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改性Ziegler-Natta体系催化乙烯/1-辛烯共聚合反应
  • ISSN号:1671-4628
  • 期刊名称:《北京化工大学学报:自然科学版》
  • 分类:TQ426[化学工程]
  • 作者机构:[1]北京化工大学碳纤维及功能高分子教育部重点实验室,北京100029, [2]中国石油石油化工研究院合成树脂重点实验室,北京100083
  • 相关基金:北京市自然科学基金(2102036);中国石油技术开发项目(H2010019)
中文摘要:

采用改性Ziegler-Natta(Z—N)催化体系(n-BuO)TiCl3/MgCl2/MEt3催化乙烯/1-辛烯共聚合。考察了聚合温度、AI/Ti物质的量比、单体投料比及乙烯压力对聚合行为的影响,并与传统Z—N催化体系TiCl4/MgCl2/A1Et3催化乙烯/1-辛烯共聚合行为进行了对比研究。采用GPC,DSC,13C—NMR,SEM对共聚物的结构、形态及性能进行了表征。结果表明,改性Z-N催化体系催化乙烯/1-辛烯共聚合时,1-辛烯的共聚能力明显高于传统Z-N催化体系,在共聚物中1-辛烯的插入量达2.26%(摩尔分数),而传统Z—N催化剂1-辛烯的插入量仅为0.34%(摩尔分数);AI/%物质的量比及单体投料比对催化剂的活性、1-辛烯的插入量、共聚物的分子量与分子量分布及共聚物的微观结构有明显的影响;根据13C-NMR结果计算了单体的竞聚率:rE=55.00,r0=0.023,其乘积rE·ro=1.27,表明该聚合物为无规共聚物。

英文摘要:

A novel modified supported Ziegler-Natta catalyst, (n-BuO)TiCl3/MgCl2 has been prepared and employed for ethylene/1-octene copolymerization, with AlEt3 as cocatalyst. The influence of varying the polymerization temperature, the Al/Ti molar ratio, the feed molar ratio of ethylene to 1-octene and the ethylene pressure on the copolymerization reaction were investigated. The structure, properties and morphology of the copolymer were charac- terized by 13C-NMR, GPC, DSC and SEM. It was found that the catalytic activity in ethylene/1-octene copolymerization of the modified Ziegler-Natta catalyst was higher than that of the traditional Ziegler-Natta catalyst. The Al/Ti molar ratio and the feed molar ratio of ethylene to 1-octene have obvious effects on the catalytic activity, the com- onomer content within the copolymer chain, the molecular weight and molecular weight distribution, and the micro- structure of the resulting copolymer. Compared with the traditional Ziegler-Natta catalyst for ethylene/1-octene co- polymerization which gives a comonomer content of 0.34% , the modified Ziegler-Natta catalyst showed higher ac- tivity for ethylene/1-octene copolymerization, and the comonomer content within the copolymer chain reached as high as 2.26 mol%. The microstructure of the copolymer was determined and the reactivity ratios of the monomers were confirmed by 13C-NMR. Values of rE =55.00 for ethylene and ro =0. 023 for 1-octene with rE-ro = 1.27 were obtained, suggesting the tendency for random distribution of the comonomers within the copolymer chain.

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期刊信息
  • 《北京化工大学学报:自然科学版》
  • 北大核心期刊(2011版)
  • 主管单位:教育部
  • 主办单位:北京化工大学
  • 主编:刘振宇
  • 地址:北京市北三环东路15号
  • 邮编:100029
  • 邮箱:bhxbzr@126.com
  • 电话:010-64434926
  • 国际标准刊号:ISSN:1671-4628
  • 国内统一刊号:ISSN:11-4755/TQ
  • 邮发代号:82-657
  • 获奖情况:
  • 1999年教育部优秀科技期刊二等奖,1997年第二届全国科技期刊评比三等奖,1995年全国重点高校自然科学学报二等奖,中国期刊方阵“双效”期刊,首届高校优秀科技期刊,全国石化行业优秀期刊一等奖
  • 国内外数据库收录:
  • 美国化学文摘(网络版),荷兰文摘与引文数据库,美国剑桥科学文摘,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版)
  • 被引量:9420