The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel ...The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts(Ni1: Ar = Ph;Ni2: Ar = 2-(C_(6)H_(5))C_(6)H_(4);Ni3: Ar = 2-[2',6'-(Me O)_(2)-C_(6)H3]C_(6)H_(4)) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities(up to 7.24×10^(6) and 9.04×10^(6)g·mol Ni^(-1)·h^(-1), respectively), and produced high-molecular-weight polyethylene(Mw up to 545.7 k Da). Complex Ni3 exhibited high activities for ethylene polymerization at the level of 10^(6) g·mol Ni^(-1)·h^(-1) across a wide range from 30 ℃ to 120 ℃, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights(Mw up to 80.5 k Da) and high polar monomer incorporation(up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.展开更多
1 Results Nanocomposite has attracted more and more interest all over the world.Polystyrene (PS) is a commercialized and mass-productive polymer,continuous research efforts have been devoted to the development of poly...1 Results Nanocomposite has attracted more and more interest all over the world.Polystyrene (PS) is a commercialized and mass-productive polymer,continuous research efforts have been devoted to the development of polystyrene/montmorillonite (PS/MMT) nanocomposites[1-2].But the polarity of styrene (St) is too small to intercalate the space between the clay layers.The polarity of hydrophilic monomer is so strong that it can intercalate the MMT easily,the intercalated smectic clays maybe exfoliated by usin...展开更多
基金financially supported by the National Natural Science Foundation of China (No. 52130307)。
文摘The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts(Ni1: Ar = Ph;Ni2: Ar = 2-(C_(6)H_(5))C_(6)H_(4);Ni3: Ar = 2-[2',6'-(Me O)_(2)-C_(6)H3]C_(6)H_(4)) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities(up to 7.24×10^(6) and 9.04×10^(6)g·mol Ni^(-1)·h^(-1), respectively), and produced high-molecular-weight polyethylene(Mw up to 545.7 k Da). Complex Ni3 exhibited high activities for ethylene polymerization at the level of 10^(6) g·mol Ni^(-1)·h^(-1) across a wide range from 30 ℃ to 120 ℃, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights(Mw up to 80.5 k Da) and high polar monomer incorporation(up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.
文摘1 Results Nanocomposite has attracted more and more interest all over the world.Polystyrene (PS) is a commercialized and mass-productive polymer,continuous research efforts have been devoted to the development of polystyrene/montmorillonite (PS/MMT) nanocomposites[1-2].But the polarity of styrene (St) is too small to intercalate the space between the clay layers.The polarity of hydrophilic monomer is so strong that it can intercalate the MMT easily,the intercalated smectic clays maybe exfoliated by usin...
