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

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

  • Aniello Vittore - , University of Insubria (Autor:in)
  • Pauline Shamraienko - , Leibniz-Institut für Polymerforschung Dresden (Autor:in)
  • Ilka Hermes - , Leibniz-Institut für Polymerforschung Dresden (Autor:in)
  • Qiong Li - , Leibniz-Institut für Polymerforschung Dresden (Autor:in)
  • Brigitte Voit - , Professur für Organische Chemie der Polymere (gB/IPF) (MTC3), Leibniz-Institut für Polymerforschung Dresden (Autor:in)
  • Lorella Izzo - , University of Insubria (Autor:in)

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

OriginalspracheEnglisch
Seiten (von - bis)3640-3649
Seitenumfang10
FachzeitschriftPolymer chemistry
Jahrgang16
Ausgabenummer32
Frühes Online-Datum15 Juli 2025
PublikationsstatusVeröffentlicht - 12 Aug. 2025
Peer-Review-StatusJa

Externe IDs

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

Schlagworte

Schlagwörter

  • Copolymers