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Synthesis of methacrylate-terminated block copolymers with reduced transesterification by controlled ring-opening polymerization

Ruiz-Cantu, Laura A.; Pearce, Amanda K.; Burroughs, Laurence; Bennett, Thomas M.; Vasey, Catherine E.; Wildman, Ricky; Irvine, Derek J.; Alexander, Cameron; Taresco, Vincenzo


Laura A. Ruiz-Cantu

Amanda K. Pearce

Laurence Burroughs

Thomas M. Bennett

Catherine E. Vasey

Professor of Multiphase Flow and Mechanics

Professor of Materials Chemistry


This work presents a robust method to achieve the synthesis of low molecular weight polyesters 26 via ring-opening polymerization (ROP) initiated by 2-hydroxyethyl-methacrylate (HEMA) 27 when using triazabicyclodecene (TBD) as catalyst. The effect that the HEMA:TBD ratio has 28 upon the final reaction rate and final polymer molecular architecture is discussed. The optimum 29 HEMA:TBD ratio and reaction conditions required to minimize competing transesterification 30 reactions were determined, in order to synthesize successfully the target ROP macromonomer 31 species containing only a single 2-methacryloyloxyethyl end-group. Additionally, to confirm 32 the terminal end-group fidelity of the product macromonomers and confirm TBD utility for 33 block copolymer manufacture, a small series of di-block polyesters were synthesized using 34 TBD and shown to exhibit good control over the final polymer structure whilst negating the 35 side transesterification reactions, irrespective of the monomers used.


Ruiz-Cantu, L. A., Pearce, A. K., Burroughs, L., Bennett, T. M., Vasey, C. E., Wildman, R., …Taresco, V. (2019). Synthesis of methacrylate-terminated block copolymers with reduced transesterification by controlled ring-opening polymerization. Macromolecular Chemistry and Physics, 220(2), Article 1800459.

Journal Article Type Article
Acceptance Date Nov 13, 2018
Online Publication Date Nov 27, 2018
Publication Date 2019-01
Deposit Date Nov 20, 2018
Publicly Available Date Nov 28, 2019
Journal Macromolecular Chemistry and Physics
Print ISSN 1022-1352
Electronic ISSN 1521-3935
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 220
Issue 2
Article Number 1800459
Public URL
Publisher URL
Additional Information This is the peer reviewed version of the article, which has been published in final form at : article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.


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