Biobased polyurethanes from microalgae. Dr Philip B. Sellars

Transcription

1 Biobased polyurethanes from microalgae Dr Philip B. Sellars

2 High value-added chemicals and BIoreSIns from algae biorefineries produced from CO 2 provided by industrial emissions

3 Project 3

4 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

5 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

6 Algae oil Algae oil from initial extraction is not clean enough for use in desired reactions Further extraction with acetone allows removal of some acetoneinsoluble 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

7 Algae oil Attempts at bleaching algae oil with adsorbents Fuller s Earth, Activated Charcoal gave poor mass return Algae oil converted to methyl ester Bleaching carried out with sodium hypochlorite, Fuller s Earth and Activated Charcoal to give amber-coloured oil 7

8 Algae oil 8

9 Project overview 9

10 Algae oil polyols Fish oil Algae oil 10

11 Algae oil polyols Fish oil Algae oil 11

12 Algae oil polyols 12

13 Algae oil polyols 13

14 Algae oil polyols 14

15 Algae oil polyols 15

16 Algae oil polyols 16

17 Algae oil polyols 17

18 Algae oil polyols 18

19 Algae oil polyols 19

20 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) oily/waxy FO epoxide (2eq) viscous & tacky FO diethanolamide slightly pliable solid FO ethanolamide epoxide solid foam AO epoxide ( 0.4eq ) oil AO epoxide ( 2eq ) viscous & tacky AO diethanolamide solid AO ethanolamide epoxide solid foam 20

21 Algae oil polyurethanes 21

22 Algae oil polyurethanes 22

23 Algae oil polyurethanes 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 23

24 Algae oil polyurethanes 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 24

25 Model isocyanate studies 25

26 Existing bio-based diisocyanates Hojabri, L.; Kong, X.; Narine, S. S. Biomacromolecules 2009, 10,

27 Model isocyanate studies 1 H 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

28 Model isocyanate studies 28

29 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

30 Acknowledgements Dr Andrew Ross Dr Stuart Coles Dr Andrew Clark Funded by the European Union Seventh Framework Programme (FP7/ ) under Grant Agreement No (BISIGODOS)