ABSTRACTThe synthesis of a polystyrene-b-polyvinylmethylsiloxane-b-polystyrene diblock and triblock copolymer functionalized with liquid crystals exhibiting a smectic C* phase on the PVMS central block is described. The synthetic route is based on the anionic polymerization of styrene and trimethyltrivinylsiloxane monomers and the functionalization of resulting triblock copolymers. The resulting polymer can self assemble into a thermoplastic elastomer where the high Tg styrene blocks serve as physical crosslinks for a low Tg siloxane block. The presence of a smectic liquid crystalline phase and the block copolymer mesophase are observed across various temperature ranges depending on the length of the spacer connecting the liquid crystalline moiety to the polymer backbone. The influence of mechanical deformation upon the morphologies of the liquid crystalline and block copolymer mesophases was investigated. The interactions between the smectic LC and the block copolymer morphologies and their influence upon their respective orientations in response to shear fields are detailed. The parallel-transverse orientation of the hexagonally close packed (HCP) cylinders of the block copolymer morphology and the smectic liquid crystalline phase, respectively, was observed for melt fiber drawn samples. However, the transverse-perpendicular orientation was observed for liquid crystalline block copolymers that experienced oscillatory shear. The transverse orientation of HCP cylinders was observed while shearing took place above the smectic to isotropic transition temperature, indicating that the presence of an isotropic liquid crystalline phase alters the orientation of the block copolymer morphology. Additionally, it was found that the spacer length was a key factor in the clearing points for the smectic liquid crystalline phase, as well as significantly influencing the nanophase segregation of the block copolymer.
Sustainable Block Copolymer-based Thermoplastic Elastomers
