Effects of organometallic cocatalysts on the polymerization of disubstituted acetylenes by TaCl5 and NbCl5
Effects of organometallic cocatalysts on the polymerization of disubstituted acetylenes by TaCl5 and NbCl5
复制标题
有机金属助催化剂对TaCl5和NbCl5二取代乙炔聚合的影响
DOI：
10.1002/pola.1987.080250609
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发表时间：
1987
期刊：
影响因子：
--
通讯作者：
T. Higashimura
中科院分区：
文献类型：
--
作者：
Akihiro Niki;T. Masuda;T. Higashimura
研究了有机金属助催化剂对二取代乙炔聚合的影响。二苯乙炔单独与 TaCl5 不聚合，但在适当的助催化剂（Me4Sn、Et3SiH 等）存在下定量生成聚合物。形成的聚(二苯乙炔)是不溶性黄色固体。 1-苯基-1-炔烃（1-苯基-1-丁炔和-1-辛炔）与TaCl5和NbCl5单独聚合得到重均分子量（Mw）约为1的聚合物。使用助催化剂（nBu4Sn等）来聚合这些单体可加速反应，并将聚合物分子量提高至约5×105。 1.5 × 106。聚(1-苯基-1-炔)是可溶性白色固体。内辛炔（2-、3-和4-辛炔）单独与TaCl5 形成聚合物和环三聚体的混合物。相反，环三聚体实际上是通过添加助催化剂选择性地形成的。因此，根据单体的种类观察到有机金属助催化剂的各种效果。
The effects of organometallic cocatalysts on the polymerization of disubstituted acetylenes were investigated. Diphenylacetylene did not polymerize with TaCl5alone, while it produced a polymer quantitatively in the presence of appropriate cocatalysts (Me4Sn, Et3SiH, etc.). The poly(diphenylacetylene) formed was an insoluble yellow solid. 1‐Phenyl‐1‐alkynes (1‐Phenyl‐1‐butyne and ‐1‐octyne) polymerized with TaCl5and NbCl5alone to yield polymers whose weight‐average molecular weights (Mw's) were ca. 5 × 105. Use of cocatalysts (nBu4Sn etc.) to the polymerization of these monomers accelerated the reaction, and increased the polymer molecular weights up to ca. 1.5 × 106. The poly(1‐phenyl‐1‐alkynes) were soluble white solids. Internal octynes (2‐, 3‐, and 4‐octynes) gave mixtures of a polymer and cyclotrimers with TaCl5alone. In contrast, cyclotrimers formed virtually selectively by addition of cocatalysts. Thus, various effects of organometallic cocatalysts were observed depending on the kind of monomer.