Biobased monomers and polymers

Biobased monomers and polymers Biobased Performance Materials Consortium Day, June15, 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)

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

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

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 Biotechnological approach; PHA MCL Fluorescent pseudomonad Soil inhabitant Intracellular reserve material Polyester consisting of 3-Hfatty acids: poly(3-hydroxyalkanoates) PHA P. oleovorans. H. Preusting, J. Kingma, B. Witholt, 1996

Renewable alkyd resins produced by biotechnology PHA MCL produced by Pseudomonas putida CH 3 CH 3 (CH 2 ) x (CH 2 ) x C CH C CH C CH 2 CH 2 CH 2 n n = 1000-3000 x = 0-1, scl - PHAs (PHB, PHV) x = 2-11, mcl - PHAs

Renewable alkyd resins produced by biotechnology Programming thermal properties of PHA MCL Fatty acid mixtures as substrate Unsaturation Coconut Rape seed Tall oil Linseed 0 99 84 58 34 1 1 15 22 25 2-1 20 21 3 - - - 20 Glass transition and melting temperature of PHA Tg ( C ) - 43.7-56.3-59.8-61.7 Tm ( C) + 42.4 - - -

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

Rigid biobased building blocks: 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

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 2 Ways to prepare isosorbide diesters by direct esterification : Starting from isosorbide H H + 2 H + 2 H 2 Directly from sorbitol H H H H H H + 2 H + 4 H 2

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!

Rigid biobased building blocks: isosorbide Incorporation of isosorbide as a co-monomer is known to increase Tg of PET

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 n * Noordover, B.A.J. et al., Biomacromolecules 2006, 7, 3406-3416

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

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 33

Rigid biobased building blocks; furans Raw materials are renewable pentose sources found in rice hulls, corn cobs etc furfural Pentoses H Me methylfuroate Pentosans are hydrolysed to pentoses, which undergo H + catalysed dehydration to furfural Further derivatisation to useful furane based building blocks

Rigid biobased building blocks; di-furans

Biobased engineering polymers PBT-related polyester resins by small scale bulk polymerisation Me H H Me + Me Me H(CH 2 ) 4 H + + Me H H T F B I H Aim - High T g - High molecular weight - Low colour Irganox 1330 Ar Ar t Bu t Bu H Reaction conditions Catalyst: [Ti( i Pr) 4 ] (Ester/Ti = 1000/1) Diol/Ester ~ 1.2 (small scale: 1.5 g) Antioxidant (bulky phenol; 0.3% mol/ester) 1. Toluene, 170-180 o C, 1h, Ar 2. 210-220 o C, 1h, Ar 3. 210-220 o C, 3h, vacuum (slowly down to 1 mbar)

T g ( o C) Biobased engineering polymers Influence of dianhydrohexitol content on T g 200 180 160 140 120 100 80 60 40 20 0 100% terephthalic acid 0 20 40 60 80 100 200 180 160 140 120 100 80 60 40 20 0 50% terephthalic acid 50% bisfuran diacid 0 20 40 60 80 100 DAH content (%) DAH content (%)

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

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)

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. 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

Acknowledgements WUR/FBR: WUR/VPPC Daan van Es Carmen Boeriu Rolf Blaauw Ben van den Broek Guus Frissen Frits van der Klis Richard Gosselink Rutger Knoop Willem Vogelzang Marinus van den Hoorn Gerrit Eggink Ruud Weusthuis Many others Johan Sanders Elinor Scott Jerome Le Notre TU Eindhoven Cor Koning Bart Noordover Rob Duchateau Rolf van Benthem EU Biosynergy-, EU Bioproduction-, Algicoat partners, CCC, DPI, Biobased Performance Materials Financial support of: Dutch Polymer Institute, CCC, EU, SenterNovem, Dutch Ministry of Agriculture