负载型茂金属催化剂用于乙烯淤浆聚合的研究  

SMAO supported metallocene catalyst for slurry polymerization of ethylene

作　　者：张倩 葛腾杰[2] 姜涛 李健 ZHANG Qian;GE Tengjie;JIANG Tao;LI Jian(College of Chemical Engineering and Materials Science,Tianjin University of Science&Technology,Tianjin 300457,China;Daqing Chemical Research Center,Petrochemical Research Institute,China National Petroleum Corporation,Heilongjiang Daqing 163714,China)

机构地区：[1]天津科技大学化工与材料学院,天津300457 [2]中国石油天然气股份有限公司石油化工研究院大庆化工研究中心,黑龙江大庆163714

出　　处：《化学工业与工程》2022年第6期29-35,共7页Chemical Industry and Engineering

基　　金：中国石油天然气集团公司项目(2020B-2620,2020B-2621)。

摘　　要：在烯烃催化聚合领域,茂金属催化剂显示出比传统Ziegler-Natta催化剂更高的活性。以苯甲酸催化三甲基铝(TMA)受控水解生成甲基铝氧烷(MAO),经热解过程后合成了一种不溶形式的固体聚甲基铝氧烷(sMAO)。以合成的sMAO为载体负载茂金属催化剂,并将该催化剂应用于乙烯淤浆聚合反应中,系统探究了聚合条件对催化行为的影响,同时对聚乙烯产品mPE的粒度、堆密度、分子量及分布和熔体流动速率等基本理化性能进行了分析表征。实验结果表明,制备的催化剂颗粒形态较好,粒子分布均匀,在5 L釜中催化淤浆反应,乙烯/1-己烯共聚活性最高可达15 302.6 g·g^(-1),并得到了相对分子质量分布均匀的中、高密度聚乙烯产品。In the field of olefin catalytic polymerization, metallocene catalysts show higher activity than traditional Ziegler-Natta catalysts. In this study, benzoic acid catalyzed the controlled hydrolysis of trimethylaluminum(TMA) to methylaluminoxane(MAO). The synthesized insoluble form of solid polymethylaluminoxane(sMAO) was used as a carrier to support the metallocene catalyst. The catalyst was employed for ethylene slurry polymerization and the role of reaction conditions on the catalytic behavior was systematically explored. The basic physical properties such as particle size, bulk density, molecular weight and distribution, melt flow rate of polyethylene were analyzed and characterized. The experimental results show that the prepared catalyst particles have good particle morphology and uniform particle distribution. The ethylene/1-hexene copolymerization activity may reach up to 15 302.6 g·g^(-1)and a uniform medium-and high polyethylene density could be obtained when the slurry reaction is performed in a 5-litre reactor.

关 键 词：固体甲基铝氧烷 茂金属催化剂 乙烯淤浆聚合 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业]