Biobased triblock thermoplastic elastomer with betulin- or carvacryl-methacrylate end-blocks by RAFT polymerization

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Aniello Vittore - , University of Insubria (Author)
  • Pauline Shamraienko - , Leibniz Institute of Polymer Research Dresden (Author)
  • Ilka Hermes - , Leibniz Institute of Polymer Research Dresden (Author)
  • Qiong Li - , Leibniz Institute of Polymer Research Dresden (Author)
  • Brigitte Voit - , Chair of Organic Chemistry of Polymers, Leibniz Institute of Polymer Research Dresden (Author)
  • Lorella Izzo - , University of Insubria (Author)

Abstract

In this work, fully biobased acrylic ABA triblock copolymers were synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization using VISIOMER® Terra C13 (ET13) as the “soft” midblock and two terpenoid-derived methacrylates, betulin methacrylate (BetuMA) and carvacryl methacrylate (CaMA), as the glassy blocks. An “R-linked” bifunctional chain transfer agent (bis-CTA) enabled the formation of ET13 macro-CTAs with controlled molecular weights and narrow dispersity (M n = 84-229 kg mol −1, Đ ≈ 1.1). RAFT homo-polymerizations of BetuMA and CaMA yielded well-defined homopolymers (M n = 20-33 kg mol −1, Đ < 1.4) with selective methacrylate reactivity. Chain extension of ET13 macro-CTAs produced a series of ABA triblocks featuring 8-39 mol% glassy content. GPC confirmed molecular weights in the range M n = 97-415 kg mol −1 (Đ < 1.7), while DSC and TGA analyses showed distinct glass transitions for soft block, close to −50 °C, and good thermal stability. AFM evidenced clear microphase separation. Mechanical testing revealed that BetuMA-based copolymers (BEB series) achieved tensile strengths up to 3.9 MPa and elongations up to 760%, outperforming CaMA-based analogs (CEC series: σ ≤ 1.2 MPa, ϵ ≤ 710%). These results demonstrate the efficacy of RAFT polymerization of terpenoid methacrylates in producing high-performance, sustainable thermoplastic elastomers, offering a viable alternative to petroleum-derived thermoplastic elastomers (TPEs).

Details

Original languageEnglish
Pages (from-to)3640-3649
Number of pages10
JournalPolymer chemistry
Volume16
Issue number32
Early online date15 Jul 2025
Publication statusPublished - 12 Aug 2025
Peer-reviewedYes

External IDs

Scopus 105012963129
ORCID /0000-0002-4531-691X/work/194254531

Keywords

Keywords

  • Copolymers