Thermodynamic analysis of the reaction‐induced phase separation of solutions of random copolymers of methyl methacrylate and N,N‐dimethylacrylamide in the precursors of a polythiourethane network

Poly(methyl methacrylate) and random copolymers of methyl methacrylate (MMA) and N,N‐dimethylacrylamide (DMA) containing 7.5, 15, or 20 wt % DMA were dissolved in a stoichiometric mixture of m‐xylylene diisocyanate and 4‐mercaptomethyl‐3,6‐dithia‐1,8‐octanedithiol, precursors of a polythiourethane network. Phase separation, which took place during polymerizations at 60, 90, and 120 °C, exhibited a lower critical solution temperature behavior. The cloud‐point conversions, which were determined by the iodometric titration of free thiol groups of samples chilled in ice at the cloud point, increased with the weight fraction of DMA in the random copolymer. This could be used to control the cloud‐point conversion and determine the characteristic size of the dispersed domains. A thermodynamic analysis was performed with the Flory–Huggins equation, taking into account the polydispersities of both the thermoplastic and thermoset polymers and using an interaction parameter depending on the temperature and on the three binary interaction energies. A reasonable fitting of the experimental curves was obtained with negative values for the interaction energies of the MMA–thermoset and DMA–thermoset pairs and with a positive value for the MMA–DMA pair. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2821–2827, 2006