高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (9): 1825.doi: 10.7503/cjcu20150312

• 高分子化学 • 上一篇    下一篇

芳氧基锆系催化剂催化乙烯齐聚与Friedel-Crafts烷基化的串联反应

秦一超, 叶健, 蒋斌波(), 王靖岱, 阳永荣   

  1. 浙江大学化学工程与生物工程学院, 化学工程联合国家重点实验室, 杭州 310027
  • 收稿日期:2015-04-16 出版日期:2015-09-10 发布日期:2015-08-14
  • 作者简介:联系人简介: 蒋斌波, 男, 博士, 副教授, 主要从事聚合反应工程研究. E-mail:jiangbb@zju.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21176208)和上海市聚烯烃核心技术重点实验室开放基金(批准号: 120DZ260400)资助

Ethylene Oligomerization and Friedel-Crafts Alkylation Tandem Action Catalyzed by Aryloxy Zirconium Catalysts

QIN Yichao, YE Jian, JIANG Binbo*(), WANG Jingdai, YANG Yongrong   

  1. State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
  • Received:2015-04-16 Online:2015-09-10 Published:2015-08-14
  • Contact: JIANG Binbo E-mail:jiangbb@zju.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21176208) and the Open Fund of Key Laboratory of Polyolefin Core Technology of Shanghai City, China(No.120DZ260400)

摘要:

从锆系催化剂的结构修饰出发, 合成了一系列具有Zr(OAr)nCl4-n·mArOH(n=1~4, m=0~7)结构的芳氧基锆系催化剂, 并研究了锆酚配比及游离ArOH含量等对乙烯齐聚行为的影响. 结果表明, Zr(OPh)3Cl·mPhOH/TEA/EtAlCl2催化体系具有较高的齐聚催化活性[6.8×104 g/(mol Zr·h)], 所得产物主要为C4~C24的α-烯烃, 无高聚物生成. 研究发现, 游离酚的存在对体系的催化性能有较大影响. 该系列芳氧基锆系催化剂可催化乙烯齐聚与Friedel-Crafts烷基化的串联反应, 即齐聚反应产物α-烯烃与甲苯溶剂发生烷基化反应而生成多取代芳香烃, 压力越大烷基化反应程度越高.

关键词: 芳氧基锆催化剂, 乙烯齐聚, Friedel-Crafts烷基化, 串联反应, α-烯烃

Abstract:

Linear α-olefins are currently produced predominantly by the oligomerization of ethylene. Among the most promising catalysts, zirconium catalysts are largely studied due to its mild reaction condition and well-distributed products. In this article, aryloxy zirconium catalysts, Zr(OAr)nCl4-n·mArOH, were synthesized via modifying the aryl ring structure. The influence of Zr/Phenol molar ratio and the free phenol content on ethylene oligomerization was studied. Among these catalytic systems, Zr(OPh)3Cl·mPhOH/TEA/EtAlCl2 was proved to be highly active with the activity up to 6.8×104 g/(mol Zr·h), while the product consisted of mainly α-olefins(C4—C24) without polymers. In addition, a suitable amount of free phenol was found to be responsible for stabilizing the active species. It was also found that increasing the ethylene pressure or altering the substituents on the benzene ring could result in the formation of a tandem catalytic system, in which the obtained α-olefins were then mostly converted into the corresponding Friedel-Crafts alkylated-toluene products.

Key words: Aryloxy zirconium catalyst, Ethylene oligomerization, Friedel-Crafts alkylated reaction, Tandem action, α-Olefin(Ed.: W.Z)

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