Synthesis and Hierarchical Self-Assembly of Rod Rod Block Copolymers via Click Chemistry between Mesogen-Jacketed Liquid Crystalline Polymers and Helical Polypeptides

A series of novel rod-rod diblock copolymers containing poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) and poly(gamma-benzyl-L-glutamate) (PBLG) were synthesized by click chemistry from alkyne- and azide-functionalized homopolymers The alpha-alkyne PM PCS homopolymers were synthesized by coppei -mediated atom ti ansfer radical polymerization with a In online-containing a-alkyne bifun( tional initiator, and a-azido PBLG homopolymers were synthesized by ring-opening polymerization of gamma-benzyl-L-glutamate N-car boxyanhydnde with an amino-containing a-azide mina tor The no struceares of the rod-rod block copcdymeis were confirmed by H-1 NM R spectroscopy, Fourier transform int) an.rd spectroscopy, and gel permeation chromatography analysis The self-assembling behavior of the rod t od block copolymers in bulk was investigated using differential scanning calonmetry, polar Ind light micro;copy, wide-angle X-ray diffraction, and transmission electron microscopy techniques A lamellar structure was observed with of f(PBLG) similar to 0 50, in which PMPCS was in a columnar nematie phase and PBLG assigned to a hexagonally packed-cylinder structure (Phi(II)) According to the TEM micrographs and simulated lengths of the copolymers. a stacked bdayei structure in a hexagon in lamella morphology for the selfassembly of the rod rod block copolymers was proposed Finally, by increasing f(PBLG) to similar to 0 69, a micro?hase-sepat riled hexagon in cylinder morphology was found, in which PM PCS formed the core of the cylinders sur rounded by PBLG in Phi(II) phase and both rods were in an inter digitated packing