Polymerization-induced Phase Separation: Phase Behavior Developments and Hydrodynamic Interaction

Abstract

The process of polymer synthesis based on polymerization-induced phase separation (PIPS) is revisited from the theoretical point of view. Cahn–Hilliard–Cook theories for spinodal decomposition are adapted to describe the kinetics of phase separation and deduce the time-resolved scattering function, while the double reaction model is used to describe the kinetics of polymerization. Coupling of these two kinetics is provided by the Carother's equation relating the fraction of reacted monomers to the degree of polymerization at time t, denoted N(t). It is argued that the approach to criticality is governed by a critical parameter, χ_c, that is different from the usual parameter for spinodal decomposition, χ_s, deduced from the second derivative of the free energy. While the latter parameter depends on the reciprocal degree of polymerization N⁻¹(t), the former one depends on its time integral. This leads to significant consequences on the phase behavior developments during the PIPS process. Hydrodynamic interactions are found to speed up the emergence of instability modes. Although the qualitative trends remain similar to those of the Rouse dynamics, important quantitative changes are found due to the long-range viscous flow effects.

Keywords:

• critical parameters
• hydrodynamics
• kinetics
• PIPS
• scattering

Acknowledgments

We are grateful to P. H. Geil for the numerous corrections and suggestions he made to improve the manuscript. This research was supported by the Ministry of Higher Education and Scientific Research of Algeria.