1. The Evolving Bioplastics Landscape For Fibers & Films ANTEC 2009Dr. Jim Lunt Jim Lunt & Associates LLC

2. Presentation Outline Basic Definitions for Bioplastics The Evolving Biobased LandscapeRenewable and Non Renewable PolymersRenewable Resource Derived MonomersFiber and Film Forming Bioplastics StatusRecent Activity in Biobased Monomers/ PolymersConclusions 3. What are Biopolymers or Bioplastics? Two Classifications: Biobased Plastics Major focus is on the origin of carbonbuilding blocks. Biodegradable Plastics Focus is on end of life or disposal.These two classes are, however, not mutually exclusive. 4. What are Biobased Plastics? To be classified as biobased, the material must be organic and contain some percentage of recently fixed (new) carbon found in biological resources or crops. This definition is the basis of ASTM D6866 5. What are Biodegradable Plastics? Biodegradable or Compostable Plastics are those which meet all scientifically recognized norms for biodegradability and compostability of plastics and plastic products independent of their carbon origin.In Europe The Composting standard is EN 13432 and in the USA ASTM D6400. 6. Projected Biomaterials Trend European Bioplastics estimates that annual global production of bioplastics will increase six-fold to 1.5 million tonnes by 2011, up from 262,000 tonnes in 2007.This will still only be 0.7% of the approximate 230 million tonnes of plastics in use today .There will be a significant increase in bio-based non-biodegradable plastics production of durable products is expected to account for almost 40% of the global total, compared with 12% in 2008. 7. The Evolving Biobased Plastics LandscapeFeedstocksPolymersAgricultural Direct FermentationBio-technological Petroleum/building blocks Origin Natural based Polyhydroxy alkanoates Polysaccharides PHAsPLAStarch blendsFats/proteinsStarch/SugarNylon 11 Nylon 6,10 AnimalsPolyethylene Nylon 6,12sLignocellulosics - OilsPHB PHBVPolypropylenePTT-wood- Casein AliphaticPHBH PBS-straws, stover etc. - Whey PolycarbonatePolyurethanesOthers - Gelatin- PectinsVegetable- Chitosan -oils- Gums - Zein - GlutenSuitable for films 8. Biobased Polymer Capacities for Major PlayersProduct Company Location Capacity/mt Price/# PLA Natureworks USA70,0000.85-1.20PLA Hisun China5,000 1.25 PHAs Metabolix USA300/50,0002.50-2.75 (2009) PHAHMeredian/Kaneka USA150,000?n/a PHBVTiananChina2,000 2.40-2.50 Materbi NovamontEu 75,0002.0-3.0 Cereplast Cereplast USA25,0001.50-2.50 HDPE/LDPE/PP. BrazchemSA 200,000 0.80-1.00 (2009) 9. Major BioplasticsFour Applications have significant growth opportunities in the immediate future: 1) Compostable single use bags/films 2) Fibers, degradable and non-degradable 3) Plastic foam cushioning blocks 4) Bioplastic molded products, degradable andnon degradable Material selection for film and fibers will be determined by therequirements of compostability /single use or multi use/ durability 10. Plastic films Market Size US plastic bag market Estimated by Omni Tech* to be 68 millionmetric tons in 2007. Growth rate of 15% per year through 2011 to 119 million metric tons Major issues facing the introduction of bio-based films in place ofpetrochemical based films are: their current cost.lack of curb-side collection and municipal compositing *http://soynewuses.org/downloads/reports/DisposalblePlasticsMOS.PDF 11. Major Markets for Biobased Films Clear wrapping films (blown and cast) for food and non food wrap Clear Biaxially orientated film for tamper proof seals and shrink wrap Translucent cast and blown film for : trash bags, Yard & Garden Industrial Refuse Kitchen and other Newspaper and magazine wrap Diaper back sheets Agricultural mulch films Almost all biobased film applications today are single use disposables where compostability is a perceived benefit along with biobased content. 12. Bioplastic Manufacturers for Film Applications Transparent rigid films: PLA,( NatureWorks LLC.) Cellulose acetate(Innovia)Translucent flexible films:Starch/PLA, and/ or Ecoflex synthetic polyester : Materbi,( Novamont), Bioplast, (Stanelco /Biotec) Ecovio, PLA/ Ecoflex ( BASF) Ecobras, Starch/ Ecoflex ( BASF) Cereplast Compostables, (Cereplast )Hydroxy propylated starch, (Plantic Technologies)PBS(polybutylene succinate), Mitsubishi 13. Major Concerns With Bioplastic FilmsCost/lb. and density v polyethylene/polypropylene lack of curb-side collection and municipal compostinginfrastructure. Poor tear propagation Moisture sensitivity for starch based products Controlled degradation times for mulch films Barrier (Moisture transmission) for starch and PLA formulations Low Temperature resistance of PLA unless orientated 14. Comparative Gas Transmission Properties of PLAResin OTRWVTRCO2 PLA38-4218-22 201PET (OPET)3-6.11-2.815-25 HDPE 130-185 0.3-0.4 400-700PP150-800 0.5-0.7 150-650 Nylon 6 2-2.6 16-2210-12EVOH 0.01-0.16 1.4-6.5 PVC 4-300.9-5.14-50 15. Film Products in the Marketplace 16. Biaxially Orientated PLA 17. Cellulose Acetate 18. Compounded Blends 19. Fiber Market SizeWorld production of manufactured textile fiber is projected to rise 5.7 percent per annum through 2012 to over 62 million metric tons. PET polyester will continue to dominate manufactured fiber output. High-end synthetic fibers to grow the most rapidly. http://www.reportlinker.com/p096689/World-Textile-Fibers- Market.html 20. Biobased Fiber versus Film Markets Fiber market is much more diverse in materials andrequirements Manufacturing/supply chain and disposal much more complexApplications span single use to multiple use applicationsBiodegradability or compostability often not a valued assetMelt spinnable biobased fiber choices are very limitedPerformance of Biobased fibers often deficient in keyproperties 21. Biobased Melt Spinnable Fiber Forming PolymersPLA (Natureworks LLC) PBS (Misubishi)Nylon 11- made from Castor oil (Arkema)Nylon 6,10 . 60% sebacic acid from castor oil (BASF)Nylon 6:12, 10:10, PTT(Du Pont) Biodegradable 22. Options For New Biobased FibersReturn to natural non melt spinnable fibers Not a viable stand alone optionBlends of existing biobased polymers with petroleum based (PLA/Ecoflex)Copolymers with biobased and oil based monomers (PTT)Produce all monomers for existing petroleum based fibers from renewable resources 23. Next Generation of Bioplastic Building BlocksMonomers from sugar/ Cellulosic Biomass Succinic acid -(DSM) Bioamber,Roquette,Mitsubishi Chemical)3-hydroxy propionic acid - (Cargill,Codexis)Acrylic acid - (Ceres, Rohm & Haas,)Aspartic acid- (China)Levulinic acid- ( China)Sorbitol - (Cargill,ADM,Roquette)Ethanol/ethylene glycol - (Brazchem, India Glycols )Propylene/propane 1,3 diol - (Brazchem, DuPont/Tate & Lyle)Butylene/butane diol - (Genomatica),Lysine/ caprolactam - (Draths)Terephthalic acid - ( Gevo)Adipic acidIsoprene - (Goodyear, Genenco) 24. Next Generation of Bioplastic Building BlocksMonomers/Intermediates from Vegetable Oils! "# $ % & 25. Other Chemicals and Polymers from Plant SugarsPolyurethanes Polycarbonate/PBT BlendsNylon 6 & 6,6Polycarbonates PBTTPEs Adipic Acid HexanediamineAliphaticPolyestersN-Methyl Pyrolidone 1,4-Butanediol THFSolventsNew monomers Crop GrowthSuccinic AcidPromotersSalt Plant Sugars Replacements ' 26. Fiber Products in the Market Today 27. Single Use disposables 28. PLA Semi Durable/Durable Applications 29. New Bio Derived Monomers On the Horizon for Film and Fibers 30. Biobased Monomers Under Development Isobutanol IsobutylenePET other polymersXylenes and terephthalic acid Isooctene other aromaticsCourtesy GEVO 31. Terephthalic Acid from Isobutanol Optimized in lab to prepare for production from Gevo isobutanol p-xylene from isooctene: >95% selectivity,highest single pass conversion in literature terepthalic acid from p-xylene: high yield and clean productFID1 A, Front Signal (S:P-XYLENE.D) FID1 A, Front Signal (S:RUN 66 CUT BOTTOM.D) 6000 5000 4000 3000 2000 1000 0510 15 20 25 Courtesy GEVO 32. Biobased Monomers Under Development HOOOHHOOOHHOO OOHL-KetalsONH2succinic acid3-hydroxypropionic acidglutamic acid O O HO OHHO O HOOH OHOOORONH2Oaspartic acidglycerol 4-hydroxybutyrolactone HOOOOOOHOH O HOHO OHOOitaconic acid levulinic acid 2,5-furandicacboxylic acid OH OH OH OH OHOOH OHOH *R=H, alkyl HOOH OH OHOH OH OHOH OH Oxylitolsorbitol glucaric acid 33. Products and Markets PlasticizersPolyols L-KetalsAdhesives Solvents Thermoplastics 34. Bioplastics Trends Summary Today' bioplastics films are primarily aimed at single-s use disposable or limited-use markets and are likely to remain so. Price and disposal routes are key issues Fibers ,are more complex spanning single use to multiple use markets. Key issues for fibers are price and performanceNext generation renewable-resource monomers for durable polymers are already beginning to appear on the radar screen. Innovation abounds , driving impressive growth 35. Thank You