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