The insertion copolymerization of polar olefins and ethylene remains a significant challenge in part due to catalysts' low activity and poor thermal stability. Herein we demonstrate a strategy toward addressing these obstacles through ligand design. Neutral nickel phosphine enolate catalysts with large phosphine substituents reaching the axial positions of Ni achieve activity of up to 7.7×103 kg mol-1 h-1 (efficiency >35×103 g copolymer/g Ni) at 110 °C, notable for ethylene/acrylate copolymerization. NMR analysis of resulting copolymers reveals highly linear microstructures with main-chain ester functionality. Structure-performance studies indicate a strong correlation between axial steric hindrance and catalyst performance.
Keywords: Acrylate; Catalysis; Copolymers; Nickel; Olefins.
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