不同路易斯酸与Fischer型卡宾组成体系催化炔烃聚合及其聚合物的性质  

CATALYTIC POLYMERIZATION FOR ALKYNE WITH FISCHERS METAL CARBENE AND SOME LEWIS ACID SYSTEMS AND PROPERTIES OF POLYMERS

作　　者：刘德海[1] 闵利[1] 

机构地区：[1]湛江师范学院化学系

出　　处：《高分子材料科学与工程》1996年第6期43-47,共5页Polymer Materials Science & Engineering

基　　金：国家自然科学基金

摘　　要：首次报导不同的路易斯酸分别与Ｆｉｓｃｈｅｒ型卡宾（ＣＯ）５ＷＣ（ＯＥｔ）Ｐｈ组成炔烃催化体系。通过对炔烃的催化聚合反应，讨论体系的催化活性中心。发现体系的活性比相应的卡宾和卡拜的催化活性皆高。从而进一步证明活性中心是桥键络合物的设想：（ＣＯ）５ＷＣＰｈＯＥｔＡｌＣｌ２Ｃｌ。并对所获得的聚合物进行了ＩＲ、ＤＴＡ和Ｘ衍射分析，测定了它们的数均分子量Ｍｎ、特性粘数η和电导率σ。The catalytic polymerization for alkyne with the systems of (CO) 5WC(OEt)Ph+MX 3(M=Al, X=Cl, I; M=B, X=Cl, Br) has been studied. It was found that the catalytic activity of the different Lewis acids in the system with (CO) 5WC(OEt)Ph for the yield of poly(1,4 diphenyl 1,3 butadiyne)(PDPBD) under the same polymerization condition decreases in the following order: AlCl 3>AlI 3>BBr 3>BCl 3 and the yield of polydiphenylacetylene catalyzed by the system of (CO) 5WC(OEt)Ph+AlCl 3 is 60.3%,but at the same polymerization condition, the polydiphenylacetylene is not obtained with the system of (CO) 5WC(OEt)Ph+BCl 3. The results showed that we can not infer that the catalytic active center is Fischers tungstencarbyne X(CO) 4W≡CPh, because the (CO) 5WC(OEt)Ph can react with AlCl 3 or BCl 3 to form a same tungsten carbyne Cl(CO) 4W≡CPh. Therefore, the (CO) 5WC(OEt)Ph reacts with MX 3 to form the bridged complex: (CO) 5W C[ZJZS;YS;YX] Ph OEt MX 2 X . The bridged complex is catalytic active center. The structure of the polymers was analysed by Fourier transform infrared spectrometer. The molecular weights ( n), the intrinsic viscosity ( η ), thermal analytic data and electric conductivity σ of these polymers were measured. The X ray diffraction of these polymers show that these polymers all are amorphous. ESR showed that the insuble PDBPD has unpaired electron concentration of 6×10 18 spins/g .

关 键 词：催化 聚合 电子接受体 高聚物 炔烃聚合物 

分 类 号：O632.17[理学—高分子化学]