Living Alternating Ring-Opening Metathesis Polymerization Based on Single Monomer Additions.

By judiciously modulating the ring strain and sterics, we developed a class of disubstituted cyclopropenes that selectively underwent single monomer addition in ring-opening metathesis but readily underwent alternating ring-opening metathesis polymerization with low-strain cyclic olefins in a living fashion. The substituents on cyclopropenes effectively inhibited homoaddition and prevented secondary metathesis on the polymer backbone. The resulting polymers had controllable molecular weights and end groups, very low dispersities, and high regularity in microstructure under optimized conditions. (1)H and (13)C NMR spectroscopy and MALDI-TOF MS showed a rigorously alternating sequence. Interestingly, disubstituted cyclopropenes were found to present zero-order kinetics, indicating their rapid single addition and the rate-determining ring opening of the low-strain olefin.

[1]  N. Sampson,et al.  Ru-Catalyzed Isomerization Provides Access to Alternating Copolymers via Ring-Opening Metathesis Polymerization , 2015, Macromolecules.

[2]  R. Schrock,et al.  Synthesis of alternating trans-AB copolymers through ring-opening metathesis polymerization initiated by molybdenum alkylidenes. , 2015, Journal of the American Chemical Society.

[3]  M. Schulz,et al.  Precision Polymers through ADMET Polymerization , 2014 .

[4]  N. Sampson,et al.  A Bicyclo[4.2.0]octene-Derived Monomer Provides Completely Linear Alternating Copolymers via Alternating Ring-Opening Metathesis Polymerization (AROMP) , 2014, Macromolecules.

[5]  Dafni Moatsou,et al.  Precision polymers: a kinetic approach for functional poly(norbornenes) , 2014 .

[6]  David R. Liu,et al.  Sequence-Controlled Polymers , 2013, Science.

[7]  M. Weck,et al.  Alternating ring-opening metathesis polymerization copolymers containing charge-transfer units , 2013 .

[8]  Jean-François Lutz,et al.  Writing on polymer chains. , 2013, Accounts of chemical research.

[9]  R. Grubbs,et al.  Catalyst-Dependent Routes to Ring-Opening Metathesis Alternating Copolymers of Substituted Oxanorbornenes and Cyclooctene , 2013 .

[10]  M. Zamfir,et al.  Ultra-precise insertion of functional monomers in chain-growth polymerizations , 2012, Nature Communications.

[11]  Margaret M Flook,et al.  Synthesis of cis,syndiotactic ROMP polymers containing alternating enantiomers. , 2011, Journal of the American Chemical Society.

[12]  M. Lautens,et al.  Enantioselective palladium-catalyzed carbozincation of cyclopropenes. , 2011, Organic letters.

[13]  N. Sampson,et al.  Cyclic alternating ring-opening metathesis polymerization (CAROMP). Rapid access to functionalized cyclic polymers. , 2010, Organic letters.

[14]  Margaret M Flook,et al.  Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by MonoAryloxidePyrrolide (MAP) Catalysts. , 2010, Macromolecules.

[15]  N. Sampson,et al.  Scope of the ring-opening metathesis polymerization (ROMP) reaction of 1-substituted cyclobutenes. , 2010, Journal of the American Chemical Society.

[16]  Peter Chen,et al.  Building stereoselectivity into a chemoselective ring-opening metathesis polymerization catalyst for alternating copolymerization. , 2010, Angewandte Chemie.

[17]  Jean-François Lutz,et al.  Sequence control in polymer synthesis. , 2009, Chemical Society reviews.

[18]  G. Coates,et al.  Polymerization of enantiopure monomers using syndiospecific catalysts: a new approach to sequence control in polymer synthesis. , 2009, Journal of the American Chemical Society.

[19]  N. Sampson,et al.  Synthesis of copolymers by alternating ROMP (AROMP). , 2009, Journal of the American Chemical Society.

[20]  M. Buchmeiser,et al.  Homologous Poly(isobutylene)s : Poly(isobutylene)/High-Density Poly(ethylene) Hybrid Polymers , 2008 .

[21]  R. Schrock,et al.  Stereospecific Ring-Opening Metathesis Polymerization of 3-Methyl-3-phenylcylopropene by Molybdenum Alkylidene Initiators , 2008 .

[22]  M. Buchmeiser,et al.  Alternating copolymerizations using a Grubbs-type initiator with an unsymmetrical, chiral N-heterocyclic carbene ligand. , 2008, Angewandte Chemie.

[23]  Ryan C. Jeske,et al.  Alternating copolymerization of epoxides and cyclic anhydrides: an improved route to aliphatic polyesters. , 2007, Journal of the American Chemical Society.

[24]  M. Bornand,et al.  Mechanistically Designed Dual-Site Catalysts for the Alternating ROMP of Norbornene and Cyclooctene , 2007 .

[25]  R. Schrock,et al.  Living Ring-Opening Metathesis Polymerization of Cyclopropenes , 2006 .

[26]  R. Waymouth,et al.  The dual-site alternating cyclocopolymerization of 1,3-butadiene with ethylene. , 2003, Journal of the American Chemical Society.

[27]  R. Waymouth,et al.  Alternating stereospecific copolymerization of cyclopentene and ethylene with constrained geometry catalysts. , 2003, Chemical communications.

[28]  R. Grubbs,et al.  A practical and highly active ruthenium-based catalyst that effects the cross metathesis of acrylonitrile. , 2002, Angewandte Chemie.

[29]  R. Grubbs,et al.  Synthesis of A,B-alternating copolymers by ring-opening-insertion-metathesis polymerization. , 2002, Angewandte Chemie.

[30]  M. F. Ilker,et al.  Alternating Copolymerizations of Polar and Nonpolar Cyclic Olefins by Ring-Opening Metathesis Polymerization , 2002 .

[31]  R. Waymouth,et al.  Alternating stereospecific copolymerization of ethylene and propylene with metallocene catalysts. , 2001, Journal of the American Chemical Society.

[32]  J. Rooney,et al.  Alternating ring-opening metathesis copolymerization of bicyclo[2.2.1]hept-2-ene and cyclopentene , 1997 .

[33]  J. Kress.  Cyclization of living polyalkenamers via intramolecular secondary metathesis : dimerization of cycloheptene into cyclotetradeca-1,8-diene initiated by well-defined tungsten-carbene catalysts , 1995 .

[34]  R. Grubbs,et al.  Modeling Ring-Chain Equilibria in Ring-Opening Polymerization of Cycloolefins , 1995 .

[35]  H. Hoecker,et al.  Kinetics and thermodynamics of the metathesis reaction of cycloolefins. 2. Molecular weight distribution , 1984 .

[36]  E. A. Ofstead,et al.  Equilibrium ring‐opening polymerization of mono‐ and multicyclic unsaturated monomers , 1972 .

[37]  G. Natta,et al.  Stereospecific Homopolymerization of Cyclopentene , 1964 .