Cationic polymerizations of 1,3-pentadiene （PD） initiated by trimethylsilyl chloride （TMSCl） incombination with TiCl4 were carried out in n-hexane at 30℃. The yield of polymer was greatly increased bythe addition of TMSCl, indicating that the TMSCl/TiCl4 combination is an efficient initiating system for PDcationic polymerization. However, the introduction of TMSCl gave rise to a drop in the molecular weight ofthe polymer. Kinetic results demonstrated that the polymerization initiated by TMSCl/TiCl4 is 4.5 times fasterthan that induced by TiCl4 alone. Various ethers were used to mediate the TMSCl/TiCl4 initiating system.Adding diphenyl ether could increase both the yield and molecular weight of the polymer. Structural evidenceillustrates that the polymerization is indeed initiated by TiCl4 in combination with HCl resulting fromhydrolysis by adventitious water.
Various ethers were used to mediate the polymerizations of 1,3-pentadiene (PD) initiated by AlCl3 and by allyl chloride (AllyCl)/AlCl3. The introduction of the ethers exert considerable effects on polymer yield and molecular weight due to its interaction with the propagating carbocation. The carbocation reactivity is reduced by this interaction which is subject to the ether’s nucleophilicity determined by the steric hindrance of groups adjacent to oxygen. The reduction of carbocation reactivity gives rise to a decrease of polymer yield owing to inhibition of propagation but results in an augmentation of molecular weight due to suppression of various side reactions such as terminations. By using suitably nucleophilic ethers such as diphenyl ether, the polymerization can be mediated to give an high molecular weight polymer in high yield.
Cationic polymerization of 1,3-pentadiene (PD) initiated by trimethylsilyl chloride/aluminium chloride (TMSCl/AlCl3) was carried out in toluene at 30℃.The polymer yield was increased by the addition of TMSC1.However,introduction of TMSC1 gave rise to a drop of the polymer molecular weight.Kinetic results demonstrated that the polymerization initiated by TMSCl/AlCl3 was 2.8 times faster than that induced by AlCl3 alone.Various ethers and ketones were used to mediate the initiating system TMSCl/AlCl3.The polymer yield and molecular weight of the polymer were decreased in the presence of ether.Ketones and ethers had different effects on the polymerization,and the polymer yield and molecular weight were lower than those initiated by AlCl3 alone or TMSCl/AlCl3 Structural evidence revealed that the polymerization was indeed initiated by AlCl3 and HCl rcsulting from hydrolysis of TMSC1 by adventitious water.
研究了阳离子引发体系 Me3 Si Cl(TMSCl) Et Al Cl2 在正己烷中引发的 1,3 戊二烯 (PD)聚合反应。研究结果表明 ,在 Et Al Cl2 引发的 PD聚合反应中引入 TMSCl后大幅度提高了聚合物产率 ,同时使聚合反应速率明显提高 ,在 [TMSCl] [Et Al Cl2 ]=0～ 1范围内 ,TMSCl Et Al Cl2 体系制备的聚合物分子量高于 Et Al Cl2 引发制备的聚合物 ,这些结果表明 Me3 Si Cl Et Al Cl2 体系对 PD具有较高的引发活性。 1 H NMR和结构分析证明 TMSCl水解生成的 HCl和 Et Al Cl2 络合物引发 PD聚合。
The cationic polymerization of 1,3-pentadiene （PD） initiated by AlCl3 in n-hexane was carried out. Effects of arenes, alkyl halides and ethers on the gel formation resulting from crosslinking reaction were investigated. The erosslinking was reduced by various arenes through a chain transfer mechanism. Alkyl halides such as tert-butyl chloride and allyl chloride could complex with AlCl3 to generate an initiating system giving rise to a gel-free polymerization, while benzyl chloride reduced the formation of gel by chain transfer. Ethers exerted two effects on the polymerization system: giving a complex initiating system with AlCl3 to produce a relatively high molecular weight polymer, or reducing crosslinking by lowering activity of carbocations.
