Various 1,3‐dialkylimidazolium and tetraalkylphosphonium ionic liquids (ILs), including novel ones, have been studied as reaction media for free radical polymerization of methyl methacrylate (MMA), acrylonitrile (AN) and 1‐vinyl‐3‐ethylimidazolium salts (ViEtIm+)Y−. The influence of IL's nature upon the polymer formulation was investigated. The use of different ionic liquids allows not only to obtain the polymers with high molecular weight (PMMA, ${\bar M}_w$ up to 5,770,000 g/mol; PAN, ${\bar M}_v$ up to 735,000 g/mol and poly[(ViEtIm+)Y−], $\bar M_z$ up to 1,130,000 g/mol) in high yields, but also to control the polymerization rate and molecular mass. The physicochemical characteristics, including mechanical properties, thermal stability and heat‐resistance of the obtained polymers were studied in order to compare with those of polymers prepared in a traditional media. It was found that elongation, tensile modulus and strength of PAN, which was synthesized in ionic liquid, are reliatively higher. The influence of IL's nature upon their ionic conductivity and the formation of conductive polymers from molten‐salt‐type vinyl monomers was investigated. Molecular design of the polymers simultaneously with the influence of IL's nature in order to achieve higher ionic conductivity is discussed. Flexible, transparent polymer films, obtained in different ways, show relatively high ionic conductivity (of about 10−5 S cm−1 at 20°C). Copyright © 2006 John Wiley & Sons, Ltd.

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) using five 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 by the 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 polydispersity indices 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 solvatochromic behavior of the polymers prepared was studied. Particularly, solutions of poly-M1 prepared by the action of Ru-based initiators displayed a high sensitivity toward traces of water in N,N-dimethylformamide.