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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

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

Shuming Du A , Jie Zhang A , Yan Guan A and Xinhua Wan A B
+ Author Affiliations
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A Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.

B Corresponding author. Email: xhwan@pku.edu.cn




Xin-Hua Wan received his BCE (1985) degree from Hefei University of Technology, MA (1988) and Ph.D. (1991) degrees from China Textile University. After working as a postdoctoral researcher at Peking University for 2 years, he became an Associate Professor (1993) and a Full Professor (1997) of polymer chemistry and physics there. He visited the University of Akron (2001) and Harvard University (2004) as a senior visiting scholar, and Hokkaido University as a visiting professor. His current research interests include optically active helical polymers, self-assembly of block copolymers, and design and synthesis of macromolecules with controlled architecture and well-defined shape.

Australian Journal of Chemistry 67(1) 39-48 https://doi.org/10.1071/CH13291
Submitted: 5 June 2012  Accepted: 15 July 2013   Published: 26 August 2013

Abstract

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 18 wt-% in concentrated sulfuric acid, whereas the latter does so at a concentration of 12 wt-%. 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.


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