Towards bio-based tapered block copolymers: the behaviour of myrcene in the statistical anionic copolymerisation

Grune, Eduard; Bareuther, Jennifer; Blankenburg, Jan; Appold, Michael; Shaw, Lloyd; Mueller, Axel H.E.; Floudas, George; Hutchings, Lian R.; Gallei, Markus; Frey, Holger

Abstract

To explore the potential of myrcene (Myr) as a bio-based monoterpene comonomer for styrenic copolymers and to establish its general applicability for the carbanionic copolymerisation, several statistical copolymerisations of myrcene and common monomers like isoprene (I), styrene (S) and 4 methylstyrene (4MS) were carried out in cyclohexane and monitored by in situ 1H NMR spectroscopy. Real-time NMR kinetic studies permitted the determination of the reactivity ratios and the composition profile for each monomer combination. While the copolymerisation of Myr/I yielded a gradient copolymer and reactivity ratios of moderate disparity (rMyr = 4.4; rI = 0.23), the statistical copolymerisation of Myr/S and Myr/4MS afforded block-like, tapered copolymers due to highly diverging reactivity ratios (rMyr = 36; rS = 0.028 and rMyr = 140; r4MS = 0.0074). Furthermore, a terpolymerisation of Myr/I/4MS was studied by real-time NMR kinetics, revealing an alteration of the composition profile of 4MS towards a more block-like structure. Based on the kinetic studies, a series of Myr/I/4MS terpolymers and Myr/S copolymers was prepared by statistical living anionic copolymerisation. All copolymers showed narrow molecular weight distributions (SEC) and two glass transition temperatures (Tg,1 = -51 to¬ 62 °C; Tg,2 = 93 ¬to 107 °C), suggesting phase segregation. TEM and SAXS measurements revealed highly ordered lamellar morphologies for all copolymers with long range correlation and confirmed the block-like structure and behaviour of Myr/S and Myr/4MS copolymers prepared by statistical carbanionic copolymerisation.

Citation

Grune, E., Bareuther, J., Blankenburg, J., Appold, M., Shaw, L., Mueller, A. H., Floudas, G., Hutchings, L. R., Gallei, M., & Frey, H. (2019). Towards bio-based tapered block copolymers: the behaviour of myrcene in the statistical anionic copolymerisation. Polymer Chemistry, 2019(10), 1213-1220. https://doi.org/10.1039/c8py01711e

• Journal Article Type: Article
• Acceptance Date: Jan 22, 2019
• Online Publication Date: Jan 23, 2019
• Publication Date: 2019
• Deposit Date: Jan 28, 2019
• Publicly Available Date: Jan 22, 2020
• Journal: Polymer Chemistry
• Print ISSN: 1759-9954
• Electronic ISSN: 1759-9962
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 2019
• Issue: 10
• Pages: 1213-1220
• DOI: https://doi.org/10.1039/c8py01711e
• Public URL: https://durham-repository.worktribe.com/output/1338941