Biobased chemicals and materials

Biobased chemicals and materials Master Class, Terneuzen, 10 November, 2011 Jacco van Haveren Programme Manager Chemicals Wageningen University and Research Center/Biobased Products

Biorefineries Existing and future biorefineries will produce feedstocks for biobased chemicals and materials

Usage of bulk (platform) chemicals Bulk chemicals are used as: Solvents Starting components for soaps, lubricants, additives (low molecular weight components) Mostly as building blocks for polymers (high molecular weight components) and hence materials Building blocks can be either aliphatic (flexible) or aromatic (rigid) nature C6, C7, C8 (B, T, X) C2 C3 C4 others (including MTBE)

Introduction McKinsey: Innovation potential of fossil building blocks appears largely exploited 4

Most chemicals end up in polymeric materials Consumption of thermoplastics in Western Europe Functionalised chemicals; C, H. N, Biobased ambition About 50.000.000 tonnes in 2010 PE PP PVC PS/EPS PET others About ¾ of volume is in commodities like PE, PP, PVC About 50 % of economic value is in other polymers!

Biomass based monomers and polymers Biobased chemicals can have Have a unique structure Same structure as fossil oil based chemicals Naturally occurring biopolymers will increase in importance, but developing biobased monomers for controlled polymerisation into biobased polymers will be the dominant development direction for replacing petrochemical based materials, e.g. Compare starch based plastic versus PLA Biomass based chemicals preferably should result from waste streams or crops avoiding food vs. non food use competition

Biomass composition Cellulose (circa 50%): polymer of β-(1,4)-glucan Cellulose Hemi-cellulose (circa 25%): short-chain branched, substituted polymer of C5 and C6 sugars Lignin (circa 25%): polymer derived from Lignin Hemi- cellulose coniferyl, coumaryl and sinapyl alcohol precursors Proteins (up to 10%, depending on the plant species): Proteins ils polymer of amino acids ils (up to 10%, depending on the plant species): e.g. esters of glycerine and fatty acids

leochemie: vele toepassingen Toepassingen van vetzuren in de VS in 2000 J. Bozell, leochemicals as a Feedstock for the Biorefinery: High Value Products from Fats and ils, Biorenewables Initiative Publications, Iowa State University, IA (2004).

Building blocks for nylons from castor oil Arkema Arkema

Building blocks for polyurethanes form vegetable oils Thermal insulation 11% ther 5% Automotive 22% Thermal insulation 11% ther 5% Automotive 18% Furniture 34% Footwear 4% Coatings 8% Construction 16% Furniture 29% Footwear 4% Coatings 15% Construction 18% Total market (1985): 3.3 million tonnes Total market (2000): 9.3 million tonnes

Building blocks for polyurethanes from vegetable oils Polyols produced by e.g. Cargill, Cognis

Building blocks for polyurethanes form vegetable oils Hydroformylation method for preparing vegetable oil based polyols; DW Chemical s Renuva Polyol Technology

Non-isocyanate polyurethanes Novel renewable polyamides and non-isocyanate polyurethanes for coating applications (NPANIC): Cooperation: Nuplex Resins, CRDA, AKZNobel, Ursa Paint, TU/Eindhoven, WUR/FBR, University of Utrecht Target: To develop scientific and applied knowledge for the generation of isocyanate free polyurethanes Intended application area: (Car refinish) Coatings Potential spin off application: Insulation materials, construction materials

Biobased composite resins Cooperation: Nuplex Resins, NPSP, Cosun, Cargill, Calendula il, WUR/FBR, RUG Target: To develop scientific and applied knowledge for the generation of well functioning composite resins based upon (styrene-free) unsaturated polyesters can be generated. Intended application area: Renewable based composite resins to be used in e.g. wind turbine blades, train noses, automotive sector, road signs, boats

Fully renewable based alkyd resins Background Alkyds for decorative paint: Solvent or waterborne il: soya, safflower, sunflower, TFA, etc. High extent of C18:2 offers the optimal properties il length: 35-85 % (renewable) R poly-alcohols: glycerol, (di)pentaerythritol, trimethylol propane, etc poly-acids: (iso-, tere-, tetrahydro-)phthalic acid, trimellitic, etc Drying: Usually accelerated by cobalt or manganese based catalysts

100 % renewable alkyd resins Starting material Sucrose H H H H H H H H H Sucrose produced from sugar beet or sugar cane by many companies including Sensus (Neth.) and rafti (Belgium) Current estimated production volume: 140 million tonnes/annum

100 % renewable alkyd resins ligomeric sucrose-linoleate binders: Parameters varied: type of chain extender/ratio chain extender/fame additional acetylation processing method; trans - or interesterification

100 % renewable alkyd resins Sucrose based alkyd resins Test VN-227 VN-228 VN-231 Low shear viscosity (dpa.s) High shear viscosity (dpa.s) 14.0 14.0 13.8 Comm. product 9.8 > 10 9.6 4.6 Solids (%) 89.6 93.7 85.7 80.5 VC (g / L) 134 83 180 260 Whiteness 77.1 75.4 74.8 76.5 Drying (RT; 50 % RV) 0 0 0 0 Drying (5 C; 90 % RV) 0 0 0 0 Gloss 98.8 88.9 83.5 85.9 Water sensitivity (4 days) 0 0 0 0 Levelling 0-1 0-1 0-1 1-2 Hiding power 1 1 1 1

Renewable alkyd resins produced by biotechnology Adhesion and flexibility test As latex (in water) As high solid paints (low VC) Very flexible, high gloss, strong adhesion Drying times need to be evaluated in presence metal driers

Alternative renewable feedstocks Alternative vegetable / FA sources: algae AlgiCoat project polyunsaturated fatty acids AkzoNobel Delesto (AkzoNobel/Essent) algae Wageningen UR residue other fatty acids other chemicals Delfzijl C 2 heat other products, heat, electricity Ingrepro / Wageningen UR

Chemicals from glycerol antivries koelvloeistof polyesters ADM coatings polymeren oplosmiddelen DW, Solvay epoxyharsen coatings polymeren Dupont FBR plastics oplosmiddelen Arkema

Biomass based monomers and polymers Top 12 chemicals from biomass (2004 US-DE study) Based on 2 nd approach Scientific fundamentals for certain choices are questionable 1 2 3 H H H H H H HC CH H H 4 5 6 7 H H H H H H H H NH NH H 2 H H 2 H 8 9 10 11 H H H H H H H H H H H 12 H H H H H

Biobased Monomers Target chemicals: Functionalised chemicals Flexible diols, diacids, hydroxy acids predominantly produced by biotechnology; Such chemicals can substitute current petrochemical based diols/diacids and potentially olefines Rigid building blocks, by chemical conversion, to substitute petrochemical based aromatics

Biobased Monomers Scientific challenges: Creating chemicals from fossil oil based feed stocks is about selectively introducing functionality Creating chemicals based upon biomass is about selectively removing functionality Dehydratation Deoxygenation Decarboxylation, decarbonylation

Some current monomers for polymers

Potential renewable based monomers

New building blocks- lactic acid Now large scale production by NatureWorks; 140kt/a name plate capacity [PET production 2008 will be approx 49 MioT] Application fields expanded to all kinds of biodegradable materials Packaging films Disposable containers (bottles, cups) Fibres (textile) Number of applications limited due to low T g of approx. 60 C Innovations required for real brake-through

PLA; Effect of Chain Structure on Properties PLA Packaging grade Copolymer of L- and D-isomers Low melting point In practice amorphous Transparent PLA Biomaterials grade Homopolymer of L-isomer High melting point In practice semi-crystalline Transparent / Hazy

Processing: 3D-foamed structures Expandable bead technique Good cell structure Density <30 g/l

Rigid biobased building blocks: sorbitol and isosorbide What is dianhydrosorbitol or isosorbide? Isosorbide is prepared by acid catalysed dehydration of sorbitol H CH 2 H CH 2 H H H H H H H H H H H H H H H H n starch glucose sorbitol isosorbide Sorbitol is prepared by hydrogenation of glucose, which can be prepared by hydrolysis of starch Routes to isosorbide starting from cellulose are being developed

Heavy metal free heat stabilisation of PVC Target; replace lead stabilisers Alternative to tin based stabilisers? effect of different types of stabilisers on early colour and long term heat stability lead compound HMF blank + uracil (0.15 phr) + BGAC (0.2 phr) HMF compound (min), SHS (Mathis oven, 200 C, 30 min)

Natural polyols as heat stabilisers Effects of polyols on early colour of HMF PVC compound blank sorbitol TMP glycerol 0 Polyols were added based on mmol primary hydroxyl groups: sorbitol and glycerol: 20 mmol TMP: 13 mmol t in min. @ 200 C in Mathis oven 30

Heavy metal free heat stabilisation of PVC AKZ-AT joint development (W0206392) R R monomeric dihydropyridines as colour stabilisers N H work via curative mechanism; reduction of polyene sequences synergistic relationship with polyols, especially sorbitol, and inorganic acid scavengers some were already known and available (D507, Sinesal-M), yet expensive and unstable

Isosorbide based plasticisers Dominant current plasticisers are esters of phthalic acid: e.g. DEHP,DINP Phthalates are potential endocrine disruptors Isosorbide plasticisers are esters of dianhydro sorbitol, or isosorbide: e.g. IsDEH (DEHP analogue)

Isosorbide; alternative plasticisers Plasticisers for poly (vinyl chloride): Phthalates: 80-90% of all plasticisers DEHP (DP) BBP Phthalates are under environmental pressure: need for non-toxic, environmentally benign and commercially viable alternatives.

Isosorbide diesters Directly from sorbitol: H H H H H H + 2 H + 4 H 2 D.S. van Es et al., Synthesis of Anhydroglycitol esters of improved colour, W 01/83488 to WUR/A&F Selective dehydration of sorbitol to isosorbide at 120 C Esterification at 140-150 C Macroporous ion exchange (Amberlyst 15) resin as catalyst Diester yields 95-99 % Proprietary technology to further remove minor impurities

Isosorbide esters; technical performance in PVC Plasticising properties: plasticising efficiencies (Shore A&D) Isosorbide esters are primary plasticisers 80 70 Required properties can be tuned by changing the alkyl chain 60 50 40 Shore A (70 phr) Shore D (35 phr) 30 IsDH IsDHep IsDEH IsD IsDiD DEHP Biobased flexible PVC makes only sense in combination with bio-plasticisers!

Isosorbide based powder coating resins Typical synthesis esterification from 180 ºC up to 250 ºC under Ar during 3-4 hrs polycondensation in vacuo (P < 5 mbar) during 4 hrs catalyst: Ti(Bu) 4 Example: H H H H H H H H + + - H 2 isosorbide 2,3-butanediol succinic acid Ti (Bu) 4 * H H Noordover, B.A.J., J. v. Haveren et al., Biomacromolecules 2006, 7, 3406-3416 n *

T g [ºC] Isosorbide based powder coating resins T g as a function of isosorbide content 70 60 50 40 30 20 10 0 50 60 70 80 90 100 isosorbide content [mol%] Figure: The effect of incorporating different amounts of isosorbide on the Tg values of terpolyesters. ; 1,3 propanediol ; neopentyl glycol ; 2,3-butanediol.

Isosorbide based powder coating resins Tri functional components (glycerol or citric acid) were included in succinic acid- dianhydrohexitol polyester synthesis to induce synthesis of H or CH functional terpolyesters HC H CH CH H H H Glycerol (0.06 molar equivalent compared to succinic acid) incorporated during synthesis polyesters at 230-250 ºC Citric acid (0.20 mol/eq); end capping of H functional resins at 150 ºC

Isosorbide based powder coating resins Accelerated weathering Experiments carried out using high intensity Mercury lamp at high temperature (~60 ºC) for 20 hours reference coating No change in film appearance: - color - gloss No cracking or other visible signs of film deterioration weathered coating IR measurements show strong increase in H, -H and C= chain scission Reduced impact resistance (similar to conventional systems) More pronounced yellowing of TPA-containing conventional systems

Furan building blocks: 2,5-FDA platform Furan dicarboxylic acid could be a bio based alternative to terephthalic acid or (iso)phthalic acid) CH HC CH CH 2,5-FDA terephthalic acid Terephthalic acid used to produce e.g. PET (bottle, fleece) or e.g. Aramid fibres Feedstocks for furans (C5, C6 sugars) are likely side streams 2 nd generation bioethanol production

Biobased PET PET wordt nu jaarlijks in miljoenen tonnen geproduceerd uitgaande van aardolie grondstoffen Er is vanuit de industrie veel belangstelling voor Biobased PET

Furan building blocks: 2,5-FDA platform HC HMFA H Biosynergy H HMF H DPI H H H H D-fructose H DPI Bioproduction Biosynergy MeC MeC H HC CH CCC Hemi-Cellulose Me-2-furoate Bioproduction (co)polyesters MeC H Bioproduction (co)polyesters (co)polyesters

2,5 FDA based polyesters Polybutylene 2,5-furanoate; 50 g scale melt polymerisation Polyesters have been described before, see e.g. Gandini et al, J. Polym. Sci, Part A, Polym. Chem. 2009,47,295, but only at 1-3 gram scale

2,5 FDA based polyesters Polybutylene 2,5-furanoate; 50 g scale Me Me Catalyst + H Anti-oxidant * H 1) 180 C, N 2 2) 220 C, N 2 3) 240 C, 10 mbar * Results ff-white brittle material after work-up M n 14,000 ( 1 H-NMR end-groups, CDCl 3 /CF 3 CD); DP = 70 T g = 28 C T c = 92 C T m = 174 C (lit. 163-165 C )

2,5 FDA based polyesters Polybutylene 2,5-furanoate; TGA (10 C/min, air) PBT T m PBF T m

2,5 FDA Polymerisation trials All polymers give colorless precipitates; Tm, Tg, Tc recorded Colorless powders or transparent fibers PEF PBT PPF PBI Mechanical properties will be determined 48

Biobased terephthalic acid Wageningen technology: Three step synthesis of aromatic di-acids from sugars Step 1 > 90 % yields starting from commercial product at about 600 tonne Step 2 > 75 % yield Step 3; currently approximately 50 % yield Based upon approximately one year of research Patent filing in progress verall yields are believed to be higher than GEV s approach

Biobased polymers with identical structure biomass to ethanol H H H H H H ethanol to ethylene biothene H H H H n Braskem has started production polyethylene based on bioethanol: Dow Chemicals previously announced production

Technologies: Bioethanol Pre-treatment required to make sugars available for fermentation

Technologies: Bioethanol Example of enzymatic hydrolysis of lignocellulose

A,B,E Research targets Improvement of product yields Metabolic engineering towards higher butanol yields Improvement of process economics Alternative substrates for fermentation: Lignocellulosics (ES-LT Biobutanol), Seaweeds (ES-LT project) B-Basic Recycling (re-use of microbial biomass as nutrient, positive effect) High-cell density cultures, in-situ product removal

A,B,E Approach Lactate Acetate Acetone Butyrate Ack acetyl-p acetoacetate C 2 Buk butyryl-p H 2 Glucose EMP pyruvate acetyl- CoA acetoacetyl- CoA butyryl- CoA C 2 Acetoin Ethanol Butanol Inhibition of acid production: No acetone production, Lower ATP yield Fig.1 Simplified glucose metabolic pathway in C. acetobutylicum

I, B,E fermentation Redirecting fermentation towards isopropanol; isopropanol is a significant product as such and a precursor to biobased propylene Table 1 : Wild type and transformants performance during fermentation on glucose (90g/L). Results obtained W W Y Z Glucose consumed [g/l] 34.30 61.99 69.26 67.79 Butyric acid [g/l] 0.21 2.02 1.08 1.06 Acetone [g/l] 0.17 5.70 0.35 0.09 Ethanol [g/l] 0.12 1.26 1.34 1.71 2-propanol [g/l] 4.47 0.10 7.27 8.37 Butanol [g/l] 8.08 8.98 11.80 12.95 Total solvent [g/l] 12.83 16.04 20.76 23.12 Culture time [h] * 33.5 49.5 29.9 28.0 Productivity [g/l/h] 0.41 0.41 0.69 0.81 Solvent yield [g solvents/g subs.] 0.37 0.26 0.30 0.34 Isopropanol selectivity [g/g] 0.35 0.01 0.35 0.36 Acetone selectivity [g/g] 0.01 0.36 0.02 0.00 Isopropanol production doubled with regard to wild type wild type

Alternative substrates for fermentation Characterization of materials: Biochemical analysis, pre-treatment hydrolysis, in collaboration with Pulp and Fibre Group Characterization of hydrolysates (sugars, furfurals, organic acids, etc) Toxicity and tolerance tests, fermentability Example: Seaweeds (ES-LT Seaweed Biorefinery) Ulva sp. (green) Alaria esculenta Palmaria palmata Laminaria digitata

Biomethanoll Develop a green technology to produce MeH from C 2 or CH 4 Project for the production fo BioMeH from C 2 is running (BioSolar program))

Styrenic and acrylic monomers Conversion of Protein Biomass into Styrene and Acrylates: Biomass Bio-ethanol J. Spekreijse, Dr. J. Le Nôtre Protein Hydrolysis DDGS Separation H PAL H NH 2 Amino Acids PAL Mixture 1) Esterification 2) Separation Esterification R PCT International Application: lefin cross-metathesis applied to biomass

Conversion(%) Co-production of bulk chemicals based upon biomass Cinnamates to Styrene and Acrylates by Ethenolysis Reactions: J. Spekreijse, J. Le Nôtre R 12.5 mol% catalyst ethene (1 bar) DCM, 40 o C, 24 h + R R Conversion into products [a] H 31% Et 28% (0.05 M, R = H, Et, n-bu) n-bu 39% ( [a] ca. 15% of stilbene was formed) Catalyst: Hoveyda-Grubbs 2 nd generation Pressure Screening: 25 0.02 M substrate, 5 mol% HG-2 nd, DCM, 40 C, 24 h 20 Higher ethene pressure leads to lower conversion 15 10 Cinnamic Acid Ethyl Acrylate 5 ther acrylic monomers potentially can be co-produced from carbohydrate based resources PCT International Application: lefin cross-metathesis applied to biomass 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Ethene pressure (bar)

Novel resources

Conclusions Both flexible as well as rigid aromatic building blocks can be created based upon renewables These building blocks can be used for the creation of novel thermoplastic or thermoset materials, or Can serve as drop in solutions (e.g. propylene, styrene, acrylates) Economical perspectives of future biorefineries can be optimised by focusing on bulk chemical production Preferably usage should be made of waste streams/crops not interfering with food production

The ambition for the future C 2 Energy Bulk chemicals Biomass and wastes Sustainable Catalytic Processes Fine/ Pharmaceuticals Recycling Source: CATCHBI project