Effect of the conformation of the alkyl chain on the catalytic miniemulsion copolymerization of ethylene and acrylates

The catalytic copolymerization of ethylene and acrylic monomers is a promising way of incorporating polar functionality into polyolefins and therefore enlarging the range of properties of these materials. This work shows that for the copolymerization of ethylene and C4 acrylates using a sterically encumbered Pd catalyst, the degree of incorporation of the acrylic monomer decreases with the degree of branching of the alkyl chain of the acrylate, the main reason being the difficulty for coordination of bulky acrylates to the catalytic site. This strongly affects the polymerization rate as well as the molecular weight, crystallinity and melting point temperature of the copolymers.

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► Catalytic copolymerization of ethylene and acrylates yields polar functional olefins.
► The degree of incorporation of the acrylate decreases with the degree of branching of its alkyl chain.
► This strongly affects kinetics and properties of the copolymers.