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Temperature Variation Enables the Design of Biobased Block Copolymers via One‐Step Anionic Copolymerization
Author(s) -
Bareuther Jennifer,
Plank Martina,
Kuttich Björn,
Kraus Tobias,
Frey Holger,
Gallei Markus
Publication year - 2021
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.202000513
Subject(s) - copolymer , polystyrene , polymer chemistry , materials science , molar mass , styrene , monomer , anionic addition polymerization , myrcene , tetrahydrofuran , polymerization , solvent , chemical engineering , chemistry , organic chemistry , polymer , composite material , chromatography , limonene , essential oil , engineering
A one‐pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature‐induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at −78 °C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (−38 °C to room temperature) leads to poly(styrene‐ block ‐myrcene) formation due to polymerization of myrcene. Well‐defined BCPs featuring molar masses in the range of 44–117.2 kg mol −1 with dispersities, Ð , of 1.09–1.21, and polymyrcene volume fractions of 30–64% are accessible. Matrix assisted laser desorption ionization‐time of flight mass spectrometry measurements reveal the temperature‐controlled polymyrcene block formation, while both transmission electron microscopy and small‐angle X‐ray scattering measurements prove the presence of clearly microphase‐separated, long range‐ordered domains in the block copolymers. The temperature‐controlled one‐pot anionic block copolymerization approach may be general for other terpene‐diene monomers.