Introduction of reactive functionality by the incorporation of divinylbiphenyl in ethylene copolymerization with styrene or 1‐hexene using aryloxo‐modified half‐titanocenes and MAO catalysts

An efficient introduction of vinyl group into poly (ethylene-co-styrene) or poly(ethylene-co−1-hexene) has been achieved by the incorporation of 3,3′-divinylbiphenyl (DVBP) in terpolymerization of ethylene, styrene, or 1-hexene with DVBP using aryloxo-modified half-titanocenes, Cp′TiCl2(O−2,6-iPr2C6H3) [Cp′ = Cp*, tBuC5H4, 1,2,4-Me3C5H2], in the presence of MAO cocatalyst, affording high-molecular-weight polymers with unimodal distributions. Efficient comonomer incorporations have been achieved by these catalysts, and the content of each comonomer could be varied by its initial concentration charged. The postpolymerization of styrene was initiated from the vinyl group remained in the side chain by treatment with n-BuLi. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2581–2587

[1]  Dong-Hyun Kim,et al.  Synthesis and structural analysis of phenoxy-substituted half-titanocenes with different anionic ligands, Cp*TiX(Y)(O-2,6-iPr2C6H3): Effect of anionic ligands (X,Y) in ethylene/styrene copolymerization , 2012 .

[2]  Dong-Hyun Kim,et al.  Effect of Cocatalyst in Ethylene/Styrene Copolymerization by Aryloxo‐Modified Half‐Titanocene–Cocatalyst Systems for Exclusive Synthesis of Copolymers at High Styrene Concentrations , 2012 .

[3]  T. C. Mike Chung,et al.  Functionalization of Polypropylene with High Dielectric Properties: Applications in Electric Energy Storage , 2012 .

[4]  Jingyu Liu,et al.  Half-titanocenes for precise olefin polymerisation: effects of ligand substituents and some mechanistic aspects. , 2011, Dalton transactions.

[5]  K. Nomura New Approaches in Precise Synthesis of Polyolefins Containing Polar Functionalities by Olefin Copolymerizations Using Transition Metal Catalysts , 2010 .

[6]  K. Nomura,et al.  Efficient Synthesis of Functionalized Polyolefin by Incorporation of 4-Vinylcyclohexene in Ethylene Copolymerization Using Half-Titanocene Catalysts , 2009 .

[7]  M. Fujiki,et al.  Copolymerization of Ethylene with α - Olefins Containing Various Substituents Catalyzed by Half-Titanocenes: Factors Affecting the Monomer Reactivities , 2009 .

[8]  T. Chung,et al.  Cross-Linked Polypropylene Prepared by PP Copolymers Containing Flexible Styrene Groups , 2009 .

[9]  Kotohiro Nomura and Boonyarach Kitiyanan Recent Progress in Precise Synthesis of Polyolefins Containing Polar Functionalities by Transition Metal Catalysis , 2008 .

[10]  M. Fujiki,et al.  Facile, efficient functionalization of polyolefins via controlled incorporation of terminal olefins by repeated 1,7-octadiene insertion. , 2007, Journal of the American Chemical Society.

[11]  Jesús Cano,et al.  How to synthesize a constrained geometry catalyst (CGC) – A survey , 2007 .

[12]  M. Fujiki,et al.  Effect of Cyclopentadienyl and Anionic Donor Ligands on Monomer Reactivities in Copolymerization of Ethylene with 2-Methyl-1-pentene by Nonbridged Half-Titanocenes−Cocatalyst Systems , 2007 .

[13]  Boonyarach Kitiyanan,et al.  Nonbridged half-metallocenes containing anionic ancillary donor ligands: New promising candidates as catalysts for precise olefin polymerization , 2007 .

[14]  G. Coates,et al.  Living alkene polymerization : New methods for the precision synthesis of polyolefins , 2007 .

[15]  Arto Puranen,et al.  Copolymerization of vinylcyclohexane with ethene and propene using zirconocene catalysts , 2006 .

[16]  L. Caporaso,et al.  A Novel Route to Graft‐Copolymers with Tailored Structures for the Compatibilization of Polymeric Blend , 2006 .

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

[18]  H. Alt Metallocene complexes as catalysts for olefin polymerization , 2006 .

[19]  Z. Hou,et al.  Scandium-Catalyzed Copolymerization of Ethylene with Dicyclopentadiene and Terpolymerization of Ethylene, Dicyclopentadiene, and Styrene , 2005 .

[20]  D. Stephan The Road to Early-Transition-Metal Phosphinimide Olefin Polymerization Catalysts , 2005 .

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

[22]  Paul D. Bolton,et al.  Transition Metal Imido Compounds as Ziegler–Natta Olefin Polymerisation Catalysts , 2005 .

[23]  P. Longo,et al.  Selective Dimerization of γ-Branched α-Olefins in the Presence of C2v Group-4 Metallocene-Based Catalysts , 2004 .

[24]  R. T. Mathers,et al.  Cross metathesis functionalization of polyolefins. , 2004, Chemical communications.

[25]  G. Fink,et al.  Alternating copolymers of ethylene and diolefins containing pendent functional groups , 2003 .

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

[27]  G. Coates,et al.  Catalysts for the living insertion polymerization of alkenes: access to new polyolefin architectures using Ziegler-Natta chemistry. , 2002, Angewandte Chemie.

[28]  B. Löfgren,et al.  Thermal studies on ethylene–vinylcyclohexane copolymers prepared with bis-indenyl type metallocene catalyst systems , 2002 .

[29]  Naofumi Naga,et al.  Ethylene/Styrene Copolymerization by Various (Cyclopentadienyl)(aryloxy)titanium(IV) Complexes-MAO Catalyst Systems , 2002 .

[30]  D. Pappalardo,et al.  Derivatization of propene/methyloctadiene copolymers: A flexible approach to side-chain-functionalized polypropenes , 2002 .

[31]  T. Heinze,et al.  Modified polypropylenes by copolymerization with nonconjugated dienes and additional chemical reactions , 2002 .

[32]  R. S. Mauler,et al.  Ethylene copolymerization with cyclic dienes using rac‐Et[Ind]2ZrCl2–Methylaluminoxane , 2002 .

[33]  R. Mülhaupt,et al.  Influence of Copolymer Composition and Curing on Toughness of Isotactic Polypropene Blended Together with Metallocene‐EPDM and Ethene/Propene/Vinylcyclohexane Terpolymers , 2001 .

[34]  T. Chung,et al.  A novel consecutive chain transfer reaction to p-methylstyrene and hydrogen during metallocene-mediated olefin polymerization. , 2001, Journal of the American Chemical Society.

[35]  Y. Imanishi,et al.  Syndiospecific styrene polymerization and efficient ethylene/styrene copolymerization catalyzed by (cyclopentadienyl)(aryloxy)titanium(IV) complexes-MAO system , 2000 .

[36]  C. Ahn,et al.  Synthesis of functionalized alternating olefin copolymer and modification to graft copolymer by hydrosilylation , 2000 .

[37]  J. Gladysz Frontiers in Metal-Catalyzed Polymerization: Designer Metallocenes, Designs on New Monomers, Demystifying MAO, Metathesis Déshabillé. , 2000, Chemical reviews.

[38]  Y. Imanishi,et al.  Effect of the Cyclopentadienyl Fragment on Monomer Reactivities and Monomer Sequence Distributions in Ethylene/α-Olefin Copolymerization by a Nonbridged (Cyclopentadienyl)(aryloxy)titanium(IV) Complex−MAO Catalyst System , 2000 .

[39]  T. Marks,et al.  Cocatalysts for metal-catalyzed olefin polymerization: activators, activation processes, and structure-activity relationships. , 2000, Chemical reviews.

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

[41]  H. Alt,et al.  Effect of the Nature of Metallocene Complexes of Group IV Metals on Their Performance in Catalytic Ethylene and Propylene Polymerization. , 2000, Chemical reviews.

[42]  J. Suzuki,et al.  Synthesis and functionalization of poly(ethylene‐co‐dicyclopentadiene) , 1999 .

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

[44]  R. Waymouth,et al.  Group 4 ansa-Cyclopentadienyl-Amido Catalysts for Olefin Polymerization. , 1998, Chemical reviews.

[45]  Naofumi Naga,et al.  Olefin Polymerization by (Cyclopentadienyl)(aryloxy)titanium(IV) Complexes−Cocatalyst Systems , 1998 .

[46]  R. Mülhaupt,et al.  Novel polyolefin materials via catalysis and reactive processing , 1998 .

[47]  Keun-byoung Yoon,et al.  Copolymerizations of olefins and dienes with homogeneous and heterogeneous catalysts , 1997 .

[48]  Walter Kaminsky,et al.  New polymers by metallocene catalysis , 1996 .

[49]  W. Kaminsky,et al.  Synthesis by metallocene/MAO catalyst and functionalization of poly(ethene-co-4-vinylcyclohexene) , 1996 .

[50]  J. Chien,et al.  Olefin terpolymerizations. III. Symmetry, sterics, and monomer structure in ansa‐zirconocenium catalysis of EPDM synthesis , 1995 .

[51]  J. Chien,et al.  Olefin terpolymerizations. II. 4‐vinylcyclohexene and cyclooctadiene , 1995 .

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

[53]  T. Chung,et al.  Synthesis and Functionalization of Unsaturated Polyethylene: Poly(ethylene-co-1,4-hexadiene) , 1994 .

[54]  S. Sivaram,et al.  Regioselective copolymerization of 5-vinyl-2-norbornene with ethylene using zirconocene-methylaluminoxane catalysts: a facile route to functional polyolefins , 1994 .

[55]  M. F. Farona,et al.  Synthesis of a polyolefin–polystyrene graft terpolymer , 1993 .

[56]  A. Guyot,et al.  Copolymerization of propene-nonconjugated dienes: Derivatization through hydroboration and epoxydation , 1993 .

[57]  C. M. Burns,et al.  Copolymerization of ethylene and vinylcyclohexane using soluble Ziegler-Natta catalysts , 1993 .