Suppression of chain transfer in catalytic acrylate polymerization via rapid and selective secondary insertion.

In catalytic copolymerization, undesired chain transfer after incorporation of a polar vinyl monomer is a fundamental problem. We show an approach to overcome this problem by a fast consecutive insertion. The second double bond of acrylic anhydride rapidly inserts intramolecularly to regio- and stereoselectively form a cyclic repeat unit and a primary alkyl favorable for chain growth (>96%). This results in significantly enhanced copolymer molecular weights vs monofunctional acrylate monomers.

[1]  B. Rieger,et al.  Copolymerization of Ethylene and 3,3,3-Trifluoropropene Using (Phosphine-sulfonate)Pd(Me)(DMSO) as Catalyst. , 2014, ACS macro letters.

[2]  Y. Ota,et al.  Quantification of the steric influence of alkylphosphine-sulfonate ligands on polymerization, leading to high-molecular-weight copolymers of ethylene and polar monomers. , 2014, Journal of the American Chemical Society.

[3]  K. Nozaki,et al.  Transition-Metal-Catalyzed Functional Polyolefin Synthesis: Effecting Control through Chelating Ancillary Ligand Design and Mechanistic Insights , 2014 .

[4]  V. Goldbach,et al.  Electronic Influences in Phosphinesulfonato Palladium(II) Polymerization Catalysts , 2013 .

[5]  Kaitlyn E. Crawford,et al.  Stereoengineering of poly(1,3-methylenecyclohexane) via two-state living coordination polymerization of 1,6-heptadiene. , 2013, Journal of the American Chemical Society.

[6]  S. Mecking,et al.  Incorporation of vinyl chloride in insertion polymerization. , 2013, Angewandte Chemie.

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

[8]  L. Cavallo,et al.  Concepts for stereoselective acrylate insertion. , 2013, Journal of the American Chemical Society.

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

[10]  Jean-Christophe Daigle,et al.  Structure-activity relationship of palladium phosphanesulfonates: toward highly active palladium-based polymerization catalysts. , 2012, Chemistry.

[11]  Jean-Christophe Daigle,et al.  Probing the Regiochemistry of Acrylate Catalytic Insertion Polymerization via Cyclocopolymerization of Allyl Acrylate and Ethylene. , 2012, ACS macro letters.

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

[13]  L. Cavallo,et al.  Breaking the regioselectivity rule for acrylate insertion in the Mizoroki–Heck reaction , 2011, Proceedings of the National Academy of Sciences.

[14]  Jean-Christophe Daigle,et al.  Preparation of Functional Polyethylenes by Catalytic Copolymerization , 2011 .

[15]  Y. Men,et al.  Stereospecific Cyclopolymerization of α,ω-Diolefins by Pyridylamidohafnium Catalyst with the Highest Activity , 2011 .

[16]  K. Nozaki,et al.  Coordination-insertion copolymerization of allyl monomers with ethylene. , 2011, Journal of the American Chemical Society.

[17]  S. Mecking,et al.  Direct synthesis of ethylene-acrylic acid copolymers by insertion polymerization. , 2010, Journal of the American Chemical Society.

[18]  K. Morokuma,et al.  Why did incorporation of acrylonitrile to a linear polyethylene become possible? Comparison of phosphine-sulfonate ligand with diphosphine and imine-phenolate ligands in the Pd-catalyzed ethylene/acrylonitrile copolymerization. , 2010, Journal of the American Chemical Society.

[19]  L. Cavallo,et al.  Mechanistic insights on acrylate insertion polymerization. , 2010, Journal of the American Chemical Society.

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

[21]  K. Nozaki,et al.  Copolymerization of vinyl acetate with ethylene by palladium/alkylphosphine-sulfonate catalysts. , 2009, Journal of the American Chemical Society.

[22]  K. Morokuma,et al.  Mechanistic studies on the formation of linear polyethylene chain catalyzed by palladium phosphine-sulfonate complexes: experiment and theoretical studies. , 2009, Journal of the American Chemical Society.

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

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

[25]  S. Mecking,et al.  Coordination copolymerization of polar vinyl monomers H2C=CHX. , 2008, Angewandte Chemie.

[26]  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.

[27]  K. Osakada,et al.  Pd-catalyzed polymerization of dienes that involves chain-walking isomerization of the growing polymer end: synthesis of polymers composed of polymethylene and five-membered-ring units. , 2007, Angewandte Chemie.

[28]  J. Vela,et al.  Copolymerization of ethylene and alkyl vinyl ethers by a (phosphine- sulfonate)PdMe catalyst. , 2007, Journal of the American Chemical Society.

[29]  K. Nozaki,et al.  Formation of linear copolymers of ethylene and acrylonitrile catalyzed by phosphine sulfonate palladium complexes. , 2007, Journal of the American Chemical Society.

[30]  K. Osakada,et al.  Pd Complex-Promoted Cyclopolymerization of Functionalized α,ω-Dienes and Copolymerization with Ethylene to Afford Polymers with Cyclic Repeating Units , 2006 .

[31]  R. van Ginkel,et al.  Palladium catalysed copolymerisation of ethene with alkylacrylates: polar comonomer built into the linear polymer chain. , 2002, Chemical communications.

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

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

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

[35]  G. Coates,et al.  Enantioselective cyclopolymerization: optically active poly(methylene-1,3-cyclopentane) , 1991 .