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)