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ABA type liquid crystalline triblock copolymers by combination of living cationic polymerizaition and ATRP: synthesis and self-assembly.

Lamellar and hexagonal-coil-cylinder self-assembled structures of ABA type triblock copolymers containing mesogen-jacketed liquid crystalline polymer (MJLCP) as the rod block, and polyisobutylene (PIB) as the coil middle block were discovered. PIB was synthesized by living cationic polymerization of isobutylene initiated by 1,4-bis(2-chloro-2-propyl)benzene (p-DCC), and then a small amount of styrene was introduced at the end of the PIB chains to form the difunctional PIB macroinitiator with -CH2CH(C6H5)Cl end groups for further atom transfer radical polymerization (ATRP). 2,5-Bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS) was block-copolymerized from the difunctional PIB macroinitiators at 110 °C. The molecular characterization of the triblock copolymers was performed with 1H NMR, 13C NMR, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Their phase structures and transitions were investigated by differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), and polarized optical microscopy experiments. It was demonstrated that the triblock copolymers formed lamellar structures at moderate rod fractions and hexagonal coil cylinders in the rod matrix at high rod fractions. The d-spacing of the microphase-separated structures was influenced by the liquid crystalline phase of rod-like PMPCS blocks.