Mechanism and polymer structure of B(C6F5)3 catalyzed polycondensation of Si—H/Si—OR

CHEN Xunjun; CUI Yingde; YIN Guoqiang; JIA Zhenyu; LIU Zhengtang

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Mechanism and polymer structure of B(C₆F₅)₃ catalyzed polycondensation of Si—H/Si—OR

更新时间：2025-12-10

- Mechanism and polymer structure of B(C₆F₅)₃ catalyzed polycondensation of Si—H/Si—OR
- CIESC Journal Issue 5, Pages: 1143-1149(2008)
- 作者机构：
  
  1. 仲恺农业技术学院绿色化工研究所
  2. 西北工业大学材料学院
- 作者简介：
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- Online First：05 May 2008，
  
  Published：05 May 2008
- 稿件说明：
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CHEN Xunjun, CUI Yingde, YIN Guoqiang, et al. Mechanism and polymer structure of B(C₆F₅)₃ catalyzed polycondensation of Si—H/Si—OR[J]. CIESC Journal, 2008, (5): 1143-1149.
DOI：

CHEN Xunjun, CUI Yingde, YIN Guoqiang, et al. Mechanism and polymer structure of B(C₆F₅)₃ catalyzed polycondensation of Si—H/Si—OR[J]. CIESC Journal, 2008, (5): 1143-1149. DOI：

摘要

根据DFT理论，用量子化学的方法对B(C6F5)3催化Si—H/Si—OR缩聚反应的机理进行了研究，用29Si NMR对1

4-双（二甲基硅基）苯（BDSB）与二甲基二甲氧基硅烷、甲基乙烯基二甲氧基硅烷、二苯基二甲氧基硅烷缩聚产物的微观结构进行了表征，结合反应机理，对单体的结构与缩聚产物的微观结构的关系进行了讨论。B(C6F5)3先与Si—H形成弱加合物，然后Si—OR进攻Si—H/B(C6F5)3加合物使Si—H断裂，形成氧钅翁离子中间体，最后H-向正电中心迁移形成产物。H-迁移方向的不同将导致3种反应：缩合、交换、逆反应。烷氧基硅烷中的乙烯基、苯基可以增加烷氧基C的正电性，并使C—O键伸长，减少Si—H/Si—OR交换反应的发生，使得缩聚产物具有更为交替的结构。

Abstract

The mechanism of B(C6F5)3 catalyzed Si—H/Si—OR polycondensation reaction was studied through the quantum chemistry methods.Poly(silphenylene-siloxane)s were prepared by polycondensation of 1

4-bis(dimethylsilyl)benzene (BDSB) and dimethyldimethoxylsilane

vinylmethyldimethoxylsilane and diphenyldimethoxylsilane respectively.The microstructure of the polymer was characterized by 29Si NMR and the influence of vinyl and phenyl groups of alkoxylsilane on the microstructure of the polymer was also discussed.B(C6F5)3 first activated Si—H to form weak adduct

then Si—OR attacked Si—H/B(C6F5)3 adduct to break Si—H and form oxonium ion complex.The decomposition of the complex occurred by the H- transfer to one of the three electrophilic centers

which explained the competition between condensation and Si—H/Si—OR exchange.Vinyl or phenyl group of alkoxysilane decreased the positive charge of Si atom and increased the positive charge of C which bonded to O

and it also reduced the strength of C—O

resulting in more alternated polymers.

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