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Abstract

Step-growth alternating interfacial polymerization between two miscible or immiscible monomer melts is investigated theoretically and by dissipative particle dynamics simulations. In both cases the kinetics for an initially bilayer system passes from the reaction to diffusion control. The polymer composed of immiscible monomers precipitates at the interface forming a film of nearly uniform density. It is demonstrated that the reaction proceeds in a narrow zone, which expands much slower than the whole film, so that newly formed polymer is extruded from the reaction zone. This concept of ldquoreactive extrusionrdquo is used to analytically predict the degree of polymerization and distribution of all components (monomers, polymer, and end groups) within the film in close agreement with the simulations. Increasing the comonomer incompatibility leads to thinner and more uniform films with the higher average degree of polymerization. The final product is considerably more polydisperse than expected for the homogeneous step-growth polymerization. The results extend the previous theoretical reports on interfacial polymerization and provide new insights into the internal film structure and polymer characteristics, which are important for membrane preparation, microencapsulation, and 3D printing technologies. A systematic way of mapping the simulation data onto laboratory scales is discussed.