环戊二烯基(或茚基)二氯化钕体系催化丁二烯聚合反应动力学

<正> 环戊二烯基(或茚基)轻烯土二氯化物C_5H_5NdCl_2·nC_4H_8O(C_5H_5为环戊二烯基、C_4H_8O为四氢呋喃、Ln代表Pr或Nd、n=0,1,2,3)、C_5H_5LnCl_2·HCl·nC_4H_8O、C_9H_7LnCl_2·nC_4H_8O和C_9H_7LnCl_2·HCl·nC_4H_8O(C_9H_7为茚基)能与烷基铝组合形成一类新型丁二烯聚合催化剂,虽然稀土催化丁二烯聚合反应动力学已有报道,但是其催化体系、聚合条件和研究方法各不相同。过去的研究多应用稳态动力学处理方法侧重于聚合速度的研究。本文的目的在于通过聚合物活性链的变化,考察C_5H_5NdCl_2·nC_4H_8O

KINETICS OF BUTADIENE POLYMERIZATION WITH CYCLOP-ENTADIENYL (OR INDENYL) NEODYMIUM DICHLORIDE-ALUMINIUM ALKYL CATALYTIC SYSTEMS

Kinetics of butadiene polymerization with C5H5NdCl2.THF(or C9H7NdCl2.HCl.THF)-i-Bu3Al catalyst systems were studied at 50℃. When Al]/Nd]=30, the process of polymerization using both catalytic systems belongs to the type of slow initiated, non-steady state reaction. If Al]/]Nd 60, the polymerization process by G9H7NdCl2. HCl.THF system becomes the type of rapid initiated, steady state reaction, while the process induced by C5H5NdCl2.THF system under this condition remains unchanged. When Al]/Nd] = 60 and at polymerization temperature 30 or 0℃ the polymerization process in these two systems changes to slow initited, non-steady state reaction again. The above results were verified by the molecular weight distribution curves.