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Universal conditions for the controlled polymerization of acrylates, methacrylates, and styrene via Cu(0)-RDRP
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Whitfield, Richard, Anastasaki, Athina, Nikolaou, Vasiliki, Jones, Glen R., Engelis, Nikolaos, Discekici, Emre H., Fleischmann, Carolin, Willenbacher, Johannes, Hawker, Craig J. and Haddleton, David M. (2017) Universal conditions for the controlled polymerization of acrylates, methacrylates, and styrene via Cu(0)-RDRP. Journal of the American Chemical Society, 139 (2). pp. 1003-1010. doi:10.1021/jacs.6b11783 ISSN 0002-7863.
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WRAP_9370782-ch-030117-universal_paper_.pdf - Accepted Version - Requires a PDF viewer. Download (919Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/jacs.6b11783
Abstract
Atom transfer radical polymerization (ATRP) typically requires various parameters to be optimized in order to achieve a high degree of control over molecular weight and dispersity (such as the type of initiator, transition metal, ligand, solvent, temperature, deactivator, added salts, and reducing agents). These components play a major role when switching monomers, e.g., from acrylic to methacrylic and/or styrenic monomers during the synthesis of homo- and block copolymers as the stability and reactivity of the carbon centered propagating radical dramatically changes. This is a challenge for both “experts” and nonexperts as choosing the appropriate conditions for successful polymerization can be time-consuming and overall an arduous task. In this work, we describe one set of universal conditions for the efficacious polymerization of acrylates, methacrylates and styrene (using an identical initiator, ligand, copper salt, and solvent) based on commercially available and inexpensive reagents (PMDETA, IPA, Cu(0) wire). The versatility of these conditions is demonstrated by the near quantitative polymerization of these monomer families to yield well-defined materials over a range of molecular weights with low dispersities (∼1.1–1.2). The control and high end group fidelity is further exemplified by in situ block copolymerization upon sequential monomer addition for the case of methacrylates and styrene furnishing higher molecular weight copolymers with minimal termination. The facile nature of these conditions, combined with readily available reagents, will greatly expand the access and availability of tailored polymeric materials to all researchers.
| Item Type: | Journal Article | ||||||||
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| Subjects: | Q Science > QD Chemistry | ||||||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||
| Library of Congress Subject Headings (LCSH): | Polymerization, Free radical reactions | ||||||||
| Journal or Publication Title: | Journal of the American Chemical Society | ||||||||
| Publisher: | American Chemical Society | ||||||||
| ISSN: | 0002-7863 | ||||||||
| Official Date: | 18 January 2017 | ||||||||
| Dates: |
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| Volume: | 139 | ||||||||
| Number: | 2 | ||||||||
| Page Range: | pp. 1003-1010 | ||||||||
| DOI: | 10.1021/jacs.6b11783 | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||||
| Date of first compliant deposit: | 5 January 2017 | ||||||||
| Date of first compliant Open Access: | 29 December 2017 | ||||||||
| Funder: | University of Warwick, Materials Research Facilities Network, Marie Sklodowska-Curie Global Fellowships |
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