High-Performance Neutral Phosphine-Sulfonate Nickel(II) Catalysts for Efficient Ethylene Polymerization and Copolymerization with Polar Monomers

Low-cost and earth-abundant nickel catalysts are of great interest for olefin copolymerization with polar monomers to generate highly desirable functionalized polyolefins. However, nickel catalysts usually suffer from poor thermal stability and low copolymer molecular weight. In this work, by combination of design strategies of sterics and electronics, a family of sterically demanding aliphatic/aromatic-substituted phosphine-sulfonate neutral nickel complexes 1–4 {[κ2(P,O)-(menthyl)ArP(C6H4SO2O)]NiMe(pyr)} (1: Ar = (MeO)3C6H2; 2: Ar = 2-(2′,6′-(MeO)2C6H3)C6H4; 3: Ar = 2-(C6H5)C6H4; 4: Ar = 2-(2′,6′-F2C6H3)C6H4) with different sterics and electronics were synthesized and fully characterized by comprehensive NMR spectroscopy, single-crystal X-ray diffraction, and elemental analysis. Among these nickel catalysts, catalysts 1 and 4 are in favor of generating polyethylenes with high molecular weights (up to 224.0 kg mol–1) in high activities (up to 1.6 × 106 g mol–1 h–1) and good thermal stabilities (up to 90 ...

[1]  Jiaxin Gao,et al.  Sterics versus electronics: Imine/phosphine-oxide-based nickel catalysts for ethylene polymerization and copolymerization , 2019, Journal of Catalysis.

[2]  Xuequan Zhang,et al.  Structurally simple dinuclear nickel catalyzed olefin copolymerization with polar monomers , 2018, Journal of Catalysis.

[3]  T. Liang,et al.  Position Makes the Difference: Electronic Effects in Nickel-Catalyzed Ethylene Polymerizations and Copolymerizations. , 2018, Inorganic chemistry.

[4]  M. Brookhart,et al.  Exploring Ethylene/Polar Vinyl Monomer Copolymerizations Using Ni and Pd α-Diimine Catalysts. , 2018, Accounts of chemical research.

[5]  Yue-sheng Li,et al.  Robust Bulky [P,O] Neutral Nickel Catalysts for Copolymerization of Ethylene with Polar Vinyl Monomers , 2018 .

[6]  Changle Chen.  Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning , 2018, Nature Reviews Chemistry.

[7]  Changle Chen,et al.  A Versatile Ligand Platform for Palladium- and Nickel-Catalyzed Ethylene Copolymerization with Polar Monomers. , 2018, Angewandte Chemie.

[8]  K. Nozaki,et al.  Nickel-Catalyzed Propylene/Polar Monomer Copolymerization. , 2018, ACS macro letters.

[9]  Changle Chen,et al.  Ethylene Polymerization and Copolymerization Using Nickel 2-Iminopyridine-N-oxide Catalysts: Modulation of Polymer Molecular Weights and Molecular-Weight Distributions , 2018 .

[10]  T. Shiono,et al.  Highly Robust Nickel Catalysts Containing Anilinonaphthoquinone Ligand for Copolymerization of Ethylene and Polar Monomers , 2017 .

[11]  Changle Chen,et al.  Influence of Polyethylene Glycol Unit on Palladium- and Nickel-Catalyzed Ethylene Polymerization and Copolymerization. , 2017, Angewandte Chemie.

[12]  O. Daugulis,et al.  Nickel-Catalyzed Copolymerization of Ethylene and Vinyltrialkoxysilanes: Catalytic Production of Cross-Linkable Polyethylene and Elucidation of the Chain-Growth Mechanism. , 2017, Journal of the American Chemical Society.

[13]  Yi Luo,et al.  A Second-Coordination-Sphere Strategy to Modulate Nickel- and Palladium-Catalyzed Olefin Polymerization and Copolymerization. , 2017, Angewandte Chemie.

[14]  T. Liang,et al.  Side-Arm Control in Phosphine-Sulfonate Palladium- and Nickel-Catalyzed Ethylene Polymerization and Copolymerization , 2017 .

[15]  Zixia Wu,et al.  Influence of Ligand Backbone Structure and Connectivity on the Properties of Phosphine-Sulfonate Pd(II)/Ni(II) Catalysts , 2017, Polymers.

[16]  Guodong Liang,et al.  Enhancing Thermal Stability and Living Fashion in α-Diimine–Nickel-Catalyzed (Co)polymerization of Ethylene and Polar Monomer by Increasing the Steric Bulk of Ligand Backbone , 2017 .

[17]  Yun-peng Zhu,et al.  Dinuclear α‐Diimine NiII and PdII Complexes that Catalyze Ethylene Polymerization and Copolymerization , 2017 .

[18]  Y. Oishi,et al.  Nickel Catalyzed Copolymerization of Ethylene and Alkyl Acrylates. , 2017, Journal of the American Chemical Society.

[19]  R. F. Jordan,et al.  Olefin Insertion into a Pd-F Bond: Catalyst Reactivation Following β-F Elimination in Ethylene/Vinyl Fluoride Copolymerization. , 2017, Angewandte Chemie.

[20]  Changle Chen,et al.  Rational Design of High-Performance Phosphine Sulfonate Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers , 2017 .

[21]  Yuguo Ma,et al.  Ethylene (Co)polymerization by Binuclear Nickel Phenoxyiminato Catalysts with Cofacial Orientation , 2016 .

[22]  K. Morokuma,et al.  Elucidating the Key Role of Phosphine−Sulfonate Ligands in Palladium-Catalyzed Ethylene Polymerization: Effect of Ligand Structure on the Molecular Weight and Linearity of Polyethylene , 2016 .

[23]  S. Mecking,et al.  Insertion Polymerization of Divinyl Formal , 2016 .

[24]  G. Coates,et al.  Semi-Crystalline Polar Polyethylene: Ester-Functionalized Linear Polyolefins Enabled by a Functional-Group-Tolerant, Cationic Nickel Catalyst. , 2016, Angewandte Chemie.

[25]  Changle Chen,et al.  Influence of Backbone Substituents on the Ethylene (Co)polymerization Properties of α-diimine Pd(II) and Ni(II) Catalysts , 2016 .

[26]  Zixia Wu,et al.  Ethylene Polymerization and Copolymerization by Palladium and Nickel Catalysts Containing Naphthalene-Bridged Phosphine–Sulfonate Ligands , 2016 .

[27]  K. Nozaki,et al.  Copolymerization of Ethylene and Polar Monomers by Using Ni/IzQO Catalysts. , 2016, Angewandte Chemie.

[28]  Lihua Guo,et al.  Palladium and Nickel Catalyzed Chain Walking Olefin Polymerization and Copolymerization , 2016 .

[29]  S. Mecking,et al.  Insertion Homo- and Copolymerization of Diallyl Ether. , 2015, Angewandte Chemie.

[30]  Yue-sheng Li,et al.  Neutral Nickel Catalysts for Olefin Homo- and Copolymerization: Relationships between Catalyst Structures and Catalytic Properties. , 2015, Chemical reviews.

[31]  S. Mecking,et al.  Suppression of chain transfer in catalytic acrylate polymerization via rapid and selective secondary insertion. , 2015, Journal of the American Chemical Society.

[32]  B. Rieger,et al.  Copolymerization of Ethylene and 3,3,3-Trifluoropropene Using (Phosphine-sulfonate)Pd(Me)(DMSO) as Catalyst. , 2014, ACS macro letters.

[33]  K. Nozaki,et al.  Transition-Metal-Catalyzed Functional Polyolefin Synthesis: Effecting Control through Chelating Ancillary Ligand Design and Mechanistic Insights , 2014 .

[34]  T. Marks,et al.  Ni(II) Phenoxyiminato Olefin Polymerization Catalysis: Striking Coordinative Modulation of Hyperbranched Polymer Microstructure and Stability by a Proximate Sulfonyl Group , 2014 .

[35]  K. Osakada,et al.  Double-decker-type dinuclear nickel catalyst for olefin polymerization: efficient incorporation of functional co-monomers. , 2013, Angewandte Chemie.

[36]  Peng Xiang,et al.  Designing polyethylenes of complex chain architectures via Pd-diimine-catalyzed "living" ethylene polymerization. , 2013, Chemical communications.

[37]  Nicole M. G. Franssen,et al.  Synthesis of functional 'polyolefins': state of the art and remaining challenges. , 2013, Chemical Society reviews.

[38]  S. Mecking,et al.  Incorporation of vinyl chloride in insertion polymerization. , 2013, Angewandte Chemie.

[39]  Ayusman Sen,et al.  Ortho-phosphinobenzenesulfonate: a superb ligand for palladium-catalyzed coordination-insertion copolymerization of polar vinyl monomers. , 2013, Accounts of chemical research.

[40]  T. Agapie,et al.  Bimetallic coordination insertion polymerization of unprotected polar monomers: copolymerization of amino olefins and ethylene by dinickel bisphenoxyiminato catalysts. , 2013, Journal of the American Chemical Society.

[41]  Y. Ota,et al.  Ethylene/allyl monomer cooligomerization by nickel/phosphine-sulfonate catalysts. , 2012, Dalton transactions.

[42]  Qing Wu,et al.  A thermally robust amine-imine nickel catalyst precursor for living polymerization of ethylene above room temperature. , 2012, Chemical communications.

[43]  S. Mecking,et al.  Mechanistic insights into polar monomer insertion polymerization from acrylamides. , 2012, Journal of the American Chemical Society.

[44]  Guang Wu,et al.  Linear, high molecular weight polyethylene from a discrete, mononuclear phosphinoarenesulfonate complex of nickel(II). , 2011, Chemical communications.

[45]  K. Nozaki,et al.  Coordination-insertion copolymerization of allyl monomers with ethylene. , 2011, Journal of the American Chemical Society.

[46]  S. Mecking,et al.  Direct synthesis of ethylene-acrylic acid copolymers by insertion polymerization. , 2010, Journal of the American Chemical Society.

[47]  R. F. Jordan,et al.  Copolymerization of Ethylene and Vinyl Fluoride by (Phosphine-bis(arenesulfonate))PdMe(pyridine) Catalysts: Insights into Inhibition Mechanisms , 2010 .

[48]  H. Möller,et al.  Noncovalent Interactions in o-Fluorinated Post-titanocene Living Ethylene Polymerization Catalyst , 2010 .

[49]  K. Nozaki,et al.  Coordination-insertion copolymerization of fundamental polar monomers. , 2009, Chemical reviews.

[50]  K. Nozaki,et al.  Copolymerization of vinyl acetate with ethylene by palladium/alkylphosphine-sulfonate catalysts. , 2009, Journal of the American Chemical Society.

[51]  K. Morokuma,et al.  Mechanistic studies on the formation of linear polyethylene chain catalyzed by palladium phosphine-sulfonate complexes: experiment and theoretical studies. , 2009, Journal of the American Chemical Society.

[52]  Z. Guan,et al.  Nickel(II) and Palladium(II) Polymerization Catalysts Bearing a Fluorinated Cyclophane Ligand: Stabilization of the Reactive Intermediate(1) , 2009 .

[53]  Philipp Roesle,et al.  Insertion polymerization of acrylate. , 2009, Journal of the American Chemical Society.

[54]  S. Mecking,et al.  Control of molecular weight in Ni(II)-catalyzed polymerization via the reaction medium. , 2008, Chemical communications.

[55]  Xiaoyuan Zhou,et al.  Base-Free Phosphine−Sulfonate Nickel Benzyl Complexes , 2008 .

[56]  R. F. Jordan,et al.  Copolymerization of ethylene and vinyl fluoride by (phosphine-sulfonate)Pd(Me)(py) catalysts. , 2007, Journal of the American Chemical Society.

[57]  I. Novák,et al.  Study of surface and adhesive properties of polypropylene grafted by maleic anhydride , 2007 .

[58]  J. Vela,et al.  Copolymerization of ethylene and alkyl vinyl ethers by a (phosphine- sulfonate)PdMe catalyst. , 2007, Journal of the American Chemical Society.

[59]  K. Nozaki,et al.  Formation of linear copolymers of ethylene and acrylonitrile catalyzed by phosphine sulfonate palladium complexes. , 2007, Journal of the American Chemical Society.

[60]  M. Hillmyer,et al.  Post-polymerization functionalization of polyolefins. , 2005, Chemical Society reviews.

[61]  R. Grubbs,et al.  Insights into the Deactivation of Neutral Nickel Ethylene Polymerization Catalysts in the Presence of Functionalized Olefins , 2004 .

[62]  W. G. Marshall,et al.  Copolymerization of Ethylene and Acrylates by Nickel Catalysts , 2003 .

[63]  Amy C. Gottfried,et al.  Living and Block Copolymerization of Ethylene and α-Olefins Using Palladium(II)−α-Diimine Catalysts , 2003 .

[64]  R. Grubbs,et al.  Linear functionalized polyethylene prepared with highly active neutral Ni(II) complexes , 2002 .

[65]  V. C. Gibson,et al.  Functionalized polyolefin synthesis using [P,O]Ni catalysts. , 2001, Chemical communications.

[66]  Amy C. Gottfried,et al.  Living Polymerization of Ethylene Using Pd(II) α-Diimine Catalysts , 2001 .

[67]  Friedrich,et al.  Neutral, single-component nickel (II) polyolefin catalysts that tolerate heteroatoms , 2000, Science.

[68]  L. Cavallo,et al.  The Role of Bulky Substituents in Brookhart-Type Ni(II) Diimine Catalyzed Olefin Polymerization: A Combined Density Functional Theory and Molecular Mechanics Study , 1997 .

[69]  Maurice Brookhart,et al.  New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins , 1995 .

[70]  S. D. Ittel,et al.  Nickel catalysis for ethylene homo- and co-polymerization , 1987 .