Polymerisation of allyl esters

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Abstract
The benzoyl peroxide catalysed polymerisation of diallyl phthalate is shown to proceed by a zero order reaction in the early stages to give a linear or lightly branched unsaturated polymer (β‐polymer). At approximately 25% conversion, gel formation occurs duo to the formation of a three‐dimensional polymer (γ‐polymer). Thereafter the β‐polymer concentration falls rapidly as the γ‐polymer content increases.The polymerisation of mixtures of unsaturated polyesters, typified by diethylene maleste, and diallyl phthalate is shown to result mainly in a three‐dimensional copolymer.The effect of temperature variation on multi‐functional polymerisation reactions of the above type is discussed. It is suggested that, as the polymerisation temperature is increased, fewer cross‐links by primary valence bonds are formed, i.e., Houwink's “Lockerstellen” theory may be extended to include polymers of this type.

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