New solutions in biopolymers for food and cosmetic industry
Biopolymers: general concepts
What is a Biopolymer? Why bio? The prefix bio is used in the world of polymers to define its natural, vegetable or animal origin. Also is used to indicate the biodegradability of the polymer. A Biobased polymer originates wholly or partly in biological material including trees, crops, grasses, algae and vegetable waste. Biobased content is determined by the method of Carbon 14 (CEN / TS 16137 ASTM 6866) which determines the ratio of C 14 in the Ctotal.
Biodegradable Plastics Plastic materials wich under certain environmental conditions, with the help of living organisms degrade, becoming completely natural elements: carbon dioxide, water and compost. Biodegradable plastics can have natural origin, biobased, or produced from fossil resources. Bioplastic It is a plastic that is made from natural raw materials (such as sugar, starch, cellulose, potatoes, cereals, molasses, soybean oil, corn, etc.) it is made in a sustainable way, it is biobased; and it may or may not be biodegradable.
Compostable A material is compostable when it biodegrades within a certain time under specific conditions that define composting. Composting is a procedure carried out by humans advancing the natural processes of biological decomposition and gives products like carbon dioxide, water, and mineral fertilizer (compost). A compostable material, by definition, is biodegradable, but a compostable material is not necessarily biodegradable. Should be met with European standard EN 13432 (US ASTM D6400 04), decomposition of 90% or greater in less than 6 months.
Types of composting Domestic composting is being performed at room temperature with moisture and microorganisms. It can be done al home. Industrial composting is being carried out at elevated temperature (50 70⁰C), high humidity and microorganisms. It is the composting of residual urban organic matter (brown container in Catalonia and the Basque Country).
Oxo degradables plastic Oxo degradable plastics are conventional plastics (generally PE) to which additives have been added. These additives function as catalysts in order to decompose the plastics by the action of light, heat or UV (photodegradable) The material does not degrade, it just breaks into smaller fragments. The material does not meet the standards of composting. The EU has recommended to its member states the total ban of oxo degradable plastics by 2018.
Sustainability: A situation or a feature by which the needs of the current population can be met without compromising the ability of future generations or people from elsewhere (UNEP). Life Cycle: Are consecutive and interconnected stages of a product from obtaining production to its end of life in landfills or incineration, through its manufacture and use in their lifetime (ISO 14044). Life Cycle Assessment (LCA): It is the collection and evaluation of the inputs, outputs and the potential environmental impacts of a product system throughout its life cycle (ISO 14044). Carbon footprint: It is the addition of emissions of greenhouse gases, expressed as carbon dioxide equivalent, in a system based on an analysis of product life cycle (ISO 14067).
Biopolymers BIO PE BIO PU BIO PA BIO PVC Starch Cellulose Cellophane PLA PHA Bio Origin Bio Origin + + Non Biodegradable Biodegradable Bio Origin PE,PP,PS ABS, PC, PMMA PUR PA PET Petrochemical + Non Biodegradable Petrochemical + Biodegradable PCL PBAT PBS PVOH/PVA PGA Biodegradability
Biodegradable Polymers Biodegradable Polymers Biopolymers from renewable sources Bioplastics Biopolymers from non renewable sources Polymer extracted from biomass: starch, cellulose, lignin, proteins Synthesized from de biomonomers PLA Produced from microorganisms PHA Petrochemical origin PCL, PBSA, PBS PBS: polybutylene polysuccinate PBSA: Poly (succinate co butylene adipate) PCL: Polycaprolactone PHA: polyhydroxyalkanoates PLA: polylactic acid
Other biopolymers, wholly or partially from biological origin, but non biodegradable: PET: 30% MEG (via fermentation) + 70% PTA (petrochemical origin). PE: ethylene (via fermentation). PTT: 1,3 propanediol (via fermentation) + PTA (petrochemical origin). PBT: 1,4 butanediol (via fermentation) + PTA (petrochemical origin). PUR: polydiol (via fermentation) + isocyanate (petrochemical origin). PA6: caprolactam (via fermentation). PA66: adipic acid (via fermentation) and hexamethylenediamine (petrochemical). PA69: chemical transformation of oleic acid. Other.
Carbon footprint Comparison of different polymers Emissions from the production of common polymers (kg. CO2 eq. per kg. of polymer from cradle to factory gate) Source: Plastics Europe (http://www.plasticseurope.org/plastics sustainability/eco profiles.aspx). 2006
Life cycle of biodegradable bioplastics
Compounds based on aliphatic polyesters biopolymers: ErcrosBio PH: Products based on PHA ErcrosBio L: Products based on PLA
General Characteristics Compounds bases on PHA ErcrosBio PH There are aliphatic polyester made directly by lips or sugars fermentation by bacteria, with a chemical structure as follows: There are around of 150 different PHA : Homopolymers: PHB :R= CH 3 PHV :R= CH 3 CH 2 PHH :R= CH 3 CH 2 CH 2 Copolymers: PHBV ó P(3HB co 3HV) PHBH ó P(3HB co 3HH)
ErcrosBio PH Applications Packaging for food and non food end use. Films: waste bags One use cutlery. Textile uses. High degradability products. Other: PVC plasticizers.
ErcrosBio PH 070 ErcrosBio PH ErcrosBio PH 110 Propiedad Método ErcrosBio PH 070 ErcrosBio PH 110 Units Melt Flow Index (M.F.I.) ISO 1133 (160ºC, 2,16 Kg) 1 2 g/10 min Density ISO 1183 1,21 1,20 g/cc Melting Temperature (Tm) DSC: ISO 11357 141 126 ºC Glass Trans.T emperature (Tg) DSC: ISO 11357 1 3 ºC Thermal propertiers TGA (método propio) 272 270 ºC
Pros Depending on PHA characteristics, different properties. Mechanical properties similar than olefins (~LDPE ). No catalyzers traces. Good barrier properties similar to aromatic polyester (~ PET). Good fat and solvents resistance. Buena for blowing process. Good hydrolysis stability. Cons Low temperature processability. Process not easy. Brittle in some cases. Low viscosity. Additives incorporation ErcrosBio PH New products development
ErcrosBio L General Characteristics: Grades in PLA: * LL600 * LL650 * LL700 * LD600
ErcrosBio L Applications Packaging for food and non food end use. Construction for foaming, profile, siding, One use cutlery Textiles uses Electric and electronic end use. Automotive
Pros: Sustainable origin made from natural sources. Compostable and burnable. Mechanical properties similar than PET y al PS. Printable. Water and fatty product resistance. Sealable at lower temperature than olefins. High Young modulus. Transparent. Similar olefin process (extrusion, injection and thermoforming). Cons: High risk of hydrolysis. Low Permeability. Stiffness. ErcrosBio L
ErcrosBio L ErcrosBio LL600, ErcrosBio LL650, EcrosBio LL700 Mechanical properties 80 3,5 Esfuerzo en el punto de fluencia (MPa) 70 60 50 40 30 20 Modulo de Young (GPa) 3 2,5 2 1,5 1 10 0,5 0 ErcrosBio LL 600 ErcrosBio LL 650 ErcrosBio LL 700 0 ErcrosBio LL 600 ErcrosBio LL 650 ErcrosBio LL 700 6 5 ErcrosBio LL700 very rigid material Elongacion a rotura (%) 4 3 2 1 0 ErcrosBio LL 600 ErcrosBio LL 650 ErcrosBio LL 700
ErcrosBio L ErcrosBio LL600, ErcrosBio LL650, EcrosBio LL700 Injection 12 10 8 6 4 2 Extrusion 0 Melt Flox Index 190ºC, 2.16Kg (g/10min) ErcrosBio LL 600 ErcrosBio LL 650 ErcrosBio LL 700 20 40 18 35 16 14 12 10 8 30 25 20 15 6 4 10 2 5 0 0 ErcrosBio LL 600 ErcrosBio LL 650 ErcrosBio LL 700 ErcrosBio LL 600 ErcrosBio LL 650 ErcrosBio LL 700 Transmision vapor de agua WTR 38ºC 90% humedad (cc/m2 d) Transmision al O2 OTR 23ºC 0% humedad (cc/m2.d)
ErcrosBio L ErcrosBio LL600, ErcrosBio LL650, EcrosBio LL700 Properties to be modified: Oxygen and water vapor permeability. Thermal properties. Stiffness. Additives incorporation New products development ErcrosBio LM
LM Transparent extrusion grades Opaque extrusion grades Transparent injection grades Opaque injection grades 72000 series 73000 series 62000 series 63000 series
Aditives ErcrosBio LM 73000 Series Extruder PLA pellets Drying Dry PLA Drying Extruder PLA Films and sheets Thermoformed products
ErcrosBio LM 73000 Series Mechanical properties 80 4 Esfuerzo en el punto de fluencia (MPa) 70 60 50 40 30 20 Modulo de Young (GPa) 3,5 3 2,5 2 1,5 1 10 0,5 0 ErcrosBio LL700 73101 73501 0 ErcrosBio LL700 73101 73501 ErcrosBio LM 73501 higher tenacity to deformation > 100% Elongacion a rotura (%) 120 100 80 60 40 20 0 ErcrosBio LL700 73101 73501
ErcrosBio LM 73000 Series Melt Flox Index 190ºC, 2.16Kg (g/10min) 7,0 6,0 5,0 4,0 3,0 2,0 1,0 Improvement in pearmeabilty in oxigen and water vapor 0,0 ErcrosBio LL700 73101 73501 25 40 Transmision vapor de agua WTR 38ºC 90% humedad (cc/m2 d) 20 15 10 5 22 % Transmision al O2 OTR 23ºC 0% humedad (cc/m2.d) 35 30 25 20 15 10 22 % 32 % 5 0 ErcrosBio LL700 73101 73501 0 ErcrosBio LL700 73101 73501
ErcrosBio LM 60000 Range of products for the production of components by injection molding and blow injection molding Transparent products: Series 62000 Opaque products: Series 63000
Aditives Extruder Dry PLA ErcrosBio LM 63000 Series Drying PLA Pellets Injecction Drying PLA End products
ErcrosBio LM 63000 Series Mechanical properties 70 4 Esfuerzo en punto de fluencia (MPa) 60 50 40 30 20 Modulo de Young (GPa) 3,5 3 2,5 2 1,5 1 10 0,5 0 ErcrosBio LL650 63101 63102 63103 63104 0 ErcrosBio LL650 63101 63102 63103 63104 ErcrosBio LM 63103 y 63104 high tenacity materials with breaking deformation > 140%, with modulus similar than standard PLA. Elongacion a rotura (%) 160 140 120 100 80 60 40 20 0 ErcrosBio LL650 63101 63102 63103 63104
ErcrosBio LM 63000 Series Melt Flox Index 190ºC, 2.16Kg (g/10min) 10,0 9,0 8,0 7,0 6,0 5,0 4,0 3,0 2,0 1,0 Improvement in permeability properties in oxygen and water vapor. 0,0 ErcrosBio LL650 63101 63102 63103 63104 45 20 3 % Transmision al O2 OTR 23ºC 0% humedad (cc/m2.d) 40 35 30 25 20 15 10 21 % 27 % 53 % Transmision vapor de agua WTR 38ºC 90% humedad (cc/m2 d) 18 16 14 12 10 8 6 4 19 % 30 % 14 % 5 2 0 ErcrosBio LL650 63101 63102 63103 63104 0 ErcrosBio LL650 63101 63102 63103 63104
CONCLUSIONS Ercros has a range of products based on PLA. With a variety of properties specifically tailored to meet the requirements for processing and to have required properties. Application for extrusion and extrusionthermoforming, injection and injection blow molding To obtain a wide variety of finished products.
Thanks for your interest! Belén Pascual, head of R&D in plastic division. bpascual@ercros.es Domingo Font, biopolymers sales manager drfont@ercros.es