Cyclopolymerization of N,N-Dipropargylamines and N,N-Dipropargyl Ammonium Salts

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• 作者：Yakov S. Vygodskii ; Alexander S. Shaplov ; Elena I. Lozinskaya ; Petr S. Vlasov ; Inna A. Malyshkina ; Nadejda D. Gavrilova ; P. Santhosh Kumar ; Michael R. Buchmeiser
• 刊名：Macromolecules
• 出版年：2008
• 出版时间：March 25, 2008
• 年：2008
• 卷：41
• 期：6
• 页码：1919 - 1928
• 全文大小：149K
• 年卷期：v.41,no.6(March 25, 2008)
• ISSN：1520-5835

文摘

The cyclopolymerization of polar, ionic N,N-dibutyl-N,N-dipropargylammonium bis(trifluoromethylsulfonyl)imide (M1), N,N-dimethyl-N,N-dipropargylammonium bis(trifluoromethylsulfonyl)imide (M2), N,N-dipropargylmorpholinium bis(trifluoromethylsulfonyl)imide (M3), and N-propyl-N,N-dipropargylamine (M4) usingfive different well-defined Schrock- and trifluoroacetate-modified Grubbs-type initiators was investigated. Ru-based initiators allowed for the polymerization of M1-M3 with average isolated polymer yields around 25-40%, however, poly-M2 and poly-M3 thus prepared consisted >95% of five-membered ring structures, i.e.,(3,4-(1H-2,5-dihydropyrrolylene)vinylene)s units. In contrast, the use of the Schrock type initiator Mo(N-2,6-iPr₂C₆H₃)(CHMe₂Ph)(OC(CH₃)(CF₃)₂)₂ allowed for quantitative polymer yields, whereas, poly-M2 prepared bythe action of this initiator was based on both five- and six-membered, i.e., (3,5-(1,2,5,6-tetrahydropyridinylene)methylidene) cyclic units. Polymers were synthesized with molecular weights M_n < 21 800 g/mol and polydispersityindices in the range of 1.04 < PDI < 1.37 and 1.01 < PDI < 1.08 with Ru- and Mo-based initiators, respectively.They were additionally investigated for their thermal stability and ionic conductivity. Finally, the solvatochromicbehavior of the polymers prepared was studied. Particularly, solutions of poly-M1 prepared by the action ofRu-based initiators displayed a high sensitivity toward traces of water in N,N-dimethylformamide.