Biobased polyurethanes from microalgae - AlgaEurope · Dr Philip B. Sellars. High value-added...

Biobased polyurethanes from microalgaeDr Philip B. Sellars

High value-added chemicals and BIoreSInsfrom alGae biorefineries produced from CO2

provided by industrial emissions

Project

3

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

4

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

5

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

6

• 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

7

Algae oil

8

Project overview

9

Fish oil

Algae oil polyols

Algae oil

10

Algae oilFish oil

Algae oil polyols

11

Algae oil polyols

12

Algae oil polyols

13

Algae oil polyols

14

Algae oil polyols

15

Algae oil polyols

16

Algae oil polyols

17

Algae oil polyols

18

Algae oil polyols

19

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

21

Algae oil polyurethanes

22

• 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

23

• 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

24

Model isocyanate studies

25

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%)

27

Model isocyanate studies

28

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)

29

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)