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化学学报
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化学学报 ›› 1998, Vol. 56 ›› Issue (10): 1032-1036. 上一篇    

研究论文

三氟甲基磺酸三甲基硅酯/四氯化钛复合体系引发 1, 3-戊二烯的阳离子聚合

邓建国;彭宇行   

  1. 中国科学院成都有机化学研究所.成都(610041)
  • 发布日期:1998-10-15

Cationic polymerization of 1, 3-pentadiene initiated by (CH~3) ~3SiOSO~2CF~3/TiCl~4 system

Deng Jianguo;Peng Yuxing   

  1. Chengdu Inst Organ Chem, CAS.Chengdu(610041)
  • Published:1998-10-15

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研究了以三氟甲基磺酸三甲基硅酯[(CH~3)~3SiOSO~2CH~3,TMSOFf]为主引发剂,TiCl~4为共引发剂的复合引发体系对1,3-戊二烯(PD)的聚合行为。TMSOTf/TiCl~4复合体系引发PD不但比单独的TiCl~4引发具有更高的引发活性,而且提高了聚合物分子量,能把聚合反应速率提高8.8倍,把聚合物的收率从TiCl~4引发的62.5%提高到95%以上。对该复合体系聚合PD的动力学,反应机理所作的研究表明:TMSOTf和TMSOTf/TiCl~4都是通过它们与体系中残存水通过水解生成的质子酸引发进行的,聚合反应属一级反应。在该体系中加入酮类后,产率和分子量均降低,但均随着酮类的位阻的增加而增大。

关键词: 阳离子聚合, 戊二烯P, 引发剂, 引发, 四氯化钛, 三氟甲基, 甲磺酸P, 三甲基硅烷类, 酯, 动力学研究

The polymerization of 1, 3-pentadiene initiated by TMSOTf/TiCl~4 initiating system is reported. The results showed that, the initiating system has an higher activity than TiCl~4 alone. It can increase the molecular weight and raise reaction rate of polymerization. The polymer yield increases with the [TMSOTf]/TiCl~4 ratio, and then keeps constantly when the [TMSOTf]/TiCl~4] ratio is not less than 0.5, the molecular weight reaches a maximum when [TMSOTf]/TiCl~4]=1. The reaction kinetic and reaction mechanism are studied. In our study, the polymerization of PD is initiated by the TiCl~4 in complexation with HOTf released by hydrolysis of TMSOTf. The yield and the molecular weight increase with steric hindrance of kentone.

Key words: CATION POLYMERIZATION, PENTADIENE P, INITIATOR, INITIATION, TITANIUM TETRACHLORIDE, TRIFLUOMETHYL, METHANESULFONIC ACID P, TRIMETHYLSILANES, ESTERS, KINETIC STUDY

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