Sequence Effects on Properties of the Poly(p-phenylene terephthalamide)-based Macroinitiators and their Comb-like Copolymers Grafted by Polystyrene Side Chains

Two poly(p-phenylene terephthalamide) (PPTA)-based macroinitiators with random and alternate sequences, i.e. poly(p-phenylene terephthalamide)-ran-poly[p-phenylene (2,2,6,6-tetramethylpiperidinyl-1-oxy)terephthalamide)] (CPPTA-ran) and poly(p-phenylene terephthalamide)-alt-poly[p-phenylene (2,2,6,6-tetramethylpiperidinyl-1-oxy)terephthalamide)] (CPPTA-alt), were prepared via copolycondensation of terephthaloyl chloride, 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-functionalized terephthaloyl chloride, and p-phenylenediamine. The graft copolymers consisting of rigid PPTA backbones and polystyrene side chains were obtained by nitroxide-mediated radical polymerization. Both macroinitiators and graft copolymers were characterized by thermal gravimetric analysis, differential scanning calorimetry, wide-angle X-ray diffraction, and polarized optical microscopy. The regular incorporation of the TEMPO-containing co-unit gives rise to remarkable effects on the thermal stability, lyotropic liquid crystallinity, and macromolecular packing in bulk. CPPTA-alt shows better thermal stability and more ordered intermolecular structure than CPPTA-ran. The former generates a nematic phase at a concentration of 18wt-% in concentrated sulfuric acid, whereas the latter does so at a concentration of 12wt-%. For the graft copolymers, the alternative main chains exhibit sharper diffraction than the random ones. However, the sequence change exerts no discernible effect on other properties.