Influence of structural parameters on the degradation of ultrahigh-molecular-weight vinyl-type network-polymer precursors during elution through size exclusion chromatography columns

Network‐polymer precursors obtained in various crosslinking monovinyl/divinyl copolymerization systems, including benzyl methacrylate/1,6‐hexanediol dimethacrylate, benzyl acrylate (BzA)/1,6‐hexanediol diacrylate (HDDA), and vinyl benzoate/divinyl adipate, were subjected to degradation during elution through size exclusion chromatography (SEC) columns, although the copolymerizations were conducted under specified conditions where the factors for the greatly delayed gelation from the Flory–Stockmayer gelation theory were reduced. The most remarkable degradation was observed for the BzA/HDDA copolymerization, which provided prepolymers with the most flexible backbone chains. Thus, the BzA/HDDA precopolymers were chosen, and their degradation behavior during elution through SEC columns was explored in detail as one of the representatives of vinyl‐type network‐polymer precursors. The results were correlated with the structural parameters of network‐polymer precursors, including primary polymer chain length, branched structure, and multiple crosslink or network structure. The degradation became more remarkable with decreased primary polymer chain length, that is, the increment of branching, whereas reduced degradation was observed with the incorporation of loop and network structures into the prepolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 577–582, 2003