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1. The Evolving Bioplastics Landscape For Fibers & Films ANTEC 2009 Dr. Jim Lunt Jim Lunt & Associates LLC 2. Presentation Outline ãBasic Definitions for…
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  • 1. The Evolving Bioplastics Landscape For Fibers & Films ANTEC 2009 Dr. Jim Lunt Jim Lunt & Associates LLC
  • 2. Presentation Outline •Basic Definitions for Bioplastics • The Evolving Biobased “Landscape” Renewable and Non Renewable Polymers Renewable Resource Derived Monomers •Fiber and Film Forming Bioplastics Status •Recent Activity in Biobased Monomers/ Polymers •Conclusions
  • 3. What are Biopolymers or Bioplastics? Two Classifications: • Biobased Plastics – Major focus is on the “origin of carbon building 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 Landscape Feedstocks Polymers Agricultural Direct Fermentation Bio-technological Petroleum/ building blocks Origin Natural based Polyhydroxy alkanoates Polysaccharides PHA’s PLA Starch blends Fats/proteins Starch/Sugar Nylon 11 Nylon 6,10 Animals Polyethylene Nylon 6,12 s Lignocellulosics - Oils PHB PHBV Polypropylene PTT -wood - Casein Aliphatic PHBH PBS -straws, stover etc. - Whey Polycarbonate Polyurethanes Others - Gelatin - Pectins Vegetable - Chitosan -oils - Gums - Zein - Gluten Suitable for films
  • 8. Biobased Polymer Capacities for Major Players Product Company Location Capacity/mt Price/# PLA Natureworks USA 70,000 0.85-1.20 PLA Hisun China 5,000 1.25 PHA’s Metabolix USA 300/50,000 2.50-2.75 (2009) PHAH Meredian/Kaneka USA 150,000? n/a PHBV Tianan China 2,000 2.40-2.50 Materbi Novamont Eu 75,000 2.0-3.0 Cereplast Cereplast USA 25,000 1.50-2.50 HDPE/LDPE/PP. Brazchem SA 200,000 0.80-1.00 (2009)
  • 9. Major Bioplastics Four 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 and non degradable Material selection for film and fibers will be determined by the requirements of compostability /single use or multi use/ durability
  • 10. Plastic films Market Size • US plastic bag market Estimated by Omni Tech* to be 68 million metric 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 of petrochemical 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 Films •Cost/lb. and density v polyethylene/polypropylene •lack of curb-side collection and municipal composting infrastructure. •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 PLA Resin OTR WVTR CO2 PLA 38-42 18-22 201 PET (OPET) 3-6.1 1-2.8 15-25 HDPE 130-185 0.3-0.4 400-700 PP 150-800 0.5-0.7 150-650 Nylon 6 2-2.6 16-22 10-12 EVOH 0.01-0.16 1.4-6.5 PVC 4-30 0.9-5.1 4-50
  • 15. Film Products in the Marketplace
  • 16. Biaxially Orientated PLA
  • 17. Cellulose Acetate
  • 18. Compounded Blends
  • 19. Fiber Market Size •World 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 and requirements • Manufacturing/supply chain and disposal much more complex •Applications span single use to multiple use applications •Biodegradability or compostability often not a valued asset •Melt spinnable biobased fiber choices are very limited •Performance of Biobased fibers often deficient in key properties
  • 21. Biobased Melt Spinnable Fiber Forming Polymers PLA (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 Fibers •Return to natural non melt spinnable fibers –Not a viable “stand alone” option •Blends 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 Blocks” Monomers 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 acid Isoprene - (Goodyear, Genenco)
  • 24. Next Generation of Bioplastic Building Blocks Monomers/Intermediates from Vegetable Oils ! " # $ % &
  • 25. Other Chemicals and Polymers from Plant Sugars Polyurethanes Polycarbonate/PBT Blends Nylon 6 & 6,6 Polycarbonates PBT TPE’s Adipic Acid Hexanediamine Aliphatic Polyesters N-Methyl Pyrolidone 1,4-Butanediol THF Solvents New monomers Crop Growth Succinic Acid Promoters Salt 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 Isobutylene PET other polymers Xylenes and terephthalic acid Isooctene other aromatics Courtesy 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 product FID1 A, Front Signal (S:P-XYLENE.D) FID1 A, Front Signal (S:RUN 66 CUT BOTTOM.D)   ¡ ¢ £ ¤ 6000 5000 4000 3000 2000 1000 0 5 10 15 20 25 ¥ £ ¦ Courtesy GEVO
  • 32. Biobased Monomers Under Development HO O OH HO O OH HO O O OH L-Ketals O NH2 succinic acid 3-hydroxypropionic acid glutamic acid O O HO OH HO O HO OH OH O O OR O NH2 O aspartic acid glycerol 4-hydroxybutyrolactone HO O O O O OH OH O HO HO OH O O itaconic acid levulinic acid 2,5-furandicacboxylic acid OH OH OH OH OH O OH OH OH *R=H, alkyl HO OH OH OH OH OH OH OH OH O xylitol sorbitol glucaric acid
  • 33. Products and Markets Plasticizers Polyols L-Ketals Adhesives 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 performance •Next generation renewable-resource monomers for durable polymers are already beginning to appear on the radar screen. • Innovation abounds , driving impressive growth
  • 35. Thank You
  • Jim lunt

    Jul 23, 2017
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