The Preparation of Supported Zirconocene Catalysts and Their Application to Ethylene Polymerization

该工作制备了一系列新型载体负载茂锆催化剂,其载体涉及到功能化无机-聚合物复合材料、功能化多孔聚合物材料和功能化无机材料.主要工作和结论如下:一.新型苯乙烯-co-4-乙烯基吡啶共聚物/SiO<,2>壳核载体负载茂锆催化剂用于乙烯聚合.二.新型grape-type孔结构的聚(4-乙烯基吡啶)聚合物载体负载茂金属催化剂用于乙烯聚合.三.改性蒙脱土负载茂金属催化剂用于乙烯聚合.四.可控层间域结构的改性蒙脱土载体负载茂金属催化剂用于乙烯聚合.In this paper, we prepared a series of novel metallocene supports including shell-core inorganic-polymeric material, polymeric material and inorganic material. The preparation of the supported catalysts, their ethylene polymerization and properties of the resulting polyethylenes were studied. (1) Shell-core poly(styrene-co-4-vinylpyridene)/SiO2 support was successfully prepared and used as support of zirconocene for ethylene polymerization. X and Y coupling reagents (X: APTEGS, 3-aminopropyltriethoxysilane; Y: ICTEOS, 3-isocyanatopropyltriethoxysilane) used in preparation of support have not only a little difference in preparation of the supported catalysts, but also a little difference in ethylene polymerization. The methods to preparing supported catalysts have important effects on preparation of the supported catalysts, ethylene polymerization and morphology of the resulting polyethylene. The PS4VPy/SiO2-supported catalyst had lower reactive activity in ethylene polymerization (1.61 X 106gPE/molZr.h), but resulted in polyethylene with higher bulk density (0.37g/cm ) than homogenous catalyst Cp2ZrCl2/MAO and PS4VPy-supportd catalyst. (2) Macroporous functionalized polymer beads of poly(4-vinylpyridine- co-l,4-divinylbenzene), P(VPy-co-DVB), were prepared by a multistep polymerization: polystyrene (PS) shape template was prepared by emulsifier-free emulsion polymerizations, linear PS seeds was prepared by the method of staged template suspension polymerization and macroporous functionalized polymer beads P(VPy-co-DVB) was prepared with a multistep seeded polymerization. The novel polyethylene was invesgtigated