Studies on Alternating Copolymerization of Ethylene and Carbon Monoxide Using Nickel‐Based Catalyst: Cocatalyst and the Polarity of Solvent

Abstract Polyketone (PK) has attracted wide attention owing to its direct utilization of carbon monoxide, excellent properties, and photodegradation performance. However, the commercialized PK is produced using Pd‐based catalysts, which accounts for the largest part of the production cost. Herein, [Ni(2‐tol)(PPh 3 )(N,O)] is used as the main catalyst for its high productivity and good tolerance to CO. Effects of the cocatalyst (Ni(COD) 2 ), the aging method in CO atmosphere, and the polarity of solvent are investigated. When Ni(COD) 2 is employed as the cocatalyst, the catalytic activity and molecular weight of PK are increased by 29% and 42.6%, respectively. Aging of catalyst system with Ni(COD) 2 in CO atmosphere leads to significant decrease in activity and molecular weight, while aging has almost no effect on the copolymerization without Ni(COD) 2 . Different catalytic mechanisms are proposed for the catalyst system with and without cocatalyst. Furthermore, it is found that the polar solvent (CH 2 Cl 2 ) significantly increases the activity by 119.2% compared to that in the nonpolar solvent (toluene). However, the thermal stability of the catalyst is much better in toluene. The study on the understanding of catalytic mechanism and improvement of activity will promote the practical application of nonprecious metal catalysts for preparation of PK.