TiCl_4/NiCl_2/SiO_2催化剂制备宽峰分布PE的研究  

Research on TiCl_4/NiCl_2/SiO_2 catalyst for broad MWD polyethylene

作　　者：豆秀丽[1] 刘伟娇[1] 义建军[2] 张明革[2] 黄启谷[1] 杨万泰[1] 高克京[3] 

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室材料科学与工程学院碳纤维及功能高分子教育部重点实验室,北京100029 [2]中国石油天然气股份有限公司石油化工研究院合成树脂重点实验室,北京100083 [3]中国石油化工股份有限公司北京化工研究院,北京100013

出　　处：《合成树脂及塑料》2010年第6期1-5,共5页China Synthetic Resin and Plastics

基　　金：中石油创新基金(07-06D01-04-04-06);北京市自然科学基金(2102036);中国石油技术开发项目(H2010019);北京市教委重点学科共建项目(XK100100540;XK 100100640)

摘　　要：以SiO_2为载体,依次加入NiCl_2或Ni(NO_3)_2、给电子体,然后负载TiCl_4,制备多相齐格勒-纳塔催化剂,以三乙基铝为助催化剂,催化乙烯均聚合及乙烯-1-己烯共聚合,均可得到宽峰分布聚乙烯(PE)。考察了NiCl_2或Ni(NO_3)_2加入量、给电子体结构与加入量、聚合温度及1-己烯加入量对催化性能的影响,并考察了催化剂的氢调敏感性。结果表明:m(NiCl_2)/m(SiO_2)为1:10,2-氯吡啶与SiO_2的摩尔比为为1:10时,80℃下陔催化剂体系可高效催化乙烯聚合,催化效率达3.5 kg/g,PE的相对分子质量分布(M_w/M_n)为15.8;在相同条件下催化乙烯-1-己烯共聚合时,1-己烯加入量为15 mL,其催化效率可达3.7 kg/g,共聚物的M_w/M_n为16.9。The authors prepared SiO2-supported heterogeneous Ziegler-Natta catalyst by adding NiCl2 or Ni（NO3）2, electron donors in turn, then loading TiCl4 on SiO2 Polymers with broad relative molecular mass distribution were obtained either by homopolymerizing ethylene or by eopolymerizing ethylene and 1-hexene in the presence of the catalyst with triethyl aluminum as eocatalyst. The effects of the amount of NiCl2 or Ni（NO3）2, the structure and dosage of the electron donors, polymerization temperature and the content of 1-hexene on performance of the catalyst were researched, and the sensitivity to hydrogen modulation of the catalyst was also studied. The catalytic efficiency reached 3.5 kg/g and the relative molecular mass distribution of polyethylene was 15.8 when the mass ratio of NiCl2 to SiO2 was 1 ： 10,molar ratio of 2-ehloropyridine to SiO2 was 1 ： 10 and the polymerization temperature was 80 ℃. When ethylene and l-hexene were eopolymerized with the catalyst under the same conditions, the catalytic efficiency reached 3.7 kg/g, and the relative molecular mass distribution of the copolymer was 16.9 in case of setting 1-hexene content at 15 mL.

关 键 词：聚乙烯 乙烯-1-己烯共聚物 多相齐格勒-纳塔催化剂 宽峰分布 

分 类 号：TQ325.12[化学工程—合成树脂塑料工业]