Design, Synthesis, and Characterization of Novel Sulfur-Containing Polyacetylenes

本项目涉及新型含硫聚乙炔的分子设计，高分子量聚合物的合成方法的开发，以及所得到的聚合物的表征。1.聚(1-正烷硫基-1-丙炔)1-正烷硫基-L丙炔(CH_3CXICSR；R=Me，Et，n-Bu，n-C_6H_&lt；13&gt；n-C_8H_&lt；17&gt；n-C_&lt；10&gt；H_&lt；21&gt；在MoCl5-Ph_3SiH(1：2)催化剂存在下，在80ﾟC的甲苯中以较好的产率(50-80%)聚合。相应的W、Nb和Ta催化剂是有效的。产物的重均相对分子质量为1×105~2×105，高于目前合成的任何含硫聚乙炔。光谱数据支持聚合物的结构为(-CCH_3=CSR-)_n。除了聚(1-甲硫基-1-丙炔)外，目前的聚合物完全溶解在甲苯和CHCl_3等常见溶剂中。它们无色，成膜，在空气中相当稳定，电绝缘，对气体中等渗透性。用过渡金属催化剂研究了1-甲硫基-1-炔烃的聚合及1-甲硫基-1-炔的聚合。MoCl5和Ph3SiH以1：2的比例混合，以30-50%的产率得到了M^-w超过1×10^5的聚合物。烷基长度对聚合反应几乎没有影响。单体MeSCXIC-n-C_6H_(13)的均聚合反应活性较低，但共聚反应活性高于MeCXIC-n-C_5H_(11)。聚(1-甲硫基-1-炔)为无色固体，长链烷基(R=n-C6H&lt；13&gt；，n-C8H&lt；17&gt；)可溶于各种有机溶剂。该聚合物的热稳定性高于相应的烃类聚合物聚(2-烯烃)。此外，还考察了几种含硫芳香烃的聚合反应。

The present project has dealt with the molecular design of novel sulfur-containing- polyacetylenes, the exploitation of methods for synthesizing high molecular weight polymers, and the characterization of the polymers obtained. The results are summarized as follows:1. Synthesis and Properties of Poly(1-n-alkylthio-1-propynes) 1-n-Alkylthio-l-propynes (CH_3CXICSR; R = Me, Et, n-Bu, n-C_6H_<13>, n-C_8H_<17>, and n-C_<10>H_<21>) polymerized in good yields (50 - 80%) in toluene at 80 ﾟC in the presence of MoCl_5-Ph_3SiH(1:2) catalyst. The corresponding W, Nb and Ta catalysts were effective. The product possessed weight-average molecular weights (M^^-___w up to 1x10^5 - 2x10^5, higher than any other sulfur-containing polyacetylenes so far synthesized. Spectroscopic data supported the polymer structure, (-CCH_3=CSR-)_n. Except poly(1-methylthio-1-propyne), the present polymers totally dissolved in common solvents such as toluene and CHCl_3. They were colorless, film-forming, thermally fairly stable in air, electrically insulating, and moderately permeable to gases.2. Polymerization of 1-Methylthio-1-alkynes and Polymer Properties Polymerization of 1-methylthio-1-alkynes (MeSCXICR; R = Et, n-Bu, n-C_6H_<13>, and n-C_8H_<17>) was studied by use of transition metal catalysts. A 1:2 mixture of MoCl_5 and Ph_3SiH provided polymers having M^^-___w over 1x10^5 in 30 - 50% yields from these monomers. The length of the alkyl group hardly affected the polymerization. The monomer, MeSCXIC-n-C_6H_<13>, showed low reactivity in homopolymerization, but higher reactivity than that of MeCXIC-n-C_5H_<11> in copolymerization. Poly(1-methylthio-1-alkynes) were colorless solids, and those with long alkyl pendants (R = n-C_6H_<13>, n-C_8H_<17>) were soluble in various organic solvents. The present polymers were thermally more stable than poly(2-alkynes), the corresponding hydrocarbon polymers.Further, polymerization of several sulfur-containing aromatic acetylenes was examined.