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Switching from Controlled Ring-Opening Polymerization (cROP) to Controlled Ring-Closing Depolymerization (cRCDP) by Adjusting the Reaction Parameters That Determine the Ceiling Temperature
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0001-6044-586X
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-5850-8873
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2016 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 17, no 12, p. 3995-4002Article in journal (Refereed) Published
Abstract [en]

Full control over the ceiling temperature (T-c) enables a selective transition between the monomeric and polymeric state. This is exemplified by the conversion of the monomer 2-allyloxymethyl-2-ethyl-trimethylene carbonate (AOMEC) to poly(AOMEC) and back to AOMEC within 10 h by controlling the reaction from conditions that favor ring opening polymerization (T-c > T-o) (where To is the reaction temperature) to conditions that favor ring-closing depolymerization (T-c < T-o). The ring-closing depolymerization (RCDP) mirrors the polymerization behavior with a clear relation between the monomer concentration and the molecular weight of the polymer, indicating that RCDP occurs at the chain end. The T-c of the polymerization system is highly dependent on the nature of the solvent, for example, in toluene, the T-c of AOMEC is 234 degrees C and in acetonitrile T-c = 142 degrees C at the same initial monomer concentration of 2 M. The control over the monomer to polymer equilibrium sets new standards for the selective degradation of polymers, the controlled release of active components, monomer synthesis and material recycling. In particular, the knowledge of the monomer to polymer equilibrium of polymers in solution under selected environmental conditions is of paramount importance for in vivo applications, where the polymer chain is subjected to both high dilution and a high polarity medium in the presence of catalysts, that is, very different conditions from which the polymer was formed.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016. Vol. 17, no 12, p. 3995-4002
National Category
Polymer Technologies
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URN: urn:nbn:se:kth:diva-199492DOI: 10.1021/acs.biomac.6b01375ISI: 000389787200016Scopus ID: 2-s2.0-85006172568OAI: oai:DiVA.org:kth-199492DiVA, id: diva2:1066980
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QC 20170119

Available from: 2017-01-19 Created: 2017-01-09 Last updated: 2017-11-29Bibliographically approved

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Odelius, Karin

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