卤代烃对Ziegler-Natta催化剂催化乙烯聚合的影响
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摘要
综述了以卤代烃为促进剂对Ziegler-Natta催化剂催化乙烯聚合的影响。介绍了两种卤代烃的加入方式,分别为在催化剂制备过程中加入和在乙烯聚合过程中加入。在催化剂制备过程中加入卤代烃时,对于不同的催化体系,需根据不同的应用选择不同的卤代烃种类及用量。分析了在乙烯聚合过程中加入卤代烃时,卤代烃种类、卤代烃与钛的摩尔比等因素对催化活性、聚乙烯相对分子质量及其分布、聚合母液中蜡含量和聚乙烯粉料中细粉含量的影响。卤代烃在具体应用时需结合催化剂及聚合工艺的特点进行筛选,以使其适用性达到最佳。
The effects of halohydrocarbons as promoters on ethylene polymerization catalyzed by Ziegler-Natta catalyst were reviewed.Two methods for adding the halohydrocarbons,namely addition in the catalyst preparation and addition in the polymerization,were introduced.For different catalyst systems and different applications,appropriate types and amount of the halohydrocarbons should be chosen.The effects of the halohydrocarbon types and molar ratio of halohydrocarbon to titanium on the catalyst activity in the ethylene polymerization,relative molecular mass of the polyethylene product and its distribution,wax content in the polymerization mother liquid and fi ne powder content in the polyethylene product were discussed when the halohydrocarbons were added in the course of the ethylene polymerization.
The effects of halohydrocarbons as promoters on ethylene polymerization catalyzed by Ziegler-Natta catalyst were reviewed.Two methods for adding the halohydrocarbons,namely addition in the catalyst preparation and addition in the polymerization,were introduced.For different catalyst systems and different applications,appropriate types and amount of the halohydrocarbons should be chosen.The effects of the halohydrocarbon types and molar ratio of halohydrocarbon to titanium on the catalyst activity in the ethylene polymerization,relative molecular mass of the polyethylene product and its distribution,wax content in the polymerization mother liquid and fi ne powder content in the polyethylene product were discussed when the halohydrocarbons were added in the course of the ethylene polymerization.
引文
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[2]联合碳化公司.乙烯聚合方法:中国,87107589[P].1987-09-30.
[3]三井化学株式会社.烯烃聚合用的固体钛催化剂制备方法以及聚烯烃制备方法:中国,1108313[P].2003-05-14.
[4]台湾聚合化学品股份有限公司.适用于烯烃聚合用的钛系系统:中国,1189505[P].1998-08-05.
[5]伊斯曼化学公司.乙烯和乙烯共聚物的聚合方法:中国,1255440[P].2006-05-10.
[6]伊斯曼化学公司.制备聚乙烯的方法:中国,1138793[P].2004-02-18.
[7]杨明生.气相流化床法线性聚乙烯催化剂及其制备方法:中国,1129617[P].2003-12-03.
[8]中国石油化工股份有限公司,中国石油化工股份有限公司北京化工研究院.用于制备双峰或宽分布聚乙烯的催化剂体系及应用:中国,1342716[P].2002-04-03.
[9]三井化学株式会社.烯烃聚合用的固体钛催化剂制备方法以及聚烯烃制备方法:中国,1198751[P].1998-11-11.
[10]中国石油化工集团公司北京化工研究院.用于乙烯聚合或共聚合的催化剂及其制法和该催化剂的应用:中国,1263895[P].2000-08-23.
[11]中国石油化工集团公司北京化工研究院.用于烯烃聚合的高效球形钛系催化剂及其制法和该催化剂的应用:中国,1268520[P].2000-10-04.
[12]韩华综合化学株式会社.乙烯聚合物的制备方法:中国,1150955[P].1997-06-04.
[13]孙怡菁,周俊领,马东,等.卤代烃促进剂对钛系聚乙烯催化剂的影响[J].石油化工,2013,42(7):771-774.
[14]Union Carbide Corporation.Impregnated Polymerization Catalyst,Process for Preparing,and Use for Ethylene Copolymerization:US,4302565[P].1979-02-16.
[15]中国石油化工集团公司北京化工研究院.用于烯烃聚合的高效球形钛系催化剂及其制法和该催化剂的应用:中国,1137153[P].2004-02-04.
[16]英国石油化学品有限公司.在流化床反应器中烯烃气相(共)聚合的方法.中国,1286862[P].2006-11-29.
[17]Luo Hekuan,Tang Ruiguo,Yang Hua,et al.Studies on Highly Efficient Promoters for Titanium-Based Ziegler-Natta Catalyst for Ethylene Polymerization[J].Appl Catal,A,2000,203(2):269-273.
[18]Bahri-Laleh N,Abbas-Abadi M S,Haghihi M N,et al.Effect of Halocarbon Promoters on Polyethylene Properties Using MgCl2(Ethoxide Type)/TiCl4/AlEt3/H2 Catalyst System[J].J Appl Polym Sci,2010,117(3):1780-1786.
[19]Kashiwa N,Yoshitake J.The Influence the Valence State of Titanium in MgCl2-Supported Titanium Catalysts on Olefin Polymerization[J].Macromol Chem Phys,1984,185(6):1133-1138.
[20]吕立新.Ziegler-Natta载体型催化剂结构和反应机理方面的研究进展:氯化钛与氯化镁结合方式,烷基铝的作用,内外给电子体的作用[J].国内外石油化工快报,2007,37(4):7-13.