Summary
Polymers based on 11-(4′-cyano-trans-4-stilbenyloxy)undecanyl vinyl ether have been synthesized by living cationic polymerization, photo-initiated cationic polymerization using onium salts and thermal initiated cationic polymerization using onium salts. The polymers have been characterized by size exclusion chromatography, nuclear magnetic resonance spectroscopy, differential scanning calorimetry and polarized light microscopy. Living cationic polymerization resulted in a polymer of low molecular mass Mn≤3 600, with a uniformity index (D) of 1.2 displaying a focal conic texture indicative of smectic A (sA) phase with preserved cyanogroup and trans-configuration. Photo-initiation using 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and diphenyliodonium hexafluorophosphate resulted in an insoluble polymer exhibiting only vague liquid crystalline textures. Initiation with phenothiazine and phenacyltetramethylenesulfonium hexafluoroantimonate also yielded a partly insoluble polymer with a disturbed sA phase. It is suggested that the monomer and polymer are sensitive towards radicals leading to cross-linking and branching. The thermal initiation on systems with α-methylbenzyltetramethylenesulfonium hexafluorophosphate and p-methoxybenzyltetramethylenesulfonium hexafluorophosphate resulted in completely soluble mesomorphic polymers of Mn≤13 000, D=1.7 and Mn≤26 000, D=2.8 respectively, in both cases with a preserved cyanogroup and a transconfiguration. Polarized light microscopy revealed a distinct focal conic structure indicative of sA in both cases.
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Hellermark, C., Gedde, U.W. & Hult, A. Synthesis and characterization of poly(11-(4′-cyano-trans-4-stilbenyloxy)undecanyl vinyl ether). Polymer Bulletin 28, 267–274 (1992). https://doi.org/10.1007/BF00294821
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DOI: https://doi.org/10.1007/BF00294821