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Heterogeneous polycondensation for composition control of poly(p‐mercaptobenzoyl‐co‐p‐benzamide) by shearing
Authors:Toshimitsu Ichimori  Shinichi Yamazaki  Kunio Kimura
Affiliation:Graduate School of Environmental Science, Okayama University, , Kita‐ku, Okayama, 700‐8530 Japan
Abstract:Composition control of aromatic poly(thioester‐amide) was examined by the reaction‐induced phase separation during polymerization of S‐acetyl‐4‐mercaptobenzoic acid (AMBA) and p‐acetylaminobenzoic acid (AABA) in aromatic solvent. The poly(thioester‐amide)s were obtained as precipitates and their yields became lower at the middle range of the content of AMBA in feed (χf). The contents of p‐mercaptobenzoyl (MB) moiety (χp) in the precipitates prepared without shearing were in good agreement with the χf values. In contrast to this, the χp values of the precipitates prepared at χf of 50–70 mol % under shearing were much lower than the χf values. The reaction rate of AMBA increased with shearing, whereas that of AABA was unchanged by shearing. This shearing effect on the reaction rates accelerated to form the homo‐oligomers. The solubility of MB oligomers enhanced by shearing, whereas that of p‐benzamide oligomers did not enhance owing to the strong interaction through hydrogen bonding. The MB oligomers were inhibited to be precipitated, resulting in the lower χp values than the χf values. The composition could be controlled by the application of the shearing to the heterogeneous polymerization. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4301–4308
Keywords:composition control  copolymerization  crystallization  polyamides  polycondensation  poly(thioester‐amide)  shear  step‐growth polymerization
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