Abstract

In this work, the polymerization of 1-trimethylsilyl-1-propyne [TMSP] using catalytic systems based on pentabromide Nb(V) and Ta(V) with organometallic cocatalysts Ph₃Bi, Ph₄Sn, Bu₄Sn, Ph₃SiH, and Et₃SiH was investigated. The use of NbBr₅-based catalytic systems has strongly marked cis-stereospecificity and gives highly cis-enriched poly(1-trimethylsilyl-1-propyne) [PTMSP] (content of cis-units above 70%), whereas the use of TaBr₅-based catalytic systems leads to the formation of PTMSP with mixed cis-/trans-composition (content of cis-units from 50 to 65%).With increasing cis-content, solvent resistance of PTMSP increases significantly. PTMSP with a content of cis-units above 70% obtained on NbBr₅-containing systems in cyclohexane acquires resistance to aliphatic and aromatic hydrocarbons, and cis-regular PTMSP obtained on NbBr₅-based systems in toluene is totally insoluble in any of the organic solvents. The results of wide-angle X-ray diffraction indicate an increase in the packing density of the polymer during the transition from a mixed configuration to a cis-regular one. Durable PTMSP film membranes exhibit ultra-high permeability coefficients for individual gases (e.g., \({{P}_{{{{{\text{O}}}_{{\text{2}}}}}}}\) = 8500–11000 barrer, \({{\alpha }_{{{{{\text{O}}}_{{\text{2}}}}{\text{/}}{{{\text{N}}}_{{\text{2}}}}}}}\) = 1.5–1.9). According to the low-temperature Ar sorption, PTMSP synthesized with NbBr₅- and TaBr₅-based catalytic systems has high BET surface areas in the range of 870–1050 m²/g, high intrinsic microporosity, and higher gas permeability coefficients of PTMSP correlate with BET surface area growth.

中文翻译：

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NbBr 5-和TaBr 5基催化体系制得的聚（1-三甲基甲硅烷基-1-丙炔）的合成，结构和性能

抽象的

在这项工作中，使用基于五溴化物Nb（V）和Ta（V）的催化体系与有机金属助催化剂Ph ₃ Bi，Ph ₄ Sn，Bu ₄ Sn，Ph ₃ SiH聚合1-三甲基甲硅烷基-1-丙炔[TMSP] ，并研究了Et ₃ SiH。使用基于NbBr ₅的催化系统具有显着的顺式-立体特异性，并提供高度顺式富集的聚（1-三甲基甲硅烷基-1-丙炔）[PTMSP]（顺式单元的含量高于70％），而使用TaBr基于₅的催化体系导致形成带有混合顺式/反式的PTMSP组成（顺式单元的含量从50％到65％）。随着顺式含量的增加，PTMSP的耐溶剂性显着提高。在环己烷中的含NbBr ₅的体系中获得的顺式单元含量高于70％的PTMSP获得对脂族和芳族烃的抗性，而在甲苯中的基于NbBr ₅的体系中获得的顺式PTMSP完全不溶于任何有机物溶剂。广角X射线衍射的结果表明，在从混合构型转变为顺式构型的过程中，聚合物的堆积密度增加了。-常规的。耐用的PTMSP薄膜膜对单个气体表现出超高的渗透系数（例如\（{{P} _ {{{{{{\ text {O}}} _ {{\ text {2}}}}}}}}}} \ ） = 8500–11000 barrer，\（{{\ alpha __ {{{{\ text {O}}} __ {{\ text {2}}}} {\ text {/}} {{{\ text {N}}} _ {{\ text {2}}}}}} \） = 1.5–1.9）。根据低温Ar吸附，使用NbBr _5-和TaBr ₅基催化体系合成的PTMSP具有BET表面积在870-1050 m ² / g范围内，具有较高的固有微孔率和较高的PTMSP气体渗透系数与BET表面积增长相关。