Vinyl polymerization of norbornene by mono‐ and trinuclear nickel complexes with indanimine ligands

A series of new indanimine ligands [ArNCC2H3(CH3)C6H2(R)OH] (Ar = Ph, R = Me (1), R = H (2), and R = Cl (3); Ar = 2,6-i-Pr2C6H3, R = Me (4), R = H (5), and R = Cl (6)) were synthesized and characterized. Reaction of indanimines with Ni(OAc)2·4H2O results in the formation of the trinuclear hexa(indaniminato)tri (nickel(II)) complexes Ni3[ArN = CC2H3(CH3)C6H2(R)O]6 (Ar = Ph, R = Me (7), R = H (8), and R = Cl (9)) and the mononuclear bis(indaniminato)nickel (II) complexes Ni[ArNCC2H3(CH3)C6H2(R)O]2 (Ar = 2,6-i-Pr2C6H3, R = Me (10), R = H (11), and R = Cl (12)). All nickel complexes were characterized by their IR, NMR spectra, and elemental analyses. In addition, X-ray structure analyses were performed for complexes 7, 10, 11, and 12. After being activated with methylaluminoxane (MAO), these nickel(II) complexes can polymerize norbornene to produce addition-type polynorbornene (PNB) with high molecular weight Mv (106 g mol−1), highly catalytic activities up to 2.18 × 107 gPNB mol−1 Ni h−1. Catalytic activities and the molecular weight of PNB have been investigated for various reaction conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 489–500, 2008

[1]  Wen‐Hua Sun,et al.  Highly active ethylene polymerization and copolymerization with norbornene using bis(imino-indolide) titanium dichloride-MAO system , 2007 .

[2]  Y. Chung,et al.  Polymerization of carboxylic ester functionalized norbornenes catalyzed by (η3‐allyl)palladium complexes bearing N‐heterocyclic carbene ligands , 2007 .

[3]  Y. Tsunogae,et al.  Synthesis and characterization of norbornene–ethylene–styrene terpolymers with a substituted ansa-fluorenylamidodimethyltitanium-based catalyst , 2007 .

[4]  Qing Wu,et al.  Copolymerization of norbornene and styrene catalyzed by a novel anilido–imino nickel complex/methylaluminoxane system , 2006 .

[5]  F. Marchetti,et al.  Vinyl Polymerization of Norbornene by Bis(salicylaldiminate)copper(II)/Methylalumoxane Catalysts , 2006 .

[6]  G. Jin,et al.  Synthesis, molecular structure and norbornene polymerization behavior of three-coordinate nickel(I) complexes with chelating anilido-imine ligands. , 2006, Dalton transactions.

[7]  Li-Ming Tang,et al.  Syntheses, structure and ethylene polymerization behavior of β-diiminato titanium complexes , 2006 .

[8]  Jun Zhang,et al.  Nickel (II) complexes with β-enaminoketonato chelate ligands: Synthesis, solid-structure characterization and reactivity toward the addition polymerization of norbornene , 2006 .

[9]  C. Janiak,et al.  Metal Complexes for the Vinyl Addition Polymerization of Norbornene: New Compound Classes and Activation Mechanism with B(C6F5)3/AlEt3 , 2006 .

[10]  A. R. Galletti,et al.  Vinyl polymerization of norbornene by bis(nitro-substituted-salicylaldiminate)nickel(II)/methylaluminoxane catalysts , 2006 .

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

[12]  Feng Bao,et al.  Vinylic and ring‐opening metathesis polymerization of norbornene with bis(β‐ketoamine) cobalt complexes , 2005 .

[13]  G. Jin,et al.  Nanofibers of polyethylene produced by SBA-15 supported zirconium catalyst [N-(3-tert-butylsalicylidene)-4′-allyloxylanilinato]2Zr(IV)Cl2 , 2005 .

[14]  David J. Williams,et al.  Discovery and optimization of new chromium catalysts for ethylene oligomerization and polymerization aided by high-throughput screening. , 2005, Journal of the American Chemical Society.

[15]  David J. Jones,et al.  Experimental evidence for large ring metallacycle intermediates in polyethylene chain growth using homogeneous chromium catalysts. , 2005, Journal of the American Chemical Society.

[16]  C. Ha,et al.  Ethylene oligomerizations to low-carbon linear α-olefins by structure modulated phenoxy-imine nickel(II) complexes combined with aluminum sesquichloride , 2005 .

[17]  G. Jin,et al.  Highly Active Neutral Nickel(II) Complexes Bearing P,N‐Chelate Ligands: Synthesis, Characterization and Their Application to Addition Polymerization of Norbornene , 2005 .

[18]  G. Coates,et al.  New phenoxyketimine titanium complexes: combining isotacticity and living behavior in propylene polymerization. , 2004, Journal of the American Chemical Society.

[19]  G. Coates,et al.  Gel permeation chromatography as a combinatorial screening method: identification of highly active heteroligated phenoxyimine polymerization catalysts. , 2004, Journal of the American Chemical Society.

[20]  L. Weng,et al.  Synthesis, Molecular Structures, and Norbornene Addition Polymerization Activity of the Neutral Nickel Catalysts Supported by β-Diketiminato [N, N], Ketiminato [N, O], and Schiff-Base [N, O] Ligands⊥ , 2004 .

[21]  G. Jin,et al.  Self-immobilized titanium and zirconium catalysts with phenoxy-imine ligands for ethylene polymerization. X-ray crystal structure of bis(N-(3-tert-butylsalicylidene)-4'-allyloxyanilinato) zirconium (IV) dichloride , 2004 .

[22]  G. Jin,et al.  Micron‐granula polyolefin with self‐immobilized nickel and iron diimine catalysts bearing one or two allyl groups , 2004 .

[23]  R. Grubbs,et al.  Synthesis of neutral nickel catalysts for ethylene polymerization--the influence of ligand size on catalyst stability. , 2003, Chemical communications.

[24]  S. Rucker,et al.  Vinyl-type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts , 2003 .

[25]  A. R. Galletti,et al.  Highly active methyl methacrylate polymerization catalysts obtained from bis(3,5-dinitro-salicylaldiminate)nickel(II) complexes and methylaluminoxane , 2003 .

[26]  Zhi Ma,et al.  Vinyl polymerization of norbornene with dinuclear diimine nickel dichloride/MAO , 2003 .

[27]  T. Nakano,et al.  Unprecedented living olefin polymerization derived from an attractive interaction between a ligand and a growing polymer chain. , 2003, Chemistry.

[28]  G. Jin,et al.  Ethylene Polymerization by Self-Immobilized Neutral Nickel Catalysts Bearing Allyl Groups , 2003 .

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

[30]  H. Terao,et al.  Syndiospecific living propylene polymerization catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands. , 2003, Journal of the American Chemical Society.

[31]  V. C. Gibson,et al.  Advances in non-metallocene olefin polymerization catalysis. , 2003, Chemical reviews.

[32]  C. Janiak,et al.  Nickel(II) and palladium(II) complexes with α‐dioxime ligands as catalysts for the vinyl polymerization of norbornene in combination with methylaluminoxane, tris(pentafluorophenyl)borane, or triethylaluminum cocatalyst systems , 2002 .

[33]  G. Coates,et al.  Insertion/isomerization polymerization of 1,5-hexadiene: synthesis of functional propylene copolymers and block copolymers. , 2002, Journal of the American Chemical Society.

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

[35]  Yue-sheng Li,et al.  Vinylic polymerization of norbornene by neutral nickel(II)‐based catalysts , 2002 .

[36]  A. R. Galletti,et al.  Ethylene oligomerization by novel catalysts based on bis(salicylaldiminate)nickel(II) complexes and organoaluminum co-catalysts , 2002 .

[37]  G. Jin,et al.  Self-immobilized catalysts for ethylene polymerization: neutral, single-component salicylaldiminato phenyl nickel(II) complexes bearing allyl substituents. , 2002, Chemical communications.

[38]  T. Nakano,et al.  Living polymerization of ethylene catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands. , 2002, Journal of the American Chemical Society.

[39]  C. Janiak,et al.  Borane activators for late-transition metal catalysts in norbornene polymerization , 2002 .

[40]  T. Nakano,et al.  A Family of Zirconium Complexes Having Two Phenoxy−Imine Chelate Ligands for Olefin Polymerization , 2001 .

[41]  A. R. Galletti,et al.  Homopolymerization of methyl methacrylate by novel Ziegler-Natta-type catalysts based on bis(chelate)-nickel(II) complexes and methylaluminoxane , 2001 .

[42]  S. Losio,et al.  Vinylic Polymerization of Norbornene by Late Transition Metal‐Based Catalysis , 2001 .

[43]  G. Coates,et al.  A new catalyst for highly syndiospecific living olefin polymerization: homopolymers and block copolymers from ethylene and propylene. , 2001, Journal of the American Chemical Society.

[44]  C. Janiak,et al.  The Vinyl Homopolymerization of Norbornene , 2001 .

[45]  V. S. Subrahmanyam,et al.  Structural characteristics and gas permeation properties of polynorbornenes with retained bicyclic structure , 2001 .

[46]  C. Janiak,et al.  Metal catalysts for the vinyl polymerization of norbornene , 2001 .

[47]  Tian,et al.  Development of a Diversity-Based Approach for the Discovery of Stereoselective Polymerization Catalysts: Identification of a Catalyst for the Synthesis of Syndiotactic Polypropylene This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineer , 2000, Angewandte Chemie.

[48]  W. M. Davis,et al.  Synthesis of Titanium, Zirconium, and Hafnium Complexes That Contain the [(MesitylN-o-C6H4)2O]2-Ligand , 2000 .

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

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

[51]  Steven J Brown,et al.  REMARKABLY ACTIVE NON-METALLOCENE ETHYLENE POLYMERIZATION CATALYSTS , 1999 .

[52]  A. Greiner,et al.  Vinyl-type polymerization of norbornene by a nickel-based catalyst with phosphoraneiminato ligands , 1999 .

[53]  G. Britovsek,et al.  The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes. , 1999, Angewandte Chemie.

[54]  M. Arndt,et al.  Transition metal catalyzed polymerisation of norbornene , 1998 .

[55]  R. Grubbs,et al.  Neutral Nickel(II)-Based Catalysts for Ethylene Polymerization , 1998 .

[56]  Maurice Brookhart,et al.  Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene , 1998 .

[57]  S. Mecking,et al.  Mechanistic Studies of the Palladium-Catalyzed Copolymerization of Ethylene and α-Olefins with Methyl Acrylate , 1998 .

[58]  W. M. Davis,et al.  Synthesis of group 4 complexes that contain the tridentate diamido ligands [(ArNCH2CH2)2O]2– (Ar = C6H3-Me2-2,6 or C6H3Pri2-2,6) , 1998 .

[59]  M. L. Hallensleben,et al.  Hydroxyindanone based polymers, 1 Synthesis of monomers, their complexing and polymerisation behaviour , 1998 .

[60]  Andrew J. P. White,et al.  Novel olefin polymerization catalysts based on iron and cobalt , 1998 .

[61]  J. Vittal,et al.  Bulky Chelating Diamide Complexes of Zirconium: Synthesis, Structure, and Reactivity of d0 Alkyl Derivatives , 1997 .

[62]  M. Maskos,et al.  Vinylic polymerization of norbornene by Pd(II)‐catalysis in the presence of ethylene , 1997 .

[63]  D. J. Tempel,et al.  Living Polymerization of α-Olefins Using NiII−α-Diimine Catalysts. Synthesis of New Block Polymers Based on α-Olefins , 1996 .

[64]  J. Wendorff,et al.  Polynorbornene: synthesis, properties and simulations , 1996 .

[65]  D. H. Mcconville,et al.  Polymerization of α-olefins by chelating diamide complexes of titanium , 1996 .

[66]  W. M. Davis,et al.  Synthesis of Group 4 Organometallic Complexes That Contain the Bis(borylamide) Ligand [Mes2BNCH2CH2NBMes2]2- , 1996 .

[67]  S. Mecking,et al.  Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II) Catalysts , 1996 .

[68]  W. Kaminsky,et al.  Hydrooligomerization of cycloolefins -a view of the microstructure of polynorbornene , 1995 .

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

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

[71]  S. Yamada,et al.  Stereochemistry of bis(N-(2,6-diisopropylphenyl)salicylideneaminato)copper(II) and nickel(II) complexes. , 1982 .

[72]  J. Chupp,et al.  Ketimine syntheses. Use of titanium tetrachloride in a new procedure for their preparation , 1967 .

[73]  H. Weingarten,et al.  A versatile new enamine synthesis , 1967 .

[74]  J. Kennedy,et al.  Carbonium Ion Polymerization of Norbornene and Its Derivatives , 1967 .

[75]  T. Saegusa,et al.  Polymerization of norbornene by modified Ziegler‐catalysts , 1965 .

[76]  R. H. Holm,et al.  Studies on Nickel(II)Complexes. IV. Bis-(N-sec-alkylsalicylaldimine) Complexes: Conformational Equilibria in Solution , 1963 .

[77]  R. H. Thomson,et al.  315. peri-Hydroxy-carbonyl compounds. Part I. The synthesis of peri-hydroxy-indanones, -tetralones, and -benzocycloheptenones , 1956 .