Bis(N-acylated imidazolin-2-imine) nickel catalyzed norbornene copolymerization with methyl acrylate

The incorporation of even a small number of polar functional groups in the polyolefin backbone is sufficient to improve the polyolefin properties. Compared with palladium catalyzed direct copolymerization of olefins with polar vinyl monomers, the development of low-cost nickel-based catalysts is more challenging because of their higher oxophilicity. On the basis of the advantage of reducing the electrophilicity of the nickel center by the installation of strongly electron-donating ligands, we herein report the synthesis of novel bis(N-acylated imidazolin-2-imine) nickel complexes for norbornene polymerization and copolymerization with polar monomers. Moreover, the phenyl substituent on the imidazoline ligand is expected to enhance the tolerance of the nickel catalyst toward polar functional groups, thus allowing the copolymerization of norbornene with commercial methyl acrylate to afford high molecular weight functionalized cyclic olefin copolymers (COCs) with moderate activity and reasonable comonomer content.

[1]  R. Xiao,et al.  Quinolinyl Imidazolidin-2-imine Nickel Catalyzed Efficient Copolymerization of Norbornene with para-Chlorostyrene , 2020, Chinese Journal of Polymer Science.

[2]  R. Xiao,et al.  Rational design of nickel catalysts containing N-acylated imidazolin-2-imine ligand for ethylene copolymerization with polar monomer , 2020 .

[3]  Changle Chen,et al.  Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers. , 2019, Angewandte Chemie.

[4]  Xiangyang Song,et al.  Optically Transparent Functional Polyolefin Elastomer with Excellent Mechanical and Thermal Properties. , 2019, ACS macro letters.

[5]  M. Eisen,et al.  Neutral Nickel(II) Complexes Bearing Aryloxide Imidazolin-2-imine Ligands for Efficient Copolymerization of Norbornene and Polar Monomers , 2018, Organometallics.

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

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

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

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

[10]  M. Eisen,et al.  Synthesis, Structures, and Norbornene Polymerization Behavior of Neutral Nickel(II) and Palladium(II) Complexes Bearing Aryloxide Imidazolidin-2-imine Ligands , 2018 .

[11]  S. Yang,et al.  Construction of Druglike 2-Amido Benzo[ d]imidazole Analogues via Desulfurative Cyclization of Thiourea Intermediate Resin on Solid-Phase. , 2018, ACS combinatorial science.

[12]  Marc D. H. Hansen,et al.  Pyridine-pyrimidine amides that prevent HGF-induced epithelial scattering by two distinct mechanisms. , 2017, Bioorganic & medicinal chemistry letters.

[13]  Zijie Wang,et al.  Copolymerization of norbornene and butyl methacrylate at elevated temperatures by a single centre nickel catalyst bearing bulky bis(α-diimine) ligand with strong electron-withdrawing groups , 2017 .

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

[15]  Xiangyang Song,et al.  Synthesis of Hydroxy-Functionalized Cyclic Olefin Copolymer and Its Block Copolymers with Semicrystalline Polyolefin Segments. , 2017, Macromolecular rapid communications.

[16]  Rolf Mülhaupt,et al.  From Multisite Polymerization Catalysis to Sustainable Materials and All-Polyolefin Composites. , 2016, Chemical reviews.

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

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

[19]  T. Shiono,et al.  Pseudo-living copolymerization of norbornene and ω-alkenylborane – Synthesis of monodisperse functionalized cycloolefin copolymer , 2015 .

[20]  S. Mecking,et al.  Post-metallocenes in the industrial production of polyolefins. , 2014, Angewandte Chemie.

[21]  C. D. Jones,et al.  Human Toll-Like Receptor 8-Selective Agonistic Activities in 1-Alkyl-1H-benzimidazol-2-amines , 2014, Journal of medicinal chemistry.

[22]  Jang-Woo Lee,et al.  Copolymerization of norbornene with ω‐alkenylaluminum as a precursor comonomer for introduction of carbonyl moieties , 2013 .

[23]  M. Sugimoto,et al.  Facile Synthesis of Hydroxy-Functionalized Cycloolefin Copolymer Using ω-Alkenylaluminium as a Comonomer , 2013 .

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

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

[26]  T. Shiono,et al.  Precise synthesis of olefin block copolymers using a syndiospecific living polymerization system , 2013, Chinese Journal of Polymer Science.

[27]  Takeshi Shiono,et al.  Living polymerization of olefins with ansa -dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts , 2011 .

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

[29]  Z. Hou,et al.  Organometallic catalysts for copolymerization of cyclic olefins , 2008 .

[30]  Jin-Yong Dong,et al.  Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry , 2006 .

[31]  Laura Boggioni,et al.  Metallocene catalyzed ethene- and propene co-norbornene polymerization: Mechanisms from a detailed microstructural analysis , 2006 .

[32]  Seunghwan Lee,et al.  Effects of tris(pentafluorophenyl)borane on the activation of zerovalent-nickel complex in the addition polymerization of norbornene , 2005 .

[33]  Robert A. Shick,et al.  Addition Polymerization of Norbornene-Type Monomers Using Neutral Nickel Complexes Containing Fluorinated Aryl Ligands , 2003 .

[34]  M. Brookhart,et al.  Late-metal catalysts for ethylene homo- and copolymerization. , 2000, Chemical reviews.

[35]  B. Novak,et al.  Copolymerization of polar monomers with olefins using transition-metal complexes. , 2000, Chemical reviews.

[36]  W. Kaminsky,et al.  New polymers by homogenous zirconocene/aluminoxane catalysts , 1991 .