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

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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.

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

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Publication details

The article was received on 02 Dec 2018, accepted on 22 Jan 2019 and first published on 23 Jan 2019


Article type: Paper
DOI: 10.1039/C8PY01711E
Citation: Polym. Chem., 2019, Advance Article

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

    E. Grune, J. Bareuther, J. Blankenburg, M. Appold, L. Shaw, A. H. E. Müller, G. Floudas, L. R. Hutchings, M. Gallei and H. Frey, Polym. Chem., 2019, Advance Article , DOI: 10.1039/C8PY01711E

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