Polymer and Materials Science
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Nucleophilic substitution of PVC with sodium thiophenate was carried out in cyclohexanone solution at 5, 25, 40, 60, and 70°C. The initial rate obeys an Arrhenius law from 25 to 60°C, with an activation energy of 70 kJ/mol. Conversion limits are observed which strongly depend on the temperature. The stereoselectivity of the reaction with respect to the configurational triads does not depend on the temperature: the distribution of configurations is only dependent on the conversion. Assuming an SN2 substitution mechanism governed by steric factors, the Monte Carlo simulation procedure described in a prior study is shown to give a good account for all temperatures above 40°C assuming for the mm, mr or rm, and rr triads a reactivity such as Rmm = 2 Rmr and Rrr nil at low temperature and very low at temperatures ≥ 40°C. The low conversion limits observed at 5 and 25°C cannot be explained by a limited accessibility of a part of the polymer. Finally, it is shown that the elimination reaction, which remains limited, does not interfere with the substitution process.
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