【摘要】 本文首次报导M（CO）₆+ CX₄（M=Mo,W;X=Cl,Br）和AlCl₃（无水）组成的体系,在光照下对各种取代炔烃的聚合催化作用.发现AlCl₃能明显地提高M（CO）₆+CX₄+hv体系的催化活性.研究了不同聚合条件对聚合反应的影响,提出和讨论了该体系催化炔烃聚合反应的机理:金属卡宾活性中心的产生、金属卡宾稳定化,催化炔烃歧化聚合反应,以及最佳聚合条件.更多还原

【Abstract】 The catalytic polymerization of alkyne (e.g.phenylacetylene, diphenyl-acetylene, 1, 4 -dichloro- 2 -butyne, 1, 4 -diphenyl-1, 3 -bu tadiyne and propargyl chloride) in the presence of M(CO)6 + CX4 + hv and A1C13(anhydrous) (M = Mo, W; X = C1, Br ) systems has been studied. It was found that the catalytic activity can be promoted by adding AlCl3 into M(CO)6 + CX4 + hv catalyst systems. The effects of polymerization condition on the yield of polymers were also investigated .The reaction mechanism and the best polymerization condition have been discussed. A possible polymerization mechanism can be presented as follows: the formation of metal-carbene, its stabilization and the subsequent metathesis polymerization of the monomer. The IR spectra, the molecular weights (Mn), the intrinsic viscosity (η) and the thermal analytic data of these poly(alkyne)s were measured. The X-ray diffraction of these poly(alkyne)s show that the poly(diphenylacetylene) is crystalline, the other products are amorphous.ESR showed that the poly(l, 4 -diphenyl-l,3-butadiyne) has unpairedelectron cocentration of 1018spins/g.更多还原