Safer bio-based solvents to replace toluene and tetrahydrofuran for the biocatalyzed synthesis of polyesters
Abstract: With increased awareness of environmental issues caused by traditional petrochemical processes, both academia and industry are making enormous efforts towards the development of sustainable practices using renewable biomass as a feedstock. In this work, the biocatalyzed synthesis of polyesters derived from renewable monomers was performed in safer, bio-derivable organic solvents. Candida antarctica lipase B (CaLB), an enzyme belonging to the Ser-hydrolase family (adsorbed on methacrylic resin, also known as Novozym 435) was tested for its performance in the synthesis of adipate- and furandicarboxylate-based polyesters. In addition, the traditional solvents toluene and tetrahydrofuran were compared with a series of green solvents, 2,2,5,5-tetramethyloxolane, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran and pinacolone for the enzymatic polymerizations. We can conclude that the monomer conversions and molecular masses of the obtained polyesters in all the tested alternative solvents were suitable, and in some cases superior, with CaLB immobilized via physisorption on acrylic resin being the optimal biocatalyst for all reactions. Strikingly, it was found that for the majority of the new solvents, lower reaction temperatures gave comparable monomer conversions and polymers with similar molecular weights whilst pinacolone yielded better polymers with Mn > 2000 Da and conversions of over 80%. Click here to read the full publication.
2,2,5,5-Tetramethyloxolane (TMO): An unusual Ether which can replace hazardous hydrocarbon solvents (Poster exhibition at the Eco-Bio Conference 2018, Dublin, Ireland)
Public report available: ‘labelling requirements for hazard communication and ecolabelling possibilities’
A report on ‘labelling requirements for hazard communication and ecolabelling possibilities’ is currently available for the public. The report is prepared by the ReSolve project partner, nova-Institute, Germany. This report focusses on relevant European regulation in a global context to assess and give recommendations for labeling requirements for hazard communication and ecolabelling possibilities for bio-based solvents. The information collected on the ecolabel will serve as a baseline for comparing the actual properties of the solvents in the project and will thus facilitate the selection of the high-potential candidates. Click here to download the full report:
A methodical selection process for the development of ketones and esters as bio-based replacements for traditional hydrocarbon solvents
Abstract: A “top down” approach to the development of sustainable, greener, low-polarity solvents is presented. Methyl butyrate, ethyl isobutyrate, methyl pivalate and pinacolone were identified as potential target solvents from trends in Hansen solubility parameters and known physical properties. Solubility, flammability and physical properties were determined which showed their potential to replace traditional, hazardous, volatile, non-polar solvents such as toluene. Each new candidate then demonstrated their suitability to replace these traditional solvents in solubility tests, despite being esters and ketones, each candidate demonstrated their similarity to traditional volatile non-polar solvents in terms of their solubility properties by their ability to dissolve natural rubber, a particularly low-polarity solute. This was reinforced by their performance in a model Menschutkin reaction and a radical-initiated polymerisation for the production of pressure-sensitive adhesives, where their performance was found to be similar to that of toluene. Importantly, a preliminary toxicity test (Ames test) suggested non-mutagenicity in all candidates. Each of the four candidates can be synthesised via a catalytic route from potentially renewable resources, thus enhancing their green credentials. Read the full article in Green Chemistry.
Public report available:‘regulatory human- and environmental safety requirements of solvents in relation to their production-volume and use’
A report on ‘regulatory human- and environmental safety requirements of solvents in relation to their production-volume and use’ is currently available for the public. The report is prepared by the ReSolve project partner, BioDetection Systems b.v, Amsterdam (WP leader 4). This report focusses on relevant European regulation in a global context. All formal requirements for registration, classification and labelling and risk assessment are reviewed and the steps required are summarized. The REACH Regulation and its registration and information requirements are a major driver as also recognized in the recent European standardization Committee standard CEN/TS16766 on bio-based solvents, requirements and test methods. This hazard information gathering may result in identification of substances having dangerous properties that are to be communicated via specific classification and labelling prescriptions. Click here to download the report.