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Polymerization of Fluorothiocarbonyl Compounds

 

作者: W.H. Sharkey,  

 

期刊: Journal of Macromolecular Science: Part A - Chemistry  (Taylor Available online 1967)
卷期: Volume 1, issue 2  

页码: 291-299

 

ISSN:0022-233X

 

年代: 1967

 

DOI:10.1080/10601326708053972

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Recently it was shown that the C˭S group in fluorothiocarbonyl compounds readily undergoes addition polymerization. This review describes polymers obtainable from such compounds as CF2˭S, CF3CF˭S, ClCF2CF˭S, HCFClCF˭S, and hexafluorothioacetone. The polymerization of CF2˭S is readily brought about in anionic systems at low temperatures, giving a high-molecular-weight poly(thiocarbonyl fluoride) with a number-average molecular weight in the range of 300,000 to 400,000. It is believed that the major portion of this polymer is composed of chains of CF3–-S—(—CF2S—)n–CF˭S. Poly(thiocarbonyl fluoride) is a highly resilient elastomer in the amorphous form but suffers the disadvantage of slow crystallization at temperatures below 35°C and concomitant loss of rubbery properties. Above 175°C it depolymerizes. Fluorothioacyl fluorides also undergo anionic polymerization, but the products are logy elastomers. Copolymers of fluorothioacyl fluorides with CF2˭S have better thermal stability but poorer resilience than poly(thiocarbonyl fluoride). Hexafluorothioacetone has been polymerized at—110°C to give a white elastomer that slowly depolymerizes at room temperature to regenerate monomer. Thiocarbonyl fluoride is also susceptible to free-radical polymerization, and in free-radical systems it copolymerizes with conventional vinyl monomers, giving a wide variety of new elastomeric products.

 

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