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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 43, Number 1
JKCSEZ 43(1)
February 20, 1999 

 
Title
Syntheses of Disubstituted Polysilanes(II):Sonochemical Study

폴리실란의 합성(II) : 초음파 화학적 연구
Author
Gyu-Hwan Lee, Tae-Ha Jeon

이규환, 전태하
Keywords
Abstract
크기가 큰 치환기의 폴리실란-[2-(R1R2-phenyl)propyl]Si[R3]-[예:R1=R2=H, R3=n-hexyl; 폴리(2-페닐프로필)(n-헥실)실란]을 초음파 화학적 방법을 사용하여 Wurtz 축합반응에 의해 합성하였다. 초음파는 톨루엔 용매 중 금속 나트륨을 분산시켜 작은 크기와 높은 표면 활성의 나트륨을 형성하였으며 이에 의해 Wurtz 축합반응이 진행되었고 또한 초음파는 부 생성물인 염화나트륨이 나트륨 표면에 침착되는 것을 방지하여 표면활성이 지속적으로 유지되도록 하여 효율적인 반응이 기대되었다. 폴리실란 생성물은 저분자량의 중합체(분자량~10^3)와 고분자량의 중합체(분자량~10^6)의 혼합물로 얻어 졌다. 전체 수득률은 75-99% 이었으나 R3가 n-hexyl기인 경우에는 혼합비율은 고분자량 중합체가 주 생성물로, cyclohexyl 또는 2-phenylethyl기인 경우에는 저분자량 중합체가 주 생성물로 얻어져 폴리실란의 치환기 종류에 영향을 받는 것으로 나타났으나 R1,R2의 변화는 영향을 나타내지 않았다.

Polysilanes with stericafly bulky substituents, -[2-(R1R2-phenyl)propyl]Si[R3]-, such as poly(2-phenylpropyl)(n-hexyl)silane [R1=R2=H, R3=n-hexyl] were prepared by Wurtz-type coupling reactions with Na using a sonochemical method. The high-intensity ultrasound provided the formation of high quality Na dispersion in toluene and its active surface which was important for the synthesis of polysilanes in Wurtz-type coupling reaction was freshly and continuously regenerated during the process. The polysilanes products were mixtures of high molecular weight polymers with Mw of ∼10^6 and low molecular weight polymers with Mw of ∼10^3. It was found that the formation of high molecular weight polymer was greatly influenced by the substituents R3, directly attached to Si. On the contrary, changes on substituents (R1, R2) gave no fiffluences at all. Overall yields for polysilanes were 75-99% in general but high molecular weight polysflanes were obtained as a major product when substituent R3 is nhexyl group and low molecular weight polysilanes were obtained as a major product when substituent R3 is cyclohexyl and 2-phenylethyl groups. Effects of reaction conditions to polysilane yields were investigated.

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