Preparation of Soluble Polyphenylsilsesquioxanes
Preparation of Soluble Polyphenylsilsesquioxanes
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可溶性聚苯基倍半硅氧烷的制备
DOI：
10.1246/nikkashi.1974.108
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发表时间：
1974
期刊：
影响因子：
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通讯作者：
Masayoshi Ueda
中科院分区：
文献类型：
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作者：
T. Takiguchi;Eri Fujikawa;Yasushi Yamamoto;Masayoshi Ueda
可溶性聚苯基硅倍半氧烷几乎定量地由苯基硅烷三三酸三钾水溶液与(1)乙酸酐和(2)氯仿的反应以及(3)苯基三氯硅烷与胺水溶液的水解按照以下方案几乎定量地获得：(1)PhSi(OK)3+312(MeCO)20。 1/n (PhSiOi.s)n + 3 MeCOOK(2) PhSi(OK)3+3/4 CHC13-1/n(PhSiOi.s)n+9/4 KC1+3/4 HCOOK(3) PhSiC13 +3/2 H20+3/2 二胺.1/n(PhSiOi.s).+2/3 二胺-2 HCIA 所有反应均按如下方式进行以 MIBK 层为介质在回流温度下的二元液体层界面。通过用 O.1% KOH 加热溶液，初始预聚物的特性粘度从 0.06 逐渐增加到 O.13。 涉及苯基三氯硅烷与等摩尔量的每种二苯基二氯硅烷和甲基苯基二氯硅烷共水解的类似反应，发现得到结构重复单元中具有环四硅氧烷链段的对应可溶性聚硅氧烷。苯基三氯硅烷-乙烯基三氯硅烷(1:1)也得到不溶且不熔的聚合物。
Soluble polyphenylsilsesquioxane was obtained almost quantitatively from the reactions of tripotassiumphenylsilanetriolate aqueous solution with (1)acetic anhydride and (2) chloroform, and from (3) hydrolysis of phenyltrichloresilane with aqueous amine solution according to the following schemes:(1) PhSi(OK)3 + 312 (MeCO)20. 1/n (PhSiOi.s)n + 3 MeCOOK(2) PhSi(OK)3+3/4 CHC13-1/n(PhSiOi.s)n+9/4 KC1+3/4 HCOOK(3) PhSiC13 +3/2 H20+3/2 diamine.1/n(PhSiOi.s).+2/3 diamine-2 HCIAll the reactions were so undertaken as to proce6d through interfaces of binary liquid layers at refluxing temperature by use of MIBK layer as a medium. Intrinsic viscosity of the initial prepolymer ranging from 0.06 to O.13 increased gradually by heating the solution with O.1% KOH.Analogous reactions which involve co-hydrolysis of phenyltrichlorosilane and equimolar amount of each diphenyldichlorosilane and of methylphenyldichlorosilane were found to give cotresponding soluble polysiloxanes with cyclotetrasiloxane segment in the structural repeating unit.Co-hydrolysis of a mixture of phenyltrichlorosilane-vinyltrichlorosilane (1:1) also gave asoluble and infusible polymer.