Premium
Bio‐Based Polyketones by Selective Ring‐Opening Radical Polymerization of α‐Pinene‐Derived Pinocarvone
Author(s) -
Miyaji Hisanari,
Satoh Kotaro,
Kamigaito Masami
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201509379
Subject(s) - polymerization , chain transfer , reversible addition−fragmentation chain transfer polymerization , polymer chemistry , ketone , polymer , chemistry , radical polymerization , raft , ring opening polymerization , conjugated system , photochemistry , materials science , organic chemistry
The most abundant naturally occurring terpene, α‐pinene, which cannot be directly polymerized into high polymers by any polymerization method, was quantitatively converted under visible‐light irradiation into pinocarvone, which possesses a reactive exo methylene group. The bicyclic vinyl ketone was quantitatively polymerized in fluoroalcohols by selective (99 %) ring‐opening radical polymerization of the four‐membered ring, which results in unique polymers containing chiral six‐membered rings with conjugated ketone units in the main chain. These polymers display good thermal properties, optical activities, and contain reactive conjugated ketone units. Reversible addition fragmentation chain transfer (RAFT) polymerization was successfully accomplished by using appropriate trithiocarbonate RAFT agents, enabling the synthesis of thermoplastic elastomers based on controlled macromolecular architectures.