溶剂或添加剂对乙炔在Ziegler型催化剂作用下聚合的影响*

溶剂或添加剂对乙炔在Ziegler型催化剂作用下聚合的影响* EFFECT OF ADDITIVES AND: POLYMERIZATION SOLVENTS ON THE POLYMERIZATION OF ACETYLENE WITH ZIEGLER TYPE CATALYSTS 王佛松 Wang Fosong 1 2 first-author 赵晓江 Zhao Xiaojiang 1 2 龚志 Gong Zhi 1 2 张伟广 Zhang Weiguang 1 2 曹镛 1 2 杨启运 1 2 钱人元 1 2 中国科学院长春应用化学研究所 中国科学院长春应用化学研究所 Changchun Institute of Applied Chemistry, Academia Sinica) Cao Yong, Yang Qiyun and Qian Renyuan Changchun Institute of Applied Chemistry, Academia Sinica) Cao Yong, Yang Qiyun and Qian Renyuan 中国科学院化学研究所 中国科学院化学研究所 研究了添加剂或聚合溶剂对乙炔在Nd(P 507 ) 3 -Al（C 2 H 5 ） 3 及Ti（OBu） 4 - Al（C 2 H 5 ） 3 催化体系作用下聚合的影响。结果表明,对于前一催化体系,在无添加剂存在下,用加氢汽油为溶剂只能得到粉末状聚乙炔。但当加入醇类或P 507 时,在一定的添加剂/Nd克分子比例下,可得到具有金属光泽的聚乙炔膜。研究了聚合物的顺式含量、形态结构、分子量及掺杂后的室温电导率（σ）,发现其顺式含量与聚合条件有关,形态结构及σ则与文献报导的用Ti催化体系得到的类似,但分子量则小得多。对于Ti（OBu） 4 -Al（C 2 H 5 ） 3 体系,改变聚合溶剂或加入给电子试剂,不仅导致催化活性的变化,而且也影响所得聚合物的结构,特别是形态结构。用纯的THF及苯甲醚为溶剂时,得到了文献未见报导的球状或颗粒状形态结构的聚乙炔膜。用碘或其他亲电子试剂掺杂后的这种形态的聚乙炔膜的σ约在100Ω -1 cm -1 以内,明显比纤维形态的低。对聚乙炔形态结构改变导致σ变化的结果,提出了初步的解释。 Effect of the additives and the polymerization solvents on the polymerization of acetylene with two catalyst systems—Nd(P 507 ) 3 -Al（C 2 H 5 ） 3 and Ti（OBu） 4 -Al（C 2 H 5 ） 3 —has been investigated. It is shown that for Nd-based catalyst in the absence of the additives only black polyacetylene（PA） powder was obtained using hydrogenated benzine as polymerization solvent, On addition of alcohols, such as propanol or butanol, and P 507 in a certain D/Nd molar ratio, PA films with metallic luster were formed at room temperature. The cis-content, morphology and molecular weight of resulting PA, as well as conductivity（σ） of PA doped with I 2 have been studied. It is found that the cis-content is dependent upon the polymerization conditions, while morphology and σ are similar to that of PA obtained with Ti-based catalyst, but molecular weight is much lower. For Ti（OBu） 4 -Al（C 2 H 5 ） 3 catalyst, variation of the polymerization solvent or additive leads not only to the change of the catalyst activity, but also to the change of structure of PA obtained, especially the morphology. When pure tetrahydrofurane or anisole were used as polymerization solvent, the PA films obtained exhibited the morphology of globules. σ of The PA films doped with I 2 and other chemical species is < 100Ω -1 cm -1 lower than that of PA films possessing morphology of fibrils. The explanation of the effect of morphology on the a was presented. 1983-04-01 2021-04-01 4