Analysis of the thermodynamic compatibility of interpenetrating networks during their synthesis

A thermodynamic analysis of interpenetrating polymer networks (IPNs), at any extent of reaction during their synthesis, is presented for both simultaneous and sequential procedures. A model IPN is assumed to be built up by the independent stepwise homopolymerization of two monomers: a tetrafunctional one, A₄, and a trifunctional one, A₃. No reaction of copolymerization or grafting is allowed between the two types of polymers. For the case of semi-IPNs, A₃ is replaced by A₂, i.e., a bifunctional monomer leading to a linear polymer. The free energy of mixing is described by a Flory-Huggins lattice model, whereas the elastic contribution is calculated by assuming affine deformation of an ideal elastic network. Results show that a sequential polymerization gives a more incompatible system (i.e., it enters the metastable region at lower conversions) than a simultaneous polymerization starting from the same monomers. In every case, a semi-IPN is shown to be more compatible than an IPN owing to the fact that the average size of the bifunctional monomer increases less with conversion than the size of the trifunctional monomer. When a sequential polymerization begins from a swollen gel at equilibrium, any increase in the extent of reaction of the solvent monomer will lead to its segregation from the swollen gel. The critical Flory-Huggins interaction parameter provides a simple way to ascertain the possibility of phase separation during a simultaneous polymerization.