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

Grune, Eduard and Bareuther, Jennifer and Blankenburg, Jan and Appold, Michael and Shaw, Lloyd and Mueller, Axel H. E. and Floudas, George and Hutchings, Lian R. and Gallei, Markus and Frey, Holger (2019) 'Towards bio-based tapered block copolymers : the behaviour of myrcene in the statistical anionic copolymerisation.', Polymer chemistry. .

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.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1039/C8PY01711E
Date accepted:22 January 2019
Date deposited:30 January 2019
Date of first online publication:23 January 2019
Date first made open access:22 January 2020

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