Abstract: The invention includes a process of preparing a coupled polymer comprising heating an admixture containing (1) at least one interpolymer of an alpha olefin and vinyl aromatic monomer and (2) a coupling amount of at least one poly(sulfonyl azide) to at least the decomposition temperature of the poly(sulfonyl azide) for a period sufficient for decomposition of at least about 80 weight percent of the poly(sulfonyl azide) and sufficient to result in a coupled polymer. The polymer preferably. comprises ethylene, and a vinyl aromatic monomer, preferably styrene. The amount of poly(sulfonyl azide) is preferably from about 0.01 to about 1 weight percent of the interpolymer and the reaction preferably takes place at a temperature greater than about 150° C., more preferably 185° C. The process optionally and in one preferred embodiment additionally comprises steps (b) fabricating an article from the coupled polymer and (c) crosslinking the fabricated coupled polymer.

Abstract: A process of polymerizing a monomer capable of undergoing free radical polymerization, comprising contacting the monomer with a diradical initiator at a temperature sufficient to initiate free radical polymerization, wherein said diradical initiator contains sites of C--C unsaturation which cyclize to form a diradical.