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

1.环取代聚二苯基乙炔的合成及其透气性研究--具有不同取代基和聚合物性质的二苯基乙炔(DPA)的气相聚合。结果表明，TaCl5/金属有机助催化剂体系对二苯乙炔的聚合反应十分有效，能以较高的产率得到高相对分子质量的聚合物。大多数产生的聚合物在有机溶剂中完全溶解。聚合物的高热稳定性和成膜能力使制备具有高透气性的坚韧薄膜成为可能。有趣的是，对于含有大量圆形对取代基的聚(DPA)，如叔丁基和三甲基硅基，观察到相当大的P_&lt；O2&gt；值(P_&lt；O2&gt；~1100 Barrer)。含大体积硅基的聚苯乙炔的合成与性能--p-[三(三甲基硅基)硅基]苯乙炔[p(Me_3Si)_3SiPA]与手性含硅(+)-1-p-{[甲基(1-萘基)苯基]硅基}…的聚合对更多苯乙炔(MeNpPhSi^*PA)进行了研究。P(Me_3Si)_3SiPA在Rh催化剂作用下均聚成不溶聚合物。另一方面，p(Me_3Si)_3SiPA与p-(三甲基硅基)苯乙炔在不同的投料比下进行共聚，得到了高相对分子质量的共聚物，且均可溶于多种有机溶剂。当投料比为80：20时，共聚物的P_(lt；O_2)和P_(t；)值达到770巴。Rh基聚(MeNpPhSi^*PA)表现出很大的旋光性。它的圆二色谱在CHCl_3中的紫外区表现出很大的棉花效应。聚(MeNpPhSi^*PA)的P_&lt；O2&gt；值为900巴。研究了含三甲基硅基和三异丙基硅基的聚二苯乙炔的气体渗透行为-含三甲基硅基和三异丙基硅基的聚二苯基乙炔的气体渗透行为。这两种聚合物的气体渗透系数都非常高，而且这些聚合物对较大的可冷凝蒸气碳氢化合物(例如正丁烷)比对较小的永久性气体(例如氢气)更具渗透性。随着温度的升高，PTMSDPA对于轻质气体(氦、氢和氮气)的渗透率增加，而对于更易凝结的气体则降低。较少

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