Journal of Polymer Science Part A: Polymer Chemistry, Vol.38, No.24, 4457-4465, 2000
Reaction of epoxy resin and hyperbranched polyacids
The condensation reaction between two different epoxy resins and a hyperbranched polyester (MAHP) [poly(allyloxy maleic acid-co-maleic anhydride)] was studied. We compared two kinds of diglycidyl ether bisphenol A type of epoxy resins with different molecular weights, that is, epoxy resin GY240 (M = 365 g/mol) and GT6064 (M = 1540 g/mol) in this reaction. The results showed a marked difference in their reaction pattern in terms of ability to form crosslinked polymer networks with MAHP. For the former low-molecular-weight epoxy resin, no crosslinking could be observed in good solvents such as THF or dioxane within the set of reaction conditions used in this study. Instead, polymers with epoxide functional degrees between 0.34 and 0.5 were formed. By contrast, the latter high-molecular-weight epoxy resin, GT6064, rapidly produced highly crosslinked materials with MAHP under the same reaction conditions. The spherical-shape model of hyperbranched polymer was applied to explain this difference in reaction behavior. Hence, we have postulated that low-molecular-weight epoxy resins such as GY240 are unable to crosslink the comparatively much bigger spherically shaped MAHP molecules. However, using high-molecular-weight epoxy resins greatly enhances the probability of crosslinking in this system. Computer simulations verified the spherical shape and condensed bond density of MAHP in good solvents, and submicron particle analysis showed that the average MAHP particle size was 9 nm in THF. Furthermore, the epoxy-functionalized polyesters were characterized by H-1 NMR and FTIR, and the molecular weights and molecular-weight distributions were determined by size-exclusion chromatography.