A MODEL OF THE KINETICS OF MACROCYCLIC BPA CARBONATE FORMATION

Cyclic oligocarbonates are synthesized by two-phase interfacial reactions of aryl bischloroformates in the presence of an amine phase transfer catalyst and an alkali: nCl-OCOArOCOCl + 4nNaOH --> (OArOCO)n + 2nNaCl + nNa2CO3 + 2nH2O. The organocarbonate product may be a macrocyclic oligomer or a linear chain polymer. A qualitative mechanism for this behavior has been proposed by Brunelle, Boden, and co-workers. Four steps are identifiable: activation of the aryl bischloroformate by the amine catalyst, hydrolysis of a portion of this intermediate at the aqueous/organic phase interface, oligomerization between activated and hydrolyzed moieties also at the interface, and chain terminating carbamate formation that leads to polymer. An important modification is made within the framework of the Brunelle and Boden mechanism. While the intramolecular cyclization reaction is formally second-order overall, it behaves as a first-order process. The kinetic constants for both this pseudo-first-order cyclization step and the corresponding second-order linearization step are simply related. It is speculated that the above relationship can be generalized for a whole class of pseudo-first- and second-order rate constants for similar macrocyclic reactions.