Poly(vinyl alcohol) (PVA) and two ethylene-vinyl alcohol copolymers were esterified with undecenoyl chloride and a mixture of undecenoyl and benzoyl chlorides to test how the double bond content and aromatic or aliphatic spacers can affect the further crosslinking reaction. In all cases crosslinking was only possible by using a peroxide initiator to prevent simultaneous thermal degradation. Isoconversional kinetic analysis was applied to dynamic DSC data. This study reveals the complexity of the crosslinking process because the activation energy depends on the conversion degree. In the polymers which contain most double bonds, diffusion is the rate limiting step at high conversion. As a general trend, Ea values increase when the number of double bonds decreases. However, when there are many benzoate moieties, Ea values are lower probably due to the more expanded conformation that the random coil must adopted.
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Giménez et al. (1999) studied this question.
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