Phenols/Al(C_(6)F_(5))_(3) Initiation Systems for Cationic Polymerizations of Isobutylene  

作　　者：Ling Cai Qi-Yuan Wang Xin-Li Liu Dong-Mei Cui 

机构地区：[1]State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China [2]Department of Polymer Science and Engineering,University of Science and Technology of China,Hefei 230026,China

出　　处：《Chinese Journal of Polymer Science》2023年第5期713-719,I0008,共8页高分子科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(Nos.U21A20279 and 21774119)。

摘　　要：We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted phenol(RPhOH).Polymers with medium and/or high molecular weights(M_(W)=4.9×10^(4)-27.7×10^(4) g·mol^(-1))can be obtained in toluene and temperatures from-20℃to 0℃.NMR spectrum analysis and DFT sim ulation reveals the in situ generated acidic coordinating complex Ak(C_(6)F_(5))_(3)·RPhOH is the initiating active species,which fu rther tran sformed into the ion-pair[Al(C_(6)F_(5))_(3)ORPh]^(-)[PIB]^(+)of the active intermediates upon growing IB monomers where the counter anion[Al(C_(6)F_(5))_(3)R^(O)Ph]-coordinates to the macrocation via the phenoxy oxygen.The catalyst performances are the concert effects of the steric bulkiness and electronics of the counter anion on the coordinating strength to the macrocation,which is significant to the stability of the active species.

关 键 词：Cationic polymerization PHENOLS Lewis super acid POLYISOBUTYLENE 

分 类 号：O631.5[理学—高分子化学]