Fabrication of oxygen permeable films of polyacetylenes bearing ester group as a side chain and its evaluation.

结果表明，在三乙胺或乙醇存在下，用Rh络合物催化剂在较温和的条件下成功地实现了单取代乙炔的超规则聚合，并用激光拉曼光谱、漫反射紫外光谱、核磁共振和电子自旋共振(ESR)等方法对产物进行了表征。因此，我们发现，即使在室温下，Rh络合物也是形成顺式反式聚乙炔的首选催化剂。以甲醇为聚合溶剂，将侧链上含有N-烷基的乙炔酯也进行了规整聚合，得到了相应的聚乙烯酯。研究发现，这些酯聚合物具有一种称为柱状的伪六方结构，这种自组装对透氧膜是有用的。聚乙炔酯是由氯仿浇铸而成，用所谓的气体渗透法估算了透氧性，即比P_&lt；O_2&gt；/P_&lt；N_2&gt；的分离系数与其他含硅聚合物相当，表明这种聚合物是一种很有前途的透氧膜新材料。此外，用Rh络合物催化剂制备的聚乙炔即使在室温下也可以通过压缩异构化，从而得到含有大量自由基的反式异构体作为孤立子。^&lt；4-6)&gt；

It has been demonstrared that strereoregular polymerization monosubstituted acetylenes were successfully achieved using Rh complex catalysts in the presence of triethylamine or alchohol under fairly mild conditions and the resulting polyacetylenes were carefully characterized using lasr Raman, diffuse reflective UV,NMR,and electron spin resonance (ESR) methods. ^<1-2)> Consequently we found that the Rh complex is a preffered catalyst for formation of cis-transoid polyacetylenes even at room temperature. Acetylene esters bearing n-akllkyl group in the side chain were aslo stereoregularly polymerized to give the corresponding polyacetylene esters' using methanol as the polymerizaion solvent. ^<3)> The ester polymers were found to have a pseudohexagonal structure called columnar as self assembly useful for the oxygen permeable films. ^<4-5,13)> The polyacetylene esters were cast from chloroform and the oxygen permeability was estimated using a so-called GAS PERM,i.e., the separationcoefficient of the ratio, P_<O2>/P_<N2> was ca. alpha=3.4 comparable for other polmers bearing silicon moieties, suggesting that this polymer is promising new materials for oxygen permeable films. Further, the polyacetylenes prepared with Rh complex catalyst was found to be isomerized by compression even at room temperature in order to give the trans isomers involving a large amount of radicals as solitons. ^<4-6)>