Synthesis of well-defined easily crosslinkable azobenzene side-chain liquid crystalline polymers via reversible addition-fragmentation chain transfer polymerization and photomechanical properties of their post-crosslinked fibers
writer:Liangjing Fang, Guang Han, Jiayang Zhang, Hongtao Zhang, Huiqi Zhang*
keywords:Azobenzene side-chain liquid crystalline polymers, easily crosslinkable, RAFT polymerization, photomechanical properties, post-crosslinked fibers
source:期刊
specific source:European Polymer Journal 2015, 69, DOI: 10.1016/j.eurpolymj.2015.01.001
Issue time:2015年
The synthesis of a series of well-defined easily crosslinkable azobenzene (azo) side-chain liquid crystalline polyacrylates (including both homopolymers with an N-hydroxysuccinimide carboxylate-substituted azo mesogen and copolymers with both the above crosslinkable azo mesogen and a non-crosslinkable azo mesogen) via reversible addition-fragmentation chain transfer (RAFT) polymerization and photomechanical properties of their post-crosslinked fibers are described. The RAFT polymerizations of the azo monomers proved to be living and well-controlled, as revealed by their linear kinetic plots as well as the linear increase of the molecular weights of the azo polymers with monomer conversions and their low molar-mass dispersities (? ? 1.17). All the obtained azo polymers exhibited high thermal stability and relatively low glass transition temperatures, but only the azo homopolymers with longer flexible spacers and azo copolymers showed liquid crystallinity. In addition, the crosslinked azo polymer fibers with easily controlled diameters and high alignment order were obtained by the first fabrication of the uncrosslinked azo polymer fibers by the simple melt spinning method and their subsequent crosslinking with a difunctional primary amine under mild conditions. The contents of the crosslinkable azo mesogen in the polymers had significant influence on the photomechanical properties of their post-crosslinked fibers, and those with appropriate crosslinking densities could exhibit fast and reversible photoinduced bending and unbending behaviors and excellent photodeformation fatigue resistance even at close to room temperature.