| Abstract: | The kinetics of the polyesterification in bulk at 200°C between o-phthalic anhydride and neopentyl glycol (2,2-dimethyl-1,3-propanediol) in a nonequimolecular ratio and in the absence of an external catalyst was investigated. The formation of the monoester and two dimeric compounds by uncatalyzed heating of o-phthalic anhydride with neopentyl glycol was virtually complete after dissolution of the anhydride. The data were analyzed statistically by a mathematical method due to Fradet and Maréchal for the estimation of the orders of reaction. This statistical adjustment of the data analysis supports the assumption that the kinetics of polyesterification in the absence of both the solvent and catalyst may be fitted to several orders of reaction over all the conversion. At first, our experimental data may be fitted to 3, or  , or 2, etc., overall orders. The results establish that the overall kinetic order of the polyesterification depend upon the goodness of the experimental results and cannot be only selected by means of a correlation coefficient. If this last criterium is adopted, the polyesterification at low, medium, as well as at high conversions may be 3 as the most probable one, order one with respect to acid group concentration, and order two with respect to alcoholic group concentration, in agreement with Flory's predictions. A mechanism consistent with the most plausible kinetic results (Im,n = 0.9990 and m, n = 1, 2) is proposed. It consists of a dimerization of the alcoholic groups followed by an attack of the acid to the dimer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2409–2431, 1997 |
