Post-polymerization modification of polymethacrylates enabled by keto–enol tautomerization

Easterling, Charles P.; Coste, Guilhem; Sanchez, Jose E.; Fanucci, Gail E.; Sumerlin, Brent S.

doi:10.1039/d0py00383b

Post-polymerization modification of polymethacrylates enabled by keto–enol tautomerization

Journal Article · Wed Apr 15 00:00:00 EDT 2020 · Polymer Chemistry

DOI:https://doi.org/10.1039/d0py00383b· OSTI ID:1781575

^[1]; Coste, Guilhem ^[2]; Sanchez, Jose E. ^[2]; Fanucci, Gail E. ^[2]; ^[2]

Univ. of Florida, Gainesville, FL (United States). Center for Macromolecular Science & Engineering, Dept. of Chemistry, George & Josephine Butler Polymer Research Lab.; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies
Univ. of Florida, Gainesville, FL (United States). Center for Macromolecular Science & Engineering, Dept. of Chemistry, George & Josephine Butler Polymer Research Lab.

We report a post-polymerization modification strategy to functionalize methacrylic copolymers through enol-ester transesterification. A new monomer, vinyl methacryloxy acetate (VMAc), containing both enol-ester and methacryloyl functionality, was successfully copolymerized with methyl methacrylate (MMA) by selective reversible addition–fragmentation chain transfer (RAFT) polymerization. Post-polymerization modification of pendent enol esters proceeded through an “irreversible” transesterification process, driven by the low nucleophilicity of the tautomerization product, to result in high conversion under mild conditions.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1781575

Alternate ID(s):: OSTI ID: 1615035

Report Number(s):: SAND--2021-5023J; 695749

Journal Information:: Polymer Chemistry, Journal Name: Polymer Chemistry Journal Issue: 17 Vol. 11; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (28)

Click Chemistry: Diverse Chemical Function from a Few Good Reactions Kolb, Hartmuth C.; Finn, M. G.; Sharpless, K. Barry Angewandte Chemie International Edition, Vol. 40, Issue 11, p. 2004-2021 https://doi.org/10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5	journal	June 2001
Synthesis of Functional Polymers by Post-Polymerization Modification Gauthier, Marc A.; Gibson, Matthew I.; Klok, Harm-Anton Angewandte Chemie International Edition, Vol. 48, Issue 1 https://doi.org/10.1002/anie.200801951	journal	November 2008
Click Chemistry: A Powerful Tool to Create Polymer‐Based Macromolecular Chimeras Le Droumaguet, Benjamin; Velonia, Kelly Macromolecular Rapid Communications, Vol. 29, Issue 12–13 https://doi.org/10.1002/marc.200800155	journal	July 2008
Direct transesterification of poly(methyl acrylate) for functional polyacrylate syntheses Kim, Jeung Gon Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 15 https://doi.org/10.1002/pola.28659	journal	May 2017
Click Chemistry for Drug Delivery Nanosystems Lallana, Enrique; Sousa-Herves, Ana; Fernandez-Trillo, Francisco Pharmaceutical Research, Vol. 29, Issue 1 https://doi.org/10.1007/s11095-011-0568-5	journal	September 2011
Efficient transesterification of ethyl acetoacetate with higher alcohols without catalysts Koval, L. I.; Dzyuba, V. I.; Ilnitska, O. L. Tetrahedron Letters, Vol. 49, Issue 10 https://doi.org/10.1016/j.tetlet.2008.01.018	journal	March 2008
Expanding the Scope of RAFT Polymerization: Recent Advances and New Horizons Hill, Megan R.; Carmean, R. Nicholas; Sumerlin, Brent S. Macromolecules, Vol. 48, Issue 16 https://doi.org/10.1021/acs.macromol.5b00342	journal	July 2015
Multifaceted Synthetic Route to Functional Polyacrylates by Transesterification of Poly(pentafluorophenyl acrylates) Das, Anindita; Theato, Patrick Macromolecules, Vol. 48, Issue 24 https://doi.org/10.1021/acs.macromol.5b02293	journal	November 2015
Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials Barlow, Tammie R.; Brendel, Johannes C.; Perrier, Sébastien Macromolecules, Vol. 49, Issue 17 https://doi.org/10.1021/acs.macromol.6b00721	journal	September 2016
50th Anniversary Perspective : Polymer Functionalization Blasco, Eva; Sims, Michael B.; Goldmann, Anja S. Macromolecules, Vol. 50, Issue 14 https://doi.org/10.1021/acs.macromol.7b00465	journal	June 2017
Full and Partial Amidation of Poly(methyl acrylate) as Basis for Functional Polyacrylamide (Co)Polymers Van Guyse, Joachim F. R.; Verjans, Jente; Vandewalle, Stef Macromolecules, Vol. 52, Issue 14 https://doi.org/10.1021/acs.macromol.9b00399	journal	June 2019
Mechanically Robust and Recyclable Cross-Linked Fibers from Melt Blown Anthracene-Functionalized Commodity Polymers Jin, Kailong; Banerji, Aditya; Kitto, David ACS Applied Materials & Interfaces, Vol. 11, Issue 13 https://doi.org/10.1021/acsami.9b00209	journal	March 2019
Radical Departure: Thermally-Triggered Degradation of Azo-Containing Poly(β-thioester)s Sun, Hao; Dobbins, Daniel J.; Dai, Yuqiong ACS Macro Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsmacrolett.6b00327	journal	May 2016
Transesterification Otera, Junzo. Chemical Reviews, Vol. 93, Issue 4 https://doi.org/10.1021/cr00020a004	journal	June 1993
Lipase-catalyzed irreversible transesterifications using enol esters as acylating reagents: preparative enantio- and regioselective syntheses of alcohols, glycerol derivatives, sugars and organometallics Wang, Yi Fong.; Lalonde, James J.; Momongan, Milagros. Journal of the American Chemical Society, Vol. 110, Issue 21 https://doi.org/10.1021/ja00229a041	journal	October 1988
Simple enols. 2. Kinetics and mechanism of the ketonization of vinyl alcohol Capon, Brian; Zucco, Cesar Journal of the American Chemical Society, Vol. 104, Issue 26 https://doi.org/10.1021/ja00390a030	journal	December 1982
Copolymerization. V. ¹ Some Copolymerizations of Vinyl Acetate Mayo, Frank R.; Walling, Cheves; Lewis, Frederick M. Journal of the American Chemical Society, Vol. 70, Issue 4 https://doi.org/10.1021/ja01184a067	journal	April 1948
Transesterification of Various Methyl Esters Under Mild Conditions Catalyzed by Tetranuclear Zinc Cluster Iwasaki, Takanori; Maegawa, Yusuke; Hayashi, Yukiko The Journal of Organic Chemistry, Vol. 73, Issue 13 https://doi.org/10.1021/jo800625v	journal	July 2008
Cyclic Guanidine Organic Catalysts: What Is Magic About Triazabicyclodecene? Kiesewetter, Matthew K.; Scholten, Marc D.; Kirn, Nicole The Journal of Organic Chemistry, Vol. 74, Issue 24 https://doi.org/10.1021/jo902369g	journal	December 2009
Acylation of Alcohols and Amines with Vinyl Acetates Catalyzed by Cp* ₂ Sm(thf) ₂ Ishii, Yasutaka; Takeno, Mitsuhiro; Kawasaki, Yumi The Journal of Organic Chemistry, Vol. 61, Issue 9 https://doi.org/10.1021/jo952168m	journal	January 1996
Investigation of Free-Radical Copolymerization Propagation Kinetics of Vinyl Acetate and Methyl Methacrylate Dossi, Marco; Liang, Kun; Hutchinson, Robin A. The Journal of Physical Chemistry B, Vol. 114, Issue 12 https://doi.org/10.1021/jp1007686	journal	April 2010
Propagation and termination processes in the free-radical copolymerization of methyl methacrylate and vinyl acetate Ma, Yung Dae; Won, You Chan; Kubo, Keiji Macromolecules, Vol. 26, Issue 25 https://doi.org/10.1021/ma00077a011	journal	December 1993
Well-Defined Polymers Bearing Pendent Alkene Functionalities via Selective RAFT Polymerization Ma, Jun; Cheng, Chong; Sun, Guorong Macromolecules, Vol. 41, Issue 23 https://doi.org/10.1021/ma802057u	journal	December 2008
Cycloalkenyl-Functionalized Polymers and Block Copolymers: Syntheses via Selective RAFT Polymerizations and Demonstration of Their Versatile Reactivity Ma, Jun; Cheng, Chong; Wooley, Karen L. Macromolecules, Vol. 42, Issue 5 https://doi.org/10.1021/ma8024255	journal	March 2009
Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFT Process Chiefari, John; Chong, Y. K. (Bill); Ercole, Frances Macromolecules, Vol. 31, Issue 16 https://doi.org/10.1021/ma9804951	journal	August 1998
Expanding the Catalytic Activity of Nucleophilic N-Heterocyclic Carbenes for Transesterification Reactions Nyce, Gregory W.; Lamboy, Jorge A.; Connor, Eric F. Organic Letters, Vol. 4, Issue 21 https://doi.org/10.1021/ol0267228	journal	October 2002
Synthetic upcycling of polyacrylates through organocatalyzed post-polymerization modification Easterling, Charles P.; Kubo, Tomohiro; Orr, Zachary M. Chem. Sci., Vol. 8, Issue 11 https://doi.org/10.1039/C7SC02574B	journal	January 2017
Conjugation of RAFT-generated polymers to proteins by two consecutive thiol–ene reactions Li, Ming; De, Priyadarsi; Li, Hongmei Polymer Chemistry, Vol. 1, Issue 6 https://doi.org/10.1039/c0py00025f	journal	January 2010

Similar Records

Detection of the keto-enol tautomerization in acetaldehyde, acetone, cyclohexanone, and methyl vinyl ketone with a novel VUV light source

Journal Article · Wed Sep 09 00:00:00 EDT 2020 · Proceedings of the Combustion Institute · OSTI ID:1778226

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Post-polymerization modification of polymethacrylates enabled by keto–enol tautomerization

Citation Formats

References (28)

Similar Records

Related Subjects