Highly isoselective coordination polymerization of ortho-methoxystyrene with β-diketiminato rare-earth-metal precursors.

Stereoselective coordination/insertion polymerization of the polar ortho-methoxystyrene has been achieved for the first time by using the cationic β-diketiminato rare-earth-metal species. High activity and excellent isoselectivity (mmmm>99 %) were acheived. The unmasked Lewis-basic methoxy group does not poison the Lewis-acidic metal center, but instead activates the polymerization through σ-π chelation to the active species together with the vinyl group, thus lower the coordination and activation energies as compared with those of styrene derivatives lacking the methoxy group.

[1]  Z. Hou,et al.  Synthesis of amino‐containing syndiotactic polystyrene as efficient polymer support for palladium nanoparticles , 2015 .

[2]  P. Topham,et al.  Controlled RAFT Polymerization and Zinc Binding Performance of Catechol-Inspired Homopolymers , 2014 .

[3]  Yue-sheng Li,et al.  Syntheses of Well-Defined Functional Isotactic Polypropylenes via Efficient Copolymerization of Propylene with ω-Halo-α-alkenes by Post-metallocene Hafnium Catalyst , 2014 .

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

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

[6]  Yong Tang,et al.  Copolymerization of Ethylene with Functionalized Olefins by [ONX] Titanium Complexes , 2013 .

[7]  K. Nozaki,et al.  Synthesis of functional polyolefins using cationic bisphosphine monoxide-palladium complexes. , 2012, Journal of the American Chemical Society.

[8]  Shih-Chieh Lin,et al.  Induced circular dichroism of stereoregular vinyl polymers. , 2012, Chemical communications.

[9]  Dongmei Cui,et al.  Ligands Dominate Highly Syndioselective Polymerization of Styrene by Using Constrained-geometry-configuration Rare-earth Metal Precursors , 2012 .

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

[11]  Shijia Tang,et al.  A lutetium allyl complex that bears a pyridyl-functionalized cyclopentadienyl ligand: dual catalysis on highly syndiospecific and cis-1,4-selective (co)polymerizations of styrene and butadiene. , 2010, Chemistry.

[12]  Xuequan Zhang,et al.  β-Diketiminato Rare-Earth Metal Complexes. Structures, Catalysis, and Active Species for Highly cis-1,4-Selective Polymerization of Isoprene , 2010 .

[13]  Changle Chen,et al.  Cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (alpha-diimine)PdMe(+) species. , 2010, Journal of the American Chemical Society.

[14]  Zheng Wang,et al.  [O-NSR]TiCl3-catalyzed copolymerization of ethylene with functionalized olefins. , 2009, Angewandte Chemie.

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

[16]  E. Chen Coordination polymerization of polar vinyl monomers by single-site metal catalysts. , 2009, Chemical reviews.

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

[18]  I. Khan,et al.  Synthesis of Optically Active Helical Poly(2-methoxystyrene). Enhancement of HeLa and Osteoblast Cell Growth on Optically Active Helical Poly(2-methoxystyrene) Surfaces , 2009, Journal of biomaterials science. Polymer edition.

[19]  H. Terao,et al.  Ethylene/polar monomer copolymerization behavior of bis(phenoxy-imine)Ti complexes: formation of polar monomer copolymers. , 2008, Journal of the American Chemical Society.

[20]  J. Carpentier,et al.  Group 3 and 4 single-site catalysts for stereospecific polymerization of styrene , 2008 .

[21]  Changle Chen,et al.  Multiple insertion of a silyl vinyl ether by (alpha-diimine)PdMe+ species. , 2008, Journal of the American Chemical Society.

[22]  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.

[23]  B. Vuillemin,et al.  Highly isospecific styrene polymerization catalyzed by single-component bridged bis(indenyl) allyl yttrium and neodymium complexes. , 2007, Angewandte Chemie.

[24]  Z. Hou,et al.  Scandium half-metallocene-catalyzed syndiospecific styrene polymerization and styrene-ethylene copolymerization: unprecedented incorporation of syndiotactic styrene-styrene sequences in styrene-ethylene copolymers. , 2004, Journal of the American Chemical Society.

[25]  A. Razavi,et al.  Highly syndiospecific polymerization of styrene catalyzed by allyl lanthanide complexes. , 2004, Journal of the American Chemical Society.

[26]  R. Mülhaupt,et al.  Ancillary ligand effect on single-site styrene polymerization: isospecificity of group 4 metal bis(phenolate) catalysts. , 2003, Journal of the American Chemical Society.

[27]  Y. Toda,et al.  Catalytic regioselective introduction of allyl alcohol into the nonpolar polyolefins: development of one-pot synthesis of hydroxyl-capped polyolefins mediated by a new metallocene IF catalyst. , 2002, Journal of the American Chemical Society.

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

[29]  T. Chung,et al.  Synthesis of syndiotactic polystyrene derivatives containing amino groups , 2000 .

[30]  G. Coates Precise control of polyolefin stereochemistry using single-site metal catalysts. , 2000, Chemical reviews.

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

[32]  W. Jo,et al.  Synthesis and Characterization of Poly(styrene-co-4-[(tert-butyldimethylsilyl)oxy]styrene) as a Precursor of Hydroxyl-Functionalized Syndiotactic Polystyrene , 1999 .

[33]  R. Waymouth,et al.  Metallocene/Borate-Catalyzed Polymerization of Amino-Functionalized α-Olefins , 1998 .

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

[35]  J. Seppälä,et al.  Synthesis of Hydroxyl Group Containing Polyolefins with Metallocene/Methylaluminoxane Catalysts , 1996 .

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

[37]  P. Aaltonen,et al.  Synthesis of Functional Polyethylenes with Soluble Metallocene/Methylaluminoxane Catalyst , 1995 .

[38]  Geoffrey W. Coates,et al.  Homogeneous Ziegler-Natta polymerization of functionalized monomers catalyzed by cationic group IV metallocenes , 1992 .

[39]  Hitoshi Yamamoto,et al.  Synthesis of monodispersed high molecular weight polymers and isolation of an organolanthanide(III) intermediate coordinated by a penultimate poly(MMA) unit , 1992 .

[40]  Masahiko Kuramoto,et al.  Crystalline syndiotactic polystyrene , 1986 .

[41]  T. Uryu,et al.  Stereoregularity of polystyrene derivatives, 1. Poly(methylstyrene)s and poly(methoxystyrene)s obtained with ziegler catalyst, cationic catalyst, or radical initiators , 1982 .

[42]  K. Hatada,et al.  Stereospecific polymerization of o‐methoxystyrene by anionic initiators , 1969 .

[43]  A. Casale,et al.  Stereospecificity in the cationic co‐ordinated polymerization of methoxystyrenes , 1962 .

[44]  P. Corradini,et al.  CRYSTALLINE HIGH POLYMERS OF α-OLEFINS , 1955 .