Solid-Supported Single-Component Pd(II) Catalysts for Polar Monomer Insertion Copolymerization

Abstract

Heterogenized representatives of neutral phosphine sulfonato Pd(II) complexes for polar monomer insertion polymerization were prepared by two different approaches.[{κ 2 -(P,O)-(2-anisyl) 2 PC 6 H 4 SO 2 O}Pd(Me)L] (L = pyr, dmso, or Cl) complexes were physisorbed on inorganic substrates, namely, clay or silica. In addition, new phosphine sulfonato complexes bearing hydroxyl linker groups at the nonchelating P-aryl moiety were prepared. These complexes were covalently tethered to cross-linked polystyrene. All immobilized palladium complexes are active in ethylene polymerization and ethylene/MA copolymerization without any additional cocatalyst. In addition, separation from the polymer solution formed and reutilization for another polymerization were demonstrated for polystyrene-bound complexes.

Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers

“…[66] However,m echanistic studies and rational catalyst design are difficult because of their multisite nature.R ecently,t he heterogenization of early transition metal based catalysts for olefin polymerization were extensively studied, leading to the commercialization of many systems. In 2014, Mecking and co-workers reported the immobilization of phosphine-sulfonate palladium catalysts onto inorganic substrates and polystyrene, [69] and studied their properties in ethylene polymerization and copolymerization with methyl acrylate. In 2014, Mecking and co-workers reported the immobilization of phosphine-sulfonate palladium catalysts onto inorganic substrates and polystyrene, [69] and studied their properties in ethylene polymerization and copolymerization with methyl acrylate.…”

Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers

“…In contrast, the corresponding studies using late‐transition‐metal catalysts, especially for the purpose of polar monomer copolymerization, have remained largely unexplored. In 2014, Mecking and co‐workers reported the immobilization of phosphine‐sulfonate palladium catalysts onto inorganic substrates and polystyrene, and studied their properties in ethylene polymerization and copolymerization with methyl acrylate. Conely and co‐workers described the immobilization of α‐diimine nickel and palladium catalysts on sulfated zirconia, and studied their properties in ethylene polymerization and copolymerization with polar monomers .…”

Synthesis and Applications in Catalysis of Metal Complexes with Chelating Phosphinosulfonate Ligands

“…135 Copolymers with low CO content were recently prepared using 3a-H ligand. 137 81 Supported palladium(II) precatalyst on polystyrene, clay, or silica were synthesized from original phosphinosulfonates.…”