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Dhr Schennink

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Dhr Schennink

  1. 1. Expanding the application opportunities of biopolymers Ir. Gerald G.J. Schennink Senior scientist Biobased Products - Wageningen UR gerald schennink@wur nlgerald.schennink@wur.nl Eindhoven – 28 Oktober 2010 Contents „ Introduction WUR-FBR-Biobased Products „ Bioplastics„ Bioplastics z Biodegradable z Biobasedz Biobased „ Classification of bioplastics L d l„ Latest developments z BPM z Biobased polymers z Heat stable PLA z Composites & foams „ Conclusions
  2. 2. What is going on ? AfbreekbaarDuurzaam Composteerbaarp Biobased Wageningen UR (University & Research centre)g g „ Three pillars: z Wageningen University z Van Hall Larenstein Univ. of Appl. Sci z DLO Applied Research Institutesz DLO - Applied Research Institutes „ Annual budget about 650 m euros „ About 6500 employeesp y „ 9000 BSc/MSc; 1200 PhD (>100 countr.) „ Extensive international network „ Active partner in Food Valley to explore the potential of nature…to explore the potential of nature to improve the quality of life…
  3. 3. Wageningen University & Research Centre Supervisory Board „ > 6000 employees Five Sciences Groups „ University: academic research Research Centres contract Life long learning Statutory tasks units Executive Board „ Five Sciences Groups„ Research Centres: contract R&D IAC, PHLO, WMS y Rikilt, CIDC Board of Directors Board of Directors Board of Directors Board of Directors Board of Directors Board of Directors Agrotechnology & Food Sciences Plant Sciences Animal Sciences Social Sciences Environmental Sciences Polymer Research facilities at WUR-FBRy „ Processing Extrusion (single/double screw)z Extrusion (single/double screw) z Co-extrusion; 1-5 layers sheet/blown film z Injection moulding Cz Compression moulding z Thermo forming „ Analysisy z Thermal (DSC, TGA, HDT) z Mechanical (tension, bending, compression, DMTA, impact, falling dart)) z Rheological (capillary, dynamic) z Structural (SAXS, FTIR, SEM) z Chemical (ss-NMR HPSEC-MALLS GPC GC)z Chemical (ss NMR, HPSEC MALLS, GPC, GC) z Biodegradation (controlled composting, pilot-scale composting, aquatic tests)
  4. 4. Biopolymers Biobased vs. biodegradable Biodegradable plasticsg p „ Biodegradation: degradation catalyzed by biological activity leading to mineralization and/or biomassactivity leading to mineralization and/or biomass „ Biodegradability: degree to which biodegradation leads to„ Biodegradability: degree to which biodegradation leads to mineralization and/or biomass „ Mineralization: the conversion of (organic) constituents in naturally occurring gasses, water and inorganicnaturally occurring gasses, water and inorganic constituents
  5. 5. Biodegradable plastics „ Environment determines type and speed of degradation z Industrial compostingz Industrial composting z Home composting z Degradation in Soil Fresh aterz Fresh water z Marine water z Anaerobic digesting Standardisation and certification is very important!„ Standardisation and certification is very important! z Demands for combination of biodegradable products & industrial composting are described in EN 13432 Biobased plastics „ Renewable or biobased polymers are polymers from which the raw materials originate directly orfrom which the raw materials originate directly or indirectly from nature Cl ifi i f bi b d l„ Classification of biobased polymers: z (Modified) natural polymers z Directly from micro-organisms or gene-modified crops z From biobased feed stock (eg via fermentation) „ Biobased plastics  biodegradable plastics
  6. 6. Why biobased?y „ Less dependency of crude oil „ Durability, less CO2 production „ (sometimes) better properties( ) p p „ (sometimes) biodegradability „„ …….. Biodegradable vs. biobased materialsg Finished product N bi d d bl Bi d d blNon-biodegradable Biodegradable Ecoflex (BASF)Traditional PE Raw Non renewable Ecoflex (BASF) Bionolle (Showa Denko) Traditional PE Biodeg h PET wmater PLA (Natureworks) Eco – LDPE (Braskem) starch based blends rials Renewable PLA (Natureworks) Rilsan (Arkema) Sorona (Dupont) PHBV (Tianan)
  7. 7. Cl ifi ti f bi (d d bl ) l tiClassification of bio(degradable)plastics Available biodegradable plasticsg p M t i t t f bi d d bl l tiMost important groups of biodegradable plastics „ Cellulose and cellulose derivatives„ Cellulose and cellulose derivatives „ Starch based plastics (thermoplastic starch) „ Polyesters z Poly lactic acid (PLA) z Poly caprolactone (PCL) z Polyhydroxy alkanoates (PHA, PHBV) z Several (co-)polyesters „ Materials based on industrial proteins „ Blends of various bioplastics (eg thermoplastic starch & polyesters)„ Blends of various bioplastics (eg thermoplastic starch & polyesters)
  8. 8. Cellulose derivatives (cellulose diacetate)( ) „ Advantages z Good mechanical properties „ Disadvantages z Price (>4€/kg)p p (like PS) z Good thermal resistance z Glossy transparent Price ( 4€/kg) z Use plasticiser z Glossy transparent appearance z Renewable „ Processing z It is advised to dry the material z Suitable for: • Injection moulding • Sheet extrusion (thermo formingSheet extrusion (thermo forming • Fibre extrusion z Processing temperature 190-240°C Th l d d ti iblz Thermal degradation possible Polylactic acid (PLA)y ( ) „ Advantages z Good mechanical properties „ Disadvantages z Only compostable inz Good mechanical properties (like PET) z Transparent z Only compostable in industrial composting facilities z Water sensitivity during processing z Price (1.8-2.0 €/kg) z Renewable y g p g „ Processing z Material needs to be dried z Suitable for: Fil t i ( d th f i )• Film extrusion (and thermo forming) • Blow molding • Injection moulding Fib t i• Fibre extrusion z Processing temperature 170-210°C
  9. 9. Starch based plasticsp „ Advantages z Good mechanical properties „ Disadvantages z Humidity dependentz Good mechanical properties (LDPE to PS) z Excellent gas barrier properties z Humidity dependent z Not completely transparent properties z Anti-static z Fast biodegradable „ Processing z Processed as delivered (no drying) z Suitable for: • Film blowing (incl multilayer) • Injection mouldingInjection moulding • Sheet extrusion (and thermo forming) • Foam extrusion z Processing temperature 120 180°Cz Processing temperature 120-180 C Poly hydroxy alkanoates (PHA’s)y y y ( ) „ Advantages z Mechanical properties can „ Disadvantages z Expensive (for now > 4€/kg) z Mechanical properties can be varied z Hydrophobic (low water bilit ) z Harvested from micro organisms z Low melt strength vapour permeability) z Rather high HDT (>100°C) z Renewable Processing„ Processing z Suitable for: • Injection mouldingInjection moulding • Sheet extrusion (and thermo forming) • (under development) film blowing, film castingcasting
  10. 10. Synthetic (co)polyesters and polyester amidesy ( )p y p y „ Not renewable (not yet)„ Not renewable (not yet) „ Mechanical properties possible from PE to PP „ Compostable „ Suitable for films and extrusion (in most cases not( for injection moulding) Production capacity biodegradable polymers (2007) „ PLA materials ton/year z Natureworks LLC Natureworks polymer USA 70.000 (140.000 in 2009) z Hisun Corp. Hisun China 4.000 (expanding) z Purac Lactide customers Europe/Asia ……. (starting up) „ Starch based materials z Novamont SpA Mater-bi Italy 60.000 z Rodenburg Solanyl The Netherlands 40.000 z Biotec GmbH Bioplast Germany 10.000 z Biop Biopar Germany 4.000 z Plantic Plantic Australiaz Plantic Plantic Australia ….. z Biograde Biograde Australia ….. z Cereplast Corp. USA >> „ Cellulose based materials z Innovia films Natureflex England 10.000 z Celanese Clarifoil England …..g z FKUR Biograde Germany 4.000 „ PHB z Tianan Enmat China 4.000 z Biomer Biomer Germany 1.000 z PHB Industrial SA Biocycle Brazil …. (starting up) T ll Mi l USA ( t ti )z Telles Mirel USA …. (starting up) „ Biodegradable polyesters z BASF Ecoflex Germany 8.000 (expanding in 2010) z Showa Denko Bionolle Japan 3.000 z Solvay/Perstorp CAPA England …… z Mitsibishi Chemical GS Pla Japan 3.000Mitsibishi Chemical GS Pla Japan 3.000 „ Others z Limagrain Cereales Biolice France …. z (Idroplast Hydrolene (PVA) Italy …. )
  11. 11. P d t & lProducts & examples Examples of (existing) packaging applicationsp ( g) p g g pp
  12. 12. Examples of (existing) agricultural applicationsp ( g) g pp L t t d l tLatest developments
  13. 13. Biobased Performance Materials Programme (BPM) „ BPM is a programme sponsored by the Dutch Ministry of Agriculture, Nature and Food Quality (LNV)Nature and Food Quality (LNV) z Aim is to create an internationally appealing programme z Dominant language in BPM communication will be English „ Programme fills an important gap in Biobased research i e ; dedicated„ Programme fills an important gap in Biobased research i.e.; dedicated research into biobased performance materials „ Is unique in its construction: z Industrial partners participate from all parts of the value chain, varying from raw materials producers, polymer producers and processors until end users BPM: Selected proposals November 2009 Chemical cluster 1. NOPANIC: Novel renewable polyamides and non-isocyanate polyurethanes for coating applications • Target: To develop scientific and applied knowledge for the generation of isocyanate free polyurethane 2. MOBIOSOL: Modification of semi-crystalline polyesters with bio-based building blocks by solid state polycondensation and by melt copolymerization • Target: To develop scientific and applied knowledge for the generation water-dispersible, hydrolytically and thermally stable, (bio)degradable/non-biodegradable, biomass-based, de-inkable, non-curing, polyesters 3 BIOCRES: Biobased Composite resins3. BIOCRES: Biobased Composite resins • Target: To develop scientific and applied knowledge for the generation of well functioning composite resins based upon (styrene-free) unsaturated polyesters can be generated. 4. ACTION: Acrylic and Styrenic Monomers from Biomassy y • To develop scientific and applied knowledge for the generation of efficient synthesis routes to acrylic and stryrenic monomers
  14. 14. BPM: Selected proposals November 2009 Material cluster 5. HI-PLA: High impact polylactic acid T t T d l i tifi d li d k l d f th ti f PLA ith• Target: To develop scientific and applied knowledge for the generation of PLA with improved of elasticity properties and melt-processability 6. FLOSTARBLEND: Blending technology for flour / starch by-product based bioplasticsbased bioplastics • Target: To develop scientific and applied knowledge for the generation of co-continuous and/or nanolayered morphology consisting out of the renewable based blend system TPS/PLA/PVAc. 7. STRAIN ENHANCED PLA: Strain-induced crystallization of PLA and its application for production of PLA bottle • Target: To develop scientific and applied knowledge for the improvement of mechanicalg p pp g p properties of PLA by strain-induced crystallization 8. FEASIBLE: Feasibility of End use Applications: SustaInaBiliLty and techno-Economic aspects • Target: Feasibility will be approached from an end user perspective taking into account both the techno-economic feasibility as well as sustainability aspects. The project generates specific information for the selected end applications. Latest developments (at WUR BBP)p ( ) „ Novel biopolymers z Replacement of oil based building blocks by renewablesReplacement of oil based building blocks by renewables z Development of novel 100% biobased polymers (rubber from dandilion) z Engineering plastics z Powder coatings „ Novel additives z Compatibilisers z PlasticisersPlasticisers z Chain extenders z Nucleating agents, PDLA (Improving heat stability of PLA) z Composites „ Novel processes z Blending of renewable / synthetic polymers (PLA / PMMA, PLA / PC, ……) z Recyclingz Recycling z Blown films, chain extenders z Foaming of PLA
  15. 15. Polymers from naturey Latest developments (at WUR BBP)p ( ) „ Novel biopolymers z Replacement of oil based building blocks by renewablesReplacement of oil based building blocks by renewables z Development of novel 100% biobased polymers (rubber from dandilion) z Engineering plastics z Powder coatings „ Novel additives z Compatibilisers z PlasticisersPlasticisers z Chain extenders z Nucleating agents, PDLA (Improving heat stability of PLA) z Composites „ Novel processes z Blending of renewable / synthetic polymers (PLA / PMMA, PLA / PC, ……) z Recyclingz Recycling z Blown films, chain extenders z Foaming of PLA
  16. 16. Solid Polymer Structure: AmorphousAmorphous vs. SemiSemi--crystallinecrystalline Amorphous polymersAmorphous polymers •• transparencytransparency •• toughnesstoughness SemiSemi--crystalline polymerscrystalline polymers •• temperature resistancetemperature resistance •• chemical resistancechemical resistance •• no melting, only softeningno melting, only softening PLAPLA- 2 PLA-1 Heat stable PLA PLA is actually a family of (co-)polymers of D- and L-Lactic units Stereo-block PLA sc-PLA PLA PLLA A PLA PLA A-PLA
  17. 17. Heat stable PLA Effect of D-isomer content in PLA chain on crystallinity & melting point 7 min 190 °C S h lit th t (135°C) 5 6 thrate/mm/m 160 170 180 intPLA(Tm)/ Spherulite growth rate (135°C) melting point 3 4 Crystalgrowt 130 140 150 MeltingPoi More D-comonomer: • less crystallinity 0 1 2 100 110 120 How to increase PLA temperature resistance (HDT)? • lower D-content in PLA • less crystallinity • lower melting point 0 2 4 6 8 10 12 14 D-lactic acid content in PLA / % lower D content in PLA • introduce crystallinity by adding nucleators or use fillers • heat setting / annealing in mold (TF, IM) • orientation, e.g. in film, fiber and foam Heat stable PLA Crystallization time (t½ in DSC) of PDLA nucleated PLA 6201D 10 NTR PLA 6201 Increasing min Increasing PDLA content 5 half-time/m 2.5% 5 stallizationh 2 5 5% PDLA effective over wide temperature range crys 1 h 2 h 40% 0 80 90 100 110 120 130 140 temperature / °C h temperature / C
  18. 18. Heat stable PLA Effect of stretching on crystallinity of PLA Fibre grade PLA stretched at 115C 60 70 40 50 g) 20 30 dH(J/g 0 10 Fibre grade Fibre grade + Additive A Fibre grade + Additive B 0 0 2 4 6 8 10 12 14 Draw ratio Polymers from nature: heat stable PLAy
  19. 19. Latest developments (at WUR BBP)p ( ) „ Novel biopolymers z Replacement of oil based building blocks by renewables z Development of novel 100% biobased polymers (rubber from dandilion) z Engineering plastics z Powder coatings „ Novel additives„ Novel additives z Compatibilisers z Plasticisers z Chain extenders z Nucleating agents, PDLA (Improving heat stability of PLA) z Composites „ Novel processes„ Novel processes z Blending of renewable / synthetic polymers (PLA / PMMA, PLA / PC, ……) z Recycling z Blown films, chain extenders z Foaming of PLA z Thermoforming of heat stable products z Composites Trends in product developmentp p Fi t ti fil th ti fil „ Research topics First generation film xth generation film p • Specialty products: (hot fill materials/microwavable materials • Coextruded/laminated/blended structures (e.g. barrier bottles, films, sheets)sheets) • Foamed structures (3-D products) • Reduction of the price of the material „ Try to maximize the added value of biodegradable materials by using a series of positive properties
  20. 20. Application: Thermoformed productspp p „ High HDT„ High HDT z PLA type N l tiz Nucleation z Processing Application: 3D-foamed structurespp „ Expandable bead techniquep q z Good cell structure z Density <30 g/lz Density 30 g/l
  21. 21. Application: PLA composite materialspp p „ Large injection moulded panels„ Large injection moulded panels z Excellent strength z Good impactz Good impact z Good processing Concluding remarksg S„ Sense z Consumer trends ask for new (food)packaging/material concepts. Natural polymers can add to a solutionNatural polymers can add to a solution z Successful product developments make use of a series of positive properties (not only biodegradability) of biodegradable plastics z Biodegradable plastic product = polymer + additive + material processing + inks, glues, tapes etc. „ Non Sense z Biodegradable plastics will overtake the market of Poly-ethyleneg p y y (within several years)
  22. 22. Questions ??? AcknowledgementsAcknowledgements This presentation was not possible without contributions of Karin Molenveld (WUR), Jacco van Haveren (WUR), Christiaan Bolck (WUR) © Wageningen UR ( ) ( ) ( ) & Sicco de Vos (PURAC)

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