高等学校化学学报

高等学校化学学报 ›› 1996, Vol. 17 ›› Issue (8): 1314.

• 论文 • 上一篇    下一篇

AlCl3/SbCl3引发α-蒎烯阳离子聚合反应──引发活性种本质研究

卢江, 梁晖, 张仁俊, 邓云祥   

  1. 中山大学化学系, 广州 510275
  • 收稿日期:1995-10-13 出版日期:1996-08-24 发布日期:1996-08-24
  • 通讯作者: 卢江,男,33岁,博士,副教授.
  • 作者简介:卢江,男,33岁,博士,副教授.
  • 基金资助:

    国家自然科学基金;广东省科学基金

Cationic Polymerization of α-Pinene Initiated by AlCl3/SbCl3──Studies on the Nature or the Initiating Species

LU Jiang, LIANG Hui, ZHANG Ren-Jun, DENG Yun-Xiang   

  1. Department of Chemistry, Zhongshan University, Guangzhou 510275
  • Received:1995-10-13 Online:1996-08-24 Published:1996-08-24

PDF (PC)

摘要： 考察了复合催化剂AlCl3/SbCl3的不同配制方法和质子捕捉剂2,6-二异丁基-4-甲基吡啶(DTBMP)对α-蒎烯阳离子聚合反应的影响。结果表明,AlCl3和SbCl3加热熔融复合比简单复合的引发聚合活性更高;DTBMP对该复合催化剂的聚合反应速率及其产物分子量分布均无明显影响,证明该复合催化剂形成的活性种本质上与质子H⊕活性种不同,是新型活性种。根据27AlNMR对该体系活性种分析结果,认为引发阳离子是[Sb(V)Cl4]⊕,抗衡阴离子是[Al2Cl7]Θ

关键词: AlCl3/SbCl3, &alpha, -蒎烯, 活性种本质

Abstract: The effects of the preparation methods of the AlCl3/SbCl3 binary catalyst and the proton trap 2,6-ditert-butyl-4-methyl pyridine(DTBMP)on the cationic polymerization of apinene were investigated respectively.The results showed that, if AlCl3 and SbCl3 were melted to form the combined catalyst,its initiating activity was higher than that of the catalyst obtained by simply mixing of AlCl3 and SbCl3.α-Pinene was hardly initiated by the simple combination of AlCl3 and SbCl3 at-78℃,howeve,the melted binary catalyst system led to a fast polymerization even at such a low temperature,The proton trap DTBMPhad no obvious effects on the AlCl3/SbCl3 catalyzed polymerization in term of the rate and the molecular weight distribution.These results indicated that new initiating species which was different from protonic species H⊕ in nature was generated by the reaction of AlCl3 and SbCl3.Furthermore,the reaction of AlCl3 and SbCl3 was examined by 27Al NMRspectrum.No signal was observed in the 27Al NMRspectrum of AlCl3 alone system because of its poor solubility in the used solvent (toluene), but there appeared a strong absorption in the spectrum of AlCl3/ SbCl3 binary system,and the chemical shifts unchanged before and after the polymerization.These show that a new Al-containing compound, soluble in toluene,was generated by AlCl3 and SbCl3 to initiate the polymerization,and that the metal atom adding to the monomer is not Al but Sb in the initiating reaction.The proposed initiating cation was[SbCl4]⊕,and the counter anion was[Al2Cl7]Θ.

Key words: AlCl3/SbCl3, α-Pinene, Nature of the initiating species

TrendMD: