JPH05331291A - Acid anhydride group-containing organopolysiloxane and its production - Google Patents
Acid anhydride group-containing organopolysiloxane and its productionInfo
- Publication number
- JPH05331291A JPH05331291A JP16838492A JP16838492A JPH05331291A JP H05331291 A JPH05331291 A JP H05331291A JP 16838492 A JP16838492 A JP 16838492A JP 16838492 A JP16838492 A JP 16838492A JP H05331291 A JPH05331291 A JP H05331291A
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid anhydride
- formula
- containing organopolysiloxane
- anhydride group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は文献未載の新規な酸無水
物基含有オルガノポリシロキサン、特にはポリイミド樹
脂などの有機樹脂の改質剤として有用される酸無水物基
含有オルガノポリシロキサンおよびその製造方法に関す
るものである。FIELD OF THE INVENTION The present invention relates to a novel acid anhydride group-containing organopolysiloxane which has not been published in the literature, and more particularly, an acid anhydride group-containing organopolysiloxane useful as a modifier for organic resins such as polyimide resins. The present invention relates to a manufacturing method thereof.
【０００２】[0002]
【従来の技術】耐熱性、耐燃性、電気・機械的特性など
を有する樹脂としてはポリイミド樹脂などが公知とされ
ており、これは銅板積層板、多層プリント配線板材料な
どの複合材料として多用されており、このものはまたＬ
ＳＩの多層配線用パッシベーション膜、メモリー素子用
α線遮断膜、磁気ヘッドなどの多層配線絶縁膜、液晶配
線向膜などのワニスとして、またフレキシブルプリント
配線板基板などのフィルムとしても利用されている。2. Description of the Related Art Polyimide resin is known as a resin having heat resistance, flame resistance, electrical and mechanical properties, etc. It is widely used as a composite material such as a copper plate laminated board and a multilayer printed wiring board material. And this one is also L
It is also used as a varnish for an SI multi-layer wiring passivation film, a memory element α-ray blocking film, a magnetic head and other multi-layer wiring insulating film, a liquid crystal wiring film, and a film for a flexible printed wiring board.
【０００３】しかし、このポリイミド樹脂はけい素や銅
といった金属およびガラスなどの無機物との自己接着性
に欠けており、またその溶解性が高沸点の極性溶剤にの
み限定され、かつワニス粘度が高く、さらには硬化物の
融点が高く、成形性、加工性に欠けるという欠点がある
ことから、より多くの用途に使用するための改質が望ま
れている。However, this polyimide resin lacks self-adhesiveness with metals such as silicon and copper and inorganic substances such as glass, and its solubility is limited to polar solvents having a high boiling point, and its varnish viscosity is high. Further, since the cured product has a high melting point and lacks moldability and processability, modification for use in more applications is desired.
【０００４】そして、このポリイミド樹脂の改質剤とし
ては、酸無水物基含有オルガノポリシロキサンが有用と
されるということが見出されているが、この酸無水物基
含有オルガノポリシロキサンについては下記の式It has been found that an acid anhydride group-containing organopolysiloxane is useful as a modifier for the polyimide resin. The acid anhydride group-containing organopolysiloxane is described below. Expression
【化４】 （ここにＲは１価の炭化水素基、Ｃは０または１以上の
整数）で示されるものが公知されている（特開昭63−27
0690号、特開昭63−316790号、特開昭64−850220号 各
公報参照）。[Chemical 4] (Wherein R is a monovalent hydrocarbon group and C is 0 or an integer of 1 or more) are known (JP-A-63-27).
0690, JP-A-63-316790, JP-A-64-850220).
【０００５】[0005]
【発明が解決しようとする課題】しかし、この公知の酸
無水物基含有オルガノポリシロキサンはそのＣ値が０の
場合にはその合成中に多くの副生成物（異性体など）が
発生するためにその精製に時間が必要とされるという欠
点があり、このものはまたその酸無水物基含有が分子鎖
両末端に限定されているために２官能性シロキサンしか
合成できないという不利がある。However, this known acid anhydride group-containing organopolysiloxane produces many by-products (isomers, etc.) during its synthesis when the C value is 0. However, it requires a long time for purification, and it also has a disadvantage that only bifunctional siloxane can be synthesized because the acid anhydride group content is limited to both ends of the molecular chain.
【０００６】[0006]
【発明が解決しようとする課題】本発明はこのような不
利を解決した酸無水物基含有オルガノポリシロキサンお
よびその製造方法に関するものであり、これは一般組成
式(1)SUMMARY OF THE INVENTION The present invention relates to an acid anhydride group-containing organopolysiloxane and a method for producing the same, which solves such disadvantages.
【化５】 〔ここにＲ1 は同一または異種の炭素数１〜18の非置換
または置換の１価炭化水素基、Ｒ2 はＲ1 と同一の１価
炭化水素基または式(2)[Chemical 5] [Wherein R 1 is the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R 2 is the same monovalent hydrocarbon group as R 1 or the formula (2)
【化６】 （ここにＲ3 は炭素数３〜12の直鎖状２価炭化水素基）
で示される１価の有機基で、Ｒ2 の少なくとも１個はこ
の式で示される基、ａおよびｂは０〜1,000 の整数〕で
示される酸無水物基含有オルガノポリシロキサンに関す
るものである。[Chemical 6] (Here, R 3 is a linear divalent hydrocarbon group having 3 to 12 carbon atoms)
A monovalent organic group represented by the formula (1), at least one of R 2 is a group represented by this formula, and a and b are integers of 0 to 1,000].
【０００７】すなわち、本発明者らは新規な酸無水物基
含有オルガノポリシロキサンを開発すべく種々に検討し
た結果、前記した組成式(1) で示されるものは文献未載
の新規なものであり、このものはポリイミド樹脂の低弾
性率化剤として、またポリアミド樹脂、ポリエステル樹
脂の表面改質剤、耐熱性向上剤、さらにはエポキシ樹脂
の可撓性は付与剤などとして有用なものになるというこ
とを見出すと共に、前記した公知の酸無水物基含有オル
ガノポリシロキサンが、酸無水物基含有を分子鎖両末端
のみに有するものであるのに対し、これは酸無水物基含
有が片末端でも両末端でもよく、さらにはこれが鎖中に
あってもよいということから重合停止剤、架橋剤などの
用途が広くなるという有利をもつものであることを確認
し、この製造方法についての研究を進めて本発明を完成
させた。以下にこれをさらに詳述する。That is, as a result of various investigations by the present inventors to develop a novel acid anhydride group-containing organopolysiloxane, the one represented by the above composition formula (1) is a novel one which has not been published in the literature. This is useful as a low-modulus agent for polyimide resins, as a surface modifier for polyamide resins and polyester resins, as a heat resistance improver, and as a flexibility imparting agent for epoxy resins. In addition to the fact that the above-mentioned known acid anhydride group-containing organopolysiloxane has an acid anhydride group only at both ends of the molecular chain, it has one end having an acid anhydride group. However, both ends may be used, and further, since it may be in the chain, it has been confirmed that it has the advantage that it can be used in a wide range of applications such as polymerization terminators and cross-linking agents. The present invention was completed by advancing researches on it. This will be described in more detail below.
【０００８】[0008]
【作用】本発明は文献未載な酸無水物基含有オルガノポ
リシロキサンおよびその製造方法に関するものであり、
この酸無水物基含有オルガノポリシロキサンは前記した
組成式(1) で示されるものであり、この製造方法はオル
ガノハイドロジェンポリシロキサンとアルケニル基と酸
無水物基を有する化合物とを付加反応させるものである
が、このようにして作られた本発明の酸無水物基含有オ
ルガノポリシロキサンはポリイミド樹脂、ポリアミド樹
脂、ポリエステル樹脂、エポキシ樹脂などの改質剤とし
て有用される。The present invention relates to an acid anhydride group-containing organopolysiloxane and a method for producing the same, which have not been described in the literature.
This acid anhydride group-containing organopolysiloxane is represented by the above-mentioned compositional formula (1), and this production method involves addition reaction of the organohydrogenpolysiloxane with a compound having an alkenyl group and an acid anhydride group. The thus prepared acid anhydride group-containing organopolysiloxane of the present invention is useful as a modifier for polyimide resins, polyamide resins, polyester resins, epoxy resins and the like.
【０００９】本発明の酸無水物基含有オルガノポリシロ
キサンは前記した組成式(1) で示されるものであるが、
このＲ1 はメチル基、エチル基、プロピル基、ブチル
基、オクチル基、ドデシル基、オクタデシル基などのア
ルキル基、シクロヘキシル基、シクロペンテル基などの
シクロアルキル基、フェニル基、トリル基、ナフテル基
などのアリール基、またはこれらの基の炭素原子に結合
している水素原子の一部または全部をハロゲン原子、シ
アノ基などで置換したクロロメチル基、トリフルオロプ
ロピル基、シアノエチル基などから選択される同一また
は異種の非置換または置換の１価炭化水素基で、Ｒ2 は
Ｒ1 と同一の１価炭化水素基または前記した式(2) で示
される１価の有機基であるものである。The acid anhydride group-containing organopolysiloxane of the present invention is represented by the above composition formula (1).
R 1 is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, an octadecyl group, a cycloalkyl group such as a cyclohexyl group, a cyclopentyl group, a phenyl group, a tolyl group, a naphthel group, etc. An aryl group of, or the same selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc., in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Alternatively, it is a different unsubstituted or substituted monovalent hydrocarbon group, and R 2 is the same monovalent hydrocarbon group as R 1 or the monovalent organic group represented by the above formula (2).
【００１０】この酸無水物基含有オルガノポリシロキサ
ンはその酸無水物基が分子鎖の片末端であるもの、両末
端にあるもの、あるいは鎖中のあるもののいずれであっ
てもよいので、重合停止剤、架橋剤など用途が広くなる
という有利性が与えられるが、これには下記のものが例
示される。Since the acid anhydride group-containing organopolysiloxane may have the acid anhydride group at one end of the molecular chain, at both ends, or in the chain, the polymerization is terminated. The advantage of widening the application such as agents and cross-linking agents is given, and the following is exemplified.
【化７】 [Chemical 7]
【化８】 [Chemical 8]
【化９】 [Chemical 9]
【化１０】 [Chemical 10]
【００１１】本発明の酸無水物基含有オルガノポリシロ
キサンは一般式(3)The acid anhydride group-containing organopolysiloxane of the present invention has the general formula (3)
【化１１】 で示され、Ｒ1 が前記した一般式(1) におけるＲ1 と同
一の１価炭化水素、Ｒ5が水素原子またはＲ1 と同一の
１価炭化水素で、その少なくとも１個が水素原子であ
り、ｄが０〜1,000 の数、ｅが０〜100 の数であるオル
ガノハイドロジェンポリシロキサンに、付加反応触媒の
存在下で、一般式(4)[Chemical 11] And R 1 is the same monovalent hydrocarbon as R 1 in the above general formula (1), R 5 is a hydrogen atom or the same monovalent hydrocarbon as R 1, and at least one of them is a hydrogen atom. In the presence of an addition reaction catalyst to an organohydrogenpolysiloxane in which d is a number of 0 to 1,000 and e is a number of 0 to 100.
【化１２】 で示され、Ｒ4 がアルケニル基含有の１価炭化水素基で
ある、酸無水物基含有の化合物を付加反応させることに
よって得ることができる。[Chemical formula 12] And R 4 is an alkenyl group-containing monovalent hydrocarbon group, which is an acid anhydride group-containing compound.
【００１２】ここに使用する一般式(3) で示されるオル
ガノハイドロジェンポリシロキサンは分子中に少なくと
も１個、好ましくは２個以上の≡Ｓｉ−Ｈ基を有するも
のであれば直鎖状、環状のいずれでもよく、このａ，ｂ
値に応じた各種の公知のものとすればよい。The organohydrogenpolysiloxane represented by the general formula (3) used herein has a linear or cyclic structure as long as it has at least one, preferably two or more .tbd.Si--H groups in the molecule. Either a, b
Various publicly known ones depending on the value may be used.
【００１３】また、ここに使用される一般式(4) で示さ
れる化合物としてはこの式中のＲ4基の種類に応じて下
記式のものが例示される。Further, as the compound represented by the general formula (4) used herein, those of the following formulas are exemplified depending on the kind of the R 4 group in the formula.
【化１３】 [Chemical 13]
【化１４】 [Chemical 14]
【化１５】 [Chemical 15]
【化１６】 [Chemical 16]
【化１７】 [Chemical 17]
【化１８】 [Chemical 18]
【化１９】 [Chemical 19]
【化２０】 [Chemical 20]
【化２１】 [Chemical 21]
【化２２】 [Chemical formula 22]
【化２３】 [Chemical formula 23]
【００１４】なお、ここに使用される付加反応触媒は公
知のものとすればよく、これには白金、塩化白金酸、塩
化白金酸誘導体などが例示される。また、この反応は有
機溶媒の存在下で行なうことがよく、したがってこれは
トルエン、キシレンなどの芳香族炭化水素、ヘキサン、
オクタンなどの脂肪族炭化水素、酢酸エチルなどのエス
テル類、アセトン、メチルエルケトンなどのケトン類、
クロロホルム、四塩化炭素などの塩素化炭化水素類、ジ
エチルエーテル、ジブチルエーテルなどのエーテル類の
存在下で行なうことがよい。The addition reaction catalyst used here may be a known one, and examples thereof include platinum, chloroplatinic acid and chloroplatinic acid derivatives. In addition, this reaction is preferably carried out in the presence of an organic solvent, and therefore, this is an aromatic hydrocarbon such as toluene or xylene, hexane,
Aliphatic hydrocarbons such as octane, esters such as ethyl acetate, ketones such as acetone and methyl elketone,
It may be carried out in the presence of chlorinated hydrocarbons such as chloroform and carbon tetrachloride and ethers such as diethyl ether and dibutyl ether.
【００１５】この反応はこれが付加反応であることから
オルガノポリシロキサンの≡Ｓｉ−Ｈ基１モルに対して
酸無水物基含有の末端アルケニル基を有する化合物を1.
0 〜1.5 モルの範囲、好ましくは、1.0 〜1.2 モルの範
囲で反応させればよいが、この反応は 20 〜 150℃、好
ましくは 80 〜 120℃の温度で反応させればよい。Since this reaction is an addition reaction, the compound having a terminal alkenyl group containing an acid anhydride group is added to 1 mol of the ≡Si-H group of the organopolysiloxane.
The reaction may be carried out in the range of 0 to 1.5 mol, preferably 1.0 to 1.2 mol, but this reaction may be carried out at a temperature of 20 to 150 ° C, preferably 80 to 120 ° C.
【００１６】このように上記した一般式(3) で示される
オルガノハイドロジェンポリシロキサンと一般式(4) で
示される化合物を付加反応させて得た組成式(1) で示さ
れる酸無水物基含有オルガノポリシロキサンは文献未載
の新規なものであるが、このものはポリイミド樹脂など
の改質剤として有用なものとされ、これを添加したポリ
イミド樹脂には低弾性率化剤になるという効果が付与さ
れ、ポリアミド樹脂、ポリエステル樹脂は耐熱性が向上
し、エポキシ樹脂は可撓性になるという有利性が与えら
れる。Thus, the acid anhydride group represented by the composition formula (1) obtained by the addition reaction of the organohydrogenpolysiloxane represented by the general formula (3) and the compound represented by the general formula (4) The contained organopolysiloxane is a novel one that has not been published in the literature, but it is said to be useful as a modifier for polyimide resins, etc. The polyamide resin and polyester resin have the advantages of improved heat resistance and the epoxy resin has the advantage of being flexible.
【００１７】つぎに本発明の実施例および応用例をあげ
る。 実施例１ 撹拌機およびコンデンサーを設けた50mlのフラスコに、
式Next, examples and application examples of the present invention will be described. Example 1 In a 50 ml flask equipped with stirrer and condenser,
formula
【化２４】 で示される化合物 11.6gを仕込み、これに塩化白金酸２
重量％のイソプロピルアルコール 0.05gを加えたのち、
オイルバスで内温が70℃になるように加熱し、撹拌下こ
れに式[Chemical formula 24] 11.6 g of the compound represented by is charged, and chloroplatinic acid 2
After adding 0.05 g of wt% isopropyl alcohol,
Heat the oil bath to an internal temperature of 70 ° C and stir it while stirring.
【化２５】 で示されるペンタメチルジシロキサン 8.15gを適下し、
適下後80℃で２時間維持したのち、ガスクロマトグラフ
ィーでチェックしたところ、原料のピークは消失してい
た。[Chemical 25] Apply 8.15 g of pentamethyldisiloxane represented by
After keeping the temperature below 80 ° C. for 2 hours and then checking by gas chromatography, the peak of the raw material disappeared.
【００１８】ついで得られた反応液を蒸留したところ、
沸点が 166〜17℃／ 7.7×10-2mmHgの化合物 15.1g（収
率76％）が得られたので、このものをＨ−ＮＭＲスペク
トル分析および質量分析したところ、つぎの結果が得ら
れたので、このものに式Then, when the obtained reaction solution was distilled,
Since 15.1 g (yield 76%) of a compound having a boiling point of 166 to 17 ° C./7.7×10 −2 mmHg was obtained, H-NMR spectrum analysis and mass spectrometry of this compound gave the following results. So the formula to this one
【化２６】 で示されるものであることが確認された。[Chemical formula 26] It was confirmed that
【００１９】〔Ｈ−ＮＭＲ(ppm) 分析値〕[H-NMR (ppm) analysis value]
【化２７】 [Chemical 27]
【００２０】実施例２ 撹拌機およびコンデンサーを設けた 500mlのフラスコ
に、式Example 2 A 500 ml flask equipped with a stirrer and condenser was charged with the formula
【化２８】 で示される化合物 25.5gを仕込み、これに塩化白金酸２
重量％のイソプロピルアルコール溶液 0.05gを加えたの
ち、オイルバスで内温で70℃となるように加熱し、撹拌
下これに式[Chemical 28] 25.5 g of the compound shown in is charged, and chloroplatinic acid 2
After adding 0.05 g of a wt% isopropyl alcohol solution, heat to an internal temperature of 70 ° C in an oil bath and stir it while stirring.
【化２９】 で示されるオルガノハイドロジェンポリシロキサン 155
g を適下し、適下後100℃で２時間撹拌したのち、ＩＲ
で≡Ｓｉ−Ｈ基の吸収の消失していることを確認した。[Chemical 29] Organohydrogenpolysiloxane represented by 155
g, and after stirring at 100 ° C for 2 hours, IR
It was confirmed that the absorption of the ≡Si—H group had disappeared.
【００２１】ついで、得られた反応液を 200℃、３mmHg
で減圧ストリップしたところ、 171g（収率98％）の生
成物が得られたので、このもののＧＰＣ（ポリスチレン
換算分子量）およびＩＲをしらべたところ、つぎの結果
が得られたので、このものは式Then, the obtained reaction solution was heated at 200 ° C. for 3 mmHg.
171 g (yield 98%) of the product was obtained by vacuum stripping with, and the GPC (polystyrene-equivalent molecular weight) and IR of this product were examined. The following results were obtained.
【化３０】 で示されるものであることが確認された。[Chemical 30] It was confirmed that
【００２２】〔ＧＰＣ（ポリスチレン換算分子量〕 Ｍｎ 2,830 Ｍｗ 3,680 分散度 Ｍｗ／Ｍｎ＝1.30 〔ＩＲcm-1〕 1,100(Si-O)、 1,260(Si-C)、 1,810(C=O) 、1,850(C=
O) 、 2,980(C-H)[GPC (Polystyrene-equivalent molecular weight) Mn 2,830 Mw 3,680 Dispersion degree Mw / Mn = 1.30 [IRcm −1 ] 1,100 (Si-O), 1,260 (Si-C), 1,810 (C = O), 1,850 (C =
O), 2,980 (CH)
【００２３】実施例３ 実施例２におけるオルガノハイドロジェンポリシロキサ
ンを式Example 3 The organohydrogenpolysiloxane of Example 2 was formulated
【化３１】 で示されるもの 237g としたほかは実施例２と同様に処
理したところ、253g（収率98％）の生成物で得られたの
で、これについてＧＰＣおよびＩＲをしらべたところ、
つぎの結果が得られたので、このものは式[Chemical 31] The product was treated in the same manner as in Example 2 except that 237 g was obtained. As a result, 253 g (yield 98%) of the product was obtained. GPC and IR of this product were examined.
We have the following result,
【化３２】 で示されるものであることが確認された。[Chemical 32] It was confirmed that
【００２４】〔ＧＰＣ（ポリスチレン換算分子量〕 Ｍｎ 2,450 Ｍｗ 2,650 分散度 Ｍｗ／Ｍｎ＝1.08 〔ＩＲcm-1〕 1,100(Si-O)、 1,265(Si-C)、 1,800(C=O) 、1,850(C=
O) 、 2,980(C-H)[GPC (Polystyrene-equivalent molecular weight) Mn 2,450 Mw 2,650 Dispersion degree Mw / Mn = 1.08 [IRcm -1 ] 1,100 (Si-O), 1,265 (Si-C), 1,800 (C = O), 1,850 (C =
O), 2,980 (CH)
【００２５】実施例４ 撹拌機およびコンデンサーを設けた 500mlのフラスコ
に、実施例１で使用したものと同一の酸無水物基を含有
する末端にアルケニル基を有する化合物 76.6gを仕込
み、これに塩化白金酸２重量％のイソプロピルアルコー
ル溶液 0.15gを加えたのち、オイルバスで内温で70℃と
なるように加熱し、撹拌下これに式Example 4 A 500 ml flask equipped with a stirrer and a condenser was charged with 76.6 g of a compound having an alkenyl group at the terminal containing the same acid anhydride group as that used in Example 1, and chlorinated. After adding 0.15 g of isopropyl alcohol solution containing 2% by weight of platinic acid, heat the mixture in an oil bath to an internal temperature of 70 ° C and stir it while stirring.
【化３３】 で示されるオルガノハイドロジェンポリシロキサン 234
g を適下し、適下後 100℃で２時間撹拌したのち、ＩＲ
で≡Ｓｉ−Ｈ基の吸収の消失していることを確認した。[Chemical 33] Organohydrogenpolysiloxane represented by 234
g, and after stirring at 100 ° C for 2 hours, IR
It was confirmed that the absorption of the ≡Si—H group had disappeared.
【００２６】ついで、得られた反応液を 200℃、３mmHg
で減圧ストリップしたところ、303g（収率98％）の生成
物が得られたので、このもののＧＰＣおよびＩＲをしら
べたところ、つぎの結果が得られたので、このものは式Then, the obtained reaction solution was heated at 200 ° C. for 3 mmHg.
When the product was stripped under reduced pressure with 303 g, a product of 303 g (yield 98%) was obtained. GPC and IR of this product were examined, and the following results were obtained.
【化３４】 で示されるものであることが確認された。[Chemical 34] It was confirmed that
【００２７】〔ＧＰＣ（ポリスチレン換算分子量〕 Ｍｎ 2,400 Ｍｗ 2,900 分散度 Ｍｗ／Ｍｎ＝1.08 〔ＩＲcm-1〕 1,100(Si-O)、 1,260(Si-C)、 1,810(C=O) 、1,860(C=
O) 、 2,980(C-H)[GPC (Polystyrene-equivalent molecular weight) Mn 2,400 Mw 2,900 Dispersion degree Mw / Mn = 1.08 [IRcm −1 ] 1,100 (Si-O), 1,260 (Si-C), 1,810 (C = O), 1,860 (C =
O), 2,980 (CH)
【００２８】実施例５ 撹拌機およびコンデンサ−を設けた500ml のフラスコ
に、実施例１で使用したものと同一の酸無水物基を含有
する末端にアルケニル基を有する化合物104gを仕込み、
これに塩化白金酸２重量％のイソプロピルアルコ−ル溶
液0.15g を加えたのち、オイルバスで内温70℃となるよ
うに加熱し、撹拌下これに式Example 5 A 500 ml flask equipped with a stirrer and a condenser was charged with 104 g of the compound having an alkenyl group at the terminal containing the same acid anhydride group as used in Example 1,
To this, 0.15 g of isopropyl alcohol solution containing 2% by weight of chloroplatinic acid was added, and then heated in an oil bath to an internal temperature of 70 ° C., and stirred to form
【化３５】 で示されるオルガノハイドロジエンポリシロキサン202g
を滴下し、滴下後100 ℃で２時間撹拌したのち、IRで≡
Si-H基の吸収の消失していることを確認した。[Chemical 35] 202 g of organohydrogenpolysiloxane represented by
Was added dropwise and after stirring for 2 hours at 100 ° C, IR ≡
It was confirmed that the absorption of the Si-H group had disappeared.
【００２９】ついで得られた反応液を200 ℃、３mmHgで
減圧ストリップしたところ、1,395g (収率95%)の生成物
が得られたので、このもののGPC およびIRをしらべたと
ころ、つぎの結果が得られたので、このものは式The resulting reaction solution was vacuum stripped at 200 ° C. and 3 mmHg, and 1395 g (yield 95%) of the product was obtained. GPC and IR of this product were examined. This yields the expression
【化３６】 で示されるものであることが確認された。 ［GPC ポリスチレン換算分子量］ Ｍｎ 1,500 Ｍｗ 2,100 分散度 Ｍｗ／Ｍｎ=1.40 [IRcm-1] 1,100(Si-O)、 1,270(Si-C)、 1,800(C=O) 1,850(C=O)、 2,950(C-H)、 1,065(Si-Ph)[Chemical 36] It was confirmed that [GPC polystyrene equivalent molecular weight] Mn 1,500 Mw 2,100 Dispersion degree Mw / Mn = 1.40 [IRcm -1 ] 1,100 (Si-O), 1,270 (Si-C), 1,800 (C = O) 1,850 (C = O), 2,950 (CH), 1,065 (Si-Ph)
【００３０】[0030]
【発明の効果】本発明は酸無水物基含有オルガノポリシ
ロキサンおよびその製造方法に関するものであり、これ
は前記したように組成式(1) で示されるものであり、こ
の製造方法はオルガノハイドロジェンポリシロキサンと
分子中に酸無水物基とアルケニル基を含有する化合物と
を付加反応させることを特徴とするものであるが、この
酸無水物基含有オルガノポリシロキサンは文献未載の新
規なもので、ポリイミド樹脂、ポリエステル樹脂、エキ
ポシ樹脂などの改質剤として有用とされるものである。INDUSTRIAL APPLICABILITY The present invention relates to an acid anhydride group-containing organopolysiloxane and a method for producing the same, which is represented by the composition formula (1) as described above. The present invention is characterized in that a polysiloxane is subjected to an addition reaction with a compound containing an acid anhydride group and an alkenyl group in the molecule. This acid anhydride group-containing organopolysiloxane is a novel one not yet published in the literature. , A polyimide resin, a polyester resin, an epoxy resin, and the like, which are useful as modifiers.
Claims (3)
または置換の１価炭化水素基、Ｒ2 はＲ1 と同一の１価
炭化水素基または式 【化２】 （ここにＲ3 は炭素数３〜12の直鎖状２価炭化水素基）
で示される１価の有機基で、Ｒ2 の少なくとも１個はこ
の式で示される基、ａおよびｂは０〜1,000 の整数〕で
示される酸無水物基含有オルガノポリシロキサン。1. A general composition formula: [Wherein R 1 is the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R 2 is the same monovalent hydrocarbon group as R 1 or a compound of the formula: (Here, R 3 is a linear divalent hydrocarbon group having 3 to 12 carbon atoms)
The acid anhydride group-containing organopolysiloxane represented by the formula (1), wherein at least one of R 2 is a group represented by this formula, and a and b are integers of 0 to 1,000.
含有するオルガノハイドロジェンポリシロキサンに一般
式 【化３】 （ここにＲ4 は炭素数１〜10の２価炭化水素）で示され
る化合物を付加反応させることを特徴とする酸無水物基
含有オルガノポリシロキサンの製造方法2. An organohydrogenpolysiloxane containing at least one .tbd.Si--H group in its molecule has the general formula: ## STR3 ## (Wherein R 4 is a divalent hydrocarbon having 1 to 10 carbon atoms) is subjected to an addition reaction to produce an acid anhydride group-containing organopolysiloxane.
Ｈ2 −基である請求項２に記載した酸無水物基含有オル
ガノポリシロキサンの製造方法。3. An R 4 group is — (CH 2 ) 5 —CH═CH—C.
The method for producing an acid anhydride group-containing organopolysiloxane according to claim 2, which is an H 2 -group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16838492A JPH05331291A (en) | 1992-06-03 | 1992-06-03 | Acid anhydride group-containing organopolysiloxane and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16838492A JPH05331291A (en) | 1992-06-03 | 1992-06-03 | Acid anhydride group-containing organopolysiloxane and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05331291A true JPH05331291A (en) | 1993-12-14 |
Family
ID=15867113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16838492A Pending JPH05331291A (en) | 1992-06-03 | 1992-06-03 | Acid anhydride group-containing organopolysiloxane and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05331291A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455640B2 (en) | 2000-04-25 | 2002-09-24 | Dow Corning Toray Silicone, Co., Ltd. | Method for producing basic amino acid-modified organopolysiloxane |
| US6576737B2 (en) * | 2000-10-04 | 2003-06-10 | Shin-Etsu Chemical Co., Ltd. | Curable compositions of fluorinated amide compounds |
| WO2004024799A1 (en) * | 2002-09-11 | 2004-03-25 | Dow Corning Toray Silicone Co., Ltd. | Organopolysiloxane-modified polysaccharide and process for producing the same |
| US7025950B2 (en) * | 2002-05-09 | 2006-04-11 | The Procter & Gamble Company | Oral care compositions comprising dicarboxy functionalized polyorganosiloxanes |
| JP2009263643A (en) * | 2008-04-03 | 2009-11-12 | Shin Etsu Chem Co Ltd | Organopolysiloxane having carboxyl groups |
| JP2011136962A (en) * | 2009-12-28 | 2011-07-14 | Dow Corning Toray Co Ltd | Organosilicon compound, method of producing the same, and curable silicone composition comprising the organosilicon compound as adhesiveness-imparting agent |
| JP2011136958A (en) * | 2009-12-28 | 2011-07-14 | Dow Corning Toray Co Ltd | Organosilicon compound, and method of producing the same |
| US8048978B2 (en) | 2007-12-14 | 2011-11-01 | Shin-Etsu Chemical Co., Ltd. | Silphenylene compound and process for producing the same |
| JP2013032498A (en) * | 2011-07-06 | 2013-02-14 | Shin-Etsu Chemical Co Ltd | Succinic anhydride group-containing cyclic organosiloxane, method for producing the same, organosiloxane composition, and thermosetting resin composition |
| US8729195B2 (en) | 2009-12-28 | 2014-05-20 | Dow Corning Toray Co., Ltd. | Organosilicon compound, method for producing thereof, and curable silicone composition containing the same |
| US8853372B2 (en) | 2010-08-23 | 2014-10-07 | Dow Corning Corporation | Saccharide siloxanes stable in aqueous environments and methods for the preparation and use of such saccharide siloxanes |
| US8877216B2 (en) | 2005-05-23 | 2014-11-04 | Dow Corning Corporation | Cosmetic and skin-care compositions comprising saccharide-siloxane copolymers |
| US8907026B2 (en) | 2004-12-23 | 2014-12-09 | Dow Corning Corporation | Crosslinkable saccharide-siloxane compositions, and networks, coatings and articles formed therefrom |
| US8968773B2 (en) | 2006-05-23 | 2015-03-03 | Dow Corning Corporation | Silicone film former for delivery of actives |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61157531A (en) * | 1984-12-27 | 1986-07-17 | ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Crosslinkable organopolysiloxane and its production |
-
1992
- 1992-06-03 JP JP16838492A patent/JPH05331291A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61157531A (en) * | 1984-12-27 | 1986-07-17 | ワツカー‐ケミー・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Crosslinkable organopolysiloxane and its production |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455640B2 (en) | 2000-04-25 | 2002-09-24 | Dow Corning Toray Silicone, Co., Ltd. | Method for producing basic amino acid-modified organopolysiloxane |
| US6576737B2 (en) * | 2000-10-04 | 2003-06-10 | Shin-Etsu Chemical Co., Ltd. | Curable compositions of fluorinated amide compounds |
| US7025950B2 (en) * | 2002-05-09 | 2006-04-11 | The Procter & Gamble Company | Oral care compositions comprising dicarboxy functionalized polyorganosiloxanes |
| WO2004024799A1 (en) * | 2002-09-11 | 2004-03-25 | Dow Corning Toray Silicone Co., Ltd. | Organopolysiloxane-modified polysaccharide and process for producing the same |
| JP2004156004A (en) * | 2002-09-11 | 2004-06-03 | Dow Corning Toray Silicone Co Ltd | Organopolysiloxane-modified polysaccharide and process for producing the same |
| US7199205B2 (en) | 2002-09-11 | 2007-04-03 | Dow Corning Toray Silicone Company, Ltd. | Organopolysiloxane-modified polysaccharide and process for producing the same |
| US8907026B2 (en) | 2004-12-23 | 2014-12-09 | Dow Corning Corporation | Crosslinkable saccharide-siloxane compositions, and networks, coatings and articles formed therefrom |
| US8877216B2 (en) | 2005-05-23 | 2014-11-04 | Dow Corning Corporation | Cosmetic and skin-care compositions comprising saccharide-siloxane copolymers |
| US8968773B2 (en) | 2006-05-23 | 2015-03-03 | Dow Corning Corporation | Silicone film former for delivery of actives |
| US8048978B2 (en) | 2007-12-14 | 2011-11-01 | Shin-Etsu Chemical Co., Ltd. | Silphenylene compound and process for producing the same |
| US8252882B2 (en) | 2007-12-14 | 2012-08-28 | Shin-Etsu Chemical Co., Ltd. | Polyimide resin produced by using silphenylene compound |
| JP2009263643A (en) * | 2008-04-03 | 2009-11-12 | Shin Etsu Chem Co Ltd | Organopolysiloxane having carboxyl groups |
| JP2011136958A (en) * | 2009-12-28 | 2011-07-14 | Dow Corning Toray Co Ltd | Organosilicon compound, and method of producing the same |
| US8729195B2 (en) | 2009-12-28 | 2014-05-20 | Dow Corning Toray Co., Ltd. | Organosilicon compound, method for producing thereof, and curable silicone composition containing the same |
| JP2011136962A (en) * | 2009-12-28 | 2011-07-14 | Dow Corning Toray Co Ltd | Organosilicon compound, method of producing the same, and curable silicone composition comprising the organosilicon compound as adhesiveness-imparting agent |
| US8853372B2 (en) | 2010-08-23 | 2014-10-07 | Dow Corning Corporation | Saccharide siloxanes stable in aqueous environments and methods for the preparation and use of such saccharide siloxanes |
| CN102942585A (en) * | 2011-07-06 | 2013-02-27 | 信越化学工业株式会社 | Succinic anhydride group containing cyclic organosiloxane, preparation thereof, organosiloxane composition and thermosetting resin composition |
| JP2013032498A (en) * | 2011-07-06 | 2013-02-14 | Shin-Etsu Chemical Co Ltd | Succinic anhydride group-containing cyclic organosiloxane, method for producing the same, organosiloxane composition, and thermosetting resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4381396A (en) | Silynorbornane anhydrides and method for making | |
| JP3813486B2 (en) | Process for the preparation of aminofunctional organosiloxanes | |
| JPH05331291A (en) | Acid anhydride group-containing organopolysiloxane and its production | |
| CN110603283B (en) | Hydrosilylation curable silicone resins | |
| JPH0517927B2 (en) | ||
| JP3279635B2 (en) | Hydrosilyl group-containing imide compound | |
| US7569652B2 (en) | Synthesis and characterization of novel cyclosiloxanes and their self- and co-condensation with silanol-terminated polydimethylsiloxane | |
| JPS58171416A (en) | Heat-resistant polymer | |
| JPH0643493B2 (en) | Anhydride-functional organo (poly) siloxane, process for its production, process for producing organopolysiloxane-polyimide copolymer and curing agent for epoxy resin | |
| JP3224830B2 (en) | Organosilicon compound and method for producing the same | |
| JP4549382B2 (en) | Novel silphenylene compound and process for producing the same | |
| JP2019199553A (en) | Silphenylene and polyether structure-containing polymer | |
| JPH01193276A (en) | Organosiloxane compound whose one terminus is terminated with aminoalkyl | |
| JPH02255689A (en) | Glycidoxy group-containing organosilicon compound | |
| JPH08127657A (en) | Production of cured diphenylsiloxane and cured product | |
| US5286890A (en) | Aromatic amine terminated silicone monomers, oligomers, and polymers therefrom | |
| JP5890288B2 (en) | Method for producing novel organosilicon compound | |
| JP2680284B2 (en) | Organosilicon compounds having a furanyl group, methods of making the compounds, compositions crosslinkable by light, and methods of making coatings | |
| JPS6352061B2 (en) | ||
| JPH0291083A (en) | Siloxane compound of one reactive terminal | |
| US3548025A (en) | Novel silicon - substituted glycol monoesters and process for their preparation | |
| RU2462467C1 (en) | Method of producing hardener for low-molecular weight epoxy resins | |
| JP5387524B2 (en) | Organohydrogenpolysiloxane and method for producing the same | |
| JPH0586071A (en) | Process for producing dianhydride-terminated polydiorganosiloxane | |
| CA1325017C (en) | Phthalic acid ester-modified organopolysiloxane and method for its preparation |