JP3287216B2 - Silicon polymer compound and method for producing the same - Google Patents
Silicon polymer compound and method for producing the sameInfo
- Publication number
- JP3287216B2 JP3287216B2 JP08328796A JP8328796A JP3287216B2 JP 3287216 B2 JP3287216 B2 JP 3287216B2 JP 08328796 A JP08328796 A JP 08328796A JP 8328796 A JP8328796 A JP 8328796A JP 3287216 B2 JP3287216 B2 JP 3287216B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- based polymer
- group
- polymer compound
- formula
- 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.)
- Expired - Fee Related
Links
Landscapes
- Silicon Polymers (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光電変換材料、導
電性材料、紫外線吸収材料、セラミック前駆体等として
有用な新規ケイ素系高分子化合物及びその製造方法に関
する。[0001] The present invention relates to a novel silicon-based polymer compound useful as a photoelectric conversion material, a conductive material, an ultraviolet absorbing material, a ceramic precursor, and the like, 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】ケイ素
−ケイ素結合はσ結合のエネルギー準位が炭素のそれに
比べて非常に高くなっており、ポリシランに見られるよ
うにσ共役や各種のπ結合との共役が知られている。し
かし、ポリシランは、その性質に興味が持たれているも
のの、反応性も高く、ポリシランの合成法がウルツ反応
をはじめとして極めて厳しい条件で行われることと相ま
って、側鎖に官能基を導入するなどのデザインを行う際
に大きな障害となっていた。2. Description of the Related Art The energy level of a sigma bond of a silicon-silicon bond is much higher than that of carbon. The conjugation with is known. However, although polysilanes are interesting in their properties, they are also highly reactive, and coupled with the fact that polysilanes are synthesized under extremely severe conditions including the Wurtz reaction, functional groups are introduced into side chains. This was a major obstacle in designing.
【０００３】例えば、関らは、ポリシランの側鎖にフェ
ニル基上での反応を利用してクロロメチル化の後、アン
モニウム塩誘導体への反応を報告している（６３日化予
稿集、２１３２（１９９２））。また、Ｍａｔｙｊａｓ
ｚｅｗｓｋｉらは、ポリシランの側鎖フェニル基をトリ
フレートで切断し、グリニャール反応などによる官能基
の導入を報告している（ＡＣＳ Ｓｅｒｉｅｓ，“Ａｄ
ｖａｎｃｅｓｉｎ Ｃｈｅｍｉｓｔｒｙ”，２２４，２
８５（１９９０））。更に、Ｗａｙｍｏｕｔｈらは、脱
水素縮合によって得られる側鎖水素のポリシランをラジ
カル反応を利用したヒドロシリル化によるアルキル化や
アルコキシ化反応を報告している（Ｊ．Ａｍ．Ｃｈｅ
ｍ．Ｓｏｃ．，１１６，９７７９（１９９４））。[0003] For example, Seki et al. Report a reaction on an ammonium salt derivative after chloromethylation using a reaction on a phenyl group in a side chain of polysilane (63-Nikkei, 2132 ( 1992)). Also, Matyjas
Zewski et al. report the introduction of a functional group by cleaving the side chain phenyl group of polysilane with triflate and Grignard reaction (ACS Series, “Ad”).
vencesin Chemistry ", 224 , 2
85 (1990)). Further, Waymouth et al. Report an alkylation or alkoxylation reaction of a polysilane of side chain hydrogen obtained by dehydrogenation condensation by hydrosilylation utilizing a radical reaction (J. Am. Che.
m. Soc. , 116 , 9779 (1994)).
【０００４】しかし、これらの方法はいずれも等量反応
によるもので、スズ試薬、トリフレートやラジカル発生
剤といった危険性の高い試薬を大量に使用する必要があ
り、このため簡便に選択性よく進行するような側鎖の置
換反応が求められていた。However, all of these methods are based on an equivalent reaction, and require the use of a large amount of highly dangerous reagents such as tin reagents, triflates and radical generators. Such a side chain substitution reaction has been required.
【０００５】[0005]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記要望に応えるため鋭意検討を行った結
果、ヒドロキシルアミン類がケイ素−水素結合を有する
ポリシラン部位を含有するケイ素系高分子化合物の該ケ
イ素−水素結合を効果的に切断し、これによってアミノ
キシ化されたポリシラン部位を含有するケイ素系高分子
化合物が効率よく得られること、この反応はほぼ定量的
に進行し、側鎖に対して任意の割合でアミノキシ基を導
入できることを知見した。更に、この系にアルコールや
シラノールを共存させた場合、アミノキシル基が順次置
き換ってアルコキシ化やシロキシ化が起こること、この
反応は触媒量のヒドロキシルアミン存在下でも室温にお
いて穏やかに進行し、ケイ素−ケイ素結合の切断も極め
て少ないこと、従ってかかる反応を利用することによ
り、脱水素縮合反応によって得られる側鎖水酸基を持つ
ポリシラン部位を含有するケイ素系高分子化合物への官
能基導入を効率よく行うことができることを知見し、本
発明をなすに至った。Means for Solving the Problems and Embodiments of the Invention The present inventor has conducted intensive studies in order to meet the above-mentioned demand. As a result, the hydroxylamines have a silicon-based polymer containing a polysilane moiety having a silicon-hydrogen bond. The silicon-hydrogen bond of the molecular compound is effectively cleaved, whereby a silicon-based polymer compound containing an aminoxylated polysilane moiety is efficiently obtained. The reaction proceeds almost quantitatively, and the side chain It has been found that aminoxy groups can be introduced at an arbitrary ratio with respect to. Furthermore, when alcohols and silanols coexist in this system, aminoxyl groups are sequentially replaced to cause alkoxylation and siloxylation.This reaction proceeds gently at room temperature even in the presence of a catalytic amount of hydroxylamine, -Very few silicon bond breaks, and therefore, by utilizing such a reaction, efficiently introduce a functional group into a silicon-based polymer compound containing a polysilane moiety having a side chain hydroxyl group obtained by a dehydrocondensation reaction. The inventors have found that the present invention can be performed, and have accomplished the present invention.
【０００６】即ち、本発明は、 （１）下記一般式（１）で示されるアミノキシル基を有
するポリシランからなる重量平均分子量５００〜１，０
００，０００のケイ素系高分子化合物、 （２）下記一般式（２）で示されるＳｉＨ基を有するポ
リシランからなるケイ素系高分子化合物を下記一般式
（３）で示されるヒドロキシルアミン化合物と反応させ
ることを特徴とする（１）記載のケイ素系高分子化合物
の製造方法、 （３）下記一般式（１）で示されるアミノキシル基を有
するポリシランからなる重量平均分子量５００〜１，０
００，０００のケイ素系高分子化合物を下記一般式
（４）で示される末端水酸基化合物と反応させることを
特徴とする下記一般式（５）で示されるポリシランから
なるケイ素系高分子化合物の製造方法を提供する。That is, the present invention relates to (1) a polysilane having an aminoxyl group represented by the following general formula (1) having a weight average molecular weight of 500 to 1,0.
(2) reacting a silicon-based polymer compound comprising a polysilane having a SiH group represented by the following general formula (2) with a hydroxylamine compound represented by the following general formula (3) (1) The method for producing a silicon-based polymer compound according to (1), (3) a weight average molecular weight of 500 to 1,0 comprising a polysilane having an aminoxyl group represented by the following general formula (1):
A method for producing a silicon-based polymer compound comprising a polysilane represented by the following general formula (5), characterized by reacting a 00000 silicon-based polymer compound with a terminal hydroxyl group compound represented by the following general formula (4). I will provide a.
【０００７】[0007]
【化７】 （式中、Ｒ1，Ｒ2，Ｒ3はそれぞれ独立に水素原子又は
炭素数１〜１２のアルキル基又はフェニル基もしくはナ
フチル基を示し、Ｒ4は炭素数１〜１２のアルキル基を
示す。また、Ｒ5はアルコール残基、シラノール残基又
はシロキサン残基を示す。ｋ，ｍは０＜ｋ≦１、０≦ｍ
＜１、ｋ＋ｍ＝１、ｐはケイ素系高分子化合物を上記重
量平均分子量とする数である。）Embedded image (In the formula, R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group or a naphthyl group, and R 4 represents an alkyl group having 1 to 12 carbon atoms. R 5 represents an alcohol residue, a silanol residue or a siloxane residue, and k and m are 0 <k ≦ 1, 0 ≦ m.
<1, k + m = 1, p is a number with the silicon-based polymer compound as the weight average molecular weight. )
【０００８】以下、本発明につき更に詳しく説明する
と、本発明のケイ素系高分子化合物は、下記一般式
（１）又は（５）のポリシランからなるものである。Hereinafter, the present invention will be described in more detail. The silicon-based polymer compound of the present invention comprises a polysilane represented by the following general formula (1) or (5).
【０００９】[0009]
【化８】 （式中、Ｒ1，Ｒ2，Ｒ3はそれぞれ独立に水素原子又は
炭素数１〜１２のアルキル基もしくはアリール基を示
し、Ｒ4は炭素数１〜１２のアルキル基を示す。また、
Ｒ5はアルコール残基、シラノール残基又はシロキサン
残基を示す。ｋ，ｍは０＜ｋ≦１、０≦ｍ＜１、ｋ＋ｍ
＝１、ｐはケイ素系高分子化合物を上記重量平均分子量
とする数である。）Embedded image (In the formula, R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an alkyl group or an aryl group having 1 to 12 carbon atoms, and R 4 represents an alkyl group having 1 to 12 carbon atoms.
R 5 represents an alcohol residue, a silanol residue or a siloxane residue. k and m are 0 <k ≦ 1, 0 ≦ m <1, k + m
= 1, p is a number with the silicon-based polymer compound as the weight average molecular weight. )
【００１０】[0010]
【００１１】[0011]
【００１２】[0012]
【００１３】ここで、Ｒ1，Ｒ2，Ｒ3はそれぞれ独立に
水素原子又は炭素数１〜１２のアルキル基又はフェニル
基もしくはナフチル基であり、アルキル基の例としては
メチル、ブチル、ヘキシル、オクチル、シクロヘキシル
などの基が挙げられる。Here, R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms or a phenyl or naphthyl group. Examples of the alkyl group are methyl, butyl, hexyl, Groups such as octyl and cyclohexyl.
【００１４】この場合、Ｒ2は水素原子、Ｒ1，Ｒ3はア
ルキル基又はフェニル基もしくはナフチル基であること
が好ましい。In this case, R 2 is preferably a hydrogen atom, and R 1 and R 3 are preferably an alkyl group, a phenyl group or a naphthyl group.
【００１５】また、Ｒ4は炭素数１〜１２のアルキル基
である。R 4 is an alkyl group having 1 to 12 carbon atoms.
【００１６】Ｒ5はアルコール残基、シラノール残基又
はシロキサン残基であり、具体的にはＲ5としては炭素
数１〜２０のアルキル基又はアリール基、ＳｉＲ6 3（Ｒ
6 は互いに同一又は異種の置換又は非置換の炭素数１〜
６、特に１〜３の一価炭化水素基、例えばアルキル基、
アルケニル基、アリール基やそれらのハロゲン置換体が
挙げられるが、アルキル基が好ましい。）などが挙げら
れる。RFiveIs an alcohol residue, silanol residue or
Is a siloxane residue, specifically RFiveAs carbon
An alkyl group or an aryl group of the formulas 1 to 20, SiR6 Three(R
6 Are the same or different, substituted or unsubstituted carbon atoms having 1 to
6, especially 1-3 monovalent hydrocarbon groups such as alkyl groups,
Alkenyl groups, aryl groups and their halogen-substituted
Although an alkyl group is preferable. )
It is.
【００１７】更に、上記式において、ｍ，ｋは０＜ｋ≦
１、０≦ｍ＜１、好ましくは０．１≦ｋ≦０．５であ
り、ｍ＋ｋ＝１である。ｐはポリシランを所定の分子量
とする数である。Further, in the above equation, m and k are 0 <k ≦
1, 0 ≦ m <1, preferably 0.1 ≦ k ≦ 0.5, and m + k = 1. p is a number that makes polysilane a predetermined molecular weight.
【００１８】本発明のケイ素系高分子化合物の重量平均
分子量は、５００〜１，０００，０００、好ましくは
１，０００〜１００，０００、より好ましくは１，００
０〜１０，０００である。The weight average molecular weight of the silicon-based polymer compound of the present invention is from 500 to 1,000,000, preferably from 1,000 to 100,000, more preferably from 1,000.
0 to 10,000.
【００１９】上記式（１）のポリシランからなるケイ素
系高分子化合物は、下記一般式（２）で示されるＳｉＨ
基を有するポリシランからなるケイ素系高分子化合物を
下記一般式（３）で示されるヒドロキシルアミン化合物
と反応させることにより得ることができる。The silicon-based polymer compound comprising the polysilane of the above formula (1) is a SiH compound represented by the following general formula (2):
It can be obtained by reacting a silicon-based polymer compound comprising a polysilane having a group with a hydroxylamine compound represented by the following general formula (3).
【００２０】[0020]
【化１０】 ＨＯＮＲ4 2 （３） （式中、Ｒ1，Ｒ2，Ｒ3，Ｒ4，ｋ，ｍ，ｐは上記と同様
の意味を示す。）Embedded image HONR 4 2 (3) (wherein, R 1 , R 2 , R 3 , R 4 , k, m, and p have the same meaning as described above.)
【００２１】[0021]
【００２２】[0022]
【００２３】この場合、この反応において、式（３）の
ヒドロキシルアミン化合物は、式（２）のポリシラン部
位に対し２〜５０％の割合で使用することが好ましい。
反応はトルエン、キシレン、ＴＨＦ等の活性水素を持た
ない溶媒を用いて行うことができ、反応温度はこれらの
溶媒の沸点以下で行うことができるが、通常は室温付近
で十分に進行する。反応時間は特に制限されないが、通
常１〜２４時間である。In this case, in this reaction, the hydroxylamine compound of the formula (3) is preferably used in a proportion of 2 to 50% based on the polysilane moiety of the formula (2).
The reaction can be carried out using a solvent having no active hydrogen such as toluene, xylene or THF, and the reaction can be carried out at a temperature not higher than the boiling point of these solvents, but usually proceeds sufficiently at around room temperature. The reaction time is not particularly limited, but is usually 1 to 24 hours.
【００２４】次に、上記式（５）のポリシランからなる
ケイ素系高分子化合物を得る方法としては、上記のよう
にして得られた式（１）のポリシランからなるケイ素系
高分子化合物を単離し、或いは反応終了後の反応液に対
して下記一般式（４）で示される末端水酸基化合物を反
応させるようにするか、又は上記式（２）のポリシラン
からなるケイ素系高分子化合物に上記式（３）のヒドロ
キシルアミン化合物と式（４）の末端水酸基化合物とを
添加して反応させることが好ましい。Next, as a method for obtaining the silicon-based polymer compound comprising the polysilane of the above formula (5), the silicon-based polymer compound comprising the polysilane of the formula (1) obtained as described above is isolated. Alternatively, the terminal hydroxyl group compound represented by the following general formula (4) is reacted with the reaction solution after the reaction is completed, or the silicon-based polymer compound comprising polysilane of the above formula (2) is reacted with the above formula ( Preferably, the hydroxylamine compound of 3) and the terminal hydroxyl compound of formula (4) are added and reacted.
【００２５】 ＨＯＲ5 （４） （式中、Ｒ5は上記と同様の意味を示す。）HORFive (4) (where RFiveHas the same meaning as described above. )
【００２６】反応は上述した溶媒と同様の溶媒中で行う
ことができ、反応温度も上記と同様でよい。また、式
（４）の末端水酸基化合物の使用量は式（１）のヒドロ
キシルアミン部位に対して１以下の場合は、反応後もヒ
ドロキシルアミン部位が残り、架橋反応等に利用するこ
とができるが、通常は２倍程度以上用いると安定性の高
いポリマーを得ることができる。なお、ヒドロキシルア
ミン化合物を触媒的に使用する場合もヒドロキシルアミ
ン化合物の使用量は上記と同様でよく、式（４）の末端
水酸基化合物の使用量は安定性の高いポリマーを得るに
は式（３）のヒドロキシルアミン化合物に対して１以
上、通常は大過剰に使用することが望ましい。The reaction can be carried out in the same solvent as described above, and the reaction temperature may be the same as described above. When the amount of the terminal hydroxyl group compound of the formula (4) is 1 or less with respect to the hydroxylamine site of the formula (1), the hydroxylamine site remains after the reaction and can be used for a cross-linking reaction or the like. When it is used about twice or more, a polymer having high stability can be obtained. When the hydroxylamine compound is used as a catalyst, the amount of the hydroxylamine compound used may be the same as described above, and the amount of the terminal hydroxyl compound of the formula (4) may be determined by the formula (3) in order to obtain a highly stable polymer. It is desirable to use one or more, usually a large excess, of the hydroxylamine compound of the above).
【００２７】なお、ヒドロキシルアミン化合物の使用量
は上記同様であり、式（４）の末端水酸基化合物の使用
量は式（２）のヒドロキシルアミン部位に対して１以
上、通常は２倍程度用いることが望ましい。The amount of the hydroxylamine compound used is the same as described above, and the amount of the terminal hydroxyl group compound of the formula (4) should be at least one, usually about twice as much as the hydroxylamine site of the formula (2). Is desirable.
【００２８】[0028]
【発明の効果】本発明によれば、ポリシラン部位を含有
するケイ素系高分子化合物に温和な条件で選択性よく簡
便かつ確実に種々の官能基を導入でき、得られたケイ素
系高分子化合物は、他の樹脂への相溶性が改善され、ま
たＴｇも低下するなど、ポリシランの持つ化学的特性を
損うことなく物理的な性質が変換されたもので、光電変
換材料、導電性材料、紫外線吸収材料、セラミック前駆
体等として有用である。According to the present invention, various functional groups can be easily and reliably introduced into a silicon-based polymer compound containing a polysilane moiety under mild conditions with good selectivity. The physical properties of polysilane have been converted without impairing the chemical properties of polysilane, such as improved compatibility with other resins and lowering of Tg. It is useful as an absorbing material, a ceramic precursor and the like.
【００２９】[0029]
【実施例】以下、実施例を示し、本発明を具体的に説明
するが、本発明は下記の実施例に制限されるものではな
い。The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.
【００３０】[0030]
【化１２】 Embedded image
【００３１】式（ｉ）の単位からなるポリ（フェニルシ
ラン）（Ｍｗ＝７３０，Ｍｎ＝７１４）１２４２ｍｇの
トルエン溶液にジエチルヒドロキシルアミン３９８ｍｇ
を加えて２４時間反応させた。反応後、直ちに水素が発
生し、淡黄色の反応液が得られた。反応終了後、濃縮
し、残留物のＮＭＲを調べた結果、３０％のＳｉＨ基の
消失が確認され、またＧＰＣにより若干の分子量の増加
（Ｍｗ＝１１９９，Ｍｎ＝７８４）も見られた。得られ
たポリマーのＵＶ吸収スペクトルは元のポリ（フェニル
シラン）とほとんど差がなく、この反応においてＳｉ−
Ｓｉ結合の開裂はほとんど起こっていないことが認めら
れ、得られたポリマーは式（ｉｉ）で示す単位を有する
ポリシランであることが認められた。398 mg of diethylhydroxylamine was added to a toluene solution of 1242 mg of poly (phenylsilane) (Mw = 730, Mn = 714) comprising the unit of the formula (i).
Was added and reacted for 24 hours. Immediately after the reaction, hydrogen was generated, and a pale yellow reaction solution was obtained. After completion of the reaction, the reaction mixture was concentrated, and the residue was analyzed by NMR. As a result, it was confirmed that 30% of SiH groups had disappeared, and a slight increase in molecular weight (Mw = 1199, Mn = 784) was also observed by GPC. The UV absorption spectrum of the obtained polymer was almost the same as that of the original poly (phenylsilane).
It was found that almost no Si bond cleavage occurred, and that the obtained polymer was a polysilane having a unit represented by the formula (ii).
【００３２】[0032]
【化１３】 Embedded image
【００３３】上記式（ｉ）の単位からなるポリ（フェニ
ルシラン）１１８２ｍｇとｔｅｒｔ−ブタノール２０９
２ｍｇを３０ｍｌのトルエンに溶解し、ジエチルヒドロ
キシルアミン１０７ｍｇを加えて７２時間室温にて反応
させた。この間に水素の発生が観測され、淡黄色の反応
液が得られた。濃縮後の残留物のＮＭＲにより２９．６
％のｔｅｒｔ−ブトキシ基が導入されていることが確認
され、またＧＰＣにより生成物の分子量の増加（Ｍｗ＝
９４０，Ｍｎ＝９１６）も確認され、得られたポリマー
が式（ｉｉｉ）の単位を有するポリシランであることが
認められた。1182 mg of poly (phenylsilane) comprising units of the above formula (i) and tert-butanol 209
2 mg was dissolved in 30 ml of toluene, and 107 mg of diethylhydroxylamine was added, followed by a reaction at room temperature for 72 hours. During this time, generation of hydrogen was observed, and a pale yellow reaction solution was obtained. NMR of the residue after concentration was 29.6.
% Of the tert-butoxy group was confirmed to have been introduced, and an increase in the molecular weight of the product (Mw =
940, Mn = 916), and it was confirmed that the obtained polymer was a polysilane having a unit of the formula (iii).
【００３４】[0034]
【化１４】 Embedded image
【００３５】ｔｅｒｔ−ブタノールの代わりにトリメチ
ルシラノールを使用した以外は実施例２と同様に操作
し、淡黄色のポリマーを得た。このポリマーのＮＭＲの
結果、３６％のＳｉＨ基の水素原子がトリメチルシロキ
シ基に置換していることが確認された。このポリマーに
おいてもＵＶ吸収スペクトルは元のポリ（フェニルシラ
ン）とほとんど差が見られなかった。また、ＧＰＣでは
若干分子量の増加（Ｍｗ＝８１０，Ｍｎ＝６９７）が見
られ、得られたポリマーが式（ｉｖ）の単位を有するポ
リシランであることが認められた。The procedure of Example 2 was repeated, except that trimethylsilanol was used instead of tert-butanol, to obtain a pale yellow polymer. NMR of this polymer confirmed that 36% of the hydrogen atoms of the SiH groups were replaced with trimethylsiloxy groups. Also in this polymer, the UV absorption spectrum showed almost no difference from the original poly (phenylsilane). GPC showed a slight increase in molecular weight (Mw = 810, Mn = 697), and it was confirmed that the obtained polymer was a polysilane having a unit of the formula (iv).
【００３６】〔実施例４〕ポリ（フェニルシラン）（Ｍ
ｗ＝１６９３，Ｍｎ＝１１０３）１ｇのトルエン溶液に
トリメチルシラノール２ｇとジエチルヒドロキシルアミ
ン０．５ｇを加えて４時間加熱還硫の後、減圧下に揮発
成分を留去し、淡褐色の粘稠なポリマーを得た。ＮＭＲ
により４６％の水素基側鎖がトリメチルシロキシ基に置
換されていることが確認された。このポリマーはポリ
（フェニルシラン）と類似のＵＶスペクトルを示し、ポ
リシラン主鎖の切断がほとんど起こっていないことが確
認された。またＧＰＣにより分子量の若干の増加（Ｍｗ
＝１８９８，Ｍｎ＝１４２０）が観測された。Example 4 Poly (phenylsilane) (M
(w = 1693, Mn = 1103) To 1 g of a toluene solution, 2 g of trimethylsilanol and 0.5 g of diethylhydroxylamine were added, and the mixture was refluxed by heating for 4 hours. A polymer was obtained. NMR
As a result, it was confirmed that 46% of the hydrogen group side chains were substituted with trimethylsiloxy groups. This polymer showed a UV spectrum similar to that of poly (phenylsilane), confirming that the polysilane main chain was hardly cleaved. In addition, a slight increase in molecular weight (Mw
= 1898, Mn = 1420) were observed.
【００３７】[0037]
【化１５】 Embedded image
【００３８】式（ｉ’）のポリ（フェニルシラン）（Ｍ
ｗ＝１６１２，Ｍｎ＝１０８３）を出発原料とし、実施
例３に準じてトリメチルシラノールとの反応を行い、淡
黄色の式（ｉｖ’）のポリマーを得た。ＮＭＲより４５
％のＳｉＨ基の水素原子がトリメチルシロキシ基に置換
されていることか確認され、このポリマーにおいてもＵ
Ｖ吸収スペクトルは元のポリ（フェニルシラン）とほと
んど差が見られず、ＧＰＣの結果はＭｗ＝１５４０，Ｍ
ｎ＝９９８であった。The poly (phenylsilane) of the formula (i ') (M
(w = 1612, Mn = 1083) as a starting material, and reacted with trimethylsilanol according to Example 3 to obtain a pale yellow polymer of the formula (iv ′). 45 from NMR
% Of the hydrogen atoms of the SiH groups were replaced with trimethylsiloxy groups, and the U
The V absorption spectrum shows little difference from the original poly (phenylsilane), and the result of GPC is Mw = 1540, M
n = 998.
Claims (3)
ル基を有するポリシランからなる重量平均分子量５００
〜１，０００，０００のケイ素系高分子化合物。 【化１】 （式中、Ｒ1，Ｒ2，Ｒ3はそれぞれ独立に水素原子又は
炭素数１〜１２のアルキル基又はフェニル基もしくはナ
フチル基を示し、Ｒ4は炭素数１〜１２のアルキル基を
示す。ｋ，ｍは０＜ｋ≦１、０≦ｍ＜１、ｋ＋ｍ＝１、
ｐはケイ素系高分子化合物を上記重量平均分子量とする
数である。）1. A weight average molecular weight of 500 comprising an aminoxyl group-containing polysilane represented by the following general formula (1):
~ 1,000,000 silicon-based polymer compounds. Embedded image (In the formula, R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group or a naphthyl group, and R 4 represents an alkyl group having 1 to 12 carbon atoms. k and m are 0 <k ≦ 1, 0 ≦ m <1, k + m = 1,
p is a number with the above-mentioned weight average molecular weight of the silicon-based polymer compound. )
有するポリシランからなるケイ素系高分子化合物を下記
一般式（３）で示されるヒドロキシルアミン化合物と反
応させることを特徴とする請求項１記載のケイ素系高分
子化合物の製造方法。 【化２】 （式中、Ｒ1，Ｒ2，Ｒ3はそれぞれ独立に水素原子又は
炭素数１〜１２のアルキル基又はフェニル基もしくはナ
フチル基を示す。ｋ，ｍは０＜ｋ≦１、０≦ｍ＜１、ｋ
＋ｍ＝１、ｐはケイ素系高分子化合物を重量平均分子量
５００〜１，０００，０００とする数である。） ＨＯＮＲ4 2 （３） （式中、Ｒ4は炭素数１〜１２のアルキル基を示す。）2. The method according to claim 1, wherein a silicon-based polymer compound comprising a polysilane having a SiH group represented by the following general formula (2) is reacted with a hydroxylamine compound represented by the following general formula (3). The method for producing the silicon-based polymer compound according to the above. Embedded image (Wherein, R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a naphthyl group. K and m are 0 <k ≦ 1, 0 ≦ m < 1, k
+ M = 1, p is a number that makes the silicon-based polymer compound a weight average molecular weight of 500 to 1,000,000. ) HONR 4 2 (3) (wherein, R 4 represents an alkyl group having 1 to 12 carbon atoms.)
ル基を有するポリシランからなる重量平均分子量５００
〜１，０００，０００のケイ素系高分子化合物を下記一
般式（４）で示される末端水酸基化合物と反応させるこ
とを特徴とする下記一般式（５）で示されるポリシラン
からなるケイ素系高分子化合物の製造方法。 【化３】 （式中、Ｒ1，Ｒ2，Ｒ3はそれぞれ独立に水素原子又は
炭素数１〜１２のアルキル基又はフェニル基もしくはナ
フチル基を示し、Ｒ4は炭素数１〜１２のアルキル基を
示す。ｋ，ｍは０＜ｋ≦１、０≦ｍ＜１、ｋ＋ｍ＝１、
ｐはケイ素系高分子化合物の重量平均分子量を５００〜
１，０００，０００とする数である。） ＨＯＲ5 （４） （式中、Ｒ5はアルコール残基、シラノール残基又はシ
ロキサン残基を示す。） 【化４】 （式中、Ｒ1，Ｒ2，Ｒ3，Ｒ5，ｋ，ｍ，ｐは上記と同様
の意味を示す。）3. A weight average molecular weight of 500 comprising an aminoxyl group-containing polysilane represented by the following general formula (1):
A silicon-based polymer compound comprising a polysilane represented by the following general formula (5), wherein a silicon-based polymer compound having a molecular weight of from 1 to 1,000,000 is reacted with a terminal hydroxyl compound represented by the following general formula (4). Manufacturing method. Embedded image (In the formula, R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group or a naphthyl group, and R 4 represents an alkyl group having 1 to 12 carbon atoms. k and m are 0 <k ≦ 1, 0 ≦ m <1, k + m = 1,
p is a weight average molecular weight of the silicon-based polymer compound of 500 to
The number is 1,000,000. HOR 5 (4) (wherein, R 5 represents an alcohol residue, a silanol residue or a siloxane residue.) (In the formula, R 1 , R 2 , R 3 , R 5 , k, m, and p have the same meaning as described above.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08328796A JP3287216B2 (en) | 1996-03-12 | 1996-03-12 | Silicon polymer compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08328796A JP3287216B2 (en) | 1996-03-12 | 1996-03-12 | Silicon polymer compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09241384A JPH09241384A (en) | 1997-09-16 |
| JP3287216B2 true JP3287216B2 (en) | 2002-06-04 |
Family
ID=13798180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08328796A Expired - Fee Related JP3287216B2 (en) | 1996-03-12 | 1996-03-12 | Silicon polymer compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3287216B2 (en) |
-
1996
- 1996-03-12 JP JP08328796A patent/JP3287216B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09241384A (en) | 1997-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5220033A (en) | Siloxane compounds and their preparation | |
| US5856392A (en) | Higher order star polymers having multiple polyisobutylene arms radiating from a condensed core of siloxanes and a method for the synthesis thereof | |
| KR20070013329A (en) | Method of making branched polysilanes | |
| JP2843620B2 (en) | One-terminal branched aminoalkyl group-blocked organopolysiloxane and method for producing the same | |
| EP0972788B1 (en) | Hyperbranched polymers containing silicon atoms | |
| US5395955A (en) | Method for the preparation of carbinol group-containing organopolysiloxane | |
| WO2010062695A2 (en) | Properties tailoring in silsesquioxanes | |
| KR100864269B1 (en) | Process for the preparation of organosilicon compounds having urethane groups | |
| EP0812870A1 (en) | Method of making alkoxylated organosilicone resins | |
| US6284908B1 (en) | Method for making polysilsesquioxanes and organohydridosilanes | |
| US5350824A (en) | Fluorosilicone polymers and methods for the preparation thereof | |
| JP3848260B2 (en) | Method for producing hydroxyalkylpolysiloxane | |
| JP2003517072A (en) | Process for producing polyorganosiloxanes by polymerization catalyzed by a catalyst system based on triflic acid or a triflic acid derivative | |
| JP3287216B2 (en) | Silicon polymer compound and method for producing the same | |
| Allcock et al. | Hybrid phosphazene-organosilicon polymers: II. High-polymer and materials synthesis and properties | |
| US5567790A (en) | Method for the preparation of diphenylsiloxane-dimethylsiloxane copolymers | |
| US20020002264A1 (en) | Multi-reactive polysiloxane compound having halogen substituents and synthetic method thereof | |
| JP3661810B2 (en) | Method for producing hydroxyl group-containing siloxane compound | |
| USH1612H (en) | Method for making silarylene-siloxane polymers | |
| JP2917619B2 (en) | Polysilane copolymer and method for producing the same | |
| JPH111560A (en) | Organocyclosiloxane and its production | |
| JP2008266301A (en) | New silicone compound, and raw material thereof and method for producing the silicone compound | |
| JP2884074B2 (en) | New silsesquioxane-containing polymer, its production method and heat-resistant material | |
| JPH064699B2 (en) | 1,2,2-Trimethyl-1-phenylpolydisilane and method for producing the same | |
| JP2800699B2 (en) | Novel branched polysilane and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080315 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110315 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110315 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120315 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120315 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130315 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140315 Year of fee payment: 12 |
|
| LAPS | Cancellation because of no payment of annual fees |