ORGANIC MODIFICATION AND FUNCTIONALIZATION OF BIOBASED AROMATICS AND
ORGANIC MODIFICATION AND FUNCTIONALIZATION OF BIOBASED AROMATICS AND THEIR USE IN INDUSTRIAL POLYMERS AND FORMULATIONS elena. benedetti@aeppolymers. com www. aeppolymers. com Elena Benedetti, Pietro Campaner, Francesca Dinon, Andrea Minigher AEP Polymers All rights reserved – © AEP Polymers 2016
CASCADING USE OF RESOURCES – ZERO WASTE CONCEPT ETHICS • Waste or byproducts/non edible resources • Are we affecting already integrated re -use chains? All rights reserved – © AEP Polymers 2016
CASCADING USE OF RESOURCES – ZERO WASTE CONCEPT ETHICS • Waste or byproducts/non ECONOMIC CONSIDERATIONS • • • edible resources Is the resource/its transformation cost Are we affecting already integrated re effective? -use chains? Are there incentives? Funded projects? Networks? All rights reserved – © AEP Polymers 2016
CASCADING USE OF RESOURCES – ZERO WASTE CONCEPT ETHICS • Waste or byproducts/non ECONOMIC CONSIDERATIONS • • LONG • • edible resources Is the resource/its transformation cost Are we SUPPLY/VOLUMES affecting already integrated re TERM effective? -useit chains? Is reasonable to foresee a long Are there incentives? Funded projects? term/high volume availability of the raw Networks? material? All rights reserved – © AEP Polymers 2016
CASCADING USE OF RESOURCES – ZERO WASTE CONCEPT ETHICS • Waste or byproducts/non ECONOMIC CONSIDERATIONS edible resources • Is the resource/its transformation cost • Are we SUPPLY/VOLUMES affecting already integrated re LONG TERM effective? -useit chains? • Is reasonable to foresee a long TECHNICAL FEASIBILITY • Are there incentives? Funded projects? term/high volume availability of the raw Networks? • Is it available as purified material? • Do we have a technical advantage from the final material? All rights reserved – © AEP Polymers 2016
CASCADING USE OF RESOURCES – ZERO WASTE CONCEPT ETHICS • Waste or byproducts/non ECONOMIC CONSIDERATIONS edible resources • Is the resource/its transformation cost • Are we SUPPLY/VOLUMES affecting already integrated re LONG TERM effective? -useit chains? • Is reasonable to foresee a long TECHNICAL FEASIBILITY • Are there incentives? Funded projects? term/high volume availability of the raw Networks? • Is it available as purified material? INDUSTRIALIZATION AND MARKET • Do we have a technical advantage from • Is the synthesis feasible on an industrial the final material? scale? • Cost vs market price • Fields of application and Market shares • Prospective customer perception All rights reserved – © AEP Polymers 2016
FROM WASTE TO INDUSTRIAL MATERIAL Purification DISTILLATION HYDROLYSIS PIROLISYS ENYMATIC ROUTE… Design and synthesis Physico-chemical, thermal and mechanical characterization Formulations and benchmarking Optimization + prototyping/ demo Scale up of the synthesys, QC… Product/process Industrialization, MKT Material, Customer contact All rights reserved – © AEP Polymers 2016
BIOBASED PRODUCTS AND APPLICATIONS CARBOHYDRATES/ GLYCOLS • Biodegradable thermoplastics • Diols: polyurethane elastomers • Polyols: polyurethane foams • Glycerol: epychlorohydrin for epoxy resins • Thermoplastic polymers o sy t tic a e : a PRO , enzim le act ersati r t x e e, v rout emistry ch , hilic p o r hyd urce : N CO d reso foo FATTY ACIDS AROMATICS • Polyols: polyurethane foams &CASE • Epoxy resins: composites • Acrylic resins: coatings • Thermoplastic polymers • Resole resins: furniture • Phenolic resins: flameretardant composites, flameretardant rigid foams • Polyurethanes (insulation, adhesives, coatings) • Epoxy resins: composites & coatings; • Amines: composites & coatings • Raw materials for thermoplastics d, -foo ce, n o an : n PRO perform high mal stance, ical r e h t resi hem fire tivity, c ersatile reac ance, v ry t st resi chemis ter a w not ources : N CO , few s ble solu rket le a m : p PRO ility, sim ilab try ava hemis c low re : N CO ture/fi pera ance m e t st al resi chanic me ce Low forman ity per eactiv r Low All rights reserved – © AEP Polymers 2016
BIOBASED PHENOLICS – The Smart. Li project SMART TECHNOLOGIES FOR THE CONVERSION OF INDUSTRIAL LIGNINS • Structural support in plants and algae • Cross-linked phenolic polymers • Recovery: pulping processes (liquors) bio-refineries (cakes) • Composition is strongly affected by type of wood and processing • The project is a three-year programme which aims to develop valorisation routes for lignin, for example, in plywood resins and composites. Glazer, A. W. , and Nikaido, H. (1995). Microbial Biotechnology: fundamentals of applied microbiology. San Francisco: W. H. Freeman, p. 340. This project has received funding from the Bio-Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme under grant agreement No 668467. All rights reserved – © AEP Polymers 2016
BIOBASED PHENOLICS – The Smart. Li project SMART TECHNOLOGIES FOR THE CONVERSION OF INDUSTRIAL LIGNINS • Technical challenges for industrial use: - Controlled depolymerization process - Colour - Fractionation step - Odour EPOXY RESIN SYSTEMS: Dispersion of Kraft Lignin and lignosulfonate as such in bisphenol-A epoxy resin: • No chemical modification/functionalization • Minimizing total energy for grinding/dispersion • • Size reduction • Use of high shear mixer Maximizing performance Next steps: improve particle reduction (mill) use of rheological modifiers This project has received funding from the Bio-Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme under grant agreement No 668467. All rights reserved – © AEP Polymers 2016
BIOBASED PHENOLICS – The Smart. Li project SMART TECHNOLOGIES FOR THE CONVERSION OF INDUSTRIAL LIGNINS LIGNIN IN POLYURETHANE FOAMS: Liquefaction approach 1: • Kraft Lignin liquefied using commercial polyether polyols and glycerol • Analytical QC tests performed • The liquefied lignin-polyol have been used in reference PU formulations (rigid and flexible foams) in combination with biobased polyols and petro-based polyols • Reactivity, compression strength, fire properties (UL-94 V) have been determined Preliminary results • Wide OH range (depending on polyether polyols type and amount and glycerol amount) • Reduced systems reactivity by 20 -30%, same final density (23 kg/m 3 flex foam, 35 kg/m 3 rigid foam) • Lower compression strength in rigid PU foams (reduction 10 -20%) • Good impact on biobased content • Good impact on fire properties (V 1 to V 0, formulation dependent) 1. Jin, Yanqiao, et al. "Liquefaction of lignin by polyethyleneglycol and glycerol. " Bioresource technology 102. 3 (2011): 3581 -3583. This project has received funding from the Bio-Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme under grant agreement No 668467. All rights reserved – © AEP Polymers 2016
BIOBASED PHENOLICS - CASHEW NUTSHELL LIQUID (CNSL) 25% food market 75% 50% bio-fuel 25% EXTRACTION PRODUCTS FOR INDUSTRIAL APPLICATIONS DISTILLATION Residol (biofuel) CNSL SYNTHESIS cardanol All rights reserved – © AEP Polymers 20156
CNSL COMPOSITION ANACARDIC ACID CARDANOL 1 - DECARBOXYLATION 2 - DISTILLATION: CARDOL 2 -METHYL CARDOL - Batch - Short path - Thin film Cardanol purity ≥ 86%, cardanol grade affects: - SYNTHESIS - MATERIAL PERFORMANCE - COST All rights reserved – © AEP Polymers 2016
CARDANOL STRUCTURE AND BENEFITS Water resistance Adhesion Humidity resistance Fast cure Corrosion resistance Low temperature cure Pot life Low viscosity Surface tension Flexibility INDUSTRIAL USES: Chemical & thermal resistance Friction particles Friction resins Marine coatings (epoxy) Flooring (epoxy) Polyurethanes (foams, adhesives, coatings) Composites All rights reserved – © AEP Polymers 2016 NEW
CNSL CHEMICAL MODIFICATION Esterification, Epoxidation Allylation, Alkylation Ethoxylation, Propoxylation Phosphatation First publication: • 1940, Harvey&Caplan 1940 -2010: • 7, 460 publications worldwide 2010 -2016: • 9, 520 publications worldwide 3, 675 patents Condensation, Nitration, Bromination, Hydrogenation, Epoxidation, Phenolation, Metathesis, Amination, Mannich reaction All rights reserved – © AEP Polymers 2016
CNSL-POLYOLS: OVERVIEW Avg OH value Viscosity (mg KOH/g) (c. Ps@25 o. C) Avg Func. Appearance 2000 -4000 ~4. 4 Red-brown liquid 395 -445 1500 -3500 ~3 Red-brown liquid CNSL Mannich 420 -465 5500 -10000 ~4 Red-brown liquid PL-13 CNSL Mannich 450 -500 8000 -13000 ~4 Red-brown liquid PL-14 CNSL Mannich 220 -270 3500 -7500 ~3 Red-brown liquid PL-15 CNSL Mannich 370 -410 1500 -3500 ~3 Red-brown liquid PL-215 CNSL Mannich ~415 -430 ~5500 -10000 ~3. 8 Red-brown liquid PL-21 CNSL Polyester diol 65 -80 950 -1850 ~2 Brown liquid PL-23 CNSL Polyester diol 80 -115 2200 -5200 ~2 Brown liquid PL-31 CNSL Aminoalcohol ~260 -310 2000 -5500 ~3 Dark yellow liquid PL-31 LV CNSL Aminoalcohol ~300 -335 2000 -3500 ~3 Yellow liquid Grade Polyol Type PL-06 CNSL Novolac 185 -225 PL-11 CNSL Mannich PL-12 All rights reserved – © AEP Polymers 2016
CNSL-POLYOLS: RIGID FOAMS CNSL-based Mannich polyols provide equal or better self-catalytic power and mechanical strength compared to petroleum-based Mannich polyols at similar FRD. All rights reserved – © AEP Polymers 2016
CNSL-POLYOLS: RIGID FOAMS Foam Formulation 1 Mannich Polyol Sucrose/glycerine based polyether Polyester polyol TCPP Silicone surfactant Water Amine catalysts Solkane 365/227 p. MDI Index 115 Foam Formulation 2 Mannich Polyol Polyester & Sucrose based polyols TCPP Silicone surfactant Water Amine catalysts Tin catalyst Solkane 365/227 p. MDI Index 115 CNSL-based Mannich polyols show less flammability than petroleum-based Mannich polyols. All rights reserved – © AEP Polymers 2016
CNSL-NOVOLACS: OVERVIEW Grade NK-01 NK-04 NK-05 1 2 Hydroxyl equivalent weight(g/eq)1 316 Viscosity Bio-content at 25°C (%)2 (c. Ps) 100, 000 at 40°C 95% 17, 000 at 50°C 3850 at 70°C 316 Calculated based on average structure Calculated 5, 500 95% 968 95% Use level (%) Pot-Life at 25°C 3 Processes 5 -25% 2 daysa 12 weeksb Hot melt pre-preg and films for coatings 5 -33% 2 daysa 12 weeksb Prepregs, Pultrusion, lamination, infusion, RTM 5 -33% 2 daysa 12 weeksb Prepregs, Pultrusion, lamination, RTM, Infusion a. With 3 2 -ethyl, 4 -methylimidazole(3. 6 phr), b with latent catalyst Time to double initial viscosity CNSL novolacs can be used in 1 k or 2 k epoxy systems with extended pot life based on selection of catalysts. All rights reserved – © AEP Polymers 2016
CNSL-NOVOLACS: WATER AND CHEMICAL RESISTANCE NK-05 Polyethereamine D-230 Weight Gain after 14 days, % Isophoronediamine 0. 7 0. 65 0. 6 0. 55 0. 5 Water Uptake at 25 C 1 Represent s the outlier weight gain(%) of Polyetheramine CNSL novolacs exhibit improved water and chemical resistance in epoxy systems Formulation with 80% DGEBA epoxy resin (epoxy equivalent weight 188 g/eq), 20% NX-05, 2. 9 phr of 2 -ethyl, 4 -methylimidazole. All rights reserved – © AEP Polymers 2016
CNSL-NOVOLACS: IMPROVED INTERLAMINAR ADHESION IMPROVED VIBRATION DAMPING Shear strength(MPa) 60 NK-01 Dicyandiamide 50 CNSL Novolac improves interlaminar 40 shear strength by 22% compared with 30 DICY cured system, indicating good 20 wetting and adhesion to Carbon fiber 10 Tan δ (G"/G') 0 0. 07 0. 06 0. 05 0. 04 0. 03 0. 02 0. 01 0 NK-01 has a higher loss modulus (Tan δ) at temperatures below the glass transition. This results in better vibration absorption Further testing confirms 37% improvement in vibration absorption Data courtesy of SHD Composites 60 70 Temperature (°C) 80 Note: Interlaminar shear strength was determined on cured carbon fiber prepreg using ASTM 2344 M-00 short beam flexural test. Tested system: Epoxy/NK-01/blocked Imidazole(100/20/0. 5), Epoxy/DICY/Substituted Urea(100/8/0. 5) All rights reserved – © AEP Polymers 2016
CONCLUSIONS -) Cascading use of resources: thinking before acting -) The industry needs design and synthesis of new structures but also scale-up, QC, demo, prototyping -) LIGNIN: High availability Complex polymer Lacking shared technical platform for depolymerization and fractionation -) CNSL: Industrialized and versatile material, used since 1940 s New Polyols: Variety of Chemical Structures, Functionality, OH Better Mechanical Properties Faster Reactvity Better Fire Resistance Novolacs: Wide range of Viscosity and Functionality Improved Water and Chemical resistance Improved Interlaminar Shear Strength and Vibration Damping All rights reserved – © AEP Polymers 2016
The composite structure of the Punch One solar car (www. solarteam. be) contains a 95% bio-based CNSL resin developed by AEP and produced by an industrial partner. THANK YOU!
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