高等学校化学学报

高等学校化学学报 ›› 1996, Vol. 17 ›› Issue (9): 1467.

• 论文 • 上一篇    下一篇

复合催化剂AlCl3/SbCl3的α-蒎烯/苯乙烯阳离子聚合反应研究

邓云祥, 彭超盼, 段雯, 张仁俊, 曾陇梅   

  1. 中山大学化学系, 广州, 510275
  • 收稿日期:1995-09-26 出版日期:1996-09-24 发布日期:1996-09-24
  • 通讯作者: 邓云祥,男,60岁,教授.
  • 作者简介:邓云祥,男,60岁,教授.
  • 基金资助:

    国家自然科学基金;广东省自然科学基金

Studies on the Cationic Copolymerization of α-Pinene and Styrene with the AlCl3 /SbCl3 Catalyst

DENG Yun-Xiang, PENG Chao-Pan, DUAN Wen, ZHANG Ren-Jun, ZENG Long-Mei   

  1. Department of Chemistry, Zhongshan University, Guangzhou, 510275
  • Received:1995-09-26 Online:1996-09-24 Published:1996-09-24

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摘要： 用微臭氧化-薄层层析法分析测定了复合催化剂AlCl3/SbCl3,在不同Sb/Al比、投料比、溶剂和温度等条件下的α-菠烯(M1)/苯乙烯(M2)共聚产物的构成,表明该复合催化剂可获得～100%共聚体,其中α-蒎烯链节含量F1可在30%～56%之间调控。在仅生成共聚体的条件下由Mayo-Lewis积分式首次测定了竞聚率。AlCl3/SbCl3和单独AlCl3相比,r1增大,r2减小,r2/r1值降低了5～6倍,使不易共聚的M1/M2变为易于共聚,可制备M1组分含量高的共聚体。确认该复合催化剂对M1/M2的优良共聚合性能在于阳离子聚合活性种的非质子和抗衡阴离子(团)的特殊结构和性质。

关键词: 复合催化剂AlCl3/SbCl3, &alpha, -蒎烯/苯乙烯阳离子共聚, 共聚产物的构成, 竞聚率测定

Abstract: The copolymerization products of a-pinene (M1) and styrene(M2)were prepared with the catalyst system SbCl3/AlCl3 by changing the Sb/Al ratio, feeding monomer ratio,solvent and polymerization temperature.The compositions of the copolymerization products were quantitatively characterized by the method of the combination of micro-ozonization and thin-layer chromatography in terms of the contents of the homopolymers and the copolymers.The results show that it was easier to obtain the higher yield(up to 80%)of the pure copolymer with the complex catalyst system than with AlCl3 alone.The F1 values could be controlled between 30%～56%.The monomer reactivity ratios were determined under the polymerization conditions under which only pure copolymer of M1 and M2 was given by using Mayo-Lewis equation.The effects of various catalyst systems and polymerization conditions on the reactivity ratio were also investigated and it was found that the r1 increase from 0.19 to 0.22～0.24 with the AlCl3/SbCl3 instead of AlCl3,but the r2 decrease significantly(from 5.00 to 1.20～1.92).On account of the r2/r1 value is decreased 4～6 times,the copolymerization of M1/M2 was changed into carried out with ease.It was supposed that this good copolymerization activity is attributed to its nonprotonic active species and the characteristic of the counteranion's structure.

Key words: Complex AlCl3/SbCl3 catalyst, Cationic copolymerization of α-pinene/styrene, Composition of copolymerization product, Monomer reactivity ratio determination

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