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Authors
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Vittore, A.; Shamraienko, P.; Hermes, I.; Li, Q.; Voit, B.; Izzo, L.
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Title
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Biobased triblock thermoplastic elastomer with betulin- or carvacryl-methacrylate end-blocks by RAFT polymerization
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Date
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15.07.2025
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Number
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0
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Abstract
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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<sub>n</sub> = 84–229 kg mol−1, Đ ≈ 1.1). RAFT homo-polymerizations of BetuMA and CaMA yielded well-defined homopolymers (M<sub>n</sub> = 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 Mn = 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).
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Publisher
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Royal Society of Chemistry
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Wikidata
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Citation
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Polymer Chemistry 16 (2025) 3640-3649
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DOI
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https://doi.org/10.1039/D5PY00540J
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