Polyesterifications in bulk of trimethylolpropane (T) with azelaic acid (Z) and o-phthalic anhydride (P) and copolyesterification of a (Z+P+T) ternary mixture have been studied by 13C nuclear magnetic resonance (n.m.r.) before and after gelation. It has been found that Z is more able than P to give covalent gels. 13C n.m.r, allows quantitative determinations of the conversions of acid functions of Z and P and alcohol functions of T as well as the distributions of monoester and diester of P and those of free, mono-, di- and triesterified T. In all cases, the actual critical conversions are larger than the theoretical ones calculated due to the Flory-Stockmeyer statistics because (i) 3-5% of free T and P are trapped and (ii) the two acid functions of P or Z and the three alcohol functions of T do not have the same reactivities. For the ternary system, four types of T triesters have been identified and quantitatively determined, and finally, reticulation should only occur if more than one-third of T are triesterified. In the copolyesterification in bulk of the (0.5Z + 0.5P + 0.8T) mixture, the distributions of Z and P on the mono-, di- and triesterified T follow Bernoullian statistics.
Посилання на статтю:
Mechanisms of the bulk copolyesterification of azelaic acid, o-phthalic anhydride and trimethylolpropane studied by 13C nuclear magnetic resonance / R. Petiaud, H. Waton and Q. T. Pham* // Polymer. – 1992. – Vol 33. – P. 5056-5065.