Kinetics of polymeric network synthesis via free‐radical mechanisms ‐ polymerization and polymer modification

Abstract The kinetics of polymeric network formation via free radical mechanisms is an attractive research area because there are many phenomena which are not well understood and in addition, the commercial potential for crosslinked systems is great. Recently, a large research/development program was initiated at the McMaster Institute for Polymer Production Technology (MIPPT) to investigate the fundamentals and applications of polymeric network, in particular, the kinetics of synthesis via free‐radical mechanisms and network characterization. The research on crosslinking involved both theoretical developments and experimentation. Herein is provided a comprehensive summary of this work. In the experimental polymerization, two comonomers, methyl methacrylate (MMA) / ethylene glycol dimethacrylate (EGDMA) and acrylamide (AAm) / N,N‐methylene bisacrylamide (Bis), as model systems were studied in considerable detail. Measurements included: monomer conversions, radical concentrations, sol/gel fractions, crosslink densities (equilibrium swelling and swollen‐state 13 C‐NMR) over the entire range of divinyl monomer levels as a function of polymerization time. In the polymer modification, high density polyethylenes were crosslinked using peroxides and γ‐radiation. For this system, crosslinking and chain scission occur simultaneously. In the theoretical studies, it was shown that in general, network formation by free‐radical mechanisms is highly irreversible requiring that the classical equilibrium gelation theories after Flory/Stockmayer be generalized. The general model which was developed using the pseudo‐kinetic rate constant method predicts the existence of a crosslink density distribution (crosslink density of a primary polymer chain depends on its birth time) with a variance which can vary widely depending on network synthesis conditions.