茂金属/有机硼化物催化体系催化1-癸烯聚合

摘要

采用茂金属催化体系 Ph2C(Cp-9-Flu)ZrCl2/C6H5NH(CH3)2B(C6F5)4/Al(iBu)3催化 1-癸烯聚合,考察了催化剂浓度、Al和Zr以及有机硼化物和Zr物质的量之比、反应温度和反应时间等工艺条件对产物的影响,并采用核磁共振对其产物与1-癸烯在Ph2C(Cp-9-Flu)ZrCl2/MAO 催化下聚合产物的结构进行了分析比较.结果表明:在Zr和1-癸烯物质的量之比为10×10-5,硼化物和Zr物质的量之比为1.5,Al和Zr物质的量之比为100,反应温度为60℃的条件下,反应时间120 min,1-癸烯的转化率为93.6%,运动黏度(100℃)为3 684 mm2/s,黏度指数为367,数均分子量为2.9×104,分子量分布为1.85;聚合时单体主要进行1,2插入,产生亚乙烯基端基.%Polymerization of 1-decene catalyzed by Ph2C(Cp-9-Flu)ZrCl2/C6H5NH(CH3)2B(C6H5)4/Al(iBu)3 catalyst system was studied. Effects of catalyst concentration, molar ratio of Al to Zr, molar ratio of origanic boranes(B) to Zr, reaction temperature and reaction time on polymer properties were investigated, and the polymers from 1-decene catalyzed by the Ph2C(Cp-9-Flu)ZrCl2/MAO catalyst system and Ph2C(Cp-9-Flu)ZrCl2/ C6H5NH(CH3)2B(C6H5)4/Al(iBu)3 catalyst system were characterized by means of nuclear magnetic resonance(NMR). The results showed that under the conditions of molar ratio of Zr to 1-decene 10×10-5, molar ratio of Al to Zr 100, reaction temperature 60℃ and reaction time 120 min, the conversion of 1-decene reached 93.6% and the kinematic viscosity (100℃) was 3 684 mm2/s, the viscosity index was 367, the number-average molecular weight (Mn) was 2.9×104, and the molecular weight distribution was 1.85. The polymerization reaction was mainly 1,2-insertion which produced vinylene end group.