β-Myrcene/isobornyl methacrylate SG1 nitroxide-mediated controlled radical polymerization: synthesis and characterization of gradient, diblock and triblock copolymers

• Published in: RSC advances Vol. 9; no. 6; pp. 3377 - 3395
• Main Authors: Métafiot, Adrien, Gagnon, Lysandre, Pruvost, Sébastien, Hubert, Pascal, Gérard, Jean-François, Defoort, Brigitte, Marić, Milan
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 25.01.2019; The Royal Society of Chemistry
• Subjects: Atomic force microscopy; Block copolymers; Bulk polymerization; Chemical synthesis; Chemistry; Copolymerization; Copolymers; Elongation; Molecular weight; NMR; Nuclear magnetic resonance; Phase separation; Polymerization; Raw materials; Thermoplastic elastomers
• ISSN: 2046-2069; 2046-2069
• DOI: 10.1039/c8ra09192g

β-Myrcene (My), a natural 1,3-diene, and isobornyl methacrylate (IBOMA), from partially bio-based raw materials sources, were copolymerized by nitroxide-mediated polymerization (NMP) in bulk using the SG1-based BlocBuilder™ alkoxyamine functionalized with an -succinimidyl ester group, NHS-BlocBuilder, at = 100 °C with initial IBOMA molar feed compositions = 0.10-0.90. Copolymer reactivity ratios were = 1.90-2.16 and = 0.02-0.07 using Fineman-Ross, Kelen-Tudos and non-linear least-squares fitting to the Mayo-Lewis terminal model and indicated the possibility of gradient My/IBOMA copolymers. A linear increase in molecular weight conversion and a low dispersity ( ≤ 1.41) were exhibited by My/IBOMA copolymerization with ≤ 0.80. My-rich and IBOMA-rich copolymers were shown to have a high degree of chain-end fidelity by performing subsequent chain-extensions with IBOMA and/or My, and by P NMR analysis. The preparation by NMP of My/IBOMA thermoplastic elastomers (TPEs), mostly bio-sourced, was then attempted. IBOMA-My-IBOMA triblock copolymers containing a minor fraction of My or styrene (S) units in the outer hard segments ( = 51-95 kg mol , = 1.91-2.23 and = 0.28-0.36) were synthesized using SG1-terminated poly(ethylene- -butylene) dialkoxyamine. The micro-phase separation was suggested by the detection of two distinct s at about -60 °C and +180 °C and confirmed by atomic force microscopy (AFM). A plastic stress-strain behavior (stress at break = 3.90 ± 0.22 MPa, elongation at break = 490 ± 31%) associated to an upper service temperature of about 140 °C were also highlighted for these triblock polymers.