Macromolecules, Vol.52, No.14, 5245-5254, 2019
Investigating Molecular Exchange between Partially Cross-Linked Polymer Particles Prepared by a Secondary Dispersion Process
We recently described a new approach to surfactant-free latex dispersions prepared by emulsification of a partially neutralized linear acrylic acid-containing styrene-acrylic copolymer without the use of an organic solvent [Polym. Chem. 2017, 8, 2931-2941]. These secondary dispersions consisted of a polymer with a molecular weight (M-n = 5000 g mol(-1) D = 3) too low to form a useful coating. In the work reported here, we built up the molecular weight of the polymer and introduced partial gel content via a reaction in the dispersed state with a bisepoxide, followed by a reaction with a monoepoxide to reduce the acid number. We monitored the reaction with bisepoxide with T-2-filtered H-1 NMR to separate signals of highly mobile small molecules from those of less mobile polymer-bound species. Fluorescence resonance energy transfer measurements were carried out both to monitor polymer exchange among nanoparticles (NPs) as the dispersions in water were annealed and to measure the extent of polymer mixing upon film formation. Our most important finding was that the reaction with the monoepoxide reduced polymer T-g and, to a limited extent, promoted polymer interdiffusion during film formation. We also found that the presence of cross-links in the NPs limited the extent of polymer mixing that can be achieved when the polymers were dissolved in a good solvent and cast as a film. The combination of cross-linking and molecular weight build-up strongly reduced the propensity for molecular exchange in the dispersed state.