Biobased polyurethanes from microalgaeDr Philip B. Sellars
High value-added chemicals and BIoreSInsfrom alGae biorefineries produced from CO2
provided by industrial emissions
Project
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Project consortium
• Microalgae strain optimisation: PHYCOSOURCE, BIO FUEL SYSTEMS
• Microalgae production and optimisation: BFS, CASPEO
• Bio-oil fractionation and thermo-chemical processing: BFS, VTT, 3V MABO SPA
• Synthesis and evaluation of diols, diisocyanates, polyurethanes: CUSA, AIMPLAS, UNIVERSITY OF WARWICK
• Amino acid production: GBR.AT
• Aromatic and heterocycle derivatives processing for surfactants, inks and anticorrosive coatings: CRODA, SUNCHEM, BECKERS, UNIVERSITY OF BANGOR, AIMPLAS
• Integrated designs for industrial-scale value chains: PDC
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Algae oil
• Nannochloropsis gaditana cultivated in vertical bioreactors by Bio Fuel Systems (Alicante, Spain)
• Extraction with ethanol carried out by VTT Technical Research Centre (Espoo, Finland)
• FAME analysis of triglyceride shows major composition is:
- 22% methyl palmitate
- 27% methyl palmitoleate
- 33% methyl eicosapentaenoate
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Algae oil
• Algae oil from initial extraction is not clean enough for use in desired reactions
• Further extraction with acetone allows removal of some acetone-insoluble phospholipids, facilitating aqueous work-up in subsequent reactions
• Dark colour of oil is transferred into reaction products – this is a problem for desired end use as an adhesive for food packaging
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• Bleaching carried out with sodium hypochlorite, Fuller’s Earth and Activated Charcoal to give amber-coloured oil
Algae oil
• Attempts at bleaching algae oil with adsorbents – Fuller’s Earth, Activated Charcoal – gave poor mass return
• Algae oil converted to methyl ester
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Algae oil
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Project overview
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Fish oil
Algae oil polyols
Algae oil
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Algae oilFish oil
Algae oil polyols
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Algae oil polyols
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Algae oil polyols
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Algae oil polyols
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Algae oil polyols
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Algae oil polyols
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Algae oil polyols
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Algae oil polyols
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Algae oil polyols
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Algae oil polyurethanes
• Small-scale polyurethane synthesis trial with fish oil and algae oil polyols
• 1:1 mixture of polyol/MDI functional groups based on hydroxyl functionality of polyol
Polyol OHV OH functionality Appearance
FO epoxide (0.4eq) 62.6 0.44 oily/waxy
FO epoxide (2eq) 196.9 1.48 viscous & tacky
FO diethanolamide 220.0 1.57 slightly pliable solid
FO ethanolamide epoxide 280.5 2.14 solid foam
AO epoxide (“0.4eq”) 70.1 0.47 oil
AO epoxide (“2eq”) 173.9 1.27 viscous & tacky
AO diethanolamide 203.5 1.30 solid
AO ethanolamide epoxide 247.5 1.81 solid foam20
Algae oil polyurethanes
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Algae oil polyurethanes
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• Larger-scale polyurethane synthesis carried out with fish oil and algae oil diethanolamide and ethanolamide epoxide polyols
• Polymer samples unsuitable for tensile testing– ethanolamide epoxide PUs were difficult to cast (rapid viscosity increase) and
led to brittle samples
– diethanolamide PUs were too soft
• DMTA of diethanolamide PUs was also unsuccessful
Algae oil polyurethanes
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• Larger-scale polyurethane synthesis carried out with fish oil and algae oil diethanolamide and ethanolamide epoxide polyols
• Polymer samples unsuitable for tensile testing– ethanolamide epoxide PUs were difficult to cast (rapid viscosity increase) and
led to brittle samples
– diethanolamide PUs were too soft
• DMTA of diethanolamide PUs was also unsuccessful
• Samples undergoing lap shear testing to determine adhesive properties
• AO epoxide (“2eq”) polyol in PU formulation testing at CUSA
Algae oil polyurethanes
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Model isocyanate studies
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Existing bio-based diisocyanates
Hojabri, L.; Kong, X.; Narine, S. S. Biomacromolecules 2009, 10, 884 26
Model isocyanate studies
• 1H NMR indicates ~ 80% conversion
• Less than 20% alkene present – reduction of double bond?
• Flash column chromatography:
3.0 g crude material 2.35 g diacid product (78%)
0.49 g oleic/stearic acid (16%)
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Model isocyanate studies
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Model isocyanate studies
• Competing dimerisation of thiolactic acid is observed
• Optimisation of reaction with polyunsaturated fatty acids is ongoing
• Alternative ene reactions also being tested (e.g. with maleic anhydride)
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Acknowledgements
• Dr Andrew Ross Dr Stuart Coles Dr Andrew Clark
• Funded by the European Union Seventh Framework Programme (FP7/2007-2013) under Grant Agreement No. 613680 (BISIGODOS)