高性能单活性中心催化剂的发展给聚烯烃分子链结构的设计与"精确调控"提供了强大的工具,然而设计、制备和优化耐高温多功能催化剂成为制备高性能、高附加值聚烯烃产品的核心。本文回顾了全系列聚烯烃材料的种类,热性能和材料类型与共单体含量之间的关系。重点综述了:1改进型CGC-Ti、半茂钛、非茂铪(锆)等耐高温乙烯/α-烯烃共聚催化剂;2半茂钛、非茂钛等乙烯/(苯乙烯、降冰片烯)系列共聚催化剂;3优化型C2/C1-对称茂锆、耐高温非茂铪等高立构丙烯均聚和等规丙烯-乙烯系列共聚催化剂;4含杂环的C2/C1-对称茂锆高等规1-丁烯本体溶液聚合催化剂。与此同时,对这些催化剂的性能及其相应产物的链结构进行了详细地讨论。最后指出,优化耐高温等规型非茂铪和含杂环或杂原子的C2/C1-对称茂锆以及间规型C1-对称茂锆等多功能催化剂是今后的研究重点。
The development of advanced single site catalysts provided us tremendous opportunities for designing and tailoring the molecular chain structure of polyolefins. However,designing,preparing and optimizing of high temperature stable multi-functional catalysts became core issue to develop high performance and high value added polyolefin products. Firstly,this paper introduced all types of series polyolefin materials and the correlation of melting properties and material behaviors with comonomer content. Secondly,we mainly reviewed:1high temperature stable ethylene/α-olefin copolymerization catalysts,covering modified CGC-titanocenes/half-titanocenes/non-metallocene hafnium; 2half-titanocene and non-metallocene titanium catalysts for ethylene/(styrene,norborene) ser-copolymerization; 3modified C2/C1-symmetric zirconium and high temperature stable non-metallocene hafnium catalysts for stereo-regular propylene homopolymerization and isotactic propylene/ethylene ser-copolymerization; 4heterocycle-containing C2/C1-symmetric zirconocenes for isotactic 1-butene bulk solution polymerization. Meanwhile,more emphases were given to the polymerization behaviors and the tailored chain structures of the corresponding products of these catalysts. At last,it was suggested that future research should be focused on optimizing isotactic non-metallocene hafniums, hetero-cycle/atom containing C2/C1- symmetric zirconocenes and syndiotactic C1-symmetric zirconocenes.