却管、滴下漏斗及び窒素導入管を取り付けた３００ミリリットル４ツ口フラスコに、ポリオキシアルキレントリグリセリルエーテル化合物(１２−Ｅ２)８１.３ｇ（０.１モル）、シリリジン基含有シリコーン化合物(Ｓ−７)１１１.２ｇ（０.１モル）、トルエン４７.８ｇ及び酢酸カリウム０.２０ｇを仕込み、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら７０℃に保持した系に、最終的に系内の触媒濃度が２０ppmとなるように塩化白金酸の２−プロパノール溶液を１時間かけて滴下した。滴下終了後、８０℃で８時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］１５ｇを加えて窒素ガスを吹き込みながらトルエンなどを減圧留去し、続いて吸着剤、酢酸カリウムをろ別することにより変性シリコーン化合物(３２−１Ｃ２Ｓ)１７８.２ｇを得た（収率９３％）。
得られた化合物の水酸基価は１１８mgKOH／ｇ、不飽和度は０.０２meq／ｇ、重量平均分子量は１,９００であった。また、赤外吸収スペクトル分析を行った。

出発原料、反応条件、分析値より、化合物(３２−１Ｃ２Ｓ)の構造は、式［３２−１Ｃ２Ｓ］であると推定した。
【化１１６】

実施例３３
撹拌装置、温度計及び窒素導入管を取り付けた１０リットル容量のオートクレーブに、ジイソプロピリデントリグリセリン［化合物(Ａ)］１６０１.９ｇ(５.０モル)と水酸化カリウム１１.７ｇを仕込み、系内を窒素ガスで置換した。昇温して８５〜９５℃に保持し、エチレンオキシド２,３１２.６ｇ（５２.５モル）を滴下して反応した。滴下終了後、８５〜９５℃でさらに２時間熟成した。熟成終了後、窒素ガスを吹き込みながら未反応の残存エチレンオキシドを減圧留去した。そして、系を２０℃まで冷却した。
系に水酸化カリウム１,１２２.２ｇ（２０.０モル）を追加し、７５〜８５℃に昇温した。ボンベに予め計量した塩化アリル５７４.０ｇ（７.５モル）を滴下して反応した。滴下終了後１１５〜１２５℃に昇温して４時間熟成した。熟成後、７５〜８５℃に冷却し、減圧下、窒素をガス吹き込みながら、過剰の塩化アリルを留去した。さらに反応液に水３,９３０ｇを加えて水洗し、静置分離して反応により生成した塩及び過剰のアルカリを除去した。塩基吸着剤［キョーワード７００、協和化学工業(株)製］１８０ｇを加えて窒素ガスを吹き込みながら減圧脱水し、続いて吸着剤をろ別することによりポリエーテル化合物(１１−Ｂ)３,５２０.２ｇを得た（収率８６％）。
得られた化合物の水酸基価は０.１mgKOH／ｇ、不飽和度は１.２４meq／ｇ、であった。出発原料、反応条件、分析値より、化合物(１１−Ｂ)の構造は、第７表に示す式［１１−Ｂ］であると推定した。
撹拌装置、温度計、冷却管、滴下漏斗及び窒素導入管を取り付けた３リットル４ツ口フラスコに、ポリオキシアルキレントリグリセリルエーテル化合物(１１−Ｂ)１,６１０.７ｇ（２.０モル）、シリリジン基含有シリコーン化合物(Ｓ−１)４４５.０ｇ（２.０モル）、トルエン５１３.９ｇ及び酢酸カリウム１.０ｇを仕込み、窒素雰囲気下で７０℃まで昇温した。かき混ぜながら７０℃に保持した系に、最終的に系内の触媒濃度が１０ppmとなるように塩化白金酸の２−プロパノール溶液を１時間かけて滴下した。滴下終了後、８０℃で５時間反応を行った。反応終了後、酸吸着剤［キョーワード３００、協和化学工業(株)製］７５ｇを加えて窒素ガスを吹き込みながらトルエンなどを減圧留去し、続いて吸着剤、酢酸カリウムをろ別することにより変性シリコーン化合物(１１−ＢＳ−１)１,９５３.９ｇを得た（収率９５％）。
得られた化合物の水酸基価は０.２mgKOH／ｇ、不飽和度は０.００meq／ｇ、であった。出発原料、反応条件、分析値より、化合物(１１−ＢＳ−１)の構造は、式［１１−ＢＳ−１］であると推定した。
【化１１７】

撹拌装置、温度計、冷却管及び窒素導入管を取り付けた２リットル４ツ口フラスコに化合物(１１−ＢＳ−１)１,０２６.４ｇ（１.０モル）と１重量％の希塩酸３４２.１ｇを仕込み、強く撹拌しつつ７５〜８５℃で４時間加水分解した。炭酸ナトリウム水溶液で系のpHを７.０に調製し、窒素ガスを吹き込みながら減圧脱水し、続いて析出した塩をろ別することにより変性シリコーン化合物(３３−３Ｃ１Ｓ)８６８.３ｇを得た（収率９２％）。
得られた化合物の水酸基価は２３７mgKOH／ｇ、不飽和度は０.００meq／ｇ、であった。出発原料、反応条件、分析値より、化合物(３３−３Ｃ１Ｓ)の構造は、式［３３−３Ｃ１Ｓ］であると推定した。
【化１１８】

撹拌装置、温度計及び窒素導入管を取り付けた１リットル容量のオートクレーブに化合物(３３−３Ｃ１Ｓ)３７８．５ｇ（０.４モル）と三フッ化ホウ素ジエチルエーテル３.１ｇを仕込み、系内を窒素ガスで置換した。昇温して５５〜６５℃に保持し、プロピレンオキシド２４３.９ｇ（４.２モル）を滴下して反応した。滴下終了後、５５〜６５℃でさらに２時間熟成した。熟成終了後、炭酸ナトリウム水溶液で系のpHを７.０に調製し、窒素ガスを吹き込みながら未反応の残存プロピレンオキシド、水などを減圧留去した。その後、ろ過することにより変性シリコーン化合物(３３−３Ｃ２Ｓ)５５６.４ｇを得た（収率８９％）。
得られた化合物の水酸基価は１４８mgKOH／ｇ、不飽和度は０.００meq／ｇ、重量平均分子量は１,５１０であった。また、赤外吸収スペクトル分析を行った。

出発原料、反応条件、分析値より、化合物(３３−３Ｃ２Ｓ)の構造は、式［３３−３Ｃ２Ｓ］であると推定した。
【化１１９】

実施例３４
１００mlの共栓付きメスシリンダーに、実施例２において合成した本発明の化合物(２−Ｃ)、実施例５において合成した本発明の化合物(５−Ｃ)、実施例１１において合成した本発明の化合物(１１−Ｃ２)、実施例１７において合成した本発明の化合物(１７−Ｃ２)、実施例１８において合成した本発明の化合物(１８−Ｅ２)の５種類のサンプル、比較例１［化合物(Ｃ)］のサンプル又は比較例２［化合物(Ｇ)］のサンプルを５ｇと、流動パラフィン４５ｇをはかり取り、２分間よく振り混ぜたのち、室温で２４時間静置して混合状態を目視で観察した。また、ＪＩＳ Ｋ ２２８３（１９６９）にしたがって、２５℃における動粘度を測定した。
なお、比較例に使用した化合物の構造式を次ぎに示す。
比較例１
式［Ｃ］で表されるトリグリセリルモノアリルエーテル。
【化１２０】

比較例２
式［Ｇ］で表されるグリセリンモノアリルエーテルのグリシドール２モル付加物。
【化１２１】

結果を第９表及び第１０表に示す。
【００５１】
【表１６】

【００５２】
【表１７】

【００５３】
第９表及び第１０表の結果から、本発明のポリオキシアルキレントリグリセリルエーテル化合物は流動パラフィンと均一に混合し、２４時間経過後も安定であるが、トリグリセリルモノアリルエーテルは、流動パラフィンと均一に混合せず、振り混ぜ直後からすでに分離することが分かる。
第９表及び第１０表の結果から、本発明のポリオキシアルキレントリグリセリルエーテル化合物は流動パラフィンと均一に混合し、２４時間経過後も安定であり、且つ混合物は低粘度であるが、トリグリセリンモノアリルエーテル及びグリセリンモノアリルエーテルのグリシドール２モル付加物は、流動パラフィンと均一に混合せず、振り混ぜ直後からすでに分離し、かつ混合物は高粘度であることが分かる。
実施例３５
実施例１９、実施例２０、実施例２５、実施例３０及び実施例３２において合成した本発明の変性シリコーン化合物(１９−１ＣＳ)、(２０−１ＣＳ)、(２５−３ＣＳ)、(３０−１Ｃ２Ｓ)及び(３２−１Ｃ２Ｓ)、ポリオキシアルキレン鎖を有しない変性シリコーン化合物である化合物(ＣＳ−１)及び(ＣＳ−３)について流動性を調べた。
５０mlスクリュー管にサンプル２０ｇを投入し、２５℃において充分静置し、液面が水平になったことを確認後、スクリュー管を傾けることにより室温での流動性の有無を観察した。結果を第１１表に示す。
【００５４】
【表１８】

【００５５】
第１１表の結果から、トリグリセリルエーテル基を有するがポリオキシアルキレン鎖を有しない比較例の変性シリコーン化合物は、非常に粘稠か又は全く流動性を示さないのに対して、本発明のポリオキシアルキレン鎖を有するトリグリセリルエーテル変性シリコーン化合物は、良好な流動性を有する取り扱いの容易な変性シリコーン化合物であることが分かる。
【００５６】
【発明の効果】
本発明のポリオキシアルキレントリグリセリルエーテル化合物は、末端に二重結合をもつアルケニル基を分子中に１個のみ有し、かつポリオキシアルキレン鎖を有する新規なポリグリセリン誘導体であり、付加させるアルキレンオキシドの種類及び付加モル数を変えることにより、低分子量から高分子量の化合物、親水性と親油性のバランスの調整など、幅広い化合物を製造することができる。またアルケニル基を有するために、シリコーン変性用の反応中間体として有用である。本発明の変性シリコーン化合物は、上記のポリオキシアルキレントリグリセリルエーテル化合物のアルケニル基と、シリコーン化合物のシリリジン基の付加反応により得られる化合物であり、低粘度で取り扱い性に優れ、ポリオキシアルキレントリグリセリルエーテル化合物及びシリコーン化合物の選択により、幅広い性能を有する界面活性剤とすることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to novel polyoxyalkylene triglyceryl ether compounds and modified silicone compounds and methods for producing them. More specifically, the present invention relates to a novel polyoxyalkylene triglyceryl ether compound useful as a reactive intermediate having a polyoxyalkylene chain and an alkenyl group having a double bond at the terminal, and a single compound modified with the compound. The present invention relates to a modified silicone compound that is easy to handle and has excellent emulsifiability and dispersibility, and an efficient method for producing these compounds.
[0002]
[Prior art]
It is well known that polyalkylene glycol ethers having a polyoxyalkylene chain can be synthesized by adding alkylene oxide to a compound having active hydrogen, such as surfactants, lubricants, cosmetics, antifoaming agents, etc. It is used. Polyalkylene glycols having an allylic double bond as an active substituent are also widely known, and are used for addition copolymerization with other olefinic monomers and modification of silicone compounds having a silylidine group. It is useful for the purpose of imparting property and imparting surface activity.
Conventionally synthesized polyalkylene glycols having an allylic double bond include linear and branched polyalkylene glycols, which are not satisfactory in terms of hydrophilicity. Since salting out with salt is likely to occur, there is a limit to the fields that can be used. In order to solve this problem, Japanese Patent Application Laid-Open No. 57-149290 discloses a polyglycerin derivative having an alkenyl group using a hydroxyl group in addition to an ether bond as a hydrophilic substituent. However, these compounds have the disadvantage that the viscosity increases as the number of hydroxyl groups in one molecule increases, making handling difficult. Therefore, there has been a demand for a compound that is easy to handle without damaging physical properties such as strong hydrophilicity.
[0003]
Furthermore, a modified silicone compound obtained by adding a isopropylidene monoglycerin monoallyl ether to a silylidine group and then performing a deacetonation reaction is disclosed in JP-A-6-157236, and diisopropylidene triglycerin. Modified silicone compounds obtained by adding a monoallyl ether to a silylidine group and then performing a deacetoneation reaction are disclosed in JP-A-4-20531 and JP-A-4-327273. The modified silicone compound has problems such as poor fluidity due to strong hydrogen bonding between hydroxyl groups and limited applications. Introducing an oxyalkylene chain is effective as a means of reducing the viscosity of a polyglycerin derivative. However, the polyglycerin derivative has only one alkenyl group having a double bond at its end in the molecule, and polyoxyalkylene. A compound having a chain is not known, and development of such a polyglycerol polyoxyalkylene glycol ether derivative and a silicone compound modified with the derivative has been demanded.
[0004]
[Problems to be solved by the invention]
The present invention is a novel polyoxyalkylene triglyceryl ether compound useful as a reactive intermediate having a polyoxyalkylene chain and an alkenyl group having a double bond at the terminal, and is easy to handle alone modified with the compound. The present invention has been made for the purpose of providing a modified silicone compound having excellent emulsifiability and dispersibility, and an efficient method for producing these compounds.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have bonded an alkenyl group to the hydroxyl group at the center of the triglycerin molecule directly or via a polyoxyalkylene chain, and to the four hydroxyl groups at both ends. A novel polyoxyalkylene triglyceryl ether compound to which a polyoxyalkylene chain is bonded has an appropriate hydrophilic / lipophilic balance and has a good reactivity with a silylidine group, and the compound reacts with a silicone compound having a silylidine group. Thus, the modified silicone compound was found to be easy to handle and have excellent emulsifiability and dispersibility, and the present invention was completed based on this finding.
That is, the present invention
(1) General formula [1]
Embedded image

(However, in the formula, A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The added mole number of O is 1 to 100, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and R ¹ , R ² , R ^Three And R ^Four Is a hydrogen atom, an acyl group having 2 to 24 carbon atoms, a 1-alkoxyalkyl group having 3 to 10 carbon atoms, or a cyclic ether group in which the carbon adjacent to oxygen is bonded to the polyoxyalkylene chain, and they are the same or different. It may be. )
A polyoxyalkylene triglyceryl ether compound represented by:
(2) A in the general formula [1] ² A polyoxyalkylene triglyceryl ether compound in which O is an oxyalkylene group having 2 to 4 carbon atoms and the number of moles a, b, c and d thereof is 1 to 50;
(3) R in the general formula [1] ¹ , R ² , R ^Three And R ^Four A polyoxyalkylene triglyceryl ether compound in which is a hydrogen atom,
(4) Z in the general formula [1] is CH ₂ = CHCH ₂ -, CH ₂ = C (CH _Three ) CH ₂ -, CH ₂ = CHC (CH _Three ) ₂ -, CH ₂ = C (CH _Three ) C (CH _Three ) ₂ -, CH ₂ = CHC (CH _Three ) ₂ CH ₂ -And CH ₂ = C (CH _Three ) C (CH _Three ) ₂ CH ₂ A polyoxyalkylene triglyceryl ether compound which is a group selected from:
(5) Formula [2]
Embedded image

In the triglycerin represented by the general formula [3]
RCOR '... [3]
(In the formula, R and R ′ are alkyl groups, and they may be the same or different.)
Is reacted with a ketone compound represented by the general formula [4]
Embedded image

(In the formula, R and R ′ are alkyl groups, and they may be the same or different.)
A compound represented by general formula [5] is optionally added, and one or more kinds of alkylene oxides having 2 to 8 carbon atoms are optionally added.
Embedded image

(However, in the formula, A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and may be one kind or two or more kinds. In the case of two or more kinds, O may be a block addition or a random addition, and n is an addition mole number of the oxyalkylene group. And R and R ′ are alkyl groups, which may be the same or different. )
To obtain a compound represented by the general formula [6]
Z-X [6]
(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and X is a halogen atom.)
And an alkenyl halide represented by the general formula [7]
Embedded image

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the end, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and may be one kind or two or more kinds. In the case of two or more kinds, O may be a block addition or a random addition, and n is an addition mole number of the oxyalkylene group. And R and R ′ are alkyl groups, which may be the same or different. )
And then reacting with an acid to give a compound represented by the general formula [8]
Embedded image

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the end, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and may be one kind or two or more kinds. In the case of two or more kinds, O may be a block addition or a random addition, and n is an addition mole number of the oxyalkylene group. 100. )
The compound represented by the general formula [1] is obtained, and after addition of one or two or more alkylene oxides having 2 to 8 carbon atoms, the terminal hydroxyl group is esterified or acetalized as desired. ]
Embedded image

(However, in the formula, A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The added mole number of O is 1 to 100, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and R ¹ , R ² , R ^Three And R ^Four Is a hydrogen atom, an acyl group having 2 to 24 carbon atoms, a 1-alkoxyalkyl group having 3 to 10 carbon atoms, or a cyclic ether group in which the carbon adjacent to oxygen is bonded to the polyoxyalkylene chain, and they are the same or different. It may be. )
A process for producing a polyoxyalkylene triglyceryl ether compound represented by:
(6) A method for producing a polyoxyalkylene triglyceryl ether compound, wherein the ketone compound represented by the general formula [3] is acetone or methyl ethyl ketone,
(7) General formula [9]
Embedded image

[(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁶ , R ⁷ And R ⁸ At least one is a group represented by the following general formula [10], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is. )
Embedded image

(In the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The number of moles of O added is 1 to 100. ]]
A modified silicone compound represented by:
(8) General formula [11]
Embedded image

(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one is a hydrogen atom, the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0-800. )
A silicone compound represented by the general formula [12]
Embedded image

(However, in the formula, A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The added mole number of O is 1 to 100, and Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal. )
And a polyoxyalkylene triglyceryl ether compound represented by the general formula [9]
Embedded image

[(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁶ , R ⁷ And R ⁸ At least one is a group represented by the following general formula [10], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is. )
Embedded image

(In the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The number of moles of O added is 1 to 100. ]]
A method for producing a modified silicone compound represented by:
(9) General formula [11]
Embedded image

(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one is a hydrogen atom, the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0-800. )
A silicone compound represented by the general formula [13]
Embedded image

(However, in the formula, A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The added mole number of O is 1 to 100, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ Is a C2-C24 acyl group, a C3-C10 1-alkoxyalkyl group or a cyclic ether group in which the carbon adjacent to oxygen is bonded to the polyoxyalkylene chain, and they are the same or different. Also good. )
After reacting with a polyoxyalkylene triglyceryl ether compound represented by ¹² , R ¹³ , R ¹⁴ And R ¹⁵ General formula [9], characterized in that is eliminated to form a hydrogen atom
Embedded image

[(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁶ , R ⁷ And R ⁸ At least one is a group represented by the following general formula [10], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is. )
Embedded image

(In the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The number of moles of O added is 1 to 100. ]]
A method for producing a modified silicone compound represented by:
(10) General formula [11]
Embedded image

(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one is a hydrogen atom, the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0-800. )
A silicone compound represented by the general formula [8]
Embedded image

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the end, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and may be one kind or two or more kinds. In the case of two or more kinds, O may be a block addition or a random addition, and n is an addition mole number of the oxyalkylene group. 100. )
1 or 2 or more types of C2-C8 alkylene oxide is added to the silicone compound obtained by making it react with the compound represented by General formula [9]
Embedded image

[(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁶ , R ⁷ And R ⁸ At least one is a group represented by the following general formula [10], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is. )
Embedded image

(In the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The number of moles of O added is 1 to 100. ]]
And a method for producing a modified silicone compound represented by:
(11) General formula [11]
Embedded image

(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one of them is hydrogen, the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0-800. )
A silicone compound represented by general formula [7]
Embedded image

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the end, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and may be one kind or two or more kinds. In the case of two or more kinds, O may be a block addition or a random addition, and n is an addition mole number of the oxyalkylene group. And R and R ′ are alkyl groups, which may be the same or different. )
1 type or 2 types or more of C2-C8 alkylene oxide is added to the silicone compound obtained by hydrolyzing an acetal group after making it react with the compound represented by this general Formula [9]
Embedded image

[(However, in the formula, R ^Five Is a methyl group or a phenyl group, and R ⁶ , R ⁷ And R ⁸ At least one is a group represented by the following general formula [10], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is. )
Embedded image

(In the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The number of moles of O added is 1 to 100. ]]
A method for producing a modified silicone compound represented by:
Is to provide.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The polyoxyalkylene triglyceryl ether compound of the present invention has the general formula [1]
Embedded image

It has the structure represented by these.
In general formula [1], A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms, and the alkylene group in the oxyalkylene group may be linear or branched, and an aromatic ring is formed in the branch. You may have. Examples of the raw material used for introducing such an oxyalkylene group include ethylene oxide, propylene oxide, butylene oxide, oxetane, tetrahydrofuran, and styrene oxide. Among these, availability is easy. From the above point, ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran having 2 to 4 carbon atoms can be preferably used.
[0007]
In the compound represented by the general formula [1], the oxyalkylene group may be only one kind, or two or more kinds. When there are two or more oxyalkylene groups, the addition state is Any of a block shape and a random shape may be used. N is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The number of moles of O added is 1 to 100. Oxyalkylene group A ¹ O and A ² The added mole number of O represents an average value, for example, A ¹ A compound represented by the general formula [1] without addition of O and A ¹ The equimolar mixture of the compound represented by the general formula [1] to which 1 mol of O is added has a value of n of 0.5. Oxyalkylene group A ¹ O or A ² When the added mole number of O exceeds 100, the viscosity of the compound represented by the general formula [1] becomes too high, and it may be difficult to produce and handle. From the ease of manufacturing and handling, hydrophilic / lipophilic balance, etc. ¹ The number of moles of O added is preferably 0 to 50, and A ² The number of added moles of O is preferably 1-50.
[0008]
In the general formula [1], Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, for example, CH ₂ = CHCH ₂ -, CH ₂ = C (CH _Three ) CH ₂ -, CH ₂ = CHC (CH _Three ) ₂ -, CH ₂ = C (CH _Three ) C (CH _Three ) ₂ -, CH ₂ = CHC (CH _Three ) ₂ CH ₂ -, CH ₂ = C (CH _Three ) C (CH _Three ) ₂ CH ₂ -Etc. can be mentioned. Of these, allyl groups (CH ₂ = CHCH ₂ -) And a methallyl group (CH ₂ = C (CH _Three ) CH ₂ -) Is preferred. In the general formula [1], R ¹ , R ² , R ^Three And R ^Four Is a cyclic ether group in which a hydrogen atom, an acyl group having 2 to 24 carbon atoms, a 1-alkoxyalkyl group having 3 to 10 carbon atoms, or a carbon adjacent to oxygen is bonded to a polyoxyalkylene chain.
[0009]
The acyl group having 2 to 24 carbon atoms may be any of an aliphatic saturated acyl group, an aliphatic unsaturated acyl group, and an aromatic acyl group. Examples of the aliphatic saturated acyl group include an acetyl group, a propionyl group, and a butyryl group. , Valeryl group, octanoyl group, decanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, etc. Examples of the aromatic acyl group include a benzoyl group, a toluoyl group, a phenylacetyl group, a cinnamoyl group, and a naphthoyl group.
Examples of the C1-C10 1-alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-propoxyethyl group, and a 1-butoxyethyl group. Examples of the cyclic ether group in which carbon adjacent to oxygen is bonded to the polyoxyalkylene chain include a 2-tetrahydrofuryl group and a 2-tetrahydropyryl group.
[0010]
The production of the polyoxyalkylene triglyceryl ether compound represented by the general formula [1] according to the method of the present invention will be described.
First, the formula [2]
Embedded image

In the triglycerin represented by the general formula [3]
RCOR '... [3]
The ketone compound represented by this is reacted. However, in General Formula [3], R and R ′ are alkyl groups, which may be the same or different. By reacting the triglycerin represented by the formula [2] with the ketone compound represented by the general formula [3] to protect two adjacent hydroxyl groups at both ends of the triglycerin, the general formula [4]
Embedded image

The diacetal compound represented by these is obtained.
[0011]
Examples of the ketone compound represented by the general formula [3] include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, pinacolone, diisopropyl ketone, and the like. Of these, acetone and methyl ethyl ketone are preferred from the standpoint of ease of reaction and elimination in a later step, and acetone can be particularly preferably used. When acetone is used, diisopropylidene triglycerin is obtained as a diacetal compound represented by the general formula [4]. Diisopropylidene triglycerin can also be obtained from the market as an industrial chemical, and commercially available diisopropylidene triglycerin can be used as a starting material for the polyoxyalkylene triglyceryl ether compound of the present invention.
[0012]
Next, if desired, one or more alkylene oxides having 2 to 8 carbon atoms are added to the diacetal compound represented by the general formula [4] to obtain the general formula [5].
Embedded image

To obtain a compound represented by: In general formula [5], A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and may be one type or two or more types, and in the case of two or more types, block addition or random addition may be used. 100, and R and R ′ may be the same or different in the alkyl group. The addition reaction of alkylene oxide is usually carried out using an alkali catalyst at 60 to 200 ° C, preferably 80 to 150 ° C. Examples of the alkali catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium metal, and the like. From the viewpoint of availability, sodium hydroxide and water. Potassium oxide and sodium methoxide can be preferably used. Examples of the alkylene oxide used in this reaction include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. Among these, ethylene oxide, propylene oxide, and butylene oxide are preferably used from the viewpoint of easy availability. can do.
[0013]
The compound represented by the general formula [5] thus obtained is added to the general formula [6].
Z-X [6]
The alkenyl halide represented by this is reacted. In the general formula [6], Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and X is a halogen atom. Examples of such alkenyl halide include CH. ₂ = CHCH ₂ X, CH ₂ = C (CH _Three ) CH ₂ X, CH ₂ = CHC (CH _Three ) ₂ X, CH ₂ = C (CH _Three ) C (CH _Three ) ₂ X, CH ₂ = CHC (CH _Three ) ₂ CH ₂ X, CH ₂ = C (CH _Three ) C (CH _Three ) ₂ CH ₂ X and the like can be mentioned. Among these, allyl halide (CH ₂ = CHCH ₂ X) and methallyl halide (CH) ₂ = C (CH _Three ) CH ₂ X) can be used particularly preferably. Examples of the halogen represented by X include chlorine, bromine, and iodine. Among these, chlorine is particularly preferable. This reaction is usually carried out at 50 to 150 ° C., preferably 70 to 130 ° C. in the presence of a dehydrohalogenating agent. A known basic compound can be used as the dehydrohalogenating agent.
[0014]
By reacting the compound represented by the general formula [5] with the alkenyl halide represented by the general formula [6], the general formula [7]
Embedded image

To obtain a compound represented by: In general formula [7], A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and it may be one kind or two or more kinds, and in the case of two or more kinds, it may be a block addition or a random addition, and n is an average addition mole number of the oxyalkylene group. ˜100, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, R and R ′ are alkyl groups, and they may be the same or different.
Next, an acid is allowed to act on the compound represented by the general formula [7] thus obtained to remove the protecting group, and the general formula [8]
Embedded image

To obtain a compound having 4 hydroxyl groups. Examples of the acid to be used include mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid, and organic acids such as acetic acid and p-toluenesulfonic acid. Among these, hydrochloric acid and phosphoric acid can be preferably used from the viewpoint of subsequent treatment. Moreover, alcohol, such as ethanol and isopropyl alcohol, can be added at the same time in order to improve contact between the compound represented by the general formula [7] and water as necessary.
[0015]
Furthermore, one or two or more kinds of alkylene oxides having 2 to 8 carbon atoms are added to the compound represented by the general formula [8] to obtain the general formula [12].
Embedded image

The polyoxyalkylene triglyceryl ether compound represented by these is obtained. In general formula [12], A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The added mole number of O is 1 to 100, and Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal. That is, the compound represented by the general formula [12] is represented by R in the general formula [1]. ¹ , R ² , R ^Three And R ^Four Are all hydrogen atoms.
This addition reaction of alkylene oxide is usually carried out using an alkali catalyst. Examples of the alkali catalyst include lithium hydroxide, sodium hydroxide, and potassium hydroxide. From the viewpoint of availability, sodium hydroxide, potassium hydroxide, and sodium methoxide can be preferably used. . If necessary, the addition reaction of alkylene oxide can be carried out at -50 to 100 ° C, preferably 0 to 70 ° C, using a Lewis acid catalyst such as stannic chloride or boron trifluoride etherate. . Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, oxetane, tetrahydrofuran, and styrene oxide. Among these, ethylene oxide and propylene having 2 to 4 carbon atoms from the viewpoint of availability. Oxides, butylene oxide and tetrahydrofuran can be preferably used.
[0016]
Finally, the hydroxyl group of the compound represented by the general formula [12] thus obtained is esterified or acetalized as desired. When esterifying, a C2-C24 fatty acid or these reactive derivatives, for example, an acid anhydride, an acid halide, a lower ester, etc. can be used. As the fatty acid or reactive derivative thereof, as an acyl group, R represented by the general formula [1] ¹ , R ² , R ^Three And R ^Four The compounds having an acyl group having 2 to 24 carbon atoms exemplified in the description of (1) can be used. By esterification, in general formula [1], R ¹ , R ² , R ^Three And R ^Four A compound in which is an acyl group having 2 to 24 carbon atoms can be obtained.
In the case of acetalization, vinyl ethers having 3 to 10 carbon atoms such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, dihydrofuran, dihydropyran and the like can be used. By acetalization, in general formula [1], R ¹ , R ² , R ^Three And R ^Four However, it is possible to obtain a compound in which a 1-alkoxyalkyl group having 3 to 10 carbon atoms or a cyclic ether group in which carbon adjacent to oxygen is bonded to a polyoxyalkylene chain.
[0017]
Next, the modified silicone compound of the present invention will be described in detail.
The modified silicone compound of the present invention has the general formula [9]
Embedded image

It has the structure represented by these. In the general formula [9], R ^Five Is a methyl group or a phenyl group, and R ⁶ , R ⁷ And R ⁸ At least one is a group represented by the following general formula [10], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is.
Embedded image

In the general formula [10], Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The number of moles of O added is 1 to 100.
As the compound represented by the general formula [9], (1) x ≧ 0 and y = 0, and R ⁶ Or R ⁸ One of the compounds represented by the general formula [10], (2) x ≧ 0 and y = 0, and R ⁶ And R ⁸ Both of the compounds represented by the general formula [10], (3) x = 0 and y> 0, R ⁷ Is a compound represented by the general formula [10], (4) x> 0 and y> 0, and R ⁷ May be a compound represented by the general formula [10], and an appropriate compound can be selected in consideration of a combination with a polyoxyalkylene chain depending on the use.
[0018]
In general formula [9], A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms. Examples of such an oxyalkylene group include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytrimethylene group, an oxytetramethylene group, and an oxystyrene group. And so on.
In general formula [9], A ² O is an oxyalkylene group having 2 to 8 carbon atoms. Examples of such an oxyalkylene group include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytrimethylene group, an oxytetramethylene group, and an oxystyrene group. And so on.
In the general formula [9], the sum of x and y is 0 to 800, preferably 1 to 400. When the total of x and y exceeds 800, the viscosity of the compound represented by the general formula [9] is increased, which may make it difficult to handle. Moreover, in general formula [10], n is 0-100, Preferably it is 0-50. When n exceeds 100, the viscosity of the compound represented by the general formula [9] is increased, which may make it difficult to handle. In the general formula [10], a, b, c and d are 1 to 100, preferably 1 to 20. When a, b, c, and d exceed 100, the viscosity of the compound represented by the general formula [9] increases, which may make handling difficult.
[0019]
Below, the manufacturing method of the modified silicone compound represented by General formula [9] is described. The modified silicone compound having a polyoxyalkylene derivative group having four hydroxyl groups represented by the general formula [10] is prepared by using the compound represented by the general formula [7] described above as a raw material and the route [1 ] To [4].
Route [1]
An acid is allowed to act on the compound represented by the general formula [7] to decompose the acetal group, and the general formula [8]
Embedded image

To obtain a compound represented by: In the general formula [8], Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal. Examples of the acid used at this time include mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid, and organic acids such as acetic acid and p-toluenesulfonic acid. From the viewpoint of subsequent treatment, hydrochloric acid and phosphoric acid are preferred. It can be preferably used. If necessary, an alcohol such as ethanol or isopropyl alcohol can be added in order to improve the contact between the compound represented by the general formula [7] and water.
Furthermore, one or two or more kinds of alkylene oxides having 2 to 8 carbon atoms are added to the compound represented by the general formula [8] to obtain the general formula [12].
Embedded image

The polyoxyalkylene triglyceryl ether compound represented by these is obtained. In general formula [12], A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The added mole number of O is 1 to 100, and Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal. That is, the compound represented by the general formula [12] is represented by R in the general formula [1]. ¹ , R ² , R ^Three And R ^Four Are all hydrogen atoms.
[0020]
This alkylene oxide addition reaction is usually carried out using an alkali catalyst, preferably at 60 to 200 ° C, more preferably at 80 to 150 ° C. Examples of the alkali catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, and sodium methoxide. From the viewpoint of easy availability, sodium hydroxide, potassium hydroxide, and sodium methoxide can be used. It can be used suitably. If necessary, the addition reaction of alkylene oxide can be carried out at -50 to 100 ° C, preferably 0 to 70 ° C, using a Lewis acid catalyst such as stannic chloride or boron trifluoride etherate. . Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, oxetane, tetrahydrofuran, and styrene oxide. Among these, ethylene oxide and propylene having 2 to 4 carbon atoms from the viewpoint of availability. Oxides, butylene oxide and tetrahydrofuran can be preferably used.
[0021]
The polyoxyalkylene triglyceryl ether compound represented by the general formula [12] thus obtained and the general formula [11]
Embedded image

Is added in the presence of a catalyst to obtain a target modified silicone compound. In the general formula [11], R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one is a hydrogen atom, the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0-800.
As a catalyst used for the reaction of the double bond of the polyoxyalkylene triglyceryl ether compound represented by the general formula [12] and the silylidine group of the silicone compound represented by the general formula [11], nickel, ruthenium, rhodium, Examples thereof include Group VIII transition metals such as palladium, iridium and platinum, or compounds thereof. Chloroplatinic acid is easily available, and the alcohol solution is a homogeneous catalyst. It is preferable to use a known method such as adding a buffering agent such as potassium acetate into the system in order to prevent the dehydrogenation reaction of the hydroxyl group and the silylidine group during the reaction between the double bond and the silylidine group. In this reaction, a solvent may or may not be used as necessary. The solvent to be used is not particularly limited as long as it does not inhibit the addition reaction, and examples thereof include carbon tetrachloride, toluene, xylene, hexane, octane, dibutyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate, and methyl ethyl ketone. be able to. Alcohol solvents such as ethanol, isopropanol, and n-butanol can also be used. In this case, a buffer agent such as potassium acetate is used to prevent or suppress the dehydrogenation reaction between the silylidine group and the hydroxyl group. It is preferable. This reaction is usually completed by carrying out the reaction at 70 to 120 ° C. for 0.5 to 30 hours. After the completion of the reaction, the catalyst and solvent are removed to obtain the target modified silicone compound represented by the general formula [9].
[0022]
Route [2]
In order to prevent a dehydrogenation reaction between the hydroxyl group of the polyoxyalkylene triglyceryl ether compound and the silylidine group of the silicone compound, a protective group is added to the hydroxyl group of the polyoxyalkylene triglyceryl ether compound represented by the general formula [12]. The general formula [13]
Embedded image

The polyoxyalkylene triglyceryl ether compound represented by these is obtained. In general formula [13], A ¹ O and A ² O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The number of moles of O added is 0 to 100, and a, b, c and d are oxyalkylene groups A ² The added mole number of O is 1 to 100, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ Is a hydroxyl-protecting group, which is an acyl group having 2 to 24 carbon atoms, a 1-alkoxyalkyl group having 3 to 10 carbon atoms, or a cyclic ether group in which a carbon adjacent to oxygen is bonded to a polyoxyalkylene chain. May be the same or different.
[0023]
An acid halide or an acid anhydride can be suitably used for protecting the hydroxyl group by esterification, and a vinyl ether can be suitably used for protecting the hydroxyl group by acetalization. Examples of acid halides and acid anhydrides include acid halides and acid anhydrides such as acetic acid, butyric acid, and propionic acid. Among these, acetyl chloride is preferred because of its availability and deacylation reaction. And acetic anhydride can be preferably used. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, dihydrofuran, and dihydropyran. Among these, dihydrofuran and dihydropyran are preferred because they are easily available and have few side reactions. It can be preferably used.
Subsequently, the polyoxyalkylene triglyceryl ether compound represented by the general formula [13] thus obtained and the silicone compound represented by the general formula [11] are subjected to an addition reaction in the presence of any platinum catalyst. R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ Is removed to make the terminal of the polyoxyalkylene chain a hydroxyl group, whereby the modified silicone compound of the present invention represented by the general formula [9] is obtained.
[0024]
Route [3]
General formula [11]
Embedded image

A silicone compound represented by the general formula [8]
Embedded image

The polyoxyalkylene triglyceryl ether compound represented by general formula [14] is subjected to an addition reaction in the presence of a platinum catalyst or the like.
Embedded image

A silicone compound represented by the formula: In general formula [11] and general formula [14], R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one of them is a hydrogen atom, the other is a methyl group or a phenyl group, and R ¹⁶ , R ¹⁷ And R ¹⁸ At least one is a group represented by the following general formula [15], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is. In the general formula [8], A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The added mole number of O is 0 to 100, and Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal.
[0025]
General formula [15]
Embedded image

In A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The added mole number of O is 0 to 100, and Y is a hydrocarbon group having 3 to 10 carbon atoms.
Further, the present invention represented by the desired general formula [9] is obtained by adding one or more kinds of alkylene oxides having 2 to 8 carbon atoms to the silicone compound represented by the general formula [14]. The modified silicone compound is obtained.
In this reaction, it is usually preferable to use a Lewis acid catalyst such as stannic chloride or boron trifluoride tetraetherate to prevent decomposition of the siloxane bond. As the alkylene oxide used in this reaction, the above-described alkylene oxide can be used.
[0026]
Route [4]
General formula [11]
Embedded image

A silicone compound represented by general formula [7]
Embedded image

The compound represented by general formula [16] is subjected to an addition reaction in the presence of a platinum catalyst or the like.
Embedded image

A silicone compound represented by the formula: In general formula [11] and general formula [16], R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one of them is a hydrogen atom, the other is a methyl group or a phenyl group, and R ¹⁹ , R ²⁰ And R ^{twenty one} At least one is a group represented by the following general formula [17], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0-800. It is. In the general formula [7], A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The added mole number of O is 0 to 100, and Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal.
[0027]
General formula [17]
Embedded image

In A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, and it may be one kind or two or more kinds, and in the case of two or more kinds, it may be a block addition or a random addition, and n is an average addition mole number of the oxyalkylene group. ˜100, Y is a hydrocarbon group having 3 to 10 carbon atoms, R and R ′ are alkyl groups, and they may be the same or different.
Next, an acid is allowed to act on the compound represented by the general formula [16] to decompose the acetal group, and the general formula [14]
Embedded image

A silicone compound represented by the formula: In general formula [11] and general formula [14], R ^Five Is a methyl group or a phenyl group, and R ⁹ , R ^Ten And R ¹¹ At least one of them is a hydrogen atom, the other is a methyl group or a phenyl group, and R ¹⁶ , R ¹⁷ And R ¹⁸ At least one is a group represented by the following general formula [15], the other is a methyl group or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800. It is. In the general formula [8], A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The added mole number of O is 0 to 100, and Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal.
[0028]
General formula [15]
Embedded image

In A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms and may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene group A ¹ The added mole number of O is 0 to 100, and Y is a hydrocarbon group having 3 to 10 carbon atoms.
Further, the present invention represented by the desired general formula [9] is obtained by adding one or more kinds of alkylene oxides having 2 to 8 carbon atoms to the silicone compound represented by the general formula [14]. The modified silicone compound is obtained.
In this reaction, it is usually preferable to use a Lewis acid catalyst such as stannic chloride or boron trifluoride tetraetherate to prevent decomposition of the siloxane bond. As the alkylene oxide used in this reaction, the above-described alkylene oxide can be used.
[0029]
【Example】
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the chemical formulas shown in the examples, EO represents an oxyethylene group, PO represents an oxypropylene group, BO represents an oxybutylene group, TMO represents an oxytetramethylene group, and [/] represents an addition of an oxyalkylene group. Indicates that the state is random.
In Examples, the hydroxyl value was measured according to JIS K 0070 (1992), and the degree of unsaturation was measured according to JIS K 1557 6.7 (1970).
In Examples 1-18, GPC analysis was performed on the following conditions and the weight average molecular weight was calculated | required.
Column: SHODEX KF-801, KF-803, KF-804
Developing solvent: Tetrahydrofuran
Flow rate: 1.0ml / min
Column temperature: 40 ° C
In Examples 19 to 33, GPC analysis was performed under the following conditions to determine the weight average molecular weight.
Column: PL gel 5 μm mix D × 3
Developing solvent: ethyl acetate
Flow rate: 1.0ml / min
Column temperature: 40 ° C
Production Example 1 (Production of triglyceryl monoallyl ether)
In a 10 liter stainless steel pressure-resistant reaction vessel equipped with a thermometer, a nitrogen gas blowing tube, and a stirrer, 3,845 g (12 mol) of diisopropylidenetriglycerin [compound (A), DITG] and potassium hydroxide 1, 346 g (24 mol) was taken and the inside of the reaction system was replaced with nitrogen gas. While maintaining the temperature in the system at 75 to 85 ° C. by raising the temperature, 1,102 g (14.4 mol) of allyl chloride weighed in advance in a bomb was dropped for 1 hour to react. After completion of dropping, the temperature was raised to 115 to 125 ° C. and aged for 4 hours. After aging, the mixture was cooled to 75 to 85 ° C., and excess allyl chloride was distilled off while blowing nitrogen gas under a reduced pressure of 3 to 5 mmHg. Further, a part of the reaction solution is taken, adjusted to pH 7.0 with acetic acid, dehydrated at 100 ° C. and 100 mmHg or less for 1 hour, cooled to 80 ° C., and the precipitated salt is separated by filtration to prepare a sample for analysis. Obtained. This compound is referred to as compound (B). The analytical value of the compound (B) was a hydroxyl value of 10.0 mgKOH / g and an unsaturation degree of 2.70 meq / g.
Further, the compound (B) was analyzed by IR.

Furthermore, 1% by weight of diluted hydrochloric acid is added to the reaction solution to adjust the pH to 1.0, and after hydrolysis at 75 to 85 ° C. for 3 hours, sodium carbonate is added to neutralize to pH 7.0, followed by dehydration filtration. As a result, 2,926 g of a light yellow liquid triglyceryl monoallyl ether [compound (C)] was obtained (yield 87%). The analytical value of the compound (C) was a hydroxyl value of 810 mgKOH / g and an unsaturation degree of 3.54 meq / g.
Further, the compound (C) was analyzed by IR.

The structures of compound (A), compound (B) and compound (C) are shown below.
Embedded image

Example 1 (Synthesis of polyoxyalkylene triglyceryl ether compound)
280 g (1 mol) of triglyceryl monoallyl ether [compound (C)] produced in Production Example 1 and potassium hydroxide were placed in a 5-liter stainless steel pressure-resistant reaction vessel equipped with a thermometer, a nitrogen gas blowing tube and a stirring device. 2.4 g was weighed and dissolved, and the reaction system was replaced with nitrogen gas. The temperature was raised and maintained at 85 to 95 ° C., and 527 g (12.0 mol) of ethylene oxide was added dropwise to react. After completion of dropping, the mixture was further aged at 85 to 95 ° C. for 2 hours. After completion of aging, unreacted residual ethylene oxide was distilled off under reduced pressure of 3 to 5 mmHg while blowing nitrogen gas. The reaction solution was neutralized with 1% by weight of diluted hydrochloric acid, then dehydrated and filtered to obtain 774 g of a pale yellow liquid polyether compound (1-C) (yield 96%). The analytical value of the compound (1-C) was a hydroxyl value of 286 mgKOH / g and an unsaturation degree of 1.22 meq / g. The weight average molecular weight by GPC analysis was 780.
In addition, compound (1-C) was analyzed by IR.

From these results, the structure of the compound (1-C) was estimated to be the formula [1-C].
Embedded image

Example 2 (Synthesis of polyoxyalkylene triglyceryl ether)
In the same manner as in Example 1, 280 g (1 mol) of triglyceryl monoallyl ether prepared in Preparation Example 1 and 3.6 g of potassium hydroxide were weighed in a reaction vessel, and 924 g of ethylene oxide was used instead of 527 g of ethylene oxide in Example 1. (21.0 mol) was used to obtain 1,156 g of a liquid pale yellow polyether compound (2-C) (yield 96%). The analytical value of the compound (2-C) was a hydroxyl value of 192 mg KOH / g and an unsaturation degree of 0.85 meq / g. The weight average molecular weight by GPC analysis was 980.
In addition, compound (2-C) was analyzed by IR.

From these results, the structure of the compound (2-C) was estimated to be the formula [2-C].
Embedded image

Example 3 (Synthesis of polyoxyalkylene triglyceryl ether)
In the same manner as in Example 1, 280 g (1 mol) of triglyceryl monoallyl ether prepared in Preparation Example 1 and 8.65 g of potassium hydroxide were weighed in a reaction vessel, and instead of 527 g of ethylene oxide in Example 1, ethylene oxide 1 , 883 g (42.8 mol) was used to obtain 2,045 g of a liquid pale yellow polyether compound (3-C) (yield 96%). The analysis values of the compound (3-C) were a hydroxyl value of 109 mgKOH / g and an unsaturation degree of 0.46 meq / g. The weight average molecular weight according to GPC analysis was 2,020.
In addition, compound (3-C) was analyzed by IR.

From these results, the structure of the compound (3-C) was estimated to be the formula [3-C].
Embedded image

Example 4 (Synthesis of polyoxyalkylene triglyceryl ether compound)
In the same manner as in Example 1, 280 g (1 mol) of triglyceryl monoallyl ether prepared in Preparation Example 1 and 16.2 g of potassium hydroxide were weighed, and 3,766 g of ethylene oxide was used instead of 527 g of ethylene oxide in Example 1. (85.6 mol) to give 3,844 g of a liquid pale yellow polyether compound (4-C) (yield 95%). The analysis values of the compound (4-C) were a hydroxyl value of 58.1 mgKOH / g and an unsaturation degree of 0.24 meq / g. The weight average molecular weight by GPC analysis was 3,800.
In addition, compound (4-C) was analyzed by IR.

From these results, the structure of the compound (4-C) was estimated to be the formula [4-C].
Embedded image

Example 5 (Synthesis of polyoxyalkylene triglyceryl ether compound)
In the same manner as in Example 1, 280 g (1 mol) of triglyceryl monoallyl ether prepared in Preparation Example 1 and 2.1 g of potassium hydroxide were weighed in a reaction vessel and mixed in advance instead of 527 g of ethylene oxide in Example 1. The reaction was carried out using 174 g (4.0 mol) of ethylene oxide and 230 g (3.97 mol) of propylene oxide to obtain 657 g of a liquid pale yellow polyether compound (5-C) (yield 96%). The analytical value of the compound (5-C) was a hydroxyl value of 340 mg KOH / g and an unsaturation degree of 1.40 meq / g. The weight average molecular weight by GPC analysis was 650.
In addition, compound (5-C) was analyzed by IR.

From these results, the structure of the compound (5-C) was estimated to be the formula [5-C].
Embedded image

Example 6 (Synthesis of polyoxyalkylene triglyceryl ether compound)
In the same manner as in Example 1, 280 g (1 mol) of triglyceryl monoallyl ether prepared in Preparation Example 1 and 2.4 g of potassium hydroxide were weighed in a reaction vessel and mixed in advance instead of 527 g of ethylene oxide in Example 1. The reaction was carried out using 334 g (7.58 mol) of ethylene oxide and 182 g (2.53 mol) of butylene oxide to obtain 731 g of a liquid pale yellow polyether compound (6-C) (yield 90%). The analytical value of the compound (6-C) was a hydroxyl value of 311 mgKOH / g and an unsaturation degree of 1.35 meq / g. The weight average molecular weight by GPC analysis was 740.
In addition, compound (6-C) was analyzed by IR.

From these results, the structure of the compound (6-C) was estimated to be the formula [6-C].
Embedded image

Example 7 (Synthesis of polyoxyalkylene triglyceryl ether compound)
In the same manner as in Example 1, 280 g (1 mol) of triglyceryl monoallyl ether prepared in Preparation Example 1 and 2.84 g of potassium hydroxide were weighed in a reaction vessel, and instead of 527 g of ethylene oxide in Example 1, propylene oxide was used. The reaction was performed using 667 g (11.5 mol) to obtain 890 g of a liquid pale yellow polyether compound (7-C) (yield 94%). The analytical value of the compound (7-C) was a hydroxyl value of 260 mgKOH / g and an unsaturation degree of 1.10 meq / g. The weight average molecular weight by GPC analysis was 860.
In addition, compound (7-C) was analyzed by IR.

From these results, the structure of the compound (7-C) was estimated to be the formula [7-C].
Embedded image

Example 8 (Synthesis of polyoxyalkylene triglyceryl ether compound)
In the same manner as in Example 1, 280 g (1 mol) of triglyceryl monoallyl ether prepared in Preparation Example 1 and 4.4 g of potassium hydroxide were weighed in a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. The temperature was raised and maintained at 85 to 95 ° C., and 957 g (16.5 mol) of propylene oxide was added dropwise to react, followed by further aging for 2 hours. Next, 242 g (5.5 mol) of ethylene oxide was added dropwise to react. After completion of dropping, the mixture was further aged for 2 hours at the same temperature. After completion of aging, unreacted residual propylene oxide and ethylene oxide were distilled off under reduced pressure of 3 to 5 mmHg while blowing nitrogen gas. The reaction solution was neutralized with 1% by weight of diluted hydrochloric acid, then dehydrated and filtered to obtain 1,405 g of a pale yellow liquid polyether compound (8-C) (yield 95%). The analytical value of the compound (8-C) was a hydroxyl value of 165 mgKOH / g and an unsaturation degree of 0.70 meq / g. The weight average molecular weight by GPC analysis was 1,380.
In addition, compound (8-C) was analyzed by IR.

From these results, the structure of the compound (8-C) was estimated to be the formula [8-C].
Embedded image

Example 9 (Synthesis of polyoxyalkylene triglyceryl ether compound)
In the same manner as in Example 1, 280 g (1 mol) of triglycerin monoallyl ether prepared in Preparation Example 1, 16.4 g of boron trifluoride diethyl ether, and 900 g (12.5 mol) of tetrahydrofuran were weighed in a reaction vessel. The system was replaced with nitrogen. The temperature was raised and maintained at 55 to 65 ° C., and 462 g (10.5 mol) of ethylene oxide was added dropwise to react. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. Thereafter, the reaction solution was neutralized with a 5% by weight aqueous sodium carbonate solution, and unreacted residual ethylene oxide and tetrahydrofuran were distilled off while blowing nitrogen under reduced pressure of 3 to 5 mmHg. Thereafter, dehydration and filtration were performed to obtain 1,440 g of a pale yellow liquid polyether compound (9-C) (yield 88%). The analysis values of the compound (9-C) were a hydroxyl value of 154 mgKOH / g and an unsaturation degree of 0.67 meq / g. The weight average molecular weight by GPC analysis was 1,450.
In addition, compound (9-C) was analyzed by IR.

From these results, the structure of the compound (9-C) was estimated to be the formula [9-C].
Embedded image

Production Example 2 (Production of triglyceryl monomethallyl ether)
In a 2 liter stainless steel pressure-resistant reaction vessel equipped with a thermometer, a nitrogen gas blowing tube and a stirring device, 641 g (2 mol) of diisopropylidenetriglycerin [compound (A), DITG] and 224 g (4 mol) of potassium hydroxide And the inside of the reaction system was replaced with nitrogen gas. While maintaining the temperature in the system at 75 to 85 ° C. by raising the temperature, 217 g (2.4 mol) of methallyl chloride weighed in advance in a cylinder was dropped and reacted in 1 hour. After completion of dropping, the temperature was raised to 115 to 125 ° C. and aged for 4 hours. After aging, the mixture was cooled to 75 to 85 ° C., and excess methallyl chloride was distilled off while blowing nitrogen gas under a reduced pressure of 3 to 5 mmHg. Further, a part of this reaction solution is taken, pH is adjusted to 7.0 with acetic acid, dehydration is performed at 100 ° C. and 100 mmHg or less for 1 hour, and after cooling at 80 ° C., the deposited salt is separated by filtration to obtain a sample for analysis. It was. The analytical value of this compound (D) was a hydroxyl value of 36.1 mgKOH / g and an unsaturation degree of 2.50 meq / g.
Furthermore, 1% by weight of diluted hydrochloric acid is added to the reaction solution to adjust the pH to 1.0, and after hydrolysis at 75 to 85 ° C. for 3 hours, sodium carbonate is added to neutralize to pH 7.0, followed by dehydration filtration. As a result, 610 g of triglyceryl monomethallyl ether [compound (E)] was obtained as a pale yellow liquid (yield 88%).
The analytical value of the compound (E) was a hydroxyl value of 783 mgKOH / g and an unsaturation degree of 3.16 meq / g. Further, the compound (E) was analyzed by IR.

From these results, it was confirmed that the structure of the compound (E) was the formula [E].
Embedded image

Example 10
In the same manner as in Example 1, 294 g (1 mol) of triglyceryl monomethallyl ether prepared in Production Example 2 and 1.6 g of sodium hydroxide were weighed in a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. The temperature was raised and maintained at 85 to 95 ° C., and 235.7 g (5.36 mol) of ethylene oxide weighed in advance was added dropwise to react. After completion of dropping, the mixture was further aged at 85 to 95 ° C. for 2 hours. After completion of aging, unreacted residual ethylene oxide was distilled off under reduced pressure of 3 to 5 mmHg while blowing nitrogen gas. The reaction solution was neutralized with 1% by weight dilute hydrochloric acid, then dehydrated and filtered to obtain 503 g of a pale yellow liquid polyether compound (10-E) (yield 95%). The analytical value of the compound (10-E) was a hydroxyl value of 440 mg KOH / g and an unsaturation degree of 1.90 meq / g. The weight average molecular weight by GPC analysis was 510.
In addition, compound (10-E) was analyzed by IR.

From these results, the structure of the compound (10-E) was estimated to be the formula [10-E].
Embedded image

The charging conditions of Examples 1 to 10 and the addition state of alkylene oxide are shown in Table 1, and the analytical values are shown in Table 2.
[0030]
[Table 1]

[0031]
[Note] The amount of alkylene oxide charged is based on 280 g (1 mol) of the raw material compound (C) and 294 g (1 mol) of compound (E). In the table, EO represents ethylene oxide, PO represents propylene oxide, BO represents butylene oxide, and THF represents tetrahydrofuran.
[0032]
[Table 2]

[0033]
[Note] The molecular weight in the table was calculated from the measured hydroxyl value.
Example 11
In a 5 liter stainless steel pressure-resistant reaction vessel equipped with a thermometer, a nitrogen gas blowing tube, and a stirring device, 960 g (3.0 mol) of diisopropylidenetriglycerin [compound (A)] and 4.6 g of potassium hydroxide were added. The sample was weighed and dissolved, and the inside of the reaction system was replaced with nitrogen gas. The temperature is raised and maintained at 85-95 ° C., 10 kg / cm ² Under the following conditions, 1,346 g (30.6 mol) of ethylene oxide was dropped and reacted for 5 hours. After completion of dropping, the mixture was further aged at 85 to 95 ° C. for 2 hours. After completion of aging, unreacted residual ethylene oxide was distilled off under reduced pressure of 3 to 5 mmHg while blowing nitrogen gas.
Next, the reaction vessel was cooled to 60 ° C., 589.1 g (10.5 mol) of potassium hydroxide was taken, and the inside of the reaction system was replaced with nitrogen gas. While maintaining the temperature inside the system at 75 to 85 ° C. by raising the temperature, 344.3 g (4.5 mol) of allyl chloride weighed in advance in a bomb was added dropwise over 1 hour to react. After completion of dropping, the temperature was raised to 115 to 125 ° C. and aged for 4 hours. After aging, the mixture was cooled to 75 to 85 ° C., and excess allyl chloride was distilled off while blowing nitrogen gas under a reduced pressure of 3 to 5 mmHg. Next, after cooling to 60 ° C, a part of this reaction solution is taken, pH is adjusted to 7.0 with acetic acid, dehydrated at 100 ° C and 100 mmHg or less for 1 hour, and cooled to 80 ° C to precipitate the deposited salt. The compound (11-B) was obtained by filtration. The analytical value of the compound (11-B) was a hydroxyl value of 0.3 mgKOH / g and an unsaturation degree of 1.24 meq / g.
From these results, the structure of the compound (11-B) was estimated to be the formula [11-B].
[Chemical Formula 86]

Further, 1% by weight of dilute hydrochloric acid was added to the reaction solution to adjust the pH to 1.0, and after hydrolysis at 75 to 85 ° C. for 3 hours, the pH was adjusted to a range of 6 to 7 with a 20% by weight aqueous sodium carbonate solution. 100 ° C., 100 mmHg or less, acetone produced in 1 hour was distilled off with water, then cooled to 80 ° C., and the precipitated salt was filtered off to obtain 1,960 g of a pale yellow liquid compound (11-C1). It was. The analytical value of the compound (11-C1) was a hydroxyl value of 310 mgKOH / g and an unsaturation degree of 1.38 meq / g. From these results, the structure of the compound (11-C1) was estimated to be the formula [11-C1].
Embedded image

Subsequently, 1,086 g (1.5 mol) of compound (11-C1) and 4.0 g of potassium hydroxide were weighed and dissolved in a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. The temperature is raised and maintained at 85-95 ° C., 10 kg / cm ² Under the following conditions, 913.5 g (15.8 mol) of propylene oxide was dropped for 4 hours to react. After completion of dropping, the mixture was further aged at 85 to 95 ° C. for 2 hours. After completion of aging, unreacted residual propylene oxide was distilled off under reduced pressure of 3 to 5 mmHg while blowing nitrogen gas. Next, after cooling to 60 ° C., the reaction solution was adjusted to pH 6.0 with 1% by weight of diluted hydrochloric acid, and dehydrated at 100 ° C. and 100 mmHg or less for 1 hour. Thereafter, the mixture was cooled to 80 ° C., and the deposited salt was separated by filtration to obtain 1,894 g of a pale yellow liquid compound (11-C2) (yield 95%). The analytical value of the compound (11-C2) was a hydroxyl value of 171 mg KOH / g and an unsaturation degree of 0.76 meq / g. From the GPC analysis, the number average molecular weight was 1,309. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (11-C2) was estimated to be the formula [11-C2].
Embedded image

Example 12
In the same manner as in Example 11, 1,120 g (3.5 mol) of diisopropylidenetriglycerin [compound (A)] and 4.3 g of potassium hydroxide were weighed in a reaction vessel, and 1,035 g (17. 9 mol) for 4 hours, and 490 g (12.3 mol) of sodium hydroxide and 401.6 g (5.3 mol) of allyl chloride were used to introduce the allyl group, and then the acetal group was hydrolyzed with dilute hydrochloric acid. After decomposition, purification was carried out to obtain 1,800 g of a liquid pale yellow compound (12-C1). The analytical value of the compound (12-C1) was a hydroxyl value of 392 mg KOH / g and an unsaturation degree of 1.74 meq / g. From these results, the structure of the compound (12-C1) was estimated to be the formula [12-C1].
Embedded image

Next, 1,145 g (2 mol) of the compound (12-C1) and 8.3 g of sodium methoxide were weighed into a reaction vessel, and 609.8 g (13.9 mol) of ethylene oxide and 332.6 g (4.6 mol) of butylene oxide were measured. The mixture was reacted for 5 hours to obtain 1,957 g of a pale yellow liquid compound (12-C2) (yield 94%). The analysis value of the compound (12-C2) was a hydroxyl value of 220 mgKOH / g and an unsaturation degree of 0.97 meq / g. From the GPC analysis, the number average molecular weight was 1,024. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (12-C2) was estimated to be the formula [12-C2].
Embedded image

Example 13
In the same manner as in Example 11, 800 g (2.5 mol) of diisopropylidenetriglycerin [compound (A)] and 9.6 g of sodium hydroxide were weighed into a reaction vessel, and 1595 g (27.5 mol) of propylene oxide was weighed. Then, allyl group was introduced using 561 g (10 mol) of potassium hydroxide and 286.9 g (3.8 mol) of allyl chloride, and then the acetal group was hydrolyzed with dilute hydrochloric acid and purified. As a result, 1,950 g of a liquid pale yellow compound (13-C1) was obtained. The analytical value of the compound (13-C1) was a hydroxyl value of 260 mgKOH / g and an unsaturation degree of 1.15 meq / g.
From these results, the structure of the compound (13-C1) was estimated to be the formula [13-C1].
Embedded image

Next, 863 g (1 mol) of compound (13-C1) and 6.1 g of sodium hydroxide are weighed in a reaction vessel, and 957 g (16.5 mol) of propylene oxide is reacted for 8 hours. (5.3 mol) was reacted for 4 hours to obtain 1,905 g of light yellow liquid compound (13-C2) (yield 93%). The analysis values of the compound (13-C2) were a hydroxyl value of 115 mgKOH / g and an unsaturation degree of 0.50 meq / g. From the GPC analysis, the number average molecular weight was 1,962. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (13-C2) was estimated to be the formula [13-C2].
Embedded image

Example 14
In the same manner as in Example 11, 320 g (1 mol) of diisopropylidenetriglycerin [compound (A)] and 16.9 g of sodium methoxide were weighed into a reaction vessel, and 2,088 g (36 mol) of propylene oxide was used. The reaction was carried out for 15 hours, and an allyl group was introduced using 336.6 g (6 mol) of potassium hydroxide and 130.1 g (1.7 mol) of allyl chloride, and then the acetal group was hydrolyzed with dilute hydrochloric acid and purified. As a result, 1,840 g of a liquid pale yellow compound (14-C1) was obtained. The analysis values of the compound (14-C1) were a hydroxyl value of 112 mgKOH / g and an unsaturation degree of 0.48 meq / g. From these results, the structure of the compound (14-C1) was estimated to be the formula [14-C1].
Embedded image

Next, 1.002 g (0.5 mol) of compound (1-C) and 4.4 g of sodium methoxide are weighed in a reaction vessel, and 462 g (10.5 mol) of ethylene oxide is reacted for 8 hours. 1,410 g of compound (14-C2) was obtained (yield 96%). The analytical value of the compound (14-C2) was a hydroxyl value of 77.2 mgKOH / g and an unsaturation degree of 0.33 meq / g. From the GPC analysis, the number average molecular weight was 2,915. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (14-C2) was estimated to be the formula [14-C2].
Embedded image

Example 15
In the same manner as in Example 11, 480 g (1.5 mol) of diisopropylidenetriglycerin [compound (A)] and 8.4 g of sodium methoxide were weighed into a reaction vessel, and 693 g (15.8 mol) of ethylene oxide and propylene were weighed. The mixture was reacted for 8 hours using a mixture of 913.5 g (15.8 mol) of oxide, and an allyl group was further introduced using 270 g (6.8 mol) of sodium hydroxide and 183.6 g (2.4 mol) of allyl chloride. Then, the acetal group was hydrolyzed with dilute hydrochloric acid and purified to obtain 1,780 g of a liquid pale yellow compound (15-C1). The analytical value of the compound (15-C1) was a hydroxyl value of 172 mg KOH / g and an unsaturation degree of 0.76 meq / g.
From these results, the structure of the compound (15-C1) was estimated to be the formula [15-C1].
Embedded image

Next, 1,305 g (1 mol) of compound (15-C1) and 5.7 g of potassium hydroxide are weighed in a reaction vessel, and 609 g (10.5 mol) of propylene oxide is reacted for 5 hours to obtain a pale yellow liquid compound. 1,814 g of (15-C2) was obtained (yield 95%). The analytical value of the compound (15-C2) was a hydroxyl value of 119 mgKOH / g and an unsaturation degree of 0.52 meq / g. From the GPC analysis, the number average molecular weight was 1,894. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (15-C2) was estimated to be the formula [15-C2].
Embedded image

Example 16
In the same manner as in Example 11, 320 g (1 mol) of diisopropylidenetriglycerin [compound (A)] and 12.8 g of potassium hydroxide were weighed in a reaction vessel, and 968 g (22 mol) of ethylene oxide and 1,276 g of propylene oxide were measured. The reaction was carried out for 12 hours using a mixture of (22 mol), further introducing an allyl group using 240 g (6 mol) of sodium hydroxide and 137.7 g (1.8 mol) of allyl chloride, and then the acetal group was diluted with dilute hydrochloric acid. Purification was carried out after hydrolysis to obtain 2,130 g of a liquid pale yellow compound (16-C1). The analytical value of the compound (16-C1) was a hydroxyl value of 96.5 mgKOH / g and an unsaturation degree of 0.42 meq / g.
From these results, the structure of the compound (16-C1) was estimated to be the formula [16-C1].
Embedded image

Next, 1,163 g (0.5 mol) of compound (16-C1) and 4.9 g of potassium hydroxide are weighed in a reaction vessel, and 462 g (10.5 mol) of ethylene oxide is reacted for 7 hours to obtain a pale yellow liquid. 1,557 g of compound (16-C2) was obtained (yield 96%). The analytical value of the compound (16-C2) was a hydroxyl value of 70.0 mgKOH / g and an unsaturation degree of 0.30 meq / g. From the GPC analysis, the number average molecular weight was 3,202. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (16-C2) was estimated to be the formula [16-C2].
Embedded image

Example 17
In the same manner as in Example 11, 800 g (2.5 mol) of diisopropylidenetriglycerin [compound (A)] and 6.9 g of sodium hydroxide were weighed in a reaction vessel, and 550 g (12.5 mol) of ethylene oxide was used. The reaction was continued for 3 hours. After aging, 945 g (13.1 mol) of butylene oxide was further reacted for 5 hours. Further, 561 g (10 mol) of potassium hydroxide and 286.9 g (3.8 mol) of allyl chloride were used. The allyl group was introduced, and then the acetal group was hydrolyzed with dilute hydrochloric acid, followed by purification to obtain 1,950 g of a liquid pale yellow compound (17-C1). The analytical value of the compound (17-C1) was a hydroxyl value of 262 mg KOH / g and an unsaturation degree of 1.14 meq / g.
From these results, the structure of the compound (17-C1) was estimated to be the formula [17-C1].
Embedded image

Next, 1,285 g (1.5 mol) of compound (17-C1) and 3.7 g of sodium hydroxide are weighed into a reaction vessel, and 242.4 g (5.5 mol) of ethylene oxide and 319.5 (5 mol) of propylene oxide are measured. (5 mol) was reacted for 5 hours to obtain 1,778 g of light yellow liquid compound (17-C2) (yield 96%). The analysis values of the compound (17-C2) were a hydroxyl value of 181 mgKOH / g and an unsaturation degree of 0.80 meq / g. From the GPC analysis, the number average molecular weight was 1,245. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (17-C2) was estimated to be the formula [17-C2].
Embedded image

Example 18
In the same manner as in Example 11, 1,120 g (3.5 mol) of diisopropylidene triglycerin [compound (A)] and 5.4 g of sodium hydroxide were weighed in a reaction vessel, and 1,035 g (17. 9 mol), and a methallyl group was further introduced using 687.2 g (12.3 mol) of potassium hydroxide and 475.1 g (5.3 mol) of methallyl chloride, and then the acetal group was diluted with dilute hydrochloric acid. The product was hydrolyzed and purified, and 1,840 g of a liquid pale yellow compound (18-E1) was obtained. The analytical value of the compound (18-E1) was a hydroxyl value of 383 mgKOH / g and an unsaturation degree of 1.70 meq / g.
From these results, the structure of the compound (18-E1) was estimated to be the formula [18-E1].
Embedded image

Next, 1,172 g (2 mol) of compound (18-E1) and 3.2 g of sodium hydroxide are weighed in a reaction vessel, and 448.8 g (10.2 mol) of ethylene oxide is reacted for 4 hours. 1,544 g of compound (18-E2) was obtained (yield 95%). The analytical value of the compound (18-E2) was a hydroxyl value of 279 mgKOH / g and an unsaturation degree of 1.23 meq / g. From the GPC analysis, the number average molecular weight was 809. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (18-E2) was estimated to be the formula [18-E2].
Embedded image

A in General Formula [1] of Examples 11-18 ¹ Table 3 shows the preparation conditions of the reaction up to the addition of alkylene oxide, alkenylation, and deacetalization of the O moiety, the addition state of the alkylene oxide, and the analytical value. ² Table 4 shows the charging conditions for the alkylene oxide addition reaction of the O moiety, the addition state of the alkylene oxide, and the analytical values.
[0034]
[Table 3]

[0035]
[Table 4]

[0036]
The symbols, structural formulas and physical properties of the polyoxyalkylene triglyceryl ether compounds used in Examples 19 to 26 are shown in Table 5, and the symbols, structural formulas and physical properties of the silicone compounds are shown in Table 6.
[0037]
[Table 5]

[0038]
[Table 6]

[0039]
[Table 7]

[0040]
[Table 8]

[0041]
[Table 9]

[0042]
[Table 10]

[0043]
Example 19 (Synthesis of modified silicone by route 1)
In a 500 ml four-necked flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device, 235.0 g of compound (2-C), 44.5 g of silicone compound (S-1), 56.0 g of toluene, 0.20 g of potassium acetate was added, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. While stirring, a chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was added dropwise to the system and reacted at 80 ° C. for 8 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added to distill off the volatile components under reduced pressure, and then the target modified silicone compound ( 193-1CS) 263.0 g was obtained (94% yield). The analytical value of the obtained compound was a hydroxyl value of 161 mgKOH / g and an unsaturation degree of 0.00 meq / g. From the GPC analysis, the weight average molecular weight was 1,400. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (19-1CS) was estimated to be the formula [19-1CS].
Embedded image

Example 20 (Synthesis of modified silicone by route 1)
In a 500 ml four-necked flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device, 143.0 g of compound (5-C), 73.0 g of silicone compound (S-2), 43.0 g of toluene, 0.20 g of potassium acetate was added, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. While stirring, a chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was added dropwise to the system and reacted at 80 ° C. for 8 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added to distill off the volatile components under reduced pressure, and then the target modified silicone compound ( 20-1CS) 177 g was obtained (82% yield). The analytical value of the obtained compound was 225 mg KOH / g of hydroxyl group and 0.000 meq / g of unsaturation.
From the GPC analysis, the weight average molecular weight was 20,500. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (20-1CS) was estimated to be the formula [20-1CS].
Embedded image

Example 21 (Synthesis of modified silicone by route 1)
In a 500 ml four-necked flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device, 111.0 g of compound (6-C), 166.8 g of silicone compound (S-3), 56.0 g of toluene, 0.20 g of potassium acetate was added, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. While stirring, a chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was added dropwise to the system and reacted at 80 ° C. for 8 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added to distill off the volatile components under reduced pressure, and then the target modified silicone compound ( 215.0)) was obtained (yield 92%). The analytical value of the obtained compound was 124 mg KOH / g of hydroxyl group and 0.01 meq / g of unsaturation.
From the GPC analysis, the weight average molecular weight was 1,800. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (21-1CS) was estimated to be the formula [21-1CS].
Embedded image

Example 22
In a 500 ml four-necked flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device, 182.0 g of compound (7-C), 87.6 g of silicone compound (S-4), 54.0 g of toluene, 0.20 g of potassium acetate was added, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. While stirring, a chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was added dropwise to the system and reacted at 80 ° C. for 8 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added to distill off the volatile components under reduced pressure, and then the target modified silicone compound ( 22-1CS) 243.1 g was obtained (90% yield). The analytical value of the obtained compound was 175 mg KOH / g of hydroxyl group and 0.00 meq / g of unsaturation.
From the GPC analysis, the weight average molecular weight was 2,600. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (22-1CS) was estimated to be the formula [22-1CS].
Embedded image

Production Example 3 (Synthesis of Modified Silicone Compound by Route 2—Protection of Hydroxyl Group)
Compound (8-C) 300g, acetic anhydride 94.6g, sodium acetate 0.15g was put into a 500ml 4-neck flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device, and 100 ± 5 ° C. The reaction was carried out for 4 hours. After the reaction, acetic acid generated in the system was neutralized using a 10% by weight aqueous sodium hydroxide solution. The sodium acetate aqueous solution separated by standing of the liquid was removed, and after dehydration while introducing nitrogen into the remaining liquid, filtration was performed. As a result, 320.3 g of a hydroxyl-protected compound (8-CP) was obtained (yield 81%). The analytical value of the obtained compound was a hydroxyl value of 0.9 mgKOH / g and an unsaturation degree of 0.62 meq / g.
Production Example 4 (Synthesis of Modified Silicone Compound by Route 2—Protection of Hydroxyl Group)
Into a 500 ml four-necked flask equipped with a thermometer, a nitrogen gas blowing tube, a cooling tube, and a stirring device, 300 g of compound (10-E), 217.7 g of dihydropyran, and 1.0 g of p-toluenesulfonic acid were added. The reaction was carried out at 40 ± 5 ° C. for 12 hours. After completion of the reaction, an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] was added to the reaction solution, and unreacted dihydropyran was distilled off while introducing nitrogen, followed by filtration. As a result, 473.1 g of a hydroxyl-protected compound (10-EP) was obtained (yield 91%). The analytical value of the obtained compound was a hydroxyl value of 1.0 mgKOH / g and an unsaturation degree of 1.15 meq / g.
Example 23 (Synthesis of modified silicone compound by route 2)
242.0 g of compound (8-CP) synthesized in Production Example 3 and 121.7 g of silicone compound (S-5) were added to a 1-liter four-necked flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device. , 73.0 g of toluene and 0.20 g of potassium acetate were added, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. While stirring, a chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was added dropwise to the system and reacted at 80 ° C. for 8 hours. After completion of the reaction, volatile components were distilled off under reduced pressure while blowing nitrogen. Subsequently, 100.0 g of methanol and 30.0 g of 5 wt% hydrochloric acid were added, and the ester was hydrolyzed at 100 ° C. for 10 hours. After completion of the reaction, neutralize with sodium carbonate, add 20 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.], distill off volatile components under reduced pressure while blowing nitrogen, and adsorbent By filtration, 270.8 g of the target modified silicone compound (23-2CS) was obtained (yield 74%). The analytical value of the obtained compound was a hydroxyl value of 103 mgKOH / g and an unsaturation degree of 0.01 meq / g.
From the GPC analysis, the weight average molecular weight was 43,400. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (23-2CS) was estimated to be the formula [23-2CS].
Embedded image

Example 24
In a 1 liter four-necked flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device, 30.0 g of the compound (24-EP) produced in Production Example 6 and 22.1 g of the silicone compound (S-6) were prepared. , 65.0 g of toluene and 0.20 g of potassium acetate were added, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. While stirring, a chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was added dropwise to the system and reacted at 80 ° C. for 8 hours. Subsequently, 150 g of methanol and 0.50 g of p-toluenesulfonic acid were added, and an acetal exchange reaction was performed at 40 ° C. for 8 hours. After completion of the reaction, 20 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added, volatile matter is distilled off under reduced pressure while blowing nitrogen, and the adsorbent is filtered off to achieve the desired modification. 172.4 g (yield 54%) of a silicone compound (24-2CS) was obtained. The analytical value of the obtained compound was a hydroxyl value of 392 mg KOH / g and an unsaturation degree of 0.00 meq / g.
From the GPC analysis, the weight average molecular weight was 23,000. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (24-2CS) was estimated to be the formula [24-2CS].
Embedded image

Production Example 5 (Synthesis of Modified Silicone Compound by Route 3—Synthesis of Triglycerin Derivative-Modified Silicone)
In a 1-liter four-necked flask equipped with a thermometer, a nitrogen gas blowing tube, a cooling tube, and a stirring device, 226.0 g of the compound (C), 178.0 g of the silicone compound (S-1), 400 g of toluene, and 0.8 mg of potassium acetate were added. 30 g was charged. The temperature was raised to 70 ° C. in a nitrogen atmosphere, and an isopropyl chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was dropped into the system while stirring, and the reaction was performed at 80 ° C. for 8 hours. After completion of the reaction, 20 g of an acid adsorbent [Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.] was added and stirred for 1 hour, and then the adsorbent was filtered off. Subsequently, 299.0 g of a modified silicone compound (CS-1) was obtained by distilling off volatile components under reduced pressure (yield 74%). The analytical value of the obtained compound was 453 mgKOH / g of hydroxyl group and 0.02 meq / g of unsaturation.
Example 25 (Synthesis of Modified Silicone Compound According to Route 3-Synthesis of Ethylene Oxide Adduct of Triglycerin Derivative Modified Silicone Compound)
In a 1 liter stainless steel pressure-resistant reaction vessel equipped with a thermometer, a nitrogen gas blowing tube, and a stirring device, 100 g of triglycerin derivative-modified silicone compound (CS-1) synthesized in Production Example 5 and boron trifluoride diethyl ether 0 .6 g was weighed and the reaction system was replaced with nitrogen gas. The temperature was raised and maintained at 55 to 65 ° C., and 158 g (3.6 mol) of ethylene oxide was added dropwise to react. After completion of the dropwise addition, the reaction was continued for 2 hours at 55 to 65 ° C. Thereafter, the reaction solution was neutralized with a 5% by weight aqueous sodium carbonate solution, and unreacted residual ethylene oxide was distilled off while blowing nitrogen under reduced pressure. Thereafter, dehydration and filtration were performed to obtain 217 g of a light yellow liquid modified silicone compound (25-3CS) (yield 84%). The analytical value of the obtained compound was a hydroxyl value of 187 mg KOH / g and an unsaturation degree of 0.00 meq / g.
From the GPC analysis, the weight average molecular weight was 1,200. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (25-3CS) was estimated to be the formula [25-3CS].
Embedded image

Production Example 6 (Synthesis of modified silicone compound by route 4-synthesis of triglycerin derivative-modified silicone compound)
In a 1 liter four-necked flask equipped with a thermometer, nitrogen gas blowing tube, cooling tube, and stirring device, 109.0 g of compound (B), 333.7 g of silicone compound (S-3), 90.0 g of toluene and potassium acetate 0.30 g was charged. The temperature was raised to 70 ° C. under a nitrogen atmosphere, and an isopropyl chloroplatinic acid isopropyl alcohol solution (20 ppm in terms of platinum) was added to the system while stirring, and the reaction was carried out at 80 ° C. for 8 hours. After completion of the reaction, 20 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added and stirred for 1 hour. After the adsorbent is filtered off, the volatile matter is subsequently distilled off under reduced pressure. 398.7 g of compound (BS-3) was obtained (90% yield). The analytical value of the obtained compound was 2.5 mg KOH / g of hydroxyl group and 0.02 meq / g of unsaturation.
Further, 100 g of methanol and 50 g of 1% by weight dilute hydrochloric acid were added to 300 g of the reaction liquid, hydrolyzed at 75 to 85 ° C. for 3 hours, neutralized by adding an aqueous sodium carbonate solution, dehydrated while blowing nitrogen, and then 20 g of toluene was added. It was charged and filtered. Subsequently, 198.1 g of a light yellow liquid modified silicone compound (CS-3) was obtained by distilling off volatile components under reduced pressure (yield 66%). The analytical value of the obtained compound was a hydroxyl value of 157 mgKOH / g and an unsaturation degree of 0.01 meq / g.
Example 26 (Synthesis of Modified Silicone Compound According to Route 4-Synthesis of Ethylene Oxide Adduct of Triglycerin Derivative Modified Silicone Compound)
In a 1 liter stainless steel pressure-resistant reaction vessel equipped with a thermometer, a nitrogen gas blowing tube, and a stirring device, 143 g of triglycerin derivative-modified silicone compound (CS-3) produced in Production Example 8 and boron trifluoride diethyl ether 0 .6 g was weighed and the reaction system was replaced with nitrogen gas. The temperature was raised and maintained at 55 to 65 ° C., and 156 g (4.0 mol) of ethylene oxide was added dropwise to react. After completion of the dropwise addition, the reaction was continued for 2 hours at 55 to 65 ° C. Thereafter, the reaction solution was neutralized with a 5% by weight aqueous sodium carbonate solution, and unreacted residual ethylene oxide was distilled off while blowing nitrogen under reduced pressure. Thereafter, dehydration and filtration were performed to obtain 124.3 g of a pale yellow liquid modified silicone compound (26-4CS) (yield 82%). The analytical value of the obtained compound was a hydroxyl value of 79.0 mgKOH / g and an unsaturation degree of 0.00 meq / g.
From the GPC analysis, the weight average molecular weight was 2,850. Further, infrared absorption spectrum analysis was performed.

From these results, the structure of the compound (26-4CS) was estimated to be the formula [26-4CS].
Embedded image

[0044]
The structural formulas and physical properties of the polyoxyalkylene triglyceryl ether compounds used in Examples 27 to 33 are shown in Table 7, and the structural formulas and physical properties of the silicone compounds are shown in Table 8.
[0045]
[Table 11]

[0046]
[Table 12]

[0047]
[Table 13]

[0048]
[Table 14]

[0049]
[Table 15]

[0050]
Example 27
In a 1 liter four-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet tube, 303.0 g (0.1 mol) of a polyoxyalkylene triglyceryl ether compound (14-C2), a silylidyl group The content silicone compound (S-7) 111.2g (0.1mol), toluene 207.1g and potassium acetate 0.25g were prepared, and it heated up to 70 degreeC under nitrogen atmosphere. A 2-propanol solution of chloroplatinic acid was added dropwise to the system maintained at 70 ° C. while stirring so that the catalyst concentration in the system finally became 10 ppm over 1 hour. After completion of dropping, the reaction was carried out at 80 ° C. for 5 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added, toluene and the like are distilled off under reduced pressure while blowing nitrogen gas, and then the adsorbent and potassium acetate are filtered off. 384.0 g of modified silicone compound (27-1C2S) was obtained (yield 93%).
The obtained compound had a hydroxyl value of 55.7 mg KOH / g, an unsaturation of 0.00 meq / g, and a weight average molecular weight of 4,090. Further, infrared absorption spectrum analysis was performed.

From the starting materials, reaction conditions, and analytical values, the structure of the compound (27-1C2S) was estimated to be the formula [27-1C2S].
Embedded image

Example 28
In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a condenser tube, a dropping funnel, and a nitrogen introducing tube, 125.0 g (0.1 mol) of polyoxyalkylene triglyceryl ether compound (17-C2), silylidin 81.0 g (0.005 mol) of a group-containing silicone compound (S-5), 206.0 g of toluene and 0.30 g of potassium acetate were charged, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. A 2-propanol solution of chloroplatinic acid was added dropwise to the system maintained at 70 ° C. with stirring so that the catalyst concentration in the system finally reached 20 ppm over 1 hour. Reaction was performed at 80 degreeC after completion | finish of dripping for 8 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added, toluene and the like are distilled off under reduced pressure while blowing nitrogen gas, and then the adsorbent and potassium acetate are filtered off. 182.5 g of modified silicone compound (28-1C2S) was obtained (yield 89%).
The obtained compound had a hydroxyl value of 112 mg KOH / g, an unsaturation of 0.00 meq / g, and a weight average molecular weight of 39,550. Further, infrared absorption spectrum analysis was performed.

From the starting material, reaction conditions, and analytical values, the structure of the modified silicone compound (28-1C2S) was estimated to be the formula [28-1C2S].
Embedded image

Example 29
In a 2 liter four-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet tube, 412.4 g (0.4 mol) of a polyoxyalkylene triglyceryl ether compound (12-C2), a silylidyl group 25.7 g (0.01 mol) of the silicone compound (S-6), 438.1 g of toluene and 0.70 g of potassium acetate were charged, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. A 2-propanol solution of chloroplatinic acid was added dropwise to the system maintained at 70 ° C. with stirring so that the catalyst concentration in the system finally reached 20 ppm over 1 hour. After completion of dropping, the reaction was carried out at 80 ° C. for 12 hours. After completion of the reaction, 30 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added, toluene and the like are distilled off under reduced pressure while blowing nitrogen gas, and then the adsorbent and potassium acetate are filtered off. 385.4 g of modified silicone compound (29-1C2S) was obtained (yield 88%).
The obtained compound had a hydroxyl value of 205 mg KOH / g, an unsaturation of 0.01 meq / g, and a weight average molecular weight of 42,130. Further, infrared absorption spectrum analysis was performed.

From the starting materials, reaction conditions, and analytical values, the structure of the compound (29-1C2S) was estimated to be the formula [29-1C2S].
Embedded image

Example 30
In a 500 ml four-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet pipe, 263.2 g (0.2 mol) of polyoxyalkylene triglyceryl ether compound (0.2 mol), silylidine group The silicone compound (S-1) 44.5g (0.2mol), toluene 76.9g and potassium acetate 0.15g were prepared, and it heated up to 70 degreeC in nitrogen atmosphere. A 2-propanol solution of chloroplatinic acid was added dropwise to the system maintained at 70 ° C. while stirring so that the catalyst concentration in the system finally became 10 ppm over 1 hour. After completion of dropping, the reaction was carried out at 80 ° C. for 5 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added, toluene and the like are distilled off under reduced pressure while blowing nitrogen gas, and then the adsorbent and potassium acetate are filtered off. 291.7 g of modified silicone compound (30-1C2S) was obtained (yield 95%).
The obtained compound had a hydroxyl value of 148 mg KOH / g, an unsaturation of 0.00 meq / g, and a weight average molecular weight of 1,520. Further, infrared absorption spectrum analysis was performed.

From the starting materials, reaction conditions, and analytical values, the structure of the compound (30-1C2S) was estimated to be the formula [30-1C2S].
Embedded image

Example 31
A 1 liter four-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet tube was charged with 20.0 g (0.1 mol) of a polyoxyalkylene triglyceryl ether compound (13-C2) and a silylidine group. Containing silicone compound formula (S-5) 81.0 g (0.005 mol), toluene 281.0 g and potassium acetate 0.50 g were charged and heated to 70 ° C. in a nitrogen atmosphere. A 2-propanol solution of chloroplatinic acid was added dropwise to the system maintained at 70 ° C. with stirring so that the catalyst concentration in the system finally reached 20 ppm over 1 hour. Reaction was performed at 80 degreeC after completion | finish of dripping for 8 hours. After completion of the reaction, 20 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added and toluene is distilled off under reduced pressure while blowing nitrogen gas, and then the adsorbent and potassium acetate are filtered off. 240.5 g of modified silicone compound (31-1C2S) was obtained (yield 86%).
The obtained compound had a hydroxyl value of 79.9 mg KOH / g, an unsaturation value of 0.00 meq / g, and a weight average molecular weight of 53,430. Further, infrared absorption spectrum analysis was performed.

From the starting materials, reaction conditions, and analysis values, the structure of the compound (31-1C2S) was estimated to be the formula [31-1C2S].
Embedded image

Example 32
A 300 ml four-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet tube was charged with 81.3 g (0.1 mol) of a polyoxyalkylene triglyceryl ether compound (12-E2) and a silylidyl group. The content silicone compound (S-7) 111.2g (0.1mol), toluene 47.8g and potassium acetate 0.20g were prepared, and it heated up to 70 degreeC under nitrogen atmosphere. A 2-propanol solution of chloroplatinic acid was added dropwise to the system maintained at 70 ° C. with stirring so that the catalyst concentration in the system finally reached 20 ppm over 1 hour. Reaction was performed at 80 degreeC after completion | finish of dripping for 8 hours. After completion of the reaction, 15 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added, toluene and the like are distilled off under reduced pressure while blowing nitrogen gas, and then the adsorbent and potassium acetate are filtered off. 178.2 g of modified silicone compound (32-1C2S) was obtained (yield 93%).
The obtained compound had a hydroxyl value of 118 mg KOH / g, an unsaturation of 0.02 meq / g, and a weight average molecular weight of 1,900. Further, infrared absorption spectrum analysis was performed.

From the starting materials, reaction conditions, and analytical values, the structure of the compound (32-1C2S) was estimated to be the formula [32-1C2S].
Embedded image

Example 33
In a 10 liter autoclave equipped with a stirrer, a thermometer and a nitrogen introduction tube, 1601.9 g (5.0 mol) of diisopropylidenetriglycerin [compound (A)] and 11.7 g of potassium hydroxide were charged. The inside was replaced with nitrogen gas. The temperature was raised and maintained at 85 to 95 ° C., and 2,312.6 g (52.5 mol) of ethylene oxide was added dropwise to react. After completion of dropping, the mixture was further aged at 85 to 95 ° C. for 2 hours. After completion of aging, unreacted residual ethylene oxide was distilled off under reduced pressure while blowing nitrogen gas. The system was then cooled to 20 ° C.
To the system, 1,122.2 g (20.0 mol) of potassium hydroxide was added, and the temperature was raised to 75 to 85 ° C. In a cylinder, 574.0 g (7.5 mol) of allyl chloride weighed in advance was dropped and reacted. After completion of dropping, the temperature was raised to 115 to 125 ° C. and aged for 4 hours. After aging, the mixture was cooled to 75 to 85 ° C., and excess allyl chloride was distilled off while blowing nitrogen gas under reduced pressure. Further, 3,930 g of water was added to the reaction solution, washed with water, and allowed to stand and separate to remove salts generated by the reaction and excess alkali. Polyether compound (11-B) 3,520 by adding 180 g of base adsorbent [KYOWARD 700, manufactured by Kyowa Chemical Industry Co., Ltd.], dehydrating under reduced pressure while blowing nitrogen gas, and then filtering the adsorbent. 0.2 g was obtained (yield 86%).
The obtained compound had a hydroxyl value of 0.1 mg KOH / g and an unsaturation of 1.24 meq / g. From the starting materials, reaction conditions, and analytical values, the structure of the compound (11-B) was estimated to be the formula [11-B] shown in Table 7.
In a 3 liter four-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet tube, 1,610.7 g (2.0 mol) of polyoxyalkylene triglyceryl ether compound (11-B), 445.0 g (2.0 mol) of a silylidine group-containing silicone compound (S-1), 513.9 g of toluene, and 1.0 g of potassium acetate were charged, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. A 2-propanol solution of chloroplatinic acid was added dropwise to the system maintained at 70 ° C. while stirring so that the catalyst concentration in the system finally became 10 ppm over 1 hour. After completion of dropping, the reaction was carried out at 80 ° C. for 5 hours. After completion of the reaction, 75 g of an acid adsorbent [KYOWARD 300, manufactured by Kyowa Chemical Industry Co., Ltd.] is added and toluene is distilled off under reduced pressure while blowing nitrogen gas, and then the adsorbent and potassium acetate are filtered off. 1,953.9 g of modified silicone compound (11-BS-1) was obtained (yield 95%).
The obtained compound had a hydroxyl value of 0.2 mg KOH / g and an unsaturation value of 0.00 meq / g. From the starting materials, reaction conditions, and analytical values, the structure of the compound (11-BS-1) was estimated to be the formula [11-BS-1].
Embedded image

In a 2 liter four-necked flask equipped with a stirrer, a thermometer, a condenser tube and a nitrogen inlet tube, 1,026.4 g (1.0 mol) of compound (11-BS-1) and 342.1 g of 1% by weight diluted hydrochloric acid Was hydrolyzed at 75 to 85 ° C. for 4 hours with vigorous stirring. The pH of the system was adjusted to 7.0 with an aqueous sodium carbonate solution, dehydrated under reduced pressure while blowing nitrogen gas, and then the precipitated salt was filtered off to obtain 868.3 g of a modified silicone compound (33-3C1S) ( Yield 92%).
The obtained compound had a hydroxyl value of 237 mg KOH / g and an unsaturation of 0.00 meq / g. From the starting materials, reaction conditions, and analysis values, the structure of the compound (33-3C1S) was estimated to be the formula [33-3C1S].
Embedded image

Into a 1 liter autoclave equipped with a stirrer, a thermometer and a nitrogen introducing tube, 378.5 g (0.4 mol) of compound (33-3C1S) and 3.1 g of boron trifluoride diethyl ether were charged, and the system was filled with nitrogen. Replaced with gas. The temperature was raised and maintained at 55 to 65 ° C., and 243.9 g (4.2 mol) of propylene oxide was added dropwise to react. After completion of dropping, the mixture was further aged at 55 to 65 ° C. for 2 hours. After completion of aging, the pH of the system was adjusted to 7.0 with an aqueous sodium carbonate solution, and unreacted residual propylene oxide, water and the like were distilled off under reduced pressure while blowing nitrogen gas. Thereafter, 556.4 g of a modified silicone compound (33-3C2S) was obtained by filtration (yield 89%).
The obtained compound had a hydroxyl value of 148 mg KOH / g, an unsaturation of 0.00 meq / g, and a weight average molecular weight of 1,510. Further, infrared absorption spectrum analysis was performed.

From the starting materials, reaction conditions, and analytical values, the structure of the compound (33-3C2S) was estimated to be the formula [33-3C2S].
Embedded image

Example 34
The compound (2-C) of the present invention synthesized in Example 2, the compound (5-C) of the present invention synthesized in Example 5, and the compound of the present invention synthesized in Example 11 were prepared in a 100 ml measuring cylinder with a stopper. Compound (11-C2), compound (17-C2) of the present invention synthesized in Example 17, five samples of compound (18-E2) of the present invention synthesized in Example 18, Comparative Example 1 [Compound ( C)] sample or Comparative Example 2 [Compound (G)] sample 5 g and liquid paraffin 45 g, shake well for 2 minutes, and then let stand at room temperature for 24 hours and visually observe the mixed state did. The kinematic viscosity at 25 ° C. was measured according to JIS K 2283 (1969).
In addition, the structural formula of the compound used for the comparative example is shown next.
Comparative Example 1
Triglyceryl monoallyl ether represented by the formula [C].
Embedded image

Comparative Example 2
A glycidol 2-mole adduct of glycerin monoallyl ether represented by the formula [G].
Embedded image

The results are shown in Tables 9 and 10.
[0051]
[Table 16]

[0052]
[Table 17]

[0053]
From the results of Tables 9 and 10, the polyoxyalkylene triglyceryl ether compound of the present invention is uniformly mixed with liquid paraffin and is stable after 24 hours, but triglyceryl monoallyl ether is liquid paraffin and It turns out that it does not mix evenly and already separates immediately after shaking.
From the results of Tables 9 and 10, the polyoxyalkylene triglyceryl ether compound of the present invention is uniformly mixed with liquid paraffin, stable after 24 hours, and the mixture has low viscosity. It can be seen that the glycidol 2-mole adduct of monoallyl ether and glycerin monoallyl ether does not mix uniformly with liquid paraffin, but has already separated immediately after shaking and the mixture is highly viscous.
Example 35
Modified silicone compounds (19-1CS), (20-1CS), (25-3CS), (30-1C2S) of the present invention synthesized in Example 19, Example 20, Example 25, Example 30 and Example 32 ) And (32-1C2S), and compounds (CS-1) and (CS-3), which are modified silicone compounds having no polyoxyalkylene chain, were examined for fluidity.
20 g of a sample was put into a 50 ml screw tube and allowed to stand still at 25 ° C. After confirming that the liquid level was horizontal, the screw tube was tilted to observe the presence or absence of fluidity at room temperature. The results are shown in Table 11.
[0054]
[Table 18]

[0055]
From the results of Table 11, the modified silicone compound of the comparative example having a triglyceryl ether group but not having a polyoxyalkylene chain is very viscous or not fluid at all, whereas It can be seen that the triglyceryl ether-modified silicone compound having an oxyalkylene chain is an easily handled modified silicone compound having good fluidity.
[0056]
【The invention's effect】
The polyoxyalkylene triglyceryl ether compound of the present invention is a novel polyglycerin derivative having only one alkenyl group having a double bond at the terminal in the molecule and having a polyoxyalkylene chain. By changing the kind and the number of added moles, a wide range of compounds such as low molecular weight to high molecular weight compounds and adjustment of the balance between hydrophilicity and lipophilicity can be produced. Moreover, since it has an alkenyl group, it is useful as a reaction intermediate for silicone modification. The modified silicone compound of the present invention is a compound obtained by the addition reaction of the alkenyl group of the above polyoxyalkylene triglyceryl ether compound and the silylidine group of the silicone compound, has low viscosity and excellent handleability, and is a polyoxyalkylene triglyceryl. By selecting an ether compound and a silicone compound, a surfactant having a wide range of performance can be obtained.

Claims (11)

General formula [1]

(However, in the formula, A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types, and in the case of two or more types, block addition or random addition may be used, n is an addition mole number of the oxyalkylene group A ¹ O and is 0 to 100, a, b, c and d are 1 to 100 addition mole number of the oxyalkylene group A ² O, and Z is double at the terminal. A hydrocarbon group having 3 to 10 carbon atoms having a bond, wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, an acyl group having 2 to 24 carbon atoms, or a 1-alkoxyalkyl group having 3 to 10 carbon atoms, or (Cyclic ether groups in which the carbon adjacent to oxygen is bonded to the polyoxyalkylene chain, which may be the same or different.)
The polyoxyalkylene triglyceryl ether compound represented by these. The polyoxyalkylene triglyceryl according to claim 1, wherein A ² O in the general formula [1] is an oxyalkylene group having 2 to 4 carbon atoms, and the number of added moles a, b, c and d thereof is 1 to 50. Ether compounds. The polyoxyalkylene triglyceryl ether compound according to claim 1 or ² , wherein R ¹ , R ² , R ³ and R ⁴ in the general formula [1] are hydrogen. Z in the general formula [1] is CH ₂ ═CHCH ₂ —, CH ₂ ═C (CH ₃ ) CH ₂ —, CH ₂ ═CHC (CH ₃ ) ₂ —, CH ₂ ═C (CH ₃ ) C (CH _{3) 2 -, CH 2 =} CHC (CH 3) 2 CH 2 - and _{CH 2 = C (CH 3)} C (CH 3) 2 CH 2 - claim 1 is a group selected from, claim 2 or The polyoxyalkylene triglyceryl ether compound according to claim 3. Formula [2]

In the triglycerin represented by the general formula [3]
RCOR '... [3]
(In the formula, R and R ′ are alkyl groups, and they may be the same or different.)
Is reacted with a ketone compound represented by the general formula [4]

(In the formula, R and R ′ are alkyl groups, and they may be the same or different.)
A compound represented by general formula [5] is optionally added, and one or more kinds of alkylene oxides having 2 to 8 carbon atoms are optionally added.

(In the formula, A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, which may be one kind or two or more kinds, and in the case of two or more kinds, a block-like addition or a random addition may be used, and n is an oxyalkylene. The number of moles of the group added is 0 to 100, and R and R ′ are alkyl groups, which may be the same or different.
To obtain a compound represented by the general formula [6]
Z-X [6]
(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and X is a halogen atom.)
And an alkenyl halide represented by the general formula [7]

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, which may be one kind or two or more kinds. In the case of two or more kinds, block addition or random addition may be used, n is 0 to 100 in terms of the number of added moles of oxyalkylene group, R and R ′ are alkyl groups, and they are the same or different. May be.)
And then reacting with an acid to give a compound represented by the general formula [8]

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, which may be one kind or two or more kinds. In the case of 2 or more types, block addition or random addition may be used, and n is 0 to 100 in terms of the number of moles of oxyalkylene group added.)
The compound represented by the general formula [1] is obtained, and after addition of one or two or more alkylene oxides having 2 to 8 carbon atoms, the terminal hydroxyl group is esterified or acetalized as desired. ]

(However, in the formula, A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types, and in the case of two or more types, block addition or random addition may be used, n is an addition mole number of the oxyalkylene group A ¹ O and is 0 to 100, a, b, c and d are 1 to 100 addition mole number of the oxyalkylene group A ² O, and Z is double at the terminal. A hydrocarbon group having 3 to 10 carbon atoms having a bond, wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, an acyl group having 2 to 24 carbon atoms, or a 1-alkoxyalkyl group having 3 to 10 carbon atoms, or (Cyclic ether groups in which the carbon adjacent to oxygen is bonded to the polyoxyalkylene chain, which may be the same or different.)
The manufacturing method of the polyoxyalkylene triglyceryl ether compound represented by these. The method for producing a polyoxyalkylene triglyceryl ether compound according to claim 5, wherein the ketone compound represented by the general formula [3] is acetone or methyl ethyl ketone. General formula [9]

[In the formula, R ⁵ is a methyl group or a phenyl group, and at least one of R ⁶ , R ⁷ and R ⁸ is a group represented by the following general formula [10]; Or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800.)

(However, in the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types. In the above case, block addition or random addition may be used, n is 0 to 100 in terms of the number of moles of oxyalkylene group A ¹ O, and a, b, c and d are moles of oxyalkylene group A ² O added. 1 to 100 in number.)]
A modified silicone compound represented by: General formula [11]

(In the formula, R ⁵ is a methyl group or a phenyl group, at least one of R ⁹ , R ¹⁰ and R ¹¹ is a hydrogen atom, the other is a methyl group or a phenyl group, and x and y are (The number of repeating units, and the sum of x and y is 0 to 800.)
A silicone compound represented by the general formula [12]

(However, in the formula, A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types, and in the case of two or more types, block addition or random addition may be used, n is an addition mole number of the oxyalkylene group A ¹ O and is 0 to 100, a, b, c and d are 1 to 100 addition mole number of the oxyalkylene group A ² O, and Z is double at the terminal. (It is a hydrocarbon group having 3 to 10 carbon atoms having a bond.)
And a polyoxyalkylene triglyceryl ether compound represented by the general formula [9]

[In the formula, R ⁵ is a methyl group or a phenyl group, and at least one of R ⁶ , R ⁷ and R ⁸ is a group represented by the following general formula [10]; Or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800.)

(However, in the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types. In the above case, block addition or random addition may be used, n is 0 to 100 in terms of the number of moles of oxyalkylene group A ¹ O, and a, b, c and d are moles of oxyalkylene group A ² O added. 1 to 100 in number.)]
The manufacturing method of the modified silicone compound represented by these. General formula [11]

(In the formula, R ⁵ is a methyl group or a phenyl group, at least one of R ⁹ , R ¹⁰ and R ¹¹ is a hydrogen atom, the other is a methyl group or a phenyl group, and x and y are (The number of repeating units, and the sum of x and y is 0 to 800.)
A silicone compound represented by the general formula [13]

(However, in the formula, A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types, and in the case of two or more types, block addition or random addition may be used, n is an addition mole number of the oxyalkylene group A ¹ O and is 0 to 100, a, b, c and d are 1 to 100 addition mole number of the oxyalkylene group A ² O, and Z is double at the terminal. A hydrocarbon group having 3 to 10 carbon atoms having a bond, wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are an acyl group having 2 to 24 carbon atoms, a 1-alkoxyalkyl group having 3 to 10 carbon atoms, or oxygen A cyclic ether group in which the carbon adjacent to is bonded to a polyoxyalkylene chain, which may be the same or different.
After reacting with the polyoxyalkylene triglyceryl ether compound represented by the general formula [9], R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are eliminated to form hydrogen atoms.

[In the formula, R ⁵ is a methyl group or a phenyl group, and at least one of R ⁶ , R ⁷ and R ⁸ is a group represented by the following general formula [10]; Or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800.)

(However, in the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types. In the above case, block addition or random addition may be used, n is 0 to 100 in terms of the number of moles of oxyalkylene group A ¹ O, and a, b, c and d are moles of oxyalkylene group A ² O added. 1 to 100 in number.)]
The manufacturing method of the modified silicone compound represented by these. General formula [11]

(In the formula, R ⁵ is a methyl group or a phenyl group, at least one of R ⁹ , R ¹⁰ and R ¹¹ is a hydrogen atom, the other is a methyl group or a phenyl group, and x and y are (The number of repeating units, and the sum of x and y is 0 to 800.)
A silicone compound represented by the general formula [8]

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, which may be one kind or two or more kinds. In the case of 2 or more types, block addition or random addition may be used, and n is 0 to 100 in terms of the number of moles of oxyalkylene group added.)
1 or 2 or more types of C2-C8 alkylene oxide is added to the silicone compound obtained by making it react with the compound represented by General formula [9]

[In the formula, R ⁵ is a methyl group or a phenyl group, and at least one of R ⁶ , R ⁷ and R ⁸ is a group represented by the following general formula [10]; Or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800.)

(However, in the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types. In the above case, block addition or random addition may be used, n is 0 to 100 in terms of the number of moles of oxyalkylene group A ¹ O, and a, b, c and d are moles of oxyalkylene group A ² O added. 1 to 100 in number.)]
The manufacturing method of the modified silicone compound represented by these. General formula [11]

(In the formula, R ⁵ is a methyl group or a phenyl group, at least one of R ⁹ , R ¹⁰ and R ¹¹ is hydrogen, and the other is a methyl group or a phenyl group, and x and y are repeated. The number of units, and the sum of x and y is 0 to 800.)
A silicone compound represented by general formula [7]

(In the formula, Z is a hydrocarbon group having 3 to 10 carbon atoms having a double bond at the terminal, and A ¹ O is an oxyalkylene group having 2 to 8 carbon atoms, which may be one kind or two or more kinds. In the case of two or more kinds, block addition or random addition may be used, n is 0 to 100 in terms of the number of added moles of oxyalkylene group, R and R ′ are alkyl groups, and they are the same or different. May be.)
1 type or 2 types or more of C2-C8 alkylene oxide is added to the silicone compound obtained by hydrolyzing an acetal group after making it react with the compound represented by this general Formula [9]

[In the formula, R ⁵ is a methyl group or a phenyl group, and at least one of R ⁶ , R ⁷ and R ⁸ is a group represented by the following general formula [10]; Or a phenyl group, x and y are the number of repeating units, and the sum of x and y is 0 to 800.)

(However, in the formula, Y is a hydrocarbon group having 3 to 10 carbon atoms, and A ¹ O and A ² O are oxyalkylene groups having 2 to 8 carbon atoms, which may be one type or two or more types. In the above case, block addition or random addition may be used, n is 0 to 100 in terms of the number of moles of oxyalkylene group A ¹ O, and a, b, c and d are moles of oxyalkylene group A ² O added. 1 to 100 in number.)]
The manufacturing method of the modified silicone compound represented by these.