Synthesis and characterization of poly(higher‐α‐olefin)s with a nickel(α‐diimine)/methylaluminoxane catalyst system: Effect of chain running on the polymer properties

Homopolymerization of octadecene-1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene-1 into a sterically hindered nickel-cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω-, 1,ω-enchainments) decreases with an increase in the carbon number of α-olefins.

[1]  H. Cramail,et al.  Polymerization of hex-1-ene initiated by diimine complexes of nickel and palladium , 2005 .

[2]  V. Busico,et al.  Reactivity of secondary metal-alkyls in catalytic propene polymerization: how dormant are "dormant chains"? , 2005, Journal of the American Chemical Society.

[3]  Y. Akpalu,et al.  PROBING THE MELTING BEHAVIOR OF A HOMOGENEOUS ETHYLENE/1-HEXENE COPOLYMER BY SMALL-ANGLE LIGHT SCATTERING , 2004 .

[4]  C. Landis,et al.  Reactivity of secondary metallocene alkyls and the question of dormant sites in catalytic alkene polymerization. , 2004, Journal of the American Chemical Society.

[5]  S. Sivaram,et al.  A study of the structure of poly(hexene-1) prepared by nickel(α-diimine)/MAO catalyst using high resolution NMR spectroscopy , 2004 .

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

[7]  R. Waymouth,et al.  Control of Sequence Distribution of Ethylene Copolymers: Influence of Comonomer Sequence on the Melting Behavior of Ethylene Copolymers , 2003 .

[8]  G. Guerra,et al.  Influence of regio- and stereoregularity of propene insertion on crystallization behavior and elasticity of ethene-propene copolymers. , 2002, Journal of the American Chemical Society.

[9]  Naofumi Naga,et al.  Recent developments in olefin polymerizations with transition metal catalysts , 2001 .

[10]  J. Soares,et al.  Effect of molecular structure on dynamic mechanical properties of polyethylene obtained with nickel–diimine catalysts , 2001 .

[11]  V. Busico,et al.  Microstructure of polypropylene , 2001 .

[12]  R. Fusco,et al.  Syndiotactic polymerization of propylene : Single-site vanadium catalysts in comparison with zirconium and nickel , 2001 .

[13]  S. Mecking Olefin Polymerization by Late Transition Metal Complexes-A Root of Ziegler Catalysts Gains New Ground. , 2001, Angewandte Chemie.

[14]  D. J. Tempel,et al.  13C and 2D NMR Analysis of Propylene Polymers Made with α-Diimine Late Metal Catalysts† , 2001 .

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

[16]  L. Cavallo,et al.  Selectivity in propene polymerization with metallocene catalysts. , 2000, Chemical reviews.

[17]  R. Mülhaupt,et al.  Short and long chain branching of polyethene prepared by means of ethene copolymerization with 1‐eicosene using MAO activated Me2Si(Me4Cp)(NtBu)TiCl2 , 2000 .

[18]  R. Mülhaupt,et al.  Influence of n-Alkyl Branches on Glass-Transition Temperatures of Branched Polyethylenes Prepared by Means of Metallocene- and Palladium-Based Catalysts , 2000 .

[19]  B. Crist,et al.  Isothermal crystallization of Random ethylene-butene copolymers : Bimodal kinetics , 1999 .

[20]  A. Alizadeh,et al.  Influence of Structural and Topological Constraints on the Crystallization and Melting Behavior of Polymers. 1. Ethylene/1-Octene Copolymers† , 1999 .

[21]  G. Guerra,et al.  Pseudohexagonal crystallinity and thermal and tensile properties of ethene-propene copolymers , 1999 .

[22]  McLain,et al.  Chain walking: A new strategy to control polymer topology , 1999, Science.

[23]  G. Talarico,et al.  Highly Regioselective Transition-Metal-Catalyzed 1-Alkene Polymerizations: A Simple Method for the Detection and Precise Determination of Regioirregular Monomer Enchainments , 1998 .

[24]  M. Arnold,et al.  Poly-α-Olefins from Polypropene to Poly-1-eicosene Made with Metallocene Catalysts , 1998 .

[25]  R. Mülhaupt,et al.  New molecular and supermolecular polymer architecturesvia transition metal catalyzed alkene polymerization , 1998 .

[26]  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 .

[27]  F. Auriemma,et al.  Molecular Organization in the Pseudo-hexagonal Crystalline Phase of Ethylene−Propylene Copolymers , 1996 .

[28]  David Fischer,et al.  Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts , 1995 .

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

[30]  Klaus Angermund,et al.  Struktur der aktiven Spezies und Erklärung des Wanderungsmechanismus bei der 2,ω‐polymerisation von α‐olefinen , 1995 .

[31]  V. Busico,et al.  Effects of regiochemical and stereochemical errors on the course of isotactic propene polyinsertion promoted by homogeneous Ziegler-Natta catalysts , 1994 .

[32]  L. Chien,et al.  Photo-Cross-Linkable and Optically Active Side-Chain Liquid-Crystalline Copolymers , 1994 .

[33]  R. Alamo,et al.  The crystallization behavior of random copolymers of ethylene , 1994 .

[34]  J. Chien,et al.  Microstructure of poly(1-hexene) produced by ansa-zirconocenium catalysis , 1994 .

[35]  R. Alamo,et al.  Crystallization kinetics of random ethylene copolymers , 1991 .

[36]  J. Ewen,et al.  13C Nuclear magnetic resonance characterization of poly(propylene) prepared with homogeneous catalysts , 1989 .

[37]  A. Grassi,et al.  Microstructure of isotactic polypropylene prepared with homogeneous catalysis: stereoregularity, regioregularity, and 1,3 insertion , 1988 .

[38]  I. R. Peat,et al.  Melting points of homogeneous random copolymers of ethylene and 1‐alkenes , 1987 .

[39]  W. Kaminsky,et al.  Isotactic polymerization of propene with (η-1,1'-ethylenedi-4,5,6,7-tetrahydroindenyl) zirconium dichloride combined with methylaluminoxane , 1987 .

[40]  Y. Doi,et al.  Carbon-13 NMR chemical shift of regioirregular polypropylene , 1987 .

[41]  M. Demura,et al.  Polymerization mechanism and conformation of poly(1-butene) , 1987 .

[42]  Thomas Taylor,et al.  Dynamic mechanical relaxations in polyethylene , 1985 .

[43]  G. Fink,et al.  Novel Polymerization of α‐Olefins with the Catalyst System Nickel/Aminobis(imino)phosphorane , 1985 .

[44]  R. Alamo,et al.  Thermodynamic and structural properties of copolymers of ethylene , 1984 .

[45]  R. Benson,et al.  Dynamic mechanical studies of α and β relaxations of polyethylenes , 1984 .

[46]  F. Bovey,et al.  Model Compounds and13C NMR Observation of Stereosequences of Polypropylene , 1975 .

[47]  C. J. Carman,et al.  Carbon-13 Magnetic Resonance of Some Branched Alkanes , 1973 .

[48]  Kenzo Shirayama,et al.  Effects of branching on some properties of ethylene/α‐olefin copolymers , 1972 .

[49]  G. Fagherazzi,et al.  Crystallization of high ethylene EPDM terpolymers in the stretched state , 1970 .

[50]  N. G. Mccrum,et al.  Origin of the γ relaxations in polyethylene and polytetrafluoroethylene , 1969 .