电化学合成聚硅烷的反应速率

Reaction Rate of Polysilanes by Electrochemical Synthesis

采用电化学法，合成出含双键聚硅烷与不含双键聚硅烷，通过FT—IR，UV，^1HNMR表征其结构。分别研究了电化学反应体系和直接化学反应体系中Si—Cl键含量的变化，以及加入引发剂蒽对反应速率的影响。结果表明：含双键聚硅烷的合成反应速率快于不含双键的聚硅烷，相同反应电量下含双键聚硅烷反应体系中的Si—Cl键含量比不含双键聚硅烷少10％～15％；在电化学合成聚硅烷的过程中。单体与镁发生的格氏反应在整个反应中占有相当的比例；引发剂葸的加入能够有效地提高不含双键聚硅烷的反应速率。本文还对电化学合成聚硅烷的反应机理进行了推测。

Polysilanes with and without double bonds were synthesized by electrochemical method. The products were characterized by FT-IR, UV, 1 H NMR. The changes of remaining Si-CI bonds were detected in the process of electrochemical synthesis. The effect of additive anthrathene on the reaction rate was investigated. The results show that the reaction rate of polysilane with double bonds was quicker than that without double bonds. The percent of remaining Si-CI bonds for the system of polysilane with double bonds was 10 % - 15% less than that of polysilane without double bonds at the same amount of electricity value. The Grignard reaction of monomer with magnesium took up quite a part in the whole chemical reaction. The additive anthracene could increase the reaction rate of polysilane without double bonds. Mechanism of the polymerization was also discussed.