ANNALS OF DUNAREA DE JOS UNIVERSITY OF GALATI FASCICLE II

ANNALS OF DUNAREA DE JOS UNIVERSITY OF GALATI MATHEMATICS, PHYSICS, THEORETICAL MECHANICS FASCICLE II, YEAR III (XXXIV) 2011

BIOPLASTICS AN OVERVIEW Fulga Tanasa*, Madalina Zanoaga

Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania, e-mail:ftanasa@icmpp.ro

Abstract This paper gives an overview of the current state in research, development and production of bioplastics. In some cases, quality and price already allow them to successfully compete with petrochemical plastics. In other cases, a significant effort is required either on the side of the raw materials or on the processing, in order to achieve useful and economic materials. Four specific groups of biopolymers (polyisoprenoids, starches, proteins and poly--hydroxyalkanoates) and their applications were singled out herein. However, many other potential sources and products may be considered, based on new raw material streams, opportunities, and processing technologies. Keywords: bioplastics, biopolymers, applications

1. INTRODUCTION
Polymers abound in nature, as wood, leaves, seeds, animal furs. For thousands of years, biopolymers have been used for food, furniture, clothing etc. After 1950s, when the crude oil and its application for large-scale synthetic polymers was discovered, the entire society turned towards plastics. Nowadays, public concern about the environment, climate change and limited fossil fuel resources are important drivers for scientific community to find alternatives to crude oil. Bioplastics synthetic plastic materials made using biopolymers with or without oilbased polymers - are in the last decades of an increasing interest due to their characteristics and taking into consideration their potential contribution to reduce the dependence on fossil fuels and the related environmental issues. Since they are manufactured from renewable raw materials, bioplastics can easily replace the fossil based plastics in many applications. Creative scientists and technicians are currently engaged not only in adapting them to conventional technologies, but also in discovering new applications (i.e. packaging materials, disposable cutlery and flower pots, electronics housings, car components and recordable media such as CDs and DVDs) [1-3]. European Bioplastics association estimated in 2008 (European Bioplastics, Proceedings of the Third European Bioplastics Conference) that the worldwide bioplastics market will exhibit nearly sixfold growth from 300 ktpa in 2007 to more than 1500 ktpa in 2011 (Fig. 1). Depending on requirements, some bioplastics have a guaranteed long life time, whilst others are highly biodegradable and naturally decompose in short intervals. In contrast to fossil resources materials, bioplastics are largely CO2-neutral. The material and energy cycles are closed. Using renewable feedstock for bioplastics production can reduce the amount of global warming greenhouse gasses (such as CO2 and CH4) released into the atmosphere when compared to conventional plastics production from fossil raw materials.

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Fig. 2. Estimated worldwide bioplastic market growth [ktpa]

The development of the emerging bio-based plastics in the past years is spectacular from a technological point of view. Many well-known processes have been revisited, such as the chemical dehydration of ethanol to ethylene, which can be subsequently converted to polyethylene (PE), polyvinyl chloride (PVC) and other plastics. Recent technological breakthroughs substantially improved the properties of novel bioplactics, such as heat-resistant poly(lactic acid) (PLA), enabling a wider range of applications. Four specific groups of biopolymers are presented herein: natural rubber and other polyisoprenes, starches, protein-based polymers and poly--hydroxyalkanoates. Some of them (polyisoprenoids, some starches and proteins) are natural plant products and their productivity, quality and harvesting may be optimized by plant breeding, biotechnology and processing, while others (such as poly--hydroxyalkanoates, soy-proteins and silk or non-ribosomal proteins) are considered for production in transgenic plants (genetically modified organisms, GMO) and microorganisms, for which a better understanding of plants genetics, metabolic pathways, storage is needed.

2. BIOPLASTICS
There are three main pathways to produce bioplastics: (a) using natural polymers, with or without modifying them (i.e., starch plastics); (b) monomers obtained by fermentation or conventionally for further polymerization (i. e., PLA); (c) production of biopolymers directly in microorganisms or in genetically modified crops. Their importance depends on crops availability, involved technologies, local social demand, etc. (Table 1).

Table 1. Biopolymers production

Biopolymers Polyisoprenoids Natural rubber (cis-PI) Balata (trans-PI) Gutta Percha (trans-PI) Starches Amylopectin (waxy) High amilose Proteins Cross-linked plant proteins Silk and others Non-ribosomal proteins Poly--hydroxyalkanoates Production source Hevea braziliensis Maize, potato, rice, etc. GMOs GMOs Single cell protein GMOs GMOs Switchgrass GMOs Notes Limited production availability There are many processes to modify starch for non-food applications Thermal polyaspartate R&D at laboratory scale for defined polymers

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Developing a new bioplastic and introducing it to the market is a major challenge because it must compete with the existing oil-based plastics, for which the production has been optimized for decades and the entire supply-demand chain is well-known. Even so, the development of new bioplastics indicates that they have a great potential to be produced on large scale and to change some of the existing production methods in the chemical industry. In the last years, it became increasingly clear that a broad range of plastics can be produced totally or partially from biomass and they can be designed to be fully or partially biodegradable [4].

2.1. Polyisoprenoids
Natural rubber (NR) and other polyisoprenes consist, basically, of (cis/trans)-polyisoprene (PI) with additional components that are keys to superior properties of these materials. For many applications (such as: heavy duty tires for trucks, busses and airplanes, latex products for the medical applications, etc.) synthetic rubber cannot replace NR. Chicle, another natural polyisoprene, is a mixture of cis- and trans-PI, produced mainly for use in chewing gums. It has been almost completely replaced by petrochemical plastics. Gutta percha and balata consist of trans-PI. Balata is hard, inelastic, tough and leathery but contains some resin, which makes it (unlike gutta-percha) useless for electrical insulation. It is used for machine belts and for covering very high-quality golf balls. Gutta percha is a brownish-grey rubbery substance. Due to its limited production availability (80% of the entire amount of NR is produced by only three countries Malaysia, Indonesia and Thailand and from one single biological resource the brazilian rubber tree Hevea brasiliensis), the NR is considered a strategic commodity, difficult to acces in case of international conflicts (e.g., second World War) or endemic crises (e.g., in 1934, the endemic leaf blight pathogen Microcyclus ulei made impossible for Brazil to restart the large-scale production, so that the present production in Brazil is only 96,000 tonnes/year). Thus, Hevea brasiliensis is studied to generate resistant varieties, with increased yields and altered properties in France and Brazil. Recently, efficient transformation of calli and regeneration of plants was shown to be possible [5]. However, the narrow genetic base, prolonged breeding cycles and juvenile period, as well as highly heterozygous nature of Hevea make breeding a time-consuming and labor-intensive challenge. In view of the critical importance of NR, these efforts appear extremely limited and investigate alternative production methods is a viable solution. Several altervative sources of polyisoprenoids are in study: guayule shrub (Parthenium argentatum) [6], Goldenrod (Solidago virgaurea minuta) [7], Russian dandelion (Taraxacum koksaghyz), Sapodilla tree (Manilkara zapota), Palaquium gutta, Manilkara Didentata, other tropical trees including several Hevea and Ficus species, as well as several tropical vines that also produce latex [8].

2.2. Starches
Starch is the second major agricultural commodity after cellulose, is the least expensive food commodity and as various industrial applications, among them packaging films and foams, disposables (e.g. cups and plates, cutlery, plant pots, bags). Starch based plastics account for 80% of the bioplastics market. They are thermoplastics that are blended with plasticizers and additives like sorbitol and glycerin. Pure starch can absorb water from the air and degrade. Organisms can also metabolize pure starch, as it is a carbohydrate. The fact that starch disintegrates in liquids makes it ideal for drug capsules. Blends of starch and other plastics are used to make plant pots, drinking cups, disposable shopping bags, cutlery, coated cardboard and diaper foil (Fig. 2). Starch esters and ethers also behave as thermoplastics but have been too expensive to put into production [9]. Starch based plastics can be prepared in a wide variety of ways. The source of the raw starch is usually corn, but could be any plant high in starch, like potatoes, rice, etc. Starch can be also chemically processed together with hydrophilic polymers, yielding in mixed copolymers. It can be foamed aiming some specific applications. In order to improve its mechanical properties, starch can also be chemically modified, numerous methods being known (acetylation, oxidation, acid thinning, etc). Thermoplastic starch is commonly prepared by melting starch at high heat and pressure. The low cost of starch makes it especially attractive for blends with synthetic polymers, like polyethylene, polystyrene, PVC, which enables more plastic to be produced while using less of the petro-plastics.

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Fig. 2. Starch-based bioplastics applications (biodegradable bags, foils, cutlery)

Due to the importance of this commodity, starch has been studied in great depth. The so-called starch-enhancement technology has increased the amount of starch relative to the other components in plants [10], the ratio between amylose and amylopectin, the branching pattern of amylopectin [11,12], synthesis of phosphate-substituted starches and starches from new or alternative crops [13]. New non-food applications are envisaged, taking into account that some starch-based thermoplasts (TPS) have promising properties. For example, high-amylose thermoplasts were reported to have a lower sensitivity towards water and are less subject to cracking and shrinking [14]. One of the main barriers to applications of TPS is its high moisture sensitivity and difficulties in processing. Such problems can be solved by chemical derivatization, e.g. by introducing ester and ether groups, which is not possible in plants. Blending is also extensively used. Both types of research have been carried out and are covered by numerous patents. New opportunities arise out of the increased availability and reduced price of bio-based polymers. Other novel research fields involve using clay for nanocomposites, making graft copolymers with latex (for coated paper) or with polyacrylate (via acrylonitril, for superadsorbants).

2.3. Protein-based bioplastics

There are three groups of protein-based bioplastics: 1) protein co-products of starch or vegetable oil production; 2) proteins with potential uses in engineering (such as spider silk, mussel adhesive protein, collagen elastin) and 3) non-ribosomally produced proteins (such as polyasparate and polylysine). The first very heterogeneous group consists of materials that can be derived from natural proteins, usually co-products of carbohydrate and vegetable oil production. Examples are bioplastics and resins based on zein (corn protein) [15], soy protein [16] and gluten from wheat [17]. These materials are produced by cross-linking proteins with glutaraldehyde, formaldehyde or other chemicals, in combination with starch, polyphosphate or other fillers. Zein is the major protein in corn and it can be used as bioplastic films and fibers. Soy protein was already used by Henry T. Ford as a source of bioplastics to construct car parts. However, after a brief bloom in the 1930s and 40s, soy protein-based plastics were replaced by petroleum-based plastics, in part because of microbial degradation and water permeability issues. Still, films, extruded foams, injection molded products are in use. Gluten-based bioplastics are being studied, but they are also too expensive for large scale use and films, coatings, resins are available in low amounts. The increased demand for biofuels may put huge amounts of waste protein on the market that cannot be absorbed by food production, enabling the development of a protein-based bioplastics industry. There is a real potential to alter the structural properties of zein and other plant proteins by genetic engineering. However, these changes must be justified by a specific increase in added-value. The second group of protein-based bioplastics contains natural protein fibers or adhesives that typically consist of short blocks of repeated amino acids. Examples are silk proteins, elastin and adhesin from mollusks. These are potentially very attractive materials, but expensive and laborintensive to produce. Heterologous expression in plants would enable production on a much larger scale and open up new markets. In addition, genetic engineering can be used to produce completely new materials such as block-copolymers, combinations of different proteins like silk and elastin,

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completely synthetic sequences with even better properties, as well as optimized sequences for production in specific plants. Presently, the production of these proteins in plants suffers from low yield [18] and difficult processing (i.e., spinning of heterologously produced silk). Some of these proteins are thermostable and can be isolated by simple heat-treatments [19]. For these proteins, microorganisms (bacteria, yeast or fungi) may be more favorable hosts, as much higher product concentrations can be attained in these organisms. In addition, if these proteins are to be used as highend engineering materials on a relatively small scale, the fermentation costs are less relevant than the material properties. The third group of protein biopolymers consists of non-ribosomally produced polypeptides such as: (a) cyanophycin (a protein-like copolymer composed of a polyasparate backbone and arginine side-groups) produced by cyanobacteria and a few non-photosynthetic bacteria; (b) polylysine, an antimicrobial polymer used as food additive and (c) polyglutamate, also used in food. Polyaspartate can be used as superadsorbant or antiscalant. Recombinant E. coli can produce cyanophycin up to 29% of CDW on protamylasse, a waste product of starch production from potato. Transgenic plants that contain up to 1.1 % cyanophycin of dry weight have been created [20]. Due to the low-price applications of these compounds, the critical question is whether production levels in plants can be high enough for cheap production.

2.4. Poly--hydroxyalkanoates
Poly--hydroxyalkanoates (PHAs) are a class of linear polyesters produced by microorganisms primarily as carbon and energy storage material. The polymer properties depend strongly on the nature of the monomer, which can range from linear C4-C16 -hydroxy fatty acids to -hydroxy acids substituted with aromatic rings or other functional-groups, or containing doublebonds. Poly--hydroxybutyrate, the simplest PHA, is a relatively hard and brittle material with a melting point slightly below the thermal decomposition temperature [21]. Inclusion of C5-monomers (as in PHBV: co-valerate) gives slightly better properties, while adding small amounts of longer monomers (C6 and longer) has resulted in materials that are much easier to process [22]. PHAs consisting of higher molecular weight monomers (C6-C16) typically are rubber-like materials with an amorphous soft-sticky consistence. It is necessary to find new applications for these polymers, apart from the production of enantiopure R-3-hydroxycarboxylic acids. As a group, PHAs are very attractive bioplastics for consumer products such as bottles, films and fibers, due to their water and air impermeability. There are numerous potential applications

for PHAs within the medical and pharmaceutical industries, primarily due to their biodegradability (sutures, suture fasteners, tacks, staples, screws, surgical mesh, repair patches, slings, cardiovascular patches, guided tissue repair/regeneration devices, nerve guides, atrial septal defect repair devices, pericardial patches, bulking and filling agents, vein valves, bone marrow scaffolds, ocular cell implants, spinal fusion cages, skin substitutes, wound dressings, hemostats etc.). As a potential large scale commodity polymer plant production
of PHAs has to be considered. Isolation of PHAs from plant tissues is likely to be always more difficult than isolation from bacteria where there is no need to break up tissues and much higher concentrations can be reached without affecting the viability of the host organisms (at least 50% for mcl-PHAs, up to 85% for PHB, PHBV and PHBH).

Poly(lactic acid) or polylactide (PLA) one of the most prominent members of the PHAs class - is a thermoplastic aliphatic polyester derived from renewable resources, such as corn starch (in the United States), tapioca (roots, chips or starch mostly in Asia) or sugarcanes (in the rest of world). It can biodegrade under certain conditions, such as the presence of oxygen, and is difficult to recycle. The physical and mechanical properties of PLA make it a good candidate to replace petro-plastics in specific applications. While the high price of PLA long restricted its use to medical and high specialty applications, recent breakthroughs in lactide and polymerization technology opened up possibilities for large-scale production of PLA.

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The monomer, lactic acid, occurs as two different isomers, D and L. Depending on the links between these isomers, different lactides with different properties can be produced (Fig. 3).

Fig. 3. PLA polylactides family

The spectrum of possible plastics is supplemented by the copolymerisation of PLA with other monomers, such as glycolic acid. Whether tough or viscous, copolymers obtained by this method can achieve almost any desired property. Polylactides and their copolymers are quickly to hardly biodegradable, depending on their composition. Whereas poly-L-lactide requires years and polyglycolide months to degrade, polylactide from D and L-lactide degrades in just a few weeks. This is an indication of the special versatility of bioplastics, which can be made to be quickly biodegradable or to retain their functions for years. Other advantages of polylactide plastics are the high stability, the transparency of films, tubs and containers, the thermoplasticity and simple use in machinery already existing in the plastics processing industry. Nevertheless, PLA also has disadvantages. Due to its low glass transition temperature (the softening point is around 60C), the material is only conditionally suitable to manufacture drinking beakers for hot beverages. Copolymerisation or the addition of fillers could yield in materials with higher heat-resistance (Fig. 4).

Fig. 4. PLA biodegradable plastic folded trays and cups

PLA is currently used in a number of biomedical applications, such as sutures, stents, dialysis media and drug delivery devices. In the form of fibers and non-woven textiles, PLA also has many potential uses, for example as upholstery, disposable garments, awnings, feminine hygiene products, and diapers, as well as a replacement for nylon in "silken" teabags. PLA has been used as the hydrophobic block of amphiphilic synthetic block copolymers used to form the vesicle membrane of polymersomes. The pharmaceutical industry uses oligolactic acid (OLA), a shorter polymer of lactic acid, in pressurized metered dose inhalers (pMDIs) as a surfactant. Studies have shown that on standing, pMDIs without OLA will yield a much higher dose than intended as compared to those containing OLA which delivers a fairly constant dosage [23].

3. ASSESSMENT OF BIOPLASTICS SOCIETAL IMPACT

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There are a series of important societal questions that must be considered with regard to bioplastics. How will bioplastics production influence our dependence on fossil fuels? Do bioplastics emit more or less carbon during production than petroleum-based plastics? How does the production of bioplastics compare in terms of costs? How does bioplastics production influence the food supply? How biodegradable are bioplastics? How much energy is consumed by the production of bioplastics? What are the health concerns of using bioplastics? It is hard to estimate in this moment what impact the switch from petro-plastics to bioplastics might have on the fossil fuel consumption, carbon emissions, economy, food production, pollution, energy consumption, human health and environment. Bioplastics have the potential to reduce fossil fuel consumption, since their feedstock is not derived from petroleum. But, their production consumes fossil fuels however, due to the farming and processing operations that commonly use fossil fuel as energy sources. On the other hand, the same farming and processing emit carbon dioxide, while replacing some petro-plastics (HDPE, LDPE) with PLA, PHB or TPS would lead to significant reduction in such emissions [24,25]. Generally, bioplastics are more expensive than the petro-plastics they are intended to replace, but prices are falling as research continues, the specific industry grows and more efficient production methods are developed and, at the same time, oil prices have become unstable. A switch to bioplastics would affect raw material prices, namely the cost of crops or combination of crops used to obtain bioplastics would certainly increase. Which will, most likely, affect the regional economic development, as well as bioplastics production facilities will be built close to major agriculture areas. Concerning the food supplies, bioplastics derived from food crops (like corn, soy, sugar cane, etc.) would directly decrease the amount of those crops that will be available for food. At the same time, bioplastics obtained from non-food crops (like switchgrass) would indirectly affect food crops production by competing for land. On the other hand, bioplastics based on algae or agricultural waste would have little to no impact on the food supply. As for the pollution and environment protection issues, bioplastics have a great recycling potential, especially when it comes to thermoplastics. One major problem in this direction is the contamination with petro-plastics: an amount of 0,1%(wt) of polyethylene terephtalate in a batch of bioplastic would make it useless. As the production and use of bioplastics will increase, it is expected that specific recycling processes will be developed, making bioplastics more and more easy to recycle [26]. Unlike petroleum-based plastics, bioplastics have not been involved, so far, in any health problem. Although bioplastics themselves have been deemed safe, some production steps can have adverse health effects, as follows: when growing crops for bioplastics, it is common to use pesticides and artificial fertilizers; some of the hazardous plasticizers found in standard petroleum-based plastics could be used in bioplastics; etc.

4. CONCLUSIONS
Despite the attributes that make the switch attractive, bioplastics have several serious drawbacks: in some cases, bioplastics production is more expensive, energy consuming and affecting the food supplies. But the factor that is affecting the switch to bioplastics in the most severe manner is that bioplastics have the mechanical characteristics to replace only a few petroleum-based plastics. It is mandatory, therefore, that research into bioplastics to be focused on: optimizing production processes, developing bioplastics with superior properties for a wider selection of applications, expanding the recycling capabilities. Bioplastics represent an emerging research field and great societal expectations reside in its development.

References
1. Siracusa V., Rocculi P., Romani S., Dalla Rosa M., Biodegradable polymers for food packaging: a review, Trends in Food Sci&Tech, 19(12), 634, 2008.

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2. Scheller J., Conrad U., Plant-based material, protein and biodegradable plastic, Current Opinion in Plant Biology, 8(2), 188, 2005. 3. Keshavarz T., Roy I., Polyhydroxyalkanoates: bioplastics with a green agenda, Current Opinion in Microbiology, 13( 3), 321, 2010. 4. Shen L., Haufe J., Pater M. K., Product overview and market projection of emerging biobased plastics, report comissioned by EPNOE and European Bioplastics, 2009. 5. Blanc G., Baptiste C., Oliver G., Martin F., Montoro P., Efficient Agrobacterium tumefaciens-mediated transformation of embryogenic calli and regeneration of Hevea brasiliensis Muell Arg. Plants, Plant Cell Reports, 24, 724, 2006. 6. Mooibroek, H., Cornish K., Alternative sources of natural rubber, Applied Microbiology And Biotechnology, 53, 355, 2000. 7. Polhamus L. G., Rubber. Botany, production and utilization, Leonard Hill Limited (ed.), London, 1962. 8. Poirier Y., Orts B., van Beilen J., Foundation Paper for the Biopolymers Flagship, EPOBIO Workshop: Products from Plants the Biorefinery Future, Netherlands, 22-24 May 2006. 9. CTC Clean Tech Consulting GmbH, Starch & Starch Blends, http://www.bioplastics24.com/content/view/69/34/lang,en/. 10. Van Camp W., Yield enhancement genes: seeds for growth, Curr. Opinion Biotech., 16, 147, 2005. 11. Blennow A., Towards predictable functionalization of starch biopolymers in planta. Recent Developments in Carbohydrate Research, 1, 95, 2003. 12. Blennow A., Wischmann B., Houborg K., Ahmt T., Jorgensen K., Engelsen S. B., Bandsholm O., Poulsen P., Structure-function relationships of transgenic starches with engineered phosphate substitution and starch branching, Intl. J. Biol. Macromol., 36, 159, 2005. 13. Jobling S., Improving starch for food and industrial applications. Current Opinion in Plant Biology, 7, 210, 2004. 14. Van Soest J. J. G., Essers P., Influence of amylose-amylopectin ratio on properties of extruded starch plastic sheets, J. Macromol. Sci., Pure&Appl. Chem., A34, 1665, 1997. 15. Lawton J. W., Zein: a history of processing and use, vol. 79, 2002. 16. Mohanty A. K., Liu W., Tummala P., Drzal L. T., Misra M., Narayan R., Soy protein-based plastics, blends, and composites, in Natural Fibers, Biopolymers and Biocomposites, pp. 699725, 2005. 17. Pallos F. M., Robertson G. H., Pavlath A. E., Orts W. J., Thermoformed Wheat Gluten Biopolymers, J. Agricul. and Food Chem., 54, 349, 2006. 18. Scheller J., Conrad U., Plant-based material, protein and biodegradable plastic, Current Opinion In Plant Biology, 8, 188, 2005. 19. Scheller, J., Henggeler D., Viviani A., Conrad U., Purification of spider silk-elastin from transgenic plants and application for human chondrocyte proliferation, Transgenic Research, 13, 51, 2004. 20. Neumann, K., Stephan D. P., Ziegler K., Huhns M., Broer I., Lockau W., Pistorius E. K., Production of cyanophycin, a suitable source for the biodegradable polymer polyaspartate, in transgenic plants, Plant Biotechnology Journal, 3, 249, 2005. 21. Lenz R. W., Marchessault R. H., Bacterial polyesters: Biosynthesis, biodegradable plastics and biotechnology, Biomacromolecules, 6, 1, 2005. 22. Noda, I., Green P. R., Satkowski M. M., Schechtman L. A., Preparation and Properties of a Novel Class of Polyhydroxyalkanoate Copolymers, Biomacromolecules, 6, 580, 2005. 23. Stefely J. S., Duan D. C., Myrdal P. B., Ross D. L., Schultz D. W., Leach C. L., Design and utility of a novel class of biocompatible excipients for HFA-based MDIs, in Respiratory Drug Delivery (Dalby R. N., Byron P. R., Farr S. J., Peart J. eds.), 7-th edition, Serentec Press, Inc., Raleigh, NC, pp. 83-90, 2000. 24. Harding K. G., Dennis J. S., von Blottnitz H., Harrison S. T. L., Environmental analysis of plastic production processes: Comparing petroleum-based

ANNALS OF DUNAREA DE JOS UNIVERSITY OF GALATI FASCICLE II

.

polypropylene and polyethylene with biologically-based poly--hydroxybutyric acid using life cycle analysis, J. Biotechnol., 130, 57, 2007. 25. Vink E. T. H., Rabago K. R., Glassner D. A., Gruber P. R., Applications of life cycle assessment to NatureWorks polylactide (PLA) production, Polym. Degrad. Stab., 80, 403, 2003. 26. http://www.americanrecycler.com/0108/growth.shtml.