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Directed backbiting as a tool for controlling copolymer sequence in ring-opening polymerization
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-3644-0839
Wallenberg Wood Science Center, Sweden; Laboratory of Organic Electronics, Department of Science and Technology, Linköping University, Norrköping, Sweden.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-5850-8873
2026 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 247, article id 114580Article in journal (Refereed) Published
Abstract [en]

Controlling monomer sequence during sequential ring-opening copolymerization is imperative to the final polymer properties, but often challenging due to transesterification reactions that scramble the sequences of repeating units of the copolymer. With a deliberate choice of catalyst, intermolecular transesterification can be avoided and instead directed to intramolecular transesterification (backbiting), with predictable frequencies. In this work, we use exactly this feature to derive a relationship to relate the synthesis of block, random, and block-gradient copolymers, to the choice of reaction conditions. The relationship considers the relative rates of propagation (k2) and backbiting (k1) to enable a correlation between sequences or homo dyads in the copolymers to concentration, free energy of polymerization, and temperature. Experimental results are in good agreement with the expected trends and copolymers of varying homo dyads were prepared for pentadecalactone (PDL), ε-caprolactone (εCL), and δ-valerolactone (δVL) mixtures. The relative rates of propagation and backbiting were related to the polymer conformation-based Jacobson-Stockmayer theory. The explored approach towards controlling polymer architecture under conditions dictated by the ring-chain equilibria (RCE) may aid the development of new tailored copolymers.

Place, publisher, year, edition, pages
Elsevier BV , 2026. Vol. 247, article id 114580
Keywords [en]
Copolymer synthesis, Directed backbiting, Microstructure control, Ring-chain equilibria, Ring-opening polymerization
National Category
Polymer Chemistry Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-379856DOI: 10.1016/j.eurpolymj.2026.114580ISI: 001696358200001Scopus ID: 2-s2.0-105034125490OAI: oai:DiVA.org:kth-379856DiVA, id: diva2:2054028
Note

QC 20260420

Available from: 2026-04-20 Created: 2026-04-20 Last updated: 2026-04-20Bibliographically approved

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Nieboer, VincentOdelius, Karin

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