Ultrahigh Molecular Weight Hydrophobic Acrylic and Styrenic Polymers through Organic-Phase Photoiniferter-Mediated Polymerization
As many physical properties of polymers scale with molecular weight, the ability to achieve polymers of nearly inaccessibly high molecular weight provides an opportunity to probe the upper size limit of macromolecular phenomena. Yet many of the most stimulating macromolecular designs remain out of r...
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| Published in | ACS macro letters Vol. 9; no. 4; pp. 613 - 618 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
United States
American Chemical Society
21.04.2020
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| Online Access | Get full text |
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| Abstract | As many physical properties of polymers scale with molecular weight, the ability to achieve polymers of nearly inaccessibly high molecular weight provides an opportunity to probe the upper size limit of macromolecular phenomena. Yet many of the most stimulating macromolecular designs remain out of reach of current ultrahigh molecular weight (UHMW) polymer synthetic approaches. Herein, we show that UHMW polymers of diverse composition can be achieved by irradiation of thiocarbonylthio photoiniferters with long-wave ultraviolet or visible light in concentrated organic solution. This facile photopolymerization strategy is general to acrylic-, acrylamido-, methacrylic-, and styrenic-based monomers, enabling the synthesis of well-defined macromolecules with molecular weights in excess of 106 g/mol. The high chain-end fidelity afforded by photoiniferter polymerization conditions facilitated the design of UHMW amphiphilic block copolymers, which were found to self-assemble into micellar morphologies up to 200 nm in diameter. |
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| AbstractList | As many physical properties of polymers scale with molecular weight, the ability to achieve polymers of nearly inaccessibly high molecular weight provides an opportunity to probe the upper size limit of macromolecular phenomena. Yet many of the most stimulating macromolecular designs remain out of reach of current ultrahigh molecular weight (UHMW) polymer synthetic approaches. Herein, we show that UHMW polymers of diverse composition can be achieved by irradiation of thiocarbonylthio photoiniferters with long-wave ultraviolet or visible light in concentrated organic solution. This facile photopolymerization strategy is general to acrylic-, acrylamido-, methacrylic-, and styrenic-based monomers, enabling the synthesis of well-defined macromolecules with molecular weights in excess of 106 g/mol. The high chain-end fidelity afforded by photoiniferter polymerization conditions facilitated the design of UHMW amphiphilic block copolymers, which were found to self-assemble into micellar morphologies up to 200 nm in diameter. As many physical properties of polymers scale with molecular weight, the ability to achieve polymers of nearly inaccessibly high molecular weight provides an opportunity to probe the upper size limit of macromolecular phenomena. Yet many of the most stimulating macromolecular designs remain out of reach of current ultrahigh molecular weight (UHMW) polymer synthetic approaches. Herein, we show that UHMW polymers of diverse composition can be achieved by irradiation of thiocarbonylthio photoiniferters with long-wave ultraviolet or visible light in concentrated organic solution. This facile photopolymerization strategy is general to acrylic-, acrylamido-, methacrylic-, and styrenic-based monomers, enabling the synthesis of well-defined macromolecules with molecular weights in excess of 10 g/mol. The high chain-end fidelity afforded by photoiniferter polymerization conditions facilitated the design of UHMW amphiphilic block copolymers, which were found to self-assemble into micellar morphologies up to 200 nm in diameter. |
| Author | Sumerlin, Brent S Figg, C. Adrian Hurst, Paul J Patterson, Joseph P Carmean, R. Nicholas Sims, Michael B |
| AuthorAffiliation | George and Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science and Engineering, Department of Chemistry Department of Chemistry |
| AuthorAffiliation_xml | – name: George and Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science and Engineering, Department of Chemistry – name: Department of Chemistry |
| Author_xml | – sequence: 1 givenname: R. Nicholas surname: Carmean fullname: Carmean, R. Nicholas organization: George and Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science and Engineering, Department of Chemistry – sequence: 2 givenname: Michael B orcidid: 0000-0002-5308-3386 surname: Sims fullname: Sims, Michael B organization: George and Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science and Engineering, Department of Chemistry – sequence: 3 givenname: C. Adrian orcidid: 0000-0003-3514-7750 surname: Figg fullname: Figg, C. Adrian organization: George and Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science and Engineering, Department of Chemistry – sequence: 4 givenname: Paul J surname: Hurst fullname: Hurst, Paul J organization: Department of Chemistry – sequence: 5 givenname: Joseph P orcidid: 0000-0002-1975-1854 surname: Patterson fullname: Patterson, Joseph P organization: Department of Chemistry – sequence: 6 givenname: Brent S orcidid: 0000-0001-5749-5444 surname: Sumerlin fullname: Sumerlin, Brent S email: sumerlin@chem.ufl.edu organization: George and Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science and Engineering, Department of Chemistry |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/35648494$$D View this record in MEDLINE/PubMed |
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| Title | Ultrahigh Molecular Weight Hydrophobic Acrylic and Styrenic Polymers through Organic-Phase Photoiniferter-Mediated Polymerization |
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