POLYMERIZATION OF SILICON-CONTAINING DIPHENYLACETYLENES AND HIGH GAS-PERMEABILITY OF THE PRODUCT POLYMERS
POLYMERIZATION OF SILICON-CONTAINING DIPHENYLACETYLENES AND HIGH GAS-PERMEABILITY OF THE PRODUCT POLYMERS
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DOI：
10.1021/ma00047a038
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发表时间：
1992-10-12
期刊：
影响因子：
5.5
通讯作者：
HIGASHIMURA, T
中科院分区：
文献类型：
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作者：
TSUCHIHARA, K;MASUDA, T;HIGASHIMURA, T
聚二苯乙炔的热稳定性很好，但不溶于任何溶剂，而不对称二取代乙炔的聚乙炔一般是可溶的。因此，通过引入三甲基硅基研究了可溶性聚二苯乙炔的合成。1-苯基-2-[对三甲基硅基)苯基]乙炔和1-phenyl-2-[m-(trimethylsilyl)phenyl]acetylene在TaCl5-助催化剂体系中聚合，得到了重均相对分子质量大于1×10(6)的新聚合物，产率超过70%。作为助催化剂，n-Bu4Sn、EtsSiH和9BBN的催化效果尤为显著。聚合物为黄色固体，具有交替的双键结构[-CPH=C(C6H4SiMe3)-]n，完全溶解于甲苯、CHCl3等，通过溶液浇铸形成韧性薄膜。TGA在空气中的失重起始温度高达约400摄氏度。它们的透氧系数都很高，约为1000桶。
Poly(diphenylacetylene) is thermally very stable, but insoluble in any solvent, whereas polyacetylenes from unsymmetrically disubstituted acetylenes are generally soluble. Hence, the synthesis of soluble poly(diphenylacetylenes) was examined by introducing the trimethylsilyl group. 1-Phenyl-2-[p(trimethylsilyl)phenyl]acetylene and 1-phenyl-2-[m-(trimethylsilyl)phenyl]acetylene polymerized with TaCl5-cocatalyst systems to provide new polymers with over 70% yields having a weight-average molecular weight over 1 x 10(6). As cocatalysts, n-Bu4Sn, EtsSiH, and 9BBN were especially effective. The polymers were yellow solids with the alternating double bond structure [-CPh=C(C6H4SiMe3)-]n. They completely dissolved in toluene, CHCl3, etc., and formed tough films by solution casting. The onset temperatures of weight loss in TGA in air were as high as ca.400-degrees-C. Their oxygen permeability coefficients were both high, ca.1000 barrers.