Theory of microphase separation in crosslinked polymer blends immersed in a θ-solvent.

The aim of this work is a theoretical study of the effects of the solvent quality on the microphase separation in crosslinked polymer blends, from a static and kinetics point of view. More precisely, we assume that the crosslinked mixture is trapped in a θ-solvent. The static microphase properties are studied through the static structure factor. The latter is computed using an extended blob model, where the crosslinked unlike chains can be viewed as sequences of blobs. We demonstrate that the presence of the θ-solvent simply leads to a multiplicative renormalization of these properties, and the renormalization factors are powers of the overall monomer volume fraction. Second, we investigate the early kinetics of the microphase separation, via the relaxation rate, τ(q), which is a function of the wave number q (at fixed temperature and monomer volume fraction). We first show that the kinetics is entirely controlled by local motions of Rouse type, since the slow motions are frozen out by the presence of crosslinks. Using the blob model, we find an explicit form for the growth rate Ω(q) = τ(q)⁻¹, which depends, in addition to the wave number q , on the overall monomer volume fraction, Φ. Also, we discuss the effect of initial entanglements that are trapped when the system is crosslinked. In fact, these play the role of true reticulation points, and then, they quantitatively contribute to the microseparation phenomenon. Finally, the results are compared to their homologous relatively to the molten state and to the good solvent case. The main conclusion is that the quality of the solvent induces drastic changes of the microphase properties.