Biodegradable plastics from renewable resources. Sergio Bocchini

Transcription

1 Biodegradable plastics from renewable resources Sergio Bocchini

2 Innovation in the field of polymeric materials: research on new materials The driving force for research in biopolymers are: the fear of a possible significant rise in prices of petroleum products law enforcement that can made obligatory (for some applications) or encouraging their use the growing issues related to the waste recovery generated by fossil polymers

3 WASTE RECOVERY ISSUES Fossil fuels Convent. polymers (PP, PE, PS, PVC) Use Dispersion in the environment Not degradable wastes Landfill Waste combustion Global environmental issue Recycling Development of green polymeric materials

4 Landfill disposal It was used in the past because simple and economic. In the 1999 (APME 2002) 8,4 millions of tons were disposed using landfills Because of hygienic problems and landfill exhaustion, CEE is trying to disincentivate this methodology (Landfill Directive European Commission 1999/31/EC In the case of biopolymers, there are some problems due to methane emission (a gas far more harmful than CO 2 from environmental point of view) in anaerobic biodegradation J.H.Song et al. Puil. Trans. R. Soc. B , 2127

5 Waste combustion for energy recover In 2002 in EU 40 million tons were burned with energy recovery in 230 incinerators It is considered quite good view because the plastic material has a GCV (gross calorific value) is comparable to or greater than that of coal This system, however, is widely criticized In principle it should be good also for biopolymers however there are no data of GCV of biopolymers. J.H.Song et al. Puil. Trans. R. Soc. B , 2127

6 Recycling This technique is growing in the field of polymers from fossil resources. The goal is to "dignify" the waste, to make them suitable for applications including high-level in substitution of the virgin polymers Biopolymers can be recycled using traditional technique Actually the lack of specific plants, can create problems in the cycle of recycling petrochemical polymers

7 Biopolymers Taking into account the previous argument the biopolymers are an area with great potential development potential because they combine high Technical potential Eco-sustainability, form the resource point of view and the end of life

8 Biopolymers Based on a marker analyses of Hannover University (Dept. of Bioprocess Engineering), it was estimated that in the 2007 there were already 26 commercial producer of biopolymers and many other were active from the R&D point of view. About 60 society were active in the biopolymers sector (Bioplastics Magazine (03/07) Vol.2 pag 31) In a more recent study (2009) of bioplastics24.com 32 producers of biopolymers were reported (Bioplastics 09/10: processing parameters and technical characteristics a global overview) On Material Data Center ( about 50 producer are cited

9 Biopolymers Despite the growing interest in the market for biopolymers, there is still some confusion regarding the definition of "biopolymer. This can lead to misunderstandings and errors in objective assessment on the market prospects and also, from the legislative point of view. therefore it is appropriate to give some definitions.

10 Biopolymers - Definition On the basis of European Bioplastics Association Biodegradable Polymers with compostability approved on the basis of EN The source (renewable or fossil fuel) is not important Polymers based on renewable source They should be biodegradable or not

11 Biopolymers Both categories presents some environmental benefits: Biodegradable polymers allow the disposal of products in composting plants without leaving residues and fragments The polymers from natural resources are "zero carbon foot print". All the CO 2 released at the end of the life cycle is "captured" by the new cultures in the following season

12 GLOBAL CARBON CYCLING THE ECO DRIVER CO 2 Biomass/Bio-organics Bio-chemical Industry 1-10years > 10-6 years Polymers, Chemicals & Fuels Chemical Industry Fossil Resources (Petroleum, Natural gas) Renewable Carbon CO 2 & Biomass Polymers Biochemical Industry Small, entreprenuerial business Green Polymers & Chemicals

13 Carbon foot print: kg CO 2 for 100 kg of plastics Intrinsic value proposition for bio feedstock R.Narayan 1^PLA World Congress, Munich 2008

14 Biodegradation ad legislation There are specific regulations, set by major international organisations (ISO, CEN, ASTM, DIN, Green PLA) for different applications and systems at the end of life

15 Biodegradation and Standards Knowledge of regulations on the biodegradation and compostable is very important for the development of biopolymers because: biodegradation can occur in very different environments This could generate errors and misunderstandings between manufacturers, customers, Associations Unlike other applications, the manufacturer finds it hard to carry out controls.

16 Standards as a communication tool Authorities Standards Producers Users

17 Biodegradation and Standards Biodegradation is a process in which substances and materials can be assimilated by microorganism and be so placed in the natural cycle. (according to Standard UNI CEN/TR ) The microorganisms that are present in every environment and assimilate organic waste play an important role in the biodegradation.

18 Biodegradation and Standards PRODUCT USE/DISPOSAL CONTROLLED UNCONTROLLED WASTEWATER SOLID WASTE OPEN WATER SOIL MARINE AEROBIC TREATMENT ANAEROBIC TREATMENT ANAEROBIC STABILIZATION COMPOSTING BIOGASIFICATION LANDFILL USE OF COMPOST IN SOIL C.Bastioli Handbook of Biodegradable Polymers, RAPRA

19 Biodegradability Order of aggression with regard to biodegradation in different environments Compost Soil Fresh Water Marine Water T + fungi + fungi + bacteria diluite bacteria bacteria bacteria C.Bastioli Handbook of Biodegradable Polymers, pag 165, RAPRA

20 Biodegradability The conversion reactions of organic carbon are different depending on whether the degradation occurs in aerobic or anaerobic environment Aerobic Biodegradation C POLIMER + O 2 CO 2 + H 2 O + C RESIDUE + C MICROBIC Anaerobic Biodegradation C POLIMER CH 4 + CO 2 + C RESIDUE + C MICROBIC Nota: C MICROBIC carbon incorporated in the (chemical compound, molecoles) of cells C RESIDUE carbon not yet degraded C.Bastioli Handbook of Biodegradable Polymers, pag 151, RAPRA

21 For regulation a material is biodegradable if : 1. It can be biodegraded in a microbiologically active environment 2. It does not introduce toxic substances in the environment 3. The concentration of heavy metals of tested material is less than one half of the corrisponding limit for the compost The biodegradation tests should be performed in parallel to the tests of biodegradation of a reference sample consisting of pure microcrystalline cellulose or from polycaprolactone

22 Biodegradation curve

23 Biodegradability - definitions Regulations give different definition of biodegradability taking into account Primary and last Biodegradability Presence of oxygen (aerobic and anaerobic biodegradability)

24 Biodegradability - definitions Primary Biodegradability (ISO regulation) : structural change (transformation) of a chemical compound by microorganisms, resulting in the loss of a specific property last Biodegradability (EN 13432) : Decomposition of an organic compound by microorganism, in presence of oxygen, in carbon dioxide, water and mineral salts and whatever other element (mineralization) and new biomass or, in absence of oxigen, in carbon dioxide, methan, mineral salts and new biomass.

25 Biodegradation It is a process than happen, usually, in two different phases: 1. Degradation Fragmentation: the action of moisture, heat, UV, and/or enzimes riduce molecular chains and the resistance of the polymer, the compounds are fragmented 2. Biodegradation: the fragments are consumed by the microorganisms as food source and energy and converted in CO 2 and H 2 O, the speed should be compatible with the environment times: Plastic Fragments CO 2 Plastic Plastic Fragments Microbs H 2 O Plastic Fragments Humus BPI Biodegradable Product Institute confused by the terms Biodegradable & Biobased

26 Biodegradation The rate and level of biodegradation is highly dependent on the environment in which the material is deposited : Moisture content (from waster with high water content) Oxygen presence ( aerobic or anaerobic environment) Temperature (high for compost, low for soil or in water) Microorganism concentration (high in waste treatment plants, low in sea water) Salt concentration Rules which provide all of these cases have been drafted

27 Overview of the main ISO standards Biodegradation standards Aerobic Tests Anaerobic tests In acqueous media soil In acqueous media ISO High solid ISO CO 2 developed ISO O 2 Demand ISO Developed CO2 Compost ISO Mineral bed Composting ISO emenda Soil ISO Other tests: marine environment (solo ASTM 5437 e 6691)

28 Other biodegradation rules There are specific rules (especially ASTM) to simulate the process of biodegradation in different environments landfill (ASTM D ). In landfill the biological activity is very low compared to compost and substrates for the production of biogas (for the lowest concentration of microorganisms) In Sea (ASTM D o ASTM D ASTM D 5209). These rules are interesting for specific applications (such as fishing lines, nets, disposable materials for boats and so on..) Resistance to mushrooms, bacteria

29 Recapitulation of the main ISO standards Of great significance are the standards for assessing the biodegradability in solids, both in compost that in soil, to evaluate the possibility of disposal is composting plants directly on the ground (mulch film, home composting, etc.). The biodegradation levell is independent from the shape and the dimension of the material for testing. However, the time to reach the level required by the rules of biodegradation depends on these factors. Consequently, if tests are conducted on different types of materials it is necessary that the shape and size of the samples are similar. In the case of powder particle size should be the same.

30 Compostability Compostability can be defined as a specific form of degradation that occurs in both industrial and home composting facilities. It is particularly important for the possibility of disposing of waste, especially from those derived from packaging or agricultural use. In particolar:

31 Compostability The composting process is the transformation of organic wastes in carbon dioxide, water, biomass and heat By action of microorganism normaly present in the environment (biodegradation). The process happens in dedicated plants that should insure the right developing of the process During the process the compost reaches C, with a moisture content of about 50-60%RH.

32 Composting At the end of the process the initial waste is transformed in a substance called compost, The smell and the appearance is of a fertile soil sanitized and stabilized as it has no pathogenic microbes (for humans and plants, insect larvae and weed seeds) and putrescible material, through the action of temperature

33 Composting In the composting plants this phenomenon is controlled and optimized in order to : Obtain high conversion rate, Effluent control, Final compost quality control, and so on

34 Composting To ensure a good composting process certain factors should be stable : Size of composting material: pregrinding is used to have good areation and easy release of CO 2 (average particle diameter between 0.5 and 5 cm) C/N Ratio Low ratio the process releases an high amount of NH 3 and there is a reduction in performance, For too high value the process slows down or stops for lack of elements necessary for microbial growth. (ISO between 20 and 30, according Piemonte Region between 15 and 40). The moisture content should be higher than 50%

35 Compostabily During the grinding, packaging and other objects in biopolymer present in compost should not interfere with the machinery and processes commonly used in composting plants. The size of the fragments obtained must be appropriate for the composting process

36 Composting Composting is a process that leads to significant benefits: Use of waste materials, derived from agriculture, urban and industrial waste, which, if not reused, can be harmful to the environment Return to the soil of organic matter that allows a return in terms of fertility in the medium and long term Allows a significant saving of chemical fertilizers by using the content of nutrients (N, P, K) in the compost

37 Level of biodegradability and compostability UNI EN Biodegradability (ISO or ISO and ISO 14851) The acceptance level is 90% to be achieved in less than 6 months Disintegrability * Samples of the test material is composted together with organic waste for 3 months. The mass of the residues of the test material with size> 2 mm must be less than 10% of the initial mass. * See ISO 14045

38 Compost quality Should not discharge toxic substances into the environment The compost is analyzed in the typical physical and chemical parameters as ph, salt content, density, N2, ammonium nitrogen, P, Mg and K Tests with life forms : Determination of germination by the method described in- UNI Annex K Determination of acute toxicity on earthworms by the method described in ISO

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42 Final biodegradability Standard ISO ASTM D 6002 JIS K 6953 ASTM D 5338 (ISO 14855)

43 Test method to determin compost quality Standard EN ASTM D 6400 Test method Ecotoxicity test with not less than two types of plants. In accordance with OECD Guideline 208. Ecotoxicity test with cress and at least two other types of plant is to be conducted in accordance with OECD Guideline 208 Chemical characterisation of the compost: Volumetric weight, total dry solids, volatile solids, salt content, ph-value Nutrient content (N, NH 4 - N, P, Mg, Ca)

44 Major Production Systems of Biopolymers from Renewable Source 1. Use natural polymers that can be modified, but remain basically unchanged (eg. Polymers from starch, cellulose) 2. Fermentation to produce biomonomers which are then polymerized (eg. PLA) 3. Produce biopolymers directly in microorganisms (eg. PHA). 4. Produce monomers and polymers from bio-monomers fossil The second of these systems is gaining importance, the third, although there are first experimental productions, seems to be still far away from mass production. In the quarter, many companies are investing (eg. BioPET coca-cola)

45 Some examples of biodegradable material from renewable raw material(1) Starch Collection treatment of corn to extract the starch Starch destructuration and addiction of a polyester to increase mechanical properties ACIDE POLYLACTIQUE (PLA) Starch destructuration to form glucose Collecti on treatment of corn to extract the starch Convesion of glucose to form lactic acid Lactic acid polymerisation

46 Some examples of biodegradable material from renewable raw material (2) POLYHYDROXYALCANOATES (PHA) Bacteria «Ralstonia eutropha» Use of biopolymer as energy stock Fermentation of sugar into polyesters Cell disintegration, formation drying polymer extraction with solvents Object made in PHA CELLULOSE ACETATE

47 Biopolymers / Biobased Polymer Renewable Resource-based Microbial syntetized Petro-based syntetic Petro-Bio (mixed) Sources Polylactic acid, PLA Starch plastics Cellulosic plastic Soy-based plastic Polyhydroxy alkanoates, PHA Polyhydroxybutyrate co-valerate, PHBV Aliphatic polyesters Aliphaticaromatic polyesters Polyester- PTT Biobased Polyurethane Biobased epoxy amides Blends etc Polyvinyl alcohols

48 Hybrid Polymers The increasing demand for biopolymers and the lack of capacity to meet demand is pushing towards the production of hybrid materials, that is obtained by mixing a biopolymer and a polymer fossil.

49 Hybrid Polymers This approach, according to the manufacturer, allows substantially reduce the use of petrochemical raw materials and environmental benefits in terms of reducing CO 2 emissions in the life cycle of the product Toyota and other Japanese companies are developing this concept for parts that require higher performance are not intended for composting. This approach must be carefully evaluated because, even if it favors the development of polymers from natural resources, can create problems at the end of life. These materials, in fact, are not compostable nor recyclable if it can create problems with the existing lines

50 Hybrid Polymers Society Trade mark Biopolymer Petro-polymer Cereplast Cereplast Hybrid ResinTM TPS PP Cerestech Cereloy Eco TPS HDPE,LDPE, LLDPE, PP CardiaBiopolymers Cardia Biohybrid TPS Polyolefins Bayer Makroblend BC PLA PC PMTC EcoHybrid PLA/PHB PP, PTU, PETG RTP RTP Hybrid PLA PC, PMMA, or ABS PolyOne Resound PLA/PHA Poliesteri Different

51 Exaple Cerestech Cereloy ECO PP 50% PP 50% Starch PP 0,9-0, > Ref.

52 A bit of history It 's interesting to underline that the biopolymers are on the market for a long time, some dating back to the origins of the development of this sector. The "celluloid" was invented in The first synthetic polymers were based on natural resources. Among the biopolymers from renewable resources "historic" include the types of cellulose, nylon 11, and the natural gums. Polycaprolactones and EVOH among biodegradable polymers have been developed since many years.

53 A bit of history With the development of cheaper technologies based on fossil resource, biopolymers had gradually lost its importance. In the '70s, after the first oil crisis, a new game was intense R & D to develop new classes of biopolymers, mainly for the packaging industry.

54 STARCH Collect Extraction of starch from corn Destrutturation of starch for recombination with a biodegradable polyester

55 Starch Starch is a carbohydrate (polysaccharide) found in many plants (corn, potatoes, wheat, etc..),widely available in nature. The annual production of starch is about 35 Million Tons of Half of U.S. Commercial use of starch hydrolyzed not food use food use

56 Amylose a): linear polysaccharide; Amylopectine b): branced polysaccharide

57 Structure and composition of starch particles in fuction of different vegetables K. Morawietz Bioplastics Conference 28/07/2007 Alessandria Italy

58 Starch Starch is present in the form of granules due to the strong intermolecular bonds between the hydroxyl groups. These supramolecular structure should be destroyed in order to use the starch as a thermoplastic material through different types of reaction. In most cases, the starch is then mixed with other polymers to obtain materials that are easily processable.

59 Starch plasticization

60 Polymers derived from Starch As a consequence, the polymers from starch can be very different : Polymers from pure starch (used as filler); Polymers from partially fermented starch; Polymers from destructured starch; Polymers from modified starch (sostitution of OH grups with ester or ether groups); Polymers from blend of starch with other polymers (polyesters, CPL, CA, PVOH). The blends obtained could be da flexible such as come PE or rigid such as PS. This makes it very difficult to make a comparison between the different grades or give indications of the properties. The differences between the different types are extremely high.

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62 Blending with other polymers requires a careful study for formulation in order to obtain a good dispersion between phases (see picture below)

63 Main producers Producer Product Capacity [ton] Espansion Novamont Mater-Bi Biotec / Sphere Bioplast (up to ) Biop Biopar (2012) (2015) Rodenburg Solanyl Végéplast Végémat (2010) Plantic Plantic Biograde CardiaBioplastics? Cereplast Cereplast Compostable

64 Other producers Producers Ever Corn (Japan Corn Starch) Limagrain Ventura Supol Potatopack Harbin Livan Biodegradable Product Product Ever Corn Biolice Floralat Supol Potatoes Livan

65 TPS with natural fibres Ventura produces a material called "Floralat" based on starch reinforced with natural fibers. In this way they can reach values of form about 4,000 MPa. Elastic Modulus [MPa] Floralat + 10% filler 4022 Floralat + 30% filler 4234 Stress at break [MPa] 34,8 33,5 Strain at break[%] 1,5 1,6 Density [g/cm 3 ] 1,34 1,34

66 Polymers from Starch The 75% of polymers from starch is used for packaging the other 25% in agricolture The quote of polymers from starch with respecto to the other biopolymers was evaluated as 75-80% (Ref. Utrecht University/Fraunhofer ISI) An interesting application is the use of starch as a filler in tire manufacturing (partial substitution of C black). The benefits in terms of noise reduction and less friction, resulting in lower consumption.

67 Other properties of polymers from starch Low barrier to water vapour Sensible to contact withh 2 O Low resistance to solvents Good barrier to oils and fat The barrier properties are highly variable depending on the formulation.

68 Polymers from starch processability The polymers from pure starch can be processed on thermoplastic lines after addition of plasticizers The modified polymers have better processability characteristics (depending on the degree of substitution, but lost in biodegradability) The blend with starch (usually polyester aliphatic / aromatic, PCL, CA, EVOH) and have better processability. It is processed in standard machines with minor modifications, eg. extrusion, thermoforming, blow film, injection molding, foaming

69 FILM PROPERTIES Low gloss, but discreet transparency Weldability on themselves or with other biopolymers, similar to that of PE and can be made at the same speed (Novamont) Excellent printability. According Novamont you can use water based inks or solvents without corona treatment Can be use for FFS (Form, Fill, Seal) Food approved Can be laminated on paper (hot glue, coating, extrusion coating or lamination) Possible lamination or extrusion coating

70 Barrier properties of films by litterature Novamont presents the data reported not to specific products, but the range in general. As you can see the permeability to O 2 covers the range from PET to HDPE C.Bastioli EPF School, Gargnano maggio 2009

71 Barrier properties Very interesting are the data submitted by Plantic. The TPS has been produced starting from high-amylose starch (80%), according to a patented technology.

72 MATER BI NF Film properties Temp melting C 110 Density gr/cm 3 1,29 MFI gr/10 min 3 σt MPa 22 Strain at break % 340 E t MPa 210 Res lacer MD/TD N/mm 36/46 Haze % 95 WVTR g30μ/m 2 24hr/90RH 850

73 Foam trays from starch polymer A very important application is that of the foam trays. They are soft and flexible with a density of g/l. The packaging can be realized with stretch film machine using up Automac HFFS film, laminates, films of cellulose (UCB Naturflex).

74 Foam trays TPS L. Garavaglia AIM Polimeri da fonti rinnovabili Bologna 2005

75 Foam trays TPS L. Garavaglia AIM Polimeri da fonti rinnovabili Bologna 2005

76 L. Garavaglia Foam trays TPS

77 TPS applications Bags for solid waste collection and composting A. Castellanza AIM Polimeri da fonti rinnovabili Bologna 2005

78 TPS applications FOOD PACKAGING MADE IN MATTER B Nets for fruits and vegetables Bags for bread Transparent windows for bags Rigid foam trays

79 TPS APPLICATIONS

80 TPS APPLICATIONS Application in the agricultural field film mulching A. Castellanza AIM Polimeri da fonti rinnovabili Bologna 2005

81 M.Malinconico Mulching films

82 World consumption of plastic materials (tons) in agriculture M.Malinconico

83 M.Malinconico

84 TPS applications Pots for nursery

85 Starch destructuration (glucose formation) PLA Collect Estraction of starch from corn Fermentation production of lactic acid from glucose Lactic acid Polymerization

86 PLA (Polylactic acid) It was one of the first commercially produced biopolymers is available from several manufacturer it is a polymer with application versatility with performance comparable to those of petrochemical polymers (PP, PS, etc...) It is, however, a brittle material with low resistance to temperature It is easy to recycle with different technique (mechanic, chemical).

87 Biodegradability of manufact made in PLA The PLA is compostable, or biodegradable in composting conditions : temperature di C in presence of high moisture level and microorganism in about days At room temperature and out of the composting conditions, PLA is chemically and physically resistant to degradation, such as traditional plastic materials (PE, PP, PS, PET, etc....) When used in normal conditions PLA made objects are equally stable and free from contamination by biodegradation, as the objects made by traditional plastics.

88 PLA production For PLA there are suppliers of technology for production of the monomer and polymerization The groups Uhde Inventa-Fischer can provide technology and engineering for the construction of a plant for the production of PLA. The production cost is estimated at 1,4 1,7 / Kg (depending on the cost of raw material) for a capacity of 20,000 tons per year of PLA. Lactic acid polymerisation grade is produced by Purac, and Galactic

89 Lactic acid Lactic acid, the monomer for the production of PLA, is a natural compound present in all animals. It is used in food, cosmetics, pharmaceutical, It is included in the positive list of permitted monomers for plastics approved for food contact. It is produced by sugar fermentation

90 Lactic acid Acidification, Purification

91 Lactic Acid Lactic acid is chiral thus there are two diastereoisomet L- or D- Lactic acid obtained by chemical synthesis it is a racemic mix (50% D and 50% L) Fermentation, instead, is very specific and essentially allows the production of a stereoisomer (99.5% di L-isomer and 0.5% of D-isomer) As a consequence, the polymers may have a different relationship between the two stereoisomers and therefore different characteristics and crystallinity

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93 PLA

94 Lactic acid Lactic acid polymerisation grade is produced from Purac, with a market share of 70%, and from Galactic. Purac has built a 110,000-ton plant in Thailand. Purac recently developed technology for the production of D-lactide (plant from 5000 t / y in Spain from August 2008) In 2007, Galactic has created a J.V. with Total Petrochemicals (Futerro) with the aim of building a plant for PLA production.

95 PLA production- 1 There are two main methods for producing polylactic acid from lactic acid monomer, which differ both in terms of chemical / equipment, and from that of the type of polymer obtained : Direct condensation polymerization ring-opening polymerization

96 PLA production- 2 Direct condensation polymerization : Waterremoval of water through condensation 1) with the use of a solvent 2) under high vacuum 3) at high temperature has the great disadvantage of producing only the value of a molecular weight polymers with low to moderate, due to the difficulty of completely eliminating water and other impurities.

97 PLA production- 3 However, there are studies for improvement of the limitations presented by this technique, the Japanese Mitsui Chemicals has in fact developed a new process based on the direct polycondensation of L-lactic acid to allow the production of PLA with high molecular weight without the use of solvents.

98 PLA production 4 ring-opening polymerization catalytic

99 PLA production - 5 As mentioned above, lactic acid is a chiral molecule, and subsequent ring-opening polymerization can produce different types of polymers, each with different properties : e.g. : in the case of high concentration of L lactide can be obtained crystalline polymers, while in the opposite case we obtain a more amorphous material.

100 PLA main producers Producer Product Production Capacity [ton] Expansion NatureWorks LLC Natureworks ? Mitsui Lacea 500 Misun Biomaterial Revoda Toyobo Bioecol 200 Futerro**?? (2009) Unitika* Terramac compounding Teijin Biofront Pyramid Bioplastics Pyramid (2010) Hycail Hycail PLA Pilot plant sell to Tate&Lyle Toyota Motors Toyota Ecopla sell in the2008 a Teijin * Unitika is a compounder ** jv Total and Galactic

101 Manufact producers Manufact type Producer Fibers Kanebo Gohsen Teijin Unitika Films Treofan EarthFirst Film Mitsubishi Unitika Tohcello Laminated Kanebo Kasei

102 PLA producers Interesting developments are expected in Europe : In Italy in 2007 that created the Bio-on who is investigating the production of PLA from molasses and juices full of sugar cane and beet byproducts of other processes. The advantage is the low cost of these materials and their availability, not being used as food. Bio-On is also exploring the production of PHA An important agreement was reached between Total (through Petrofina) and Galactic (producer of lactic acid) to develop a production technology of PLA in a joint venture (Futerro).

103 PLA properties The properties can be modulated using the racemic form or co-lactic acid with other monomers Mechanical properties Tensile strength MPa Modulus MPa Strain 1 5 % Izod J/m Thermal properties Tg ~ 60 C, Tf C, Tc C Vicat 65 C Above 60 C tends to degrade in the presence of moisture

104 PLA properties: a comparison

105 PLA properties Density 1,25 g/cm 3 Trasparent, with high gloss Good resistance to UV Good barrier properties for smell moderate to O 2, CO 2, acqua, Weldable with different technique (hot, with ultrasounds, with RF ) Excellent behavior in permanent torsion and bending (dead fold) Can be used in contact with food

106 Trasparency (%) Comparison PLA vs. Competitors Trasparency PP alta trasp. SBS OPS A-PET PLA Materiale Luc Bosiers AIM 14 gennaio 2005 Bologna

107 PLA critical points As mentioned above, the critical points of PLA are: The low thermal resistance which makes it impossible to use for use with hot drinks, microwave, and ironing because of deformation of the artifacts in the transport The weakness that creates problems in thermoforming and film technology (breaks in the cutting, trimming, etc.). The low melt strength, which creates problems in blown film and in the process of foaming

108 Thermal resistance The PLA crystallizes very slowly and is therefore difficult to raise the level of crystallinity at speeds of conventional process. As a result, the thermal resistance remains low (around 60 C). The thermal resistance can be improved: accelerating the rate of crystallization nucleating heterogeneous or through the use of d-lactide, which acts as a seed of crystallization (stereocomplex), resulting in reduced molding cycles with the addition of natural fibers

109 THERMAL RESISTANCE According to Purac * d-lactide is much more effective than talc as nucleating agent and can considerably enhance The temperature of crystallization, Crystallinity level Crystallization rate. Consequently it improves the moulding cycle, that, according to Mazda, can be reduced to 1/5, and thermal resistance (T m C) The same advantages can be obtained, according Unitika ** who developed this technique, with a heterogeneous nucleating agent. *1 European Bioplastics Conference, Bruxelles 21 novembre 2006 ** 2 European Bioplastics Conference, Parigi, 21 novembre 2007

110 THERMAL RESISTANCE The developed technology developed from Purac is based on: Mixing PDLA with a standard PLA resin with the formation of crystallites sterocomplex. The mixture can be made standard for compounding machines (extruders, internal mixers) even if the rotating twin screw extruders are recommended. Purac Application data

111 After mixing THERMAL RESISTANCE It has a rapid formation of steroecomplex crystallites which act as nucleating agents and accelerate the solidification of PLA during processing (molding, extrusion..). It is important to operate at a higher temperature than the melting point of the PLA but less than that of steroecomplex Itis important precristallize the sterocomplex before transformation. In injection molding is necessary to have the temperature of the mold C (annealing) to promote the crystallization Purac Application data

112 Relative Cristallinity Effect of heterogeneous nucleating agent Isothermal crystallization of PLA 1,0 from 200 C to C/min 0,8 0,6 0,4 0,2 0, Time (min) S.Murase 2^ European Bioplastics Conference, Paris 21-22/11/2007

113 Properties of TE-7300 and TE-8300

114 The effect of fiber reinforce T. Yanagisawa 2^ European Bioplastics Conference, Paris 21-22/11/2007

115 Poor impact resistance To improve the impact resistance of PLA have been developed impact resistance agents, compatible with the same PLA. Some of the producers are Arkema (Biostrength), DuPont (Biomax) e Rohm and Haas (Paraloid). As an example we report the data obtained with a polyacrylate:

116 14 [%] 12 Impact resistance effect of a polyacrylate 3,5 3 [J] 10 2, ,5 Haze [%] Dart Drop Impact [J] , ,5 10 % BPM 500 in PLA B.Azimipour 2^ European Bioplastics Conference, Paris 21-22/11/2007 0

117 PLA % Impact Modifier Formulation Temp. mould ( C) Resilience (KJ/m 2 ) PLA 3051D 60 13,10 PLA 3051D + BIOSTRENGTH ,91 PLA 3051D + BIOSTRENGTH ,87

118 Low melt strength The use of chain extenders modify the rheologic behaviour of PLA Source: Bioplastics Magazine 03/2008 pg. 35

119 The use of chain extender: Low melt strength In the case of blown film extrusion, facilitates the maintenance of the bubble and the ability to increase the diameter, you increase the extrusion speed. It has the side effect of a slight decrease in the transparency In the case of foaming, it facilitates the formation of small cells with smooth surfaces and a reduction in weight by 10-15% K.Jacobs,D. Haff Bioplastics Magazine 03/08, n3, pag 34

120 PLA possible applications Source Utrecht University, Fraunhofer ISI Sector % Today % 2020 Packaging Agricolture 1 Automotive 0 20 E/E 1 10 Fibers, textile Total

121 PLA: drying If the resin is left out of the original packaging drying it is necessary before processing. Dehumidifiers for PET can be used under similar conditions, but temperatures of C for 6 hours or more. It is recommended a maximum moisture content of 250 ppm, although for safety, it is preferable a level of ppm. If long times of stocking are foreseen moisture should be reduced to 50 ppm.

122 Moisture content (ppm) Drying Curve Amorphous 40 C Amorphous 50 C Cristalline 50 C Cristalline 80 C Time (hours) Drying curve of PLA pellets at different temperatures. Flow 'air: 0.25 cfm / lb of grain. Dew-point -40 C NatureWork Technical literature

123 PLA - Processabily - The PLA can be processed with all the known technologies including thermoforming, injection molding, extrusion blow molding, film extrusion, fiber extrusion using standard thermoplastic machines (PET or PS) slightly modified (Gruber and O'Brien, 2002, Galactic).. PLA is degraded by moisture at temperatures above 100 C or in the molten state with loss in molecular weight, it is necessary to use hoppers with dehumidifier to prevent moisture absorption during molding. Because the PLA has. a low viscosity reduction of stress (shear thinning) may require more power in the processes of transformation

124 Viscosity (Poise) Rheologic curves of PLA and PS 1.00E E+04 PLA 1.00E+03 PS 1.00E+02 0, Shear Rate (rad./sec) NatureWork Technical literature

125 PLA - Processabily - Injection moulding The standard type require Moulding temperatures between C (T max 240 C) and Mould temperature between C The heat-resistant types, respectively Moulding temperatures between C and Mould temperature between C.

126 PLA Processabily Extrusion General-purpose single screw extruders with compression ratio of 2.5-3, and L/D 24 to 36 and cooled feed opening should be appropriate for the PLA. Generally, shorter extruders determine a lower melt temperature at the exit from the die. It is generally recommended to have an element of mixing and using a static mixer prior to the supply chain to ensure a uniform temperature and a 'good dispersion of additives and homogeneity of the melt. (Ref. Plastics technology articolo 2007/02/fa1)

127 PLA films The PLA is particularly attractive for application in the film because of its stiffness, transparency and brightness comparable to that of PET and PS. It has a high specific weight in relation to the polypropylene Very polar without sealing layer (tie layer) does not adhere to PP or PE film Can be used in contact with food

128 PLA Films A current limiting factor is the low thermal resistance, which poses problems for storage and shipment and reduce the number of applications. The problems of resistance to cracking, which can arise in some applications, can be reduced with the use of impact modifiers

129 PLA films The films are usually obtained with a flat head (tenter method). In the case of blown film there may be problems (such as difficulty bubble collapse, wrinkling) due to the low melt strength. Problems in the use of lines for PO for the different rheological properties of materials The fragility of the PLA, which can cause cracks in the cut, you must have a system for efficient cutting (Rotary shear)

130 PLA films

131 PLA films With regard to barrier properties, the levels of permeability of the films of PLA respect to PET and PP can be estimated as: PET PP O 2 x 8-10 x 0,2-0,3 H 2 O x 8-12 x CO 2 x x 0,3-0,4

132 Barrier properties The barrier properties are: Advantageous in some cases (eg. Bags of Salad ready to eat) Suitable for consumer products fast (eg. Yoghurt, gastronomy) Disadvantageous in the case of long-life products (eg. Meat, fish, margarine) Not relevant to applications without the cover (eg. Egg Confections, packing of tomatoes, etc.).

133 PLA films They are used for food packaging for consumer durables, as top of the foam trays and window envelope The barrier can be significantly improved using the coating with oxides of silicon or metallization with Al They can also be easily coupled with other materials

134 PLA films producers The major producers of the film are: Earth First represented in Europe by Sidaplax Biophan It was manufactured by Treofan now sold the business to Polyfilms Mitsubishi Plastics (Ecolojou) In Europe there are contacts of Min Chinese Technology There are many producers in Asian countries (China, Korea, etc..) That are hard to reach from Europe

135 Termoforming One of the major fields of application is represented by the PLA thermoformed packaging for foods: The easy processability that allow to makes thermoforming in-line and off-line The properties that are very similar to those of PET and PS It easy to process PLA on the existing thermoforming lines for PET/PS and, although with some limitations, PP (the withdrawal is similar to that of PS and PET) at speeds comparable to those of PET, a bit lower than that of PS.

136 PLA vs other fibers (Polylacticfibers D.W.Farrington etaltri)

137 PLA fibers vs Traditional fibers

138 PLA fibers Recently, Teijin, a leading global manufacturer of fiber, developed in collaboration with the Mazda, a new fiber (Biofront) with a melting point significantly higher, 210 C, using the technique of stereocomplex first discussed. It is expected that this fiber, can be stretched and be able to compete not only with the PP, but also with polyester fibers.

139 Processability: Foam trays - PLA PLA has a good extrusion processability The expansion is not easy and requires modifications to the extrusion plan As said before this feature can be improved with the use of chain extenders Good processability in thermoforming

140 Foam trays- PLA Characteristics: Density 400 g/l (PS foam 50 g/l) Good resistance (mechanical resistance 30N PLA vs 40 PS) Good sealability No alteration in the presence of moisture or water Maximum temperature of use and storage of 45 C

141 Bottles Injection stretch blow-molding process(isbm) It can be done with machinery for PET under the thermal conditions already indicated a) single-stage process: no special problems. Biaxial Stretching is similar to that of PET b) two-stage process: the molding of the preforms without any problems. Blow molding process window than that of PET c) Need to change the molds for PET to optimize the result

142 Bottle characteristics Excellent transparency and brilliance. Mechanical properties quite similar to those of PET, except for a higher creep. a) Barrier properties: 1) good for aromas Bottles 2) low to water vapour (similar to Nylon), 3) better than PP vs. O 2 and CO 2 but lower performance respect to PET b) Recycling: identified by automatic readers, compostable or recyclable through mechanical/chemical recycling

143 Bottles Beverage areas Sparcling Water and carbonated beverage: no Natural water: for sizes greater than 500 cl, there may be structural problems The PLA is currently used in the fresh (raw milk, centrifuged and drinks in the short term) Possible areas Cosmetics and detergents

144 PLA Bottles

145 PLA applications Film with small thickness (< 40 micron) L. Boisiers AIM Polimeri da fonti rinnovabili Bologna 2005

146 PLA applications Film with small thickness (< 40 micron)

147 PLA applications Rigid packaging without barrier

148 PLA applications Rigid packaging without barrier

149 PLA applications Rigid packaging not food applications

150 Foam Trays PLA applications

151 PLA applications Rigid packaging without barrier R.Pianesani AIM Polimeri da fonti rinnovabili Bologna 2005

152 PLA applications food trays

153 PLA applications Fornitures

154 Bacteria «Ralstonia eutropha» PHA is used as energy stock Sugar fermentation Cells rupture, extraction, purification, PHA products PHA

155 Polyhydroxialcanoates PHA The polyhydroxyalkanoates are aliphatic polyesters produced by directly by microorganisms by fermentation of carbon substrate of natural products PHA Can be produced as homopolymers (polyhydroxybutirate) or copolymers (polyhydroxybutirate-copolyhydroxyvalerate), depending on the type of microorganism and the raw material. The properties depend on the content of comonomer

156 Polyhydroxialcanoates They are semi-crystalline polymers with potentially interesting qualities. They are available at very high prices and limited quantities. There are several ongoing investment, which should lead to wider availability and a significant reduction in costs. The objective of the major producers is to go down to 1,8 2 $/lb

157 Main producers Producer Product Productive capacity [ton] Growt Telles (Metabolix) Mirel Tianan Biologic Material (Cina) Enmat Meredian*?? (2009) PHB Industrial Biocycle Biomer Biomer R&D Pilota Mitsubishi Gas Chemical Biogreen R&D Pilota BioMatera BioMatera PHA Bio-On Minerv PHA?? Tianjin Green Bio-Science Co., Ltd (con DSM) GreenBio * P&G Technology

158 PHA properties Technology Injection Molding Injection Molding Extrusion Coating Type High fluidity High modulus Extrusion Stress at break,mpa Flexural modulus, Mpa Izod c.i. KJ/m 2 3,2 2,6 - Strain at break, % Vicat, C Ref. Metabolix Telles Schede tecniche Mirel

159 Copolymers properties (3HB-co-3HV) Propriety PHB PHBV (10% HV) PHBV (20% HV) Melting point, C Stress at break, Mpa Flexural modulus, Mpa Strain at break, % C.Bastioli Handbook of Biodegradable Polymers Rapra 2005, p.189

160 Glass transition and melt Temperature similar to PP Property P (3HB) PP PET PA66 Temp. Fusion ( C) Glass Trans. ( C) Cristallinity (%) Density (g/cm 3 ) 1,250 0,905 1,385 1,14 Moisture Ass. (% weight) 0,2 0,0 0,4 4,5 Young Modulus (GPa) 3,5 1,7 2,9 2,8 Stress at break (MPa) Strain at break (%) Problems: Fragility, thermal instability at T > T fusione

161 PHB PP comparison Ref. D, Scherzer NIChE February , Orlando (USA)

162 Properties PHA and PLA PHA (Polyhydroxyalcanoates) PLA (Polylactic Acid) Natural polymers biodegradable Stable at humid conditions Semicrystalline, not transparent Wide range of monomers Wide range of comonomers Natural monomer Hydrolysable Instable at higher temperatures (>60 C) Low crystallinity, transparent D- and L-lactic acid Comonomers reduce thermal stability further Tg from 35 C to +10 C Tg 50 C Strong and ductile Temperature exercise <120 C Fragile Temperature exercise <60 C

163 Insoluble in H 2 O Other Properties Can be used hot, even for hot liquids (HDT >120 C) for its resistance to hydrolytic degradation Highly resistant to solvents, oils, fats High UV resistance, bases and acids Good printability

164 PHA Processability It can transform the typical technology of thermoplastics In injection molding of a screw is recommended for PE with D / L of 20:1 The granules must contain 0.1% moisture The degradation temperature is similar to melting temperature thus it is better avoid injection pressures and screw speed too high Avoid long times of processing The mould temperature can be raised up to 60 C To cast Film extrusion conventional lines can be used. Temperatures of rolls and calendar around 80 C are recommended to promote crystallization

165 PHA Films Films with thickness between 25µ and 375µ can be produced with conventional lines good weldability They had WVTR (water vapor transmission rate) better than those of other biopolymers, whose size depends on the morphology (20 to 150 g). The mechanical properties are similar to those of the PE: Tensile strength from 11 to 25 Mpa, modules from 400 to 1000 Mpa

166 PHA films With regard to the permeability properties of the levels of PHA films (not oriented) these are the evaluation by Metabolix: LDPE HDPE opet PHA O 2 x 0,10-0,03 x 0,8-0,1 x 4-6 x 7,5-9,5 H 2 O x 4-15 x x 8-12 x 0,2 0,75 D.Gilliland NPE 2006

167 Other polycondensates As mentioned above, large groups are working to produce biodegradable and polycondensates polycondensates by biomonomers : - Polyesters - Polyamides - Polyurethanes -Acrylic monomers If successful, these biopolymers can fully replace the equivalent polymers from petrochemical monomers. The most advanced studies cover the polyesters. The aliphatic polyester / aromatic hydrocarbons are biodegradable

168 Polyesters from Bio-based monomers Polymer Monomer Monomer Chemical Name Trade Name(s) Potentially bio-based Petrochemical Poly(trimethylene terephthalate) PTT Sorona (DuPont) Corterra (Shell) PDO PTA/DMT Poly(butylene terephthalate) PBT various BDO PTA/DMT Poly(butylene succinate) PBS Bionolle 1000 (Showa Denko) BDO Succinic acid Poly(butylene succinate adipate) PBSA Bionolle 3000 (Showa Denko) BDO Succinic acid Adipic acid Poly(butylene succinate terephthalate) PBST Biomax (DuPont) BDO Succinic acid PTA/DMT Poly(butylene adipate terephthalate) PBAT Ecoflex (Basf) BDO Adipic acid PTA/DMT PDO: 1,3- propandiolo PTA: acido terftalico BDO: 1,3-butandiolo DMT: dimetil-tereftalato Ref. Utrecht University/Fraunhofer ISI

169 DuPont activity The DuPont use Bio-PDO (Susterra), made in jv with Tate & Lyle, for two families of products : Sorona EP, technopolymer with characteristics similar to those of PBT and Sorona Polymers be used for fibers and textiles Cerenol liquid polyols (polietherdiols) that can be used as intermediates in the production of elastic fibers in the production of thermoplastic elastomers (Hytrel) Besides these, in collaboration with Plantic, DuPont has developed a TPS (Biomax RS) to use as a reinforcing of biopolymers

170 PDO Production There are trhee main steps: Fermentation of glucose to glycerol Bacterial fermentation of glycerol to PDO Separation by filtration, concentration by evaporation, purification by distillation

171 DuPont Activity The Sorona has a melting point of 228 C, a Tg of 50 C, is transparent but becomes opaque after crystallization. It can be transformed with all the technology of thermoplastic (spinning, blow molding, injection molding and extrusion).

172 DuPont Activity As fiber is similar to PET has lower but form the best features of elastic recovery. As film because of the lowest Mp can be extruded into cast films in conditions comparable to those of PP or PA. It is also possible to produce biaxially oriented films

173 Strength vs Stiffness Ref. Sito DuPont

174 PDO per thermosettings The Ashland Composite Polymers, the American company Ashland Inc. using the Bio-PDO Susterra to produce resins with a lower environmental impact. Two different grades are already in production ENVIREZ L 86300, resin coating to make rolled by hand or spray ENVIREZ INF for the infusion process, formulated to maximize wetting of the reinforcement

175 Showa s Bionolle Bionolle is a polybutilen succinate (PBS) PBS is a polyester produced by polymerization of succinic acid and of the 1,4 BDO Succinic acid + 1,4 BDO Bionolle (PBS)

176 Showa s Bionolle Bionolle for its property is suitable for the production of films It is currently used for film mulching and compost bags. Applications are under development in the field of building, household goods and Fishery

177 PBS and PBSA Properties Units PBS PBSA PP HDPE LDPE Density g/l Heat of combustion kj/g H.D.T.(at 0.45 MPa) C Degree of crystallinity % Melting point (Tm) C Glass transition temp. C

178 Bionolle grades Grade PBS 1001 PBS 1020 PBS 1903* PBSA 3001 PBSA 3020 PP HDPE LDPE MFR (190 C) g/10 min (23 0 C) 2 2 Crystallization temp. C Flexural modulus MPa Tensile yield strength MPa Tensile break strength MPa Tensile elongation % Structure - Linear LCB* Linear Linear Linear * LCB means a long chain branched molecule. #1903 of LCB has a higher melt strength and crystallizing temperature than those of other linear-type grades.

179 Biodegradable Polyesters BASF is very active in this area. He developed an aliphaticaromatic copolyester based on 1,4-butanediol, adipic acid and terephthalic acid (Ecoflex), which is widely used in blends with other biopolymers, for the excellent compatibility. It 's a biodegradable material because of the flexibility of the molecule, aliphatic. The adipic acid could potentially be synthesized from renewable resources. Recently, BASF announced a significant increase from current capacity of 14,000 t to 60,000 t to be achieved by 2010.

180 Biodegradable Polyesters Ecoflex is a copolyester synthesized from : Thereftalic Acid Adipic Acid 1-4 butandiol L Ecoflex has been optimized to provide the best compromise between biodegradability and excellent mechanical properties, and ease of processing with standard machines

181 Proprieties alifatic-aromatic copolyester compared with PE Ecoflex F BX 7011 (Basf) propriety Unit test Ecoflex Lupolen 2420F Density g/cm 3 ISO ,25-1,27 0,922-0,925 MFR g/10 ISO ,7-2,9 0,6-0,9 Melting point C DSC Shore D ISO Vicat C ISO

182 Aliphatic-aromatic copolyester Ecoflex is a material with good clarity, stable up to 230 C, with good processability in blown film lines, where you can get up to a thickness of 10μ: BASF suggests the use of lines for LDPE and LLDPE, having characteristics similar processability This material may be used as films for packaging applications such as in agriculture and laminated with other films for the production of trays The PHE can be used, as well as blown film, even in lines for extrusion coating and cast film

183 Aliphatic-aromatic copolyester This material is also used in combination with other biopolymers. The use of Ecoflex can improve the performance of film based on PLA, starch, PHA, and so on. improving the mechanical strength, grease, moisture BASF also provides agents with anti-lock master, or titanium dioxide, carbon black

184 Blown film properties(50 µ) Propriety Unit Test Ecoflex FBX 7011 Lupolen 2420 F Trasparency % ASTM D Tens. Strength N/mm 2 ISO /44 26/20 elongation at break % ISO / /600 Energy failure J/m/m DIN ,5 Permeability Oxigen cm 3 /(m 2 d. bar) DIN Water g/m 2. d DIN ,7

185 Alifatic aromatic copolyester/pla Blends BASF also recently presented its blend of aliphatic aromatic copolymer with PLA (Ecovio) for specific applications. A version with a 1:1 ratio is used for the production of blown films. A second version with a ratio of 25/75 was studied for the production of foam products for packaging. It is used in lines for the expansion ofrigid PS.

186 Ecovio L BX 8145 Blown film properties(50 µ) Propriety Unit Test Ecovio LBX 8145 Lupolen 2420 F Trasparency % ASTM D Modulus MPa ISO / Tens. Strength N/mm 2 ISO /27 26/20 elongation at break % ISO / /600 Energy failure J/m/m DIN ,5 Permeability Oxigen cm 3 /(m 2 d. bar) DIN Water g/m 2. d DIN ,7

187 BioPolyamides Poliammide monomero source Polyamide aminoundecanoic Acid Castor oil Polyamide 610 Sebacic acid Castor oil Polyamide 6 Caprolactame Sugar fermentation Polyamide 66 Adipic acid Fermentation Polyamide 69 Hexamethylenediami ne / azelaic acid Azelaic acid from oleic acid ozonolysis

188 Cellulosic polymers The cellulosic polymers have been the first polymers to be produced. They were used for the production of granules and semi which film (cellophane) and fibers (rayon, viscose) with special features, especially aesthetic and sensory.

189 Cellulosic polymers Their use has not increased over time, despite the great development of the sector, and It has been linked to niche applications for the most economical and most flexible petrochemicals polymers which has allowed the optimization of special grades for specific applications.

190 Cellulosic polymers The cellulosic polymers are produced by chemical modification of cellulose, a major constituent of plants not lignified (eg cotton) or lignified. Cellulose is a complex polysaccharide similar to starch from which differs in the glucosidic bond between the groups (steric configuration). Compared to starch is more resistant to hydrolysis because of the stronger hydrogen bonds

191 Cellulosic polymers To obtain high-quality cellulose polymers start from short cotton fibers. There are, as plastic materials, other cellulose esters (acetate, acetobutirrato, acetate propionate, etc.).. Compared to acetate esters the mixed esters shows: lower moisture absorbtion, Higher compatibility with plasticizers, higher impact strength The properties depend on the types and content of esters and the amount of plasticizer

192 Cellulosic polymers The cellulosic polymers are manufactured with complex processes, with the cellulose in contact with anhydrides in the presence of solvents and catalysts. There are specific processes for fibers (viscose process, cupro process).

193 Cellulosic polymers The cellulose esters are thermoplastic materials, usually with added plasticizer to promote printability, characterized by transparency, excellent surface appearance, scratch resistance, antistatic properties, pleasant touch feel. For these characteristics have been used historically for the production of items listed for contact with human body (comb, glasses, etc..) and for clothing. They were also used for small appliances, etc.. In these applications, however, have been gradually replaced by fossil polymers for the lowest cost.

194 Cellulosic polymers cellulose acetate, CA Cellulose propionate, CP Cellulosa acetylbutyrate, CAB Specific Weight 1,26-1,32 1,19-1,23 1,16-1,21 Mp (Tg) C HDT, 18,8 C Traction MPa Strain at breack % Modulus MPa Hardness, R Scale Izod Kg/cm/cm ,

195 Cellulosic polymers Main producers are: Mazzucchelli (Bioceta) FkuR (Biograde) Albis (Cellidor) IFA (Fasal) Eastman (Tenite)

196 Cellulosic Films The cellulose films have been known for a long time. (The historical name was cellophane) There produced from regenerated cellulose film (cellophane) and the cellulose esters. Today there are new producers : Innovia (brand NatureFlex and cellophane) with many products including multi-layer) Goodfellow is made of cellulose acetate that regenerated cellulose Celanese (brand) Clarifoil available in different types and thicknesses

197 Cellulosic films The films from cellulose acetate compared with cellophane have gas barrier slightly lower, but higher WVTR They are produced in many variations : monolayer, multilayer, coated, metallized. By varying the surface layers (PVDC, nitrocellulose, PVC / PVA) is possible to vary the barrier properties and sealability They are used for packaging film, window envelopes, labels.

198 Cellulosic films They have excellent surface appearance and transparency. They are stable at high temperatures (176 F), easy to be bonded with adhesives or with solvent water, crop and print. Bend without whitening. They are produced as a multilayer with layers at different levels of barrier or metallic They have a very low oxygen permeability ( μ. Cm3 / m2/24hr at 0% RH) and very high permeability to water (1500 g. 27.7% RH μ/m2 24hr/90 offering many advantages for the packaging of wet materials (eg fruit) because it avoided the fogging, thus keeping long-transparency. The same characteristics make them suitable for the production of labels

199 Cellulosic films Fonte: Clarifoil

200 Cellulosic films Fonte: Clarifoil

201 Polycaprolactone The biodegradable polymer polycaprolactone is from fossil source. The starting monomer, cyclic caprolactone, is produced commercially by oxidation of cyclohexanone with peracetic acid (CH 2 ) 5 O CO

202 Polycaprolactone It is a biodegradable polymer crystal with Tm of 62 C. The polymerization is conducted with a glycol as an initiator : -[-(CH 2 ) 5 COO-] n - It 's a polyester useful as a prepolymer for the preparation of polyurethane elastomers by reaction or as a diisocyanate, which is important in the field of biopolymers, such as modifying agent in blends with other polymers, for its unusually high compatibility. It is one of the main modifiers for thermoplastic starch polymers

203 Polycaprolactone These are materials with modules on MPa, elongation at break about %, tenacious, with very low Tg (-60 C) Recently there have been acquisitions of leading manufacturers. The Dow has purchased the business from Union Carbide (Tone) and Perstorp from Solvay (CAPA). The capacity of this plant is estimated at 45,000 t/y

204 Applications of Bioplastics (da fonte European Bioplastics ) Agriculture / Horticulture Photo: Novamont Covering Film Mulching Film Tying Film Peat sacks Fertilizer tape Binding Material Photo: BASF

205 Applications of Bioplastics (da fonte European Bioplastics ) Packaging Loose fill foil, film Hallow bodies, bottles Trays, blisterpacks, Nets, sacks, bags Photo: Ihr Platz Photo: BASF

206 Applications of Bioplastics (da fonte European Bioplastics ) Fibres / Textiles Clothing Technical textiles Fabric Medical Implants Operation materials Oral hygiene Gloves Photo: Novamont Photo: NatureWorks

207 Photo: NatureWorks Fast Food / Catering Stand Crockery Cutlery Applications of Bioplastics (da fonte European Bioplastics ) Straws Beakers Photo: Birkel Photo: FKuR

208 Other Applications Hanger Cell Phone Clip Applications of Bioplastics (da fonte European Bioplastics ) Photo: FKuR Photo: Unitika Photo: Unitika

209 Large Groups Politics Since the 80s many large groups (ICI, Monsanto, Procter & Gamble, Montedison, Dow, Bayer, Basf...) committed themselves in the field of biopolymers. Had gradually gone out of business or were sold to small companies specializing in biochemistry. In recent years we are witnessing a new progressive engagement, particularly with regard to the use of polymers to produce biomonomers "traditional.

210 Biopolymers, why The renewed interest in biopolymers is dictated by growing engagement in environmental issues and fear of potential crises related to petroleum products. According to the Ministry of Economics and Technology German biopolymers have a high potential for the development of a competitive and high-tech industry can create opportunities for skilled employment and economic growth (K. Wagner 3^ EBC 5/11/2008) Even in France it is estimated that biopolymers can allow you to create many new jobs in agriculture over the next 5 years.

211 Large Groups Politics PHA In the '70s Zeneca (ICI) had developed the Biopol which was sold to Monsanto in '96, it sold in '01 to Metabolix. In 2006, Metabolix has developed a J.V. with ADM (Telles). In the '80s Chemie Linz has developed the Biomer sold to Biomer-D In early 2000, Procter & Gamble developed the Nodax. The product was not marketed. The technology was purchased in 2007 by the American Meredian

212 Large Groups Politics PLA Dow left the business with Cargill. In society, NatureWork LLC, had entered the Teijin with a market share of 50%, but recently it solds it to Cargill, for reasons of economic crisis. It will continue to market under the trademark Biofront degrees heat resistant

213 Large Groups Politics Product from Starch : Enimont / Montedison had sold its shares of Novamont to an investement found Polyesters from fossil fuel : Bayer ceased the activity La Eastman sell its business (Easter Bio) to Novamont that are developing a new plant in Terni (trade mark OrigoBi) Basf, Showa Denko and other groups produce aliphatic polyester / aromatic biodegradable

214 Large Groups Politics Polyesters from bio-monomers : DuPont are doing high investements in the fiels of biomonomers (Sorona, Hytrel, Surlyn, Biomax, Cerenol) MG are doing investements for producing from renewevable resources ethylenic glycol and thus, on longer times, polyesters Other monomers: : Dow, Solvay e Braskem are investing in production of ethylene from ethanol Arkema developed acrylic acid from glycerol DSM, Dow, Cargill, Bayer and other minor societies are developing polyols from soy seeds

215 Biopolymers market Today the market for biopolymers is still a niche, mainly restricted to the packaging market and agriculture and can be estimated at around % of the total consumption of plastics with a high growth rate (according to a study by the Freedonia Group of 13% per year until 2013). There are no accurate statistics, some estimates of the European Bioplastics Association on production capacity will be reported later In some applications, agricultural and packaging, the use of biopolymers also provides economic benefits (mulch film, waste collection, food packaging, etc.).

216 Biopolymers prices The prices of biopolymers decreased 5-fold over 10 years ago. According to the European Bioplastics Association today is still higher than those of petrochemicals and polymers can be estimated about 1.5 to 4 Euro / kg. For specific cases, however, is appropriate to request specific information to producers for the wide range of polymers available in the market and the rapidly changing nature of the sector

217 Biopolymers market (2) In an interesting report written by the University of Utrecht and the Fraunhofer * for the European Commission in 2005 are reported on biopolymers: detailed information on properties, uses, LCA and producers of various materials, an assessment of the possibilities for market development and technical potential of the different biopolymers, according to various parameters. *( From this study one can draw interesting conclusions are interesting and still valid :

218 EU P&M: con supporto politico e misure di sostegno Note: The estimates of European Bioplastics for the long term provide a development is much higher. In the EU alone in 2020 estimated a potential market of 2-5 Myton.

219 Technical substitution potential Ref. Utrecht University/Fraunhofer ISI According to European Bioplastics Association it already exist the potential for substitution technique can be estimated to 5-10% of the consumption of plastic materials (in the long run much higher)

220 Biopolymers Market Based on these elements, recently there has been a significant change in the lines of development of biopolymers. We have realized that the traditional factors which were the basis of research and innovation in recent years, that are: Competitive prices Legal and Polytic support Rules on degradability/compostability Availability and optimization of composting processes Though still valid, are no longer sufficient to ensure sustained development.

221 Biopolymers Market To allow the exit of biopolymers a niche and have a great future from an industry perspective, it is necessary to extend the applications by extending its use for most critical applications and include realization of: durable goods Technical applications (Transport sectors, construction, electrical / electronic / electrical appliances, leisure, etc...) in many cases, applications in these areas are already at an advanced stage of development. Even textiles and fibers are gaining importance with the development of fibers with high thermal resistance