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1.1 POLYSTYRENE Polystyrene (PS) is a multipurpose polymer that is used in varied applications in rigid and foamed form. General purpose polystyrene (GPS) is clear and hard which is used in packaging, laboratory ware, and electronics. The excellent physical and processing properties make polystyrene suitable for a lot of applications than any other plastic (Meenakshi et al., 2002). Styrofoam is the trade name given to expanded polystyrene (EPS) which is used in foam form for packaging as well as insulation in various industrial fields in the world (Kan and Demirboga, 2009). EPS is moulded into sheets for thermoforming into trays for packaging of fish, meat and cheeses, egg crates, tubs for food and cups. Both foamed sheets and molded tubs are extensively used in take out restaurants because they are lightweight, stiff and have excellent thermal insulation capability. Polystyrene is a vinyl polymer, which make up a large family of polymers that are made from vinyl monomers containing C=C bonds. Polystyrene molecules possess long hydrocarbon backbone, with a benzene ring linked to every other carbon atom. Styrene is used to produce polystyrene by free radical polymerization (Fig.1.1). On the basis of structure polystyrene can be classified into three forms (Fig.1.2). The polystyrene containing all of the phenyl groups on one side is termed as isotactic polystyrene. If the phenyl groups are randomly distributed then it is called atactic polystyrene. The free radical vinyl polymerization process yields atactic polystyrene. The polystyrene containing phenyl groups on alternating sides of the chain is described as syndiotactic polystyrene (sPS), which is highly crystalline. It has the tendency to crystallize very quickly which gives it the favourable properties of high melting temperature and chemical resistance. Structurally sPS can have more than one crystalline form and it shows a complex polymorphic behaviour. Four main crystalline modifications and several subforms of sPs are known (Saitoh et al., 2003; Gupper and Kazarian, 2005).

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Figure 1.1

Polymerization of styrene to produce polystyrene

Figure 1.2

Types of polystyrene

Chapter1 1.2 HISTORY OF POLYSTYRENE

Introduction

Edward Simon accidently discovered polystyrene in 1839 in Germany. From the resin of Turkish sweetgum tree, Liquidambar orientalis he obtained an oily substance, which thickened into jelly in air; he described it as styrol oxide. In 1845 John Blyth and August Wilhelm von Hofmann observed that the same changes occur in styrol in the absence of oxygen. They named it as metastyrol. Marcelin Berthelot in 1866 identified that it is a polymerization process that change styrol to metastyrol. It was described in the thesis of Hermann Staudinger (1881-1965) that a chain reaction occurs in styrol by heating resulting in the formation of macromolecules which was later called polystyrene. In Germany, I. G. Farben, company in 1931 started producing polystyrene in Ludwigshafen. The Koppers Company in Pittsburgh, Pennsylvania produced expanded polystyrene in 1959. Polystyrene with syndiotactic conformation was synthesized for the first time in the early 1980s. 1.3 SYNTHESIS OF POLYSTYRENE The polystyrene synthesis begins by heating the natural gas or crude oil in a "cracking process." The yield of ethylene is dependent on the cracking temperature and is more than 30% at 850C. The next step in polystyrene production is alkylation of benzene with ethylene to form ethyl-benzene. Dehydrogenation of ethylbenzene forms styrene, which is then polymerized to yield polystyrene. Polystyrene products are made by injection blow molding, extrusion, injection stretch blow molding and thermoforming depending upon their applications. Extrusion and injection molding is mostly used for clear, hard and brittle type of general purpose polystyrene products. Extruded polystyrene foam is produced by extrusion in the form of sheets for insulation in construction industry and other insulation purposes. Expanded polystyrene foam products are mostly produced by thermoforming. 1.3.1 Synthesis of Expanded Polystyrene Expanded polystyrene (EPS) is produced by using a blowing agent (pentane) to expand the polymeric chains in order to achieve a low density foamed polystyrene. The polystyrene (90-95%) with blowing agent (5-10%) is placed in the chamber and then heated (100-110 C) by dry or wet steam, above the glass transition temperature

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of polystyrene (98 C). The blowing agent starts vaporising (iso-pentane at 28 C, normal-pentane at 35 C and cyclo-pentane at 49 C) and permeates through the polymer. The rising temperature causes the polymer chains to become softer and the internal pressure of the blowing agent causes the polymer to expand. The expanded beads are then cooled for aging purpose. The EPS beads are moulded into sheets or tubs, cups etc by heating with steam that causes the external surface to become soft and beads stick to each other. 1.4 OTHER POLYSTYRENE BLENDS AND COPOLYMERS Styrene polymers have unique properties useful to produce wide range of products (Meenakshi et al., 2002). To achieve specific properties for a particular application styrene is mixed with other monomers such as butadiene, acrylonitrile etc. to make blends, copolymers, graft copolymers. The improvement of the impact properties are achieved by producing styrenic polymers such as high-impact polystyrene (HIPS) or ABS (Vishwa-Prasad and Singh, 1997) which are used in electrical and electronic equipment (Brennan et al., 2002). 1.4.1 High Impact Polystyrene Poly(styrene-butadiene-styrene), or SBS is a hard rubber used in the manufacture of tyres and tyre products also contain polystyrene in it. SBS rubber usually called as high-impact polystyrene, or HIPS is a thermoplastic elastomer. Polybutadiene (PB) has double bonds in it that cause polymerization with styrene as a graft copolymer. The HIPS polymer is a multiphase system in which Polybutadiene is dispersed in a rigid polystyrene (PS) matrix. Thus HIPS has improved fracture resistance, reduced transparency, modulus and tensile strength (Vishwa-Prasad and Singh, 1997). 1.4.2 Polystyrene- Polyacrylonitrile copolymer (SAN) Polyacrylonitrile (PAN) and polystyrene have favourable properties for use in automotive industry, architecture, railway and aerospace. SAN copolymer has better mechanical properties as compared to the Polyacrylonitrile and polystyrene. Polystyrenepolyacrylonitrile is generally utilised in the automobile making, home wiring and other applications (Wang et al., 2008).

Chapter1 1.4.3 Acrylonitrile-butadiene-styrene (ABS)

Introduction

Acrylonitrile-butadiene-styrene (ABS) is a blend that is manufactured by SAN and polybutadiene rubber (Arnold et al., 2009). ABS has flexibility of composition, structure and properties on the basis of ratio of monomer for diverse applications. Styrene component imparts rigidity and easy processibility, acrylonitrile give chemical and heat stability while, toughness and impact strength are dependet on butadiene. ABS is used in the electronics for manufacturing parts of electronics and automobile industry. ABS is also blended with other polymers for different applications such as ABS/polycarbonate and ABS/polyvinyl chloride. 1.5 USES OF POLYSTYRENE Polystyrene is used in packaging, electronics, construction, house and medical ware and disposable food services (Meenakshi et al., 2002). Expanded polystyrene (EPS) is used for protective packaging in electrical, pharmaceutical and retail industries etc., because of light weight, shock resistance, cushioning properties, and flexibility in design possibilities. Because of thermal insulation properties, EPS is used in cold rooms, refrigeration and building insulation (Kannan et al., 2009). End-functionalized polystyrene act as lubricants and polymeric surfactants because they modify the wetting behaviour of surfaces (Park et al., 2008). Organic crystals such as polystyrene coated Meta-nitroaniline have their uses in optical devices (Adhyapak et al., 2008). Polymeric material with a biomolecule is used for the manufacture of biosensors, bioreactors and in the medical field (Hagiwara et al., 2008). Polystyrene is commonly used for cell culture (Shim et al., 2008). It is used in disposable Petri plates and other biomedical containers for its optical transparency, durability and cost effectiveness, inert nature and nontoxicity. When a polymer matrix is mixed with inorganic nanoparticles, the thermal (Garcia et al., 2009), mechanical (Uhl and Wilke, 2002), optical, electrical, magnetic and flammability properties of such a nanocomposite are much different from the polymer matrix itself (Manzi-Nshuti et al., 2009).

Chapter1 1.6 ENVIRONMENTAL EFFECTS OF POLYSTYRENE

Introduction

Synthetic plastics are used in many fields such as packing, household, agricultural, marine and architectural. Plastics have replaced natural resources like cotton, wood and metals because of their light-weight, and durability. The average growth rate of plastic industry in Pakistan is 15% per annum. The medium sized plastic processing units are situated in different places in Pakistan (Sabir, 2004). Polystyrene (PS) is a widely used thermoplastic. Its hardness, hydrophobic nature and chemical composition cause it to persist in nature without any decomposition for longer period of time thus cause environmental pollution (Singh and Sharma, 2008). Floating marine debris include a large proportion of plastics especially Styrofoam that pose a serious problem to marine life and natural ecosystems (Hinojosa and Thiel, 2009). Polystyrene packaging products are discarded in dumps, landfills or simple litter after their useful application (Kiatkamjornwong et al., 1999). As the waste plastic material has become a serious problem, so recycling is taking attention to save environment and resource recovery (Pantano et al., 2009). Polystyrene waste requires the transportation of big volume waste, which is costly and make recycling economically unfeasible. Waste EPS doesnt decompose in nature and causes environmental pollutions (Kan and Demirboga, 2009) 1.7 HEALTH EFFECTS Polystyrene is manufactured from monomer styrene. Styrene is a volatile, colourless, strong-smelling, oily liquid. Styrene is not harmful in very small amounts in air or food. Styrene exposure for a short time can result in eye and mucous membrane irritation and gastrointestinal problems in humans. Styrene and its metabolites are known to cause serious negative effects on human health (Mooney et al., 2006) Styrene causes neurological impairment, toxic effect on liver, central nervous system. Styrene is metabolised by a number of microbes in natural environments. Styrene biotransformation causes the production of styrene oxide that is more toxic to human health. Migration of styrene from expanded polystyrene cups into the hot beverages is reported which is dependent on the fat content, Exposure temperature and time (Khaksar and Ghazi-Khansari, 2009).

Chapter1 1.8 DEGRADATION OF POLYSTYRENE

Introduction

Polymers are weathered due to environmental factors like light and temperature. The conditions of use play key role in the degradation of plastics. Polystyrene losses its mechanical and tensile properties due to effect of UV light and heat (Kiatkamjornwong et al., 1999). UV light induces the production of free radicals by oxidation. Free radicals cause the chains of polymer to breakdown. 1.8.1 Biodegradation of Polystyrene Biodegradation is the breakdown of a substance by the activity of living thing or a product of living thing e.g. enzyme. Biodegradation of plastics involves extracellular and intracellular enzymes. Extracellular enzymes chop down the long chains of polymer molecules into simpler water soluble compounds that are easily taken up by the cell membranes of microorganisms. The intracellular enzymes further convert these molecules into the forms that can enter into the biochemical and synthetic pathways of the cellular metabolism. There are few reports of polystyrene biodegradation in literature mostly carried out by bacterial species i.e. actinomycete Rhodococcus ruber (Mor and Sivan, 2008), Bacillus, Xanthomonas,

Sphingobacterium (Eisaku et al., 2003), Serratia marcescens, Pseudomonas sp. and Bacillus sp. (Galgali et al., 2002), Bacillus coagulans (Kiatkamjornwong et al., 1999). The fungi reported to carry out biodegradation of polystyrene include Curvularia species (Motta et al., 2009), brown rot Gleophyllum trabeum and white rot Basidiomycete, P. chrysosporium, Trametes versicolor and Pleurotus ostreatus (Milstein et al., 1992). Synthetic polymers are resistance to biodegradation due to high molecular weight structural complexity and hydrophobic surfaces. These properties make the polymer inaccessible to the microbial enzymes. For improved biodegradation polymers are blended with natural polymers like starch, cellulose and lignin that increase the microbial adherence and attack on the polymer and when the biodegradable part is consumed the synthetic polymer losses its mechanical properties. Fungi are the major decomposers in natural ecosystems and are able to colonise a wide variety of diverse environmental conditions possessing an extremely important ecological niches. In nature Fungi are the major causative agents of spoilage of food,
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timber, cotton, paper etc (Pinzari et al., 2006). Fungi are successfully used to degrade plastics and other xenobiotics (Francesc et al., 2006). Excellent adherence and colonisation properties give advantage to the fungi for bioremediation. Once established on a surface the fungi cover the whole area by forming mycellial mat. Fungi are able to withstand longer periods of stress conditions and due to saprotrophic nature they are capable of producing a diverse arsenal of enzymes that are able to degrade the recalcitrant compounds (Gu and Gu, 2005). AIM AND OBJECTIVES The aim of the present study was to investigate the biodegradation of polystyrene by indigenous fungal isolates and methods to accelerate the biodegradation process. The aim was achieved by the following specific objectives. To Isolate and characterise the fungal strains associated with polystyrene films. To study biodegradation of polystyrene in solid and liquid media using selected fungal isolates. To analyse the biodegradation products of polystyrene by HPLC, NMR and FTIR for possible degradation pathway. To Study mineralisation of polystyrene by Sturm test analysis To study the effect of UV and thermal pre-treatment on biodegradation