Abstract

AbstractTen unsaturated polyester prepolymers differing by the nature of the diol, by the maleate/phthalate molar ratio, or by the chain length, were crosslinked by about 40% by weight of styrene and then analyzed by IR spectrophotometry, solid state NMR, and rubbery elasticity measurements.The spectrometric measurements revealed a practically complete conversion of the styrene/fumarate copolymerization. The rubbery elastic modulus varies in a complex way with the presumed network structure.A non‐ideality factor f was defined from the current theories; f is a decreasing function of the average number of flexible bonds between crosslinks.The networks based on dimeric diols display a practically ideal behavior.The influence of dangling chains, corresponding essentially to polyester chain ends, is taken into account by the Graessley's formula in which trifunctional and tetrafunctional crosslinks are distinguished. A method for the estimation of the nature and weight fraction of dangling chains was proposed.

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