Synthesis and characterization of liquid crystalline copolymethacrylates, copolyacrylates, and copolysiloxanes containing 4‐methoxy‐4′‐hydroxy‐α‐methylstilbene and 4‐hydroxy‐4′‐methoxy‐α‐methylstilbene constitutional isomers as side‐groups

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Abstract
The synthesis of methacrylates and acrylates containing 4‐methoxy‐4′‐hydroxy‐α‐methylstilbene and 4‐hydroxy‐4′‐methoxy‐α‐methylstilbene constitutional isomers attached to the polymerizable group through flexible spacers containing 11, 8, 6, 3, and respectively 2 methylenic units is described. The radical copolymerization of a 1/2 or 2/1 mole ratio of the two constitutional isomeric monomers led to thermotropic side‐chain liquid crystalline polymers in all cases. The synthesis of copolysiloxanes based on the same constitutional isomeric mesogens as side groups, and flexible spacers containing 11, 8, 6, 5, and respectively 3 methylenic units is also described. All polymers were characterized by differential scanning calorimetry and optical polarization microscopy. The polymers containing 11 methylenic units in the spacer exhibit Sc mesomorphism, while the other polymers are nematic. Copolymethacrylates do not undergo side‐chain crystallization. Only the copolyacrylate containing 11 methylenic units in the spacer exhibits side‐chain crystallization. All the copolysiloxanes display side‐chain crystallization. The number of melting transitions seen for these polymers decreases with increasing spacer length. Copolysiloxanes containing dissimilar spacer length were also prepared. Only the copolymer synthesized with highly dissimilar spacer lengths, i.e., containing 3 and 11 methylenic units, does not undergo side‐chain crystallization. These results have demonstrated that while the type of mesophase is dictated only by the spacer length, the degree of decoupling of the motion of the side‐groups from the motion of the main chain is strongly dependent on the nature of the polymer backbone. For the same mesogenic unit and spacer length, the thermal stability of the mesophase is also dictated by the nature of the polymer backbone. The use of constitutional isomers of mesogenic units as side groups in liquid crystalline polymers provides at least qualitative information on the degree of decoupling of the side groups from the polymer main chain.

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