Interfacial polycondensation .2. Fundamentals of polymer formation at liquid interfaces

If a solution of a fast-reacting diacid halide in a water-immiscible solvent is brought together with an aqueous solution of a diamine without stirring, a thin film of high polymer is formed at once at the interface. Polyurethanes and polyamides in particular form tough films which can be grasped and pulled continuously from the interface as a folded rope of film. This unstirred interfacial polycondensation not only provides a dramatic demonstration of polymer formation but has permitted the observation of polymerization behavior and the study of the effects of many variables upon the process. The polymer-forming reactions proceed by nucleophilic displacement, and many have rate constants of at least 10(2)-10(4) l. mole(-1) sec.(-1). Polymers derived from diamines were found to form in the organic solvent phase. Therefore the rate of polymer formation is controlled by the transfer of diamine from the aqueous phase. It is believed that the liquid interface does not have any beneficial orienting effect on the reactants but that it provides for the regulated flow of one reactant into an excess of the other. Furthermore, the aqueous phase provides for the removal of the interfering byproduct, hydrogen halide, from the polymerization site. Some of the interrelated variables which have been studied and which are discussed in relation to the physical mechanism are the solvent sensitivity of the polymer, partition coefficients of the reactants, reactant concentration, duration of the polymerization, and the addition of monofunctional reactants, detergents, and salts. The formation of polyphenyl esters is discussed briefly.