Development of Polymer Membranes for Gas/Organic Vapor Separation by Using Substituted Polyacetylenes

1.含环取代基聚二苯乙炔的合成及其透气性研究了含不同取代基的二苯乙炔的聚合及聚合物的性能。TaCl_5/有机金属助催化剂体系对二苯基乙炔的聚合反应是十分有效的，可得到高分子量的聚合物。大多数生产的聚合物完全溶于有机溶剂。聚合物的高热稳定性和成膜能力使得制备具有高透气性的薄而坚韧的膜成为可能。有趣的是，<O2><O2>当聚（DPAs）中含有大量的圆形对位取代基如叔丁基和三甲基硅烷基时，观察到了相当大的P_值（P_p = 1100 barrer）.含大硅基聚苯乙炔的合成与性能研究--对-[三（三甲基硅基）硅基]苯乙炔[p（Me_3Si）_3SiPA]与手性含硅（+）-1-对-{[甲基（1-萘基）苯基]硅基}的聚合 ...更多信息 研究了苯乙炔（MeNpPhSi^*PA）。在Rh催化剂作用下，p（Me_3Si）_3SiPA均聚得到不溶性聚合物。另一方面，p（Me_3Si）_3SiPA与对三甲基硅基苯乙炔在不同投料比下的共聚反应得到了高分子量的共聚物，这些共聚物均溶于多种有机溶剂。投<O2>料比为80：20时，共聚物的P值达到770 barrer。Rh基聚（MeNpPhSi^*PA）显示出非常大的旋光度。在CHCl_3溶液中，其圆二色性光谱在紫外区表现出很大的Cotton效应。聚<O2>（MeNpPhSi^*PA）的P_值为900巴。含三甲基硅基和三异丙基硅基聚二苯乙炔的气体渗透行为研究了含三甲基硅基和三异丙基硅基聚二苯乙炔（PTMSDPA和PTPSDPA）的气体渗透行为。两种聚合物的气体渗透系数都非常高，并且这些聚合物对较大的可冷凝蒸气烃（例如，正丁烷）而不是小的永久性气体（例如，氢）。随着温度的升高，PTMSDPA中的渗透性对于轻气体（氦气、氢气和氮气）增加，并且对于更可冷凝的气体降低。少

1. Synthesis of Poly (diphenylacetylenes) with Ring-Substituents and Its Gas Permeability-Polymerization of diphenylacetylenes (DPA) with various substituent and polymer properties were investigated. TaCl_5/organometallic cocatalyst systems proved to be quite effective for the polymerization of diphenylacetylenes, providing high molecular weight polymers in good yields. Most of the produced polymers are completely soluble in organic solvents. High thermal stability and film-forming ability of the polymers make it possible to prepare thin tough membranes with high gas permeability. Interestingly, quite large P_<O2> values (P_<O2>〜1100 barrer) were observed with poly (DPAs) bearing bulky round-shaped para-substituents such as tert-butyl and trimethylsilyl.2. Synthesis and Properties of Poly (phenylacetylene) with Bulky Silyl Groups-Polymerization of p-[tris (trimethylsilyl) silyl] phenylacetylene [p (Me_3Si)_3SiPA] and chiral silicon-containing (+)-1-p-{[methyl (1-naphthyl) phenyl]silyl} … More phenylacetylene (MeNpPhSi^*PA) was studied. Homopolymerization of p(Me_3Si)_3SiPA by Rh catalyst provided insoluble polymer. On the other hand, copolymerization of p(Me_3Si)_3SiPA with p-(trimethylsilyl) phenylacetylene at various feed ratios afforded high molecular weigh copolymers in high yields, all of which were soluble in many organic solvents. The P_<O2> value of the copolymer for the 80 : 20 feed ratio reached 770 barrer. The Rh-based poly (MeNpPhSi^*PA) showed a very large optical rotation. Its circular dichroism spectrum exhibited very large Cotton effects in the UV region in CHCl_3. The P_<O2> value of poly (MeNpPhSi^*PA) was 900 barrers.3. Gas-Permeation Behavior of Poly (diphenylacetylene) with Trimethylsilyl and Triisopropylsilyl Groups-Gas permeation behavior of poly (diphenylacetylenes) with trimethylsilyl and triisopropylsilyl groups (PTMSDPA and PTPSDPA, respectively) was investigated. The gas permeability coefficients of both polymers were very high, and these polymers were more permeable to larger, condensable vapors hydrocarbons (e.g., n-butane) than to small, permanent gases (e.g., hydrogen). As temperature increased, the permeability in PTMSDPA increased for light gases (helium, hydrogen, and nitrogen) and decreased for more condensable gases. Less