title: Green process for green materials: viable low-temperature lipase-catalysed synthesis of renewable telechelics in supercritical CO2.
abstract: We present a novel near-ambient-temperature approach to telechelic renewable polyesters by exploiting the unique properties of supercritical CO(2) (scCO(2)). Bio-based commercially available monomers have been polymerized and functional telechelic materials with targeted molecular weight prepared by end-capping the chains with molecules containing reactive moieties in a one-pot reaction. The use of scCO(2) as a reaction medium facilitates the effective use of Candida antarctica Lipase B (CaLB) as a catalyst at a temperature as low as 35°C, hence avoiding side reactions, maintaining the end-capper functionality and preserving the enzyme activity. The functionalized polymer products have been characterized by (1)H nuclear magnetic resonance spectroscopy, matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry, gel permeation chromatography and differential scanning calorimetry in order to carefully assess their structural and thermal properties. We demonstrate that telechelic materials can be produced enzymatically at mild temperatures, in a solvent-free system and using renewably sourced monomers without pre-modification, by exploiting the unique properties of scCO(2). The macromolecules we prepare are ideal green precursors that can be further reacted to prepare useful bio-derived films and coatings.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: S
authors.identifier: http://orcid.org/0000-0003-3386-7199
authors.initials: S
authors.lastname: Curia
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: A F
authors.initials: AF
authors.lastname: Barclay
authors.affiliation: Department of Fibre and Polymer Technology, KTH Royal Institute of Technology, 100 44 Stockholm, Sweden.
authors.forename: S
authors.initials: S
authors.lastname: Torron
authors.affiliation: Department of Fibre and Polymer Technology, KTH Royal Institute of Technology, 100 44 Stockholm, Sweden.
authors.forename: M
authors.initials: M
authors.lastname: Johansson
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK steve.howdle@nottingham.ac.uk.
authors.forename: S M
authors.initials: SM
authors.lastname: Howdle
keywords: azelaic acid; lipase; supercritical CO2; telechelics