Theory and computation of photopolymerization-induced phase transition and morphology development in blends of crystalline polymer and photoreactive monomer.

A hypothetical phase diagram of a crystalline polymer/photoreactive monomer mixture has been calculated on the basis of phase field (PF) free energy of crystal solidification in conjunction with Flory-Huggins (FH) free energy of liquid-liquid demixing to guide the morphology development during photopolymerization of poly(ethylene oxide)/triacrylate blend. The self-consistent solution of the combined PF-FH theory exhibits a crystalline-amorphous phase diagram showing the coexistence of solid+liquid gap bound by the liquidus and solidus lines, followed by an upper critical solution temperature at a lower temperature. When photopolymerization was triggered in the isotropic region, i.e., slightly above the crystal melting transition temperatures, the depressed melting transition line moves upward. When it surpasses the reaction temperature, both crystallization and phase separation occur. The temporal evolution of phase morphology is examined in the context of time-dependent Ginzburg-Landau equations coupled with the energy balance (heat conduction) equation using the aforementioned PF-FH free-energy densities. Of particular interest is that the emerged morphology in the crystalline blends depends on the competition between dynamics of liquid-liquid phase separation and/or liquid-solid phase transition (i.e., crystallization) and photopolymerization rates.