Reactivity of Phosphino‐naphtholate Nickel Complexes and Their Catalysis of Copolymerization with Polar Monomers

Abstract

Coordination-insertion copolymerization of ethylene with polar monomers can directly provide value-added functionalized polyolefins. Studies on the reactivity of catalysts toward polar monomers can help understand the copolymerization process and then tune the polymerization strategically. In this contribution, the reactivity picture of 2-diphenylphosphonyl-8-phenylnaphthol nickel complex toward fundamental polar monomers was explored by stoichiometric reactions. The insertion rates are in the order of methyl acrylate (MA) > n-butyl acrylate (BA) > N, N-dimethylacrylamide (DMAA) > methyl methacrylate (MMA) > vinyl triethoxysilane (VTEoS) > N-vinyl-pyrrolidinone (NVP). Acrylic derivatives of MA, BA and DMAA with electronwithdrawing group favor 2,1-fashion while non-acrylic NVP with electron-donating group prefers 1,2-fashion. Notably, the 1,1disubstituted MMA and bulky VTEoS perform a preferential 1,2insertion accompanying by 2,1-insertion in the percentage of 82 : 18 and 62 : 38, respectively, because of the stronger steric effect. These insights correlate to the copolymerization of polar monomers with ethylene. Linear functional polyethylene with in-chain and terminal incorporation of BA, DMAA or VTEoS is afforded at a high activity.

The role of photo‐catalytically synthesized poly (N‐vinyl pyrrolidone‐methyl methacrylate)/CuO‐rGO nanocomposite as a filler for the reinforcement for epoxy system

“…27 nm indicates the oxidation to the graphitic structure confirming the formation of GO from graphite. Other peaks obtained at 28.08 and at 46 are due to the graphitic disorder after the oxidation process, and it arises due to the (002) graphitic plane.…”

“…The combination of NVP and MMA in copolymerization can be accomplished through different methods, including solution polymerization, emulsion polymerization, and miniemulsion polymerization, as indicated by various sources. 26,27 The selection of the polymerization method and specific reaction conditions significantly impacts the copolymer's composition, molecular weight, and overall properties.…”

“…The copolymerization of these two monomers results in a polymer with tuneable properties, making it suitable for various applications including drug delivery systems, biomaterials, coatings, and more. The combination of NVP and MMA in copolymerization can be accomplished through different methods, including solution polymerization, emulsion polymerization, and mini‐emulsion polymerization, as indicated by various sources 26,27 . The selection of the polymerization method and specific reaction conditions significantly impacts the copolymer's composition, molecular weight, and overall properties.…”

Recent Advances in the Copolymerization of Ethylene with Polar Comonomers by Nickel Catalysts

“…Based on this catalytic system, they further reported a coherent study of insertion rate, insertion mode and copolymerization reaction on various fundamental polar monomers, affording directions to rationally design catalysts. The acrylic derivatives displayed higher reactivity than non-acrylic polar monomers in the order of MA > n-butyl acrylate (BA) > N,N-dimethylacrylamide (DMAA) > MMA > vinyl triethoxysilane (VTEOS) > N-vinyl-pyrrolidinone (NVP), and the electron-deficient acrylic derivatives prefer 2,1-fashion while the electron-rich vinyl polar monomers favor 1,2-insertion [110]. Instead of tuning steric bulk from the "P"-side, Theodor Agapie et al reported two neutral Ni(II) catalysts 19 (Figure 16) that displayed steric bulk on the "O"-side of the phosphino-phenoxide ligand as a rotationally flexible phosphine substituent (POP ligand 19a) and a rigid aryl derivative (PONap ligand, 19b) [111].…”

Phosphine–Imidate-Supported Nickel Catalysts for Ethylene/Acrylate Copolymerization

“…This has been the motivation for the significant growth in this area in recent years. As a result, several substantial improvements have been made in catalyst stability and copolymerization activity in the presence of a variety of polar functional groups. − ,− …”