JP2624060B2 - One-end diol siloxane compound and method for producing the same - Google Patents
One-end diol siloxane compound and method for producing the sameInfo
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- JP2624060B2 JP2624060B2 JP29095291A JP29095291A JP2624060B2 JP 2624060 B2 JP2624060 B2 JP 2624060B2 JP 29095291 A JP29095291 A JP 29095291A JP 29095291 A JP29095291 A JP 29095291A JP 2624060 B2 JP2624060 B2 JP 2624060B2
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Description
【０００１】[0001]
【産業上の利用分野】本発明は新規片末端ジオールシロ
キサン化合物及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel one-terminal diol siloxane compound and a method for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
片末端にアルコール性ヒドロキシル基を２個有する片末
端ジオールシロキサン化合物として、特開昭６２−１９
５３８９号公報には、下記式（３）で示される化合物が
記載されている。2. Description of the Related Art
As one-terminal diol siloxane compounds having two alcoholic hydroxyl groups at one terminal, JP-A-62-19
No. 5389 describes a compound represented by the following formula (3).
【０００３】[0003]
【化３】 Embedded image
【０００４】しかし、式（３）の片末端ジオールシロキ
サン化合物は片末端の２個のヒドロキシル基のうち、一
方が第１級ヒドロキシル基、他方が第２級ヒドロキシル
基であるため、２個のヒドロキシル基の反応性が相違す
る。即ち、第２級ヒドロキシル基はカルボキシル基とは
高温でしか反応せず、また、イソシアネート基との反応
性もきわめて低い。このため、上記式（３）の化合物を
例えばジカルボン酸化合物やジイソシアネート化合物と
交差共重合させ、ポリエステル、ポリウレタンを製造す
る場合、均一な交差共重合体が得られないという問題が
ある。However, the diol siloxane compound at one end of the formula (3) has two hydroxyl groups, one of which is a primary hydroxyl group and the other of which is a secondary hydroxyl group. The reactivity of the groups is different. That is, the secondary hydroxyl group reacts only with the carboxyl group at a high temperature, and has very low reactivity with the isocyanate group. For this reason, when the compound of the formula (3) is cross-copolymerized with, for example, a dicarboxylic acid compound or a diisocyanate compound to produce a polyester or polyurethane, there is a problem that a uniform cross-copolymer cannot be obtained.
【０００５】本発明は、上記問題点を解決するためにな
されたもので、反応性が等価な第１級ヒドロキシル基を
片末端に２個有する新規な片末端ジオールシロキサン化
合物及びその製造方法を提供することを目的とする。The present invention has been made to solve the above problems, and provides a novel single-terminal diol siloxane compound having two primary hydroxyl groups having equivalent reactivity at one terminal, and a method for producing the same. The purpose is to do.
【０００６】[0006]
【課題を解決するための手段及び作用】本発明者は、上
記目的を達成するため、鋭意検討を行った結果、下記式
（２）で示されるビニル基含有化合物と片末端ハイドロ
ジェンシロキサンとを付加反応させた後、脱シリル化す
ることにより、下記式（１）で示される新規な片末端ジ
オールシロキサン化合物が得られると共に、この式
（１）の片末端ジオールシロキサン化合物の２個のヒド
ロキシル基はいずれも第１級ヒドロキシル基で互に反応
性が等価であり、このため例えばポリウレタン、ポリエ
ステル等の重合体の製造において、この新規片末端ジオ
ールシロキサン化合物を共重合成分として用いると、側
鎖にポリジメチルシロキサン鎖を有し、撥水性、耐摩耗
性、潤滑性等の表面特性が優れた重合体が得られること
を知見し、本発明をなすに至った。Means and Effect of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a vinyl group-containing compound represented by the following formula (2) and a one-terminal hydrogen siloxane can be used. After the addition reaction, desilylation is performed to obtain a novel one-terminal diol siloxane compound represented by the following formula (1), and two hydroxyl groups of the one-terminal diol siloxane compound of the formula (1) are obtained. Are equivalent to each other at the primary hydroxyl group. Therefore, for example, in the production of polymers such as polyurethane and polyester, when this novel one-terminal diol siloxane compound is used as a copolymerization component, The present inventors have found that a polymer having a polydimethylsiloxane chain and having excellent surface properties such as water repellency, abrasion resistance, and lubricity can be obtained. It led to.
【０００７】従って、本発明は、 （１）下記一般式（１）Accordingly, the present invention provides: (1) the following general formula (1)
【０００８】[0008]
【化４】 （式中ｎは０〜１０００の整数、ａは２〜８の整数であ
る。）で表わされる片末端ジオールシロキサン化合物、
及び、 （２）片末端ハイドロジェンシロキサンのＳｉＨ基に下
記一般式（２）Embedded image (Wherein n is an integer of 0 to 1000, and a is an integer of 2 to 8).
And (2) the following general formula (2):
【０００９】[0009]
【化５】 （式中Ｒ1，Ｒ2，Ｒ3はそれぞれ互に同一又は異種の置
換又は未置換の炭素数１〜２０の炭化水素基、ａは２〜
８の整数である。）で示される化合物のＣＨ2＝ＣＨ基
を付加した後、ＳｉＲ1Ｒ2Ｒ3基を脱離することを特徴
とする片末端ジオールシロキサン化合物の製造方法を提
供する。Embedded image (Wherein R 1 , R 2 , and R 3 are the same or different and each is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a is
It is an integer of 8. A) adding a CH 2 ＣＨCH group to the compound of formula (1), and then removing the SiR 1 R 2 R 3 group.
【００１０】以下、本発明につき更に詳述すると、本発
明の新規片末端ジオールシロキサン化合物は、上述した
ように、下記一般式（１）Hereinafter, the present invention will be described in more detail. The novel diol siloxane compound having one terminal at one end, as described above, has the following general formula (1):
【００１１】[0011]
【化６】 で示されるものである。Embedded image It is shown by.
【００１２】ここで、ｎは０〜１０００、好ましくは０
〜２００の整数であり、ａは２〜８、好ましくは２〜４
の整数である。Here, n is 0 to 1000, preferably 0.
A is an integer of 2 to 200, and a is 2 to 8, preferably 2 to 4
Is an integer.
【００１３】上記の如き片末端ジオールシロキサン化合
物を得る方法としては、出発原料として下記一般式
（２）で示される化合物を使用する。As a method for obtaining a diol siloxane compound having one terminal as described above, a compound represented by the following general formula (2) is used as a starting material.
【００１４】[0014]
【化７】 Embedded image
【００１５】ここで、Ｒ1，Ｒ2，Ｒ3はそれぞれ互に同
一又は異種の置換又は未置換の炭素数１〜２０、より好
ましくは１〜３の一価炭化水素基であり、具体的には、
メチル、エチル、プロピル、イソプロピル、ブチル、イ
ソブチル、ｔ−ブチル、フェニル、ｐ−トリルなどであ
る。なお、ａは上記と同様の意味を示す。Here, R 1 , R 2 and R 3 are the same or different and each is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20, more preferably 1 to 3, carbon atoms. In
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, phenyl, p-tolyl and the like. Note that a has the same meaning as described above.
【００１６】この式（２）の化合物は、例えば、グリセ
リンと式（４）のＲ1Ｒ2Ｒ3ＳｉＣｌで示される３置換
クロルシランとを脱塩酸剤の存在下に反応させることに
より得られる式（５）のビスシリル化物に式（６）の不
飽和ハロゲン化物を塩基性物質の存在下に反応させるこ
とによって得ることができる。The compound of the formula (2) is obtained, for example, by reacting glycerin with trisubstituted chlorosilane represented by the formula (4) R 1 R 2 R 3 SiCl in the presence of a dehydrochlorinating agent. It can be obtained by reacting the bissilylated compound of (5) with an unsaturated halide of formula (6) in the presence of a basic substance.
【００１７】[0017]
【化８】 Embedded image
【００１８】この場合、まず式（５）のビスシリル化物
を得るために用いる式（４）の３置換クロルシランとし
ては、トリメチルクロルシラン、プロピルジメチルクロ
ルシラン、イソプロピルジメチルクロルシラン、イソブ
チルジメチルクロルシラン、ｔ−ブチルジメチルクロル
シラン、フェニルジメチルクロルシランなどが具体的に
挙げられる。In this case, the trisubstituted chlorosilane of the formula (4) used for obtaining the bissilylated compound of the formula (5) is trimethylchlorosilane, propyldimethylchlorosilane, isopropyldimethylchlorosilane, isobutyldimethylchlorosilane, t Specific examples include -butyldimethylchlorosilane, phenyldimethylchlorosilane and the like.
【００１９】これらのクロルシランは、グリセリン１モ
ルに対し２〜２．５モル、特に２．０〜２．１モルとす
ることが好ましい。The chlorosilane is preferably used in an amount of 2 to 2.5 mol, particularly 2.0 to 2.1 mol, per 1 mol of glycerin.
【００２０】上記式（５）のビスシリル化物は、上記ク
ロルシランをグリセリンと好ましくは上記モル比の範囲
で反応させることにより得られるが、この際この反応は
脱塩酸剤の存在下で行う。脱塩酸剤としては、例えばト
リエチルアミン、ピリジン、トリブチルアミン、トリメ
チルアミン、トリプロピルアミン、Ｎ，Ｎ−ジメチルア
ニリン、キノリン、ピペリジン、ピペラジン等の第３級
アミン類などが好適に用いられる。なお、脱塩酸剤はそ
の１種を単独で又は２種以上を併用して使用することが
できる。これら脱塩酸剤の使用量は、特に制限されるも
のであるが、上記クロルシラン１モルに対して１〜３モ
ル、特に１〜１．５モルとすることが好ましい。The bissilylated compound of the above formula (5) can be obtained by reacting the above-mentioned chlorosilane with glycerin, preferably in the above-mentioned molar ratio, and this reaction is carried out in the presence of a dehydrochlorinating agent. As the dehydrochlorinating agent, for example, tertiary amines such as triethylamine, pyridine, tributylamine, trimethylamine, tripropylamine, N, N-dimethylaniline, quinoline, piperidine and piperazine are preferably used. The dehydrochlorinating agent can be used alone or in combination of two or more. The use amount of these dehydrochlorinating agents is not particularly limited, but is preferably 1 to 3 mol, particularly preferably 1 to 1.5 mol, per 1 mol of the chlorosilane.
【００２１】上記反応は、好ましくはトルエン等の溶媒
中で行う。反応温度は０〜１５０℃、特に０〜８０℃と
することが好ましい。反応時間は通常１〜５時間であ
る。The above reaction is preferably carried out in a solvent such as toluene. The reaction temperature is preferably 0 to 150 ° C, particularly preferably 0 to 80 ° C. The reaction time is usually 1 to 5 hours.
【００２２】上記式（５）のビスシリル化物は、必要に
より脱シリル化し、次いでこれを再度シリル化すること
により、上記３置換クロルシランとグリセリンとの反応
で得られたビスシリル化物のＳｉＲ1Ｒ2Ｒ3をこれと異
なる種類のＳｉＲ1Ｒ2Ｒ3と交換することができる。The bissilylated compound of the above formula (5) is desilylated, if necessary, and then silylated again to obtain the SiR 1 R 2 R of the bissilylated product obtained by the reaction of the trisubstituted chlorosilane with glycerin. 3 can be exchanged for a different type of SiR 1 R 2 R 3 .
【００２３】特に式（４）の化合物としてｔ−ブチルジ
メチルクロルシランを用いた場合、脱シリル化−再シリ
ル化の方法が有効である。即ち、ｔ−ブチルジメチルク
ロルシランを用いた場合、脱シリル化はＦ-を有する化
合物（例えばテトラブチルアンモニウムフルオライドな
ど）を用いることが好適であるが、脱シリル化するとき
にシロキサン鎖があると切断される可能性があるため、
実施例１の（ｃ），（ｄ）の工程で示したように一度ｔ
−ブチルジメチルシリル基を脱離させ、その後トリメチ
ルシリル化することが好ましい。In particular, when t-butyldimethylchlorosilane is used as the compound of the formula (4), the method of desilylation / resilylation is effective. That is, when using a t- butyl dimethylchlorosilane, desilylation F - but it is preferable to use a compound having a (e.g. tetrabutylammonium fluoride, etc.), there is a siloxane chain when desilylation And may be disconnected,
As shown in steps (c) and (d) of the first embodiment, once
It is preferred to remove the -butyldimethylsilyl group, followed by trimethylsilylation.
【００２４】この場合、この脱シリル化及びシリル化は
常法に従って行うことができる。In this case, the desilylation and silylation can be carried out according to a conventional method.
【００２５】このようにして得られた式（５）のビスシ
リル化物は、これを式（６）の不飽和ハロゲン化物と塩
基性物質の存在下に反応させることにより、式（２）の
化合物を得る。The bissilylated compound of the formula (5) thus obtained is reacted with an unsaturated halide of the formula (6) in the presence of a basic substance to give the compound of the formula (2). obtain.
【００２６】[0026]
【化９】 Embedded image
【００２７】この反応において、式（５）のビスシリル
化物と式（６）の不飽和ハロゲン化物とは、前者１モル
に対し後者１〜２モル、特に１．２〜１．５モルの割合
で使用することが好ましい。In this reaction, the bissilylated compound of the formula (5) and the unsaturated halide of the formula (6) are used in a ratio of 1 to 2 mol, preferably 1.2 to 1.5 mol, of the former to 1 mol. It is preferred to use.
【００２８】また、塩基性物質としては水酸化ナトリウ
ム、水酸化カリウム、ナトリウム、水素化ナトリウム、
リチウムなどが使用され、その使用量は式（５）のビス
シリル化物１モルに対して１〜２モル、特に１．１〜
１．５モルとすることが好ましい。As the basic substance, sodium hydroxide, potassium hydroxide, sodium, sodium hydride,
Lithium or the like is used, and the amount used is 1 to 2 mol, particularly 1.1 to 1 mol, per 1 mol of the bissilylated compound of the formula (5).
Preferably it is 1.5 mol.
【００２９】反応は、ジエチルエーテル、テトラヒドロ
フラン、トルエン、キシレン、Ｎ，Ｎ−ジメチルホルム
アミドなどの溶媒を用いて行うことができ、反応温度は
２０〜２００℃、特に４０〜１３０℃とすることが好ま
しい。また、反応時間は通常５〜８時間である。The reaction can be carried out using a solvent such as diethyl ether, tetrahydrofuran, toluene, xylene, N, N-dimethylformamide and the like, and the reaction temperature is preferably 20 to 200 ° C., particularly preferably 40 to 130 ° C. . The reaction time is usually 5 to 8 hours.
【００３０】以上のようにして合成される式（２）の化
合物は、片末端ハイドロジェンシロキサン、特に式
（１）の片末端ジオールシロキサン化合物を得る場合
は、下記式（７）の片末端ハイドロジェンシロキサンと
反応させて、式（８）の如きシロキサン化合物を得、こ
れを脱シリル化することにより、式（１）のような片末
端ジオールシロキサン化合物を製造する。The compound of the formula (2) synthesized as described above can be used to obtain a hydrogen siloxane compound having one end, particularly a diol siloxane compound having one end, represented by the following formula (7). The siloxane compound is reacted with gensiloxane to obtain a siloxane compound represented by the formula (8), which is subjected to desilylation to produce a diol siloxane compound having a single terminal as represented by the formula (1).
【００３１】[0031]
【化１０】 Embedded image
【００３２】ここで、式（２）の化合物と片末端ハイド
ロジェンシロキサンとの付加反応は、公知の付加反応触
媒、例えば塩化白金酸、塩化白金酸の誘導体等の白金や
白金化合物などを用いることができる。Here, the addition reaction of the compound of the formula (2) with the hydrogen siloxane at one end is carried out by using a known addition reaction catalyst, for example, platinum or a platinum compound such as chloroplatinic acid or a derivative of chloroplatinic acid. Can be.
【００３３】また、この付加反応は活性水素を含有しな
い溶媒、例えばトルエン、キシレン、ヘキサン、ジエチ
ルエーテル、テトラヒドロフラン、酢酸エチルなどを用
い、式（２）の化合物１モルに対し片末端ハイドロジェ
ンシロキサンを０．７〜１．０モル、特に０．８〜０．
９モルの範囲で使用して行うことができる。この場合、
反応温度は０〜２００℃、より望ましくは５０〜１２０
℃が好ましく、反応時間は通常２〜５時間である。In this addition reaction, a solvent containing no active hydrogen, for example, toluene, xylene, hexane, diethyl ether, tetrahydrofuran, ethyl acetate or the like is used. 0.7 to 1.0 mole, especially 0.8 to 0.
It can be carried out using a range of 9 moles. in this case,
The reaction temperature is 0 to 200 ° C, more preferably 50 to 120.
C is preferable, and the reaction time is usually 2 to 5 hours.
【００３４】上記式（８）の化合物の脱シリル化反応
は、通常式（８）の化合物にメタノールを大過剰加え、
還流温度で加熱することにより行うことができる。The desilylation reaction of the compound of the above formula (8) is usually carried out by adding a large excess of methanol to the compound of the formula (8).
It can be carried out by heating at the reflux temperature.
【００３５】[0035]
【発明の効果】本発明の片末端ジオールシロキサン化合
物は、その末端ジオールが互に反応性が等価な第１級ヒ
ドロキシル基であり、カルボキシル基やイソシアネート
基と容易に反応し、ジカルボン酸化合物やジイソシアネ
ート化合物と交差共重合させることにより、ポリエステ
ル、ポリウレタンの側鎖にポリジメチルシロキサン鎖を
有し、撥水性、耐摩耗性、潤滑性等の表面特性が優れた
重合体を得ることができる。このため、この重合体は感
熱転写紙用耐熱コーティング剤、合成皮革、繊維処理
剤、ポリエチレンテレフタレートの表面特性改質、ポリ
ウレタンの表面特性改良等の用途に好適に使用すること
ができる。The diol siloxane compound at one terminal of the present invention has a terminal diol which is a primary hydroxyl group equivalent in reactivity to one another, easily reacts with a carboxyl group or an isocyanate group, and forms a dicarboxylic acid compound or a diisocyanate. By cross-copolymerizing with a compound, a polymer having a polydimethylsiloxane chain in the side chain of polyester or polyurethane and having excellent surface properties such as water repellency, abrasion resistance and lubricity can be obtained. Therefore, this polymer can be suitably used for applications such as a heat-resistant coating agent for thermal transfer paper, a synthetic leather, a fiber treatment agent, a surface property modification of polyethylene terephthalate, and a surface property improvement of polyurethane.
【００３６】また、本発明の製造方法によれば、かかる
片末端ジオールシロキサン化合物を簡単かつ確実に製造
することができる。Further, according to the production method of the present invention, such a one-terminal diol siloxane compound can be produced simply and reliably.
【００３７】[0037]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明は下記の実施例に制限されるものではな
い。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
【００３８】〔実施例１〕 （ａ）１リットルのセパラブルフラスコにグリセリン９
２ｇ、ピリジン１６６ｇ、ＤＭＦ１５０ｇを仕込み、こ
れにｔ−ブチルジメチルクロルシラン３０１ｇをトルエ
ン２００ｇに溶解した溶液を滴下し、滴下終了後そのま
ま２時間撹拌した。析出した塩を濾過し、蒸留し、下記
式（９）で示されるグリセリンのビスシリル化物を２３
０ｇ（収率７２％，１１４−１１７℃／２ｍｍＨｇ）得
た。Example 1 (a) Glycerin 9 was placed in a 1-liter separable flask.
2 g, 166 g of pyridine and 150 g of DMF were charged, and a solution prepared by dissolving 301 g of t-butyldimethylchlorosilane in 200 g of toluene was added dropwise. After completion of the addition, the mixture was stirred for 2 hours. The precipitated salt was filtered and distilled to obtain a bis-silylated glycerin represented by the following formula (9).
0 g (yield 72%, 114-117 ° C./2 mmHg) was obtained.
【００３９】[0039]
【化１１】 Embedded image
【００４０】[0040]
【化１２】 Embedded image
【００４１】（ｂ）５００ｍｌのセパラブルフラスコに
水素化ナトリウム９．６ｇ、テトラヒドロフラン１００
ｇを加え、撹拌しながら上記式（９）のグリセリンのビ
スシリル化物７０ｇを滴下した。３０分撹拌した後、ア
リルブロマイド５３ｇを滴下し、滴下終了後、還流下に
８時間反応させた。生成した塩を濾別し、蒸留すること
により、式（１０）の化合物を５２．８ｇ（収率６７
％，１２１−１２４℃／２ｍｍＨｇ）得た。(B) 9.6 g of sodium hydride and 100 parts of tetrahydrofuran were placed in a 500 ml separable flask.
g, and 70 g of bis-silylated glycerin of the above formula (9) was added dropwise with stirring. After stirring for 30 minutes, 53 g of allyl bromide was added dropwise, and after completion of the addition, the mixture was reacted under reflux for 8 hours. The resulting salt was filtered off and distilled to obtain 52.8 g of the compound of the formula (10) (yield 67).
%, 121-124 ° C / 2 mmHg).
【００４２】[0042]
【化１３】 Embedded image
【００４３】[0043]
【化１４】 Embedded image
【００４４】（ｃ）１００ｍｌのナスフラスコに式（１
０）のビスシリル化物３０ｇとテトラブチルアンモニウ
ムフロリド（テトラヒドロフラン１ｍｏｌ／ｌ溶液）５
ｇを加え、３時間室温で撹拌した後、蒸留し、式（１
１）のジオールを６．１ｇ（収率５５％，１０９−１１
３℃／２ｍｍＨｇ）得た。(C) Formula (1) is placed in a 100 ml eggplant flask.
30 g of bissilylated compound of 0) and tetrabutylammonium fluoride (1 mol / l solution of tetrahydrofuran) 5
g, and the mixture was stirred at room temperature for 3 hours.
6.1 g of the diol of 1) (55% yield, 109-11
3 ° C./2 mmHg).
【００４５】[0045]
【化１５】 Embedded image
【００４６】[0046]
【化１６】 Embedded image
【００４７】（ｄ）５０ｍｌのナスフラスコに式（１
１）のジオール６ｇを入れ、ヘキサメチルジシラザン
８．７ｇを加え、２時間撹拌した。その後蒸留し、式
（１２）のビスメチルシリル化物を１０ｇ（収率８０
％，１１５−１１７℃／２ｍｍＨｇ）得た。(D) Formula (1) is placed in a 50 ml eggplant flask.
6 g of the diol of 1) was added, 8.7 g of hexamethyldisilazane was added, and the mixture was stirred for 2 hours. Thereafter, distillation was carried out to obtain 10 g of bismethylsilylated compound of the formula (12) (yield: 80).
%, 115-117 ° C / 2 mmHg).
【００４８】[0048]
【化１７】 Embedded image
【００４９】[0049]
【化１８】 Embedded image
【００５０】（ｅ）５０ｍｌのナスフラスコに式（１
２）のビストリメチルシリル化物８ｇ、トルエン５ｇ、
塩化白金酸１％イソプロピルアルコール溶液を１滴加
え、６０℃に昇温した。そこに、ペンタメチルジシロキ
サン４．３ｇを滴下し、８０℃で３時間反応させた。そ
の後蒸留して、下記式（１３）の化合物９．６ｇ（収率
７８％，１３１−１３４℃／１ｍｍＨｇ）を得た。(E) Formula (1) is placed in a 50 ml eggplant flask.
8 g of bistrimethylsilyl compound of 2), 5 g of toluene,
One drop of a 1% chloroplatinic acid isopropyl alcohol solution was added, and the temperature was raised to 60 ° C. Thereto, 4.3 g of pentamethyldisiloxane was added dropwise and reacted at 80 ° C. for 3 hours. Thereafter, distillation was performed to obtain 9.6 g (yield: 78%, 131-134 ° C./1 mmHg) of the compound of the following formula (13).
【００５１】[0051]
【化１９】 Embedded image
【００５２】[0052]
【化２０】 Embedded image
【００５３】（ｆ）５０ｍｌのナスフラスコに式（１
３）の化合物７．０ｇ、メタノール１０ｇを入れ、３時
間加熱還流下に反応させ、その後蒸留して下記式（１
ａ）３．１ｇ（収率６７％，１２６−１２９℃／１ｍｍ
Ｈｇ）を得た。(F) Formula (1) is placed in a 50 ml eggplant flask.
7.0 g of the compound of 3) and 10 g of methanol were added and reacted under heating and refluxing for 3 hours, followed by distillation to obtain the following formula (1)
a) 3.1 g (67% yield, 126-129 ° C / 1 mm
Hg).
【００５４】[0054]
【化２１】 Embedded image
【００５５】[0055]
【化２２】 Embedded image
【００５６】〔実施例２〕１リットルのセパラブルフラ
スコに実施例１の工程（ｄ）で得られた式（１２）のビ
ストリメチルシリル化物５ｇ、下記平均式（１４）の片
末端ハイドロジェンポリシロキサン７５ｇ、トルエン３
０ｇ、及び塩化白金酸１％イソプロピルアルコール溶液
０．１ｇを加え、１００℃で５時間反応させた。得られ
た混合物にメタノール５０ｇを加え、３時間加熱還流さ
せた後、減圧ストリップして、下記式（１ｂ）で示され
る油状物６８ｇを得た。Example 2 5 g of the bistrimethylsilylated compound of the formula (12) obtained in the step (d) of the example 1 was placed in a 1-liter separable flask, and hydrogen-terminated at one end of the following formula (14). 75 g, toluene 3
0 g and 0.1 g of chloroplatinic acid 1% isopropyl alcohol solution were added, and the mixture was reacted at 100 ° C. for 5 hours. 50 g of methanol was added to the obtained mixture, and the mixture was heated under reflux for 3 hours, and then stripped under reduced pressure to obtain 68 g of an oil represented by the following formula (1b).
【００５７】[0057]
【化２３】 Embedded image
【００５８】[0058]
【化２４】 化合物（１ｂ）の特性値は下記の通りであった。 水酸基価：２３．１ＫＯＨｍｇ／ｇ ＧＰＣ ：ポリスチレン換算分子量 Ｍn：４５３０ Ｍw：４８６０ 分散度 Ｍw／Ｍn＝１．０７1 Ｈ−ＮＭＲ：実施例１で得られた式（１ａ）のシロキ
サン化合物と同一の化学シフトにピークが現われた。 ＩＲ：３３５０ｃｍ-1（ＯＨ），２９７０ｃｍ-1（Ｃ−
Ｈ），１２６０ｃｍ-1（Ｓｉ−Ｃ），１１２０〜１０５
０ｃｍ-1（Ｓｉ−Ｏ）Embedded image The characteristic values of the compound (1b) were as follows. Hydroxyl value: 23.1KOHmg / g GPC: polystyrene equivalent molecular weight M n: 4530 M w: 4860 dispersity M w / M n = 1.07 1 H-NMR: siloxane of the formula obtained in Example 1 (1a) A peak appeared at the same chemical shift as the compound. IR: 3350 cm -1 (OH), 2970 cm -1 (C-
H), 1260 cm -1 (Si-C), 1120-105
0 cm -1 (Si-O)
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−60935（ＪＰ，Ａ) 特開 平２−255688（ＪＰ，Ａ) 特開 平４−304224（ＪＰ，Ａ) 特開 昭57−149290（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-60935 (JP, A) JP-A-2-255688 (JP, A) JP-A-4-304224 (JP, A) JP-A-57- 149290 (JP, A)
Claims (2)
る。）で表わされる片末端ジオールシロキサン化合物。[Claim 1] The following general formula (1) (Where n is an integer of 0 to 1000 and a is an integer of 2 to 8).
Ｈ基に下記一般式（２） 【化２】 （式中Ｒ1，Ｒ2，Ｒ3はそれぞれ互に同一又は異種の置
換又は未置換の炭素数１〜２０の炭化水素基、ａは２〜
８の整数である。）で示される化合物のＣＨ2＝ＣＨ基
を付加した後、ＳｉＲ1Ｒ2Ｒ3基を脱離することを特徴
とする片末端ジオールシロキサン化合物の製造方法。2. The one-terminal hydrogen siloxane of Si
The H group has the following general formula (2): (Wherein R 1 , R 2 , and R 3 are the same or different and each is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and a is
It is an integer of 8. A method for producing a diol siloxane compound having one terminal, which comprises adding a CH 2 ＣＨCH group of the compound represented by the formula ( 1) and then removing the SiR 1 R 2 R 3 group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29095291A JP2624060B2 (en) | 1991-10-09 | 1991-10-09 | One-end diol siloxane compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29095291A JP2624060B2 (en) | 1991-10-09 | 1991-10-09 | One-end diol siloxane compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0597868A JPH0597868A (en) | 1993-04-20 |
| JP2624060B2 true JP2624060B2 (en) | 1997-06-25 |
Family
ID=17762606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29095291A Expired - Lifetime JP2624060B2 (en) | 1991-10-09 | 1991-10-09 | One-end diol siloxane compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2624060B2 (en) |
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