MODULE 8

Environmental pollution by polymers

Prof Dr Seng-Neon Gan, SengGan, Chemistry Department, University of Malaya, 50603 Kuala Lumpur

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SYNTHETIC POLYMERS BY-PRODUCTS OF PETROLEUM INDUSTRY

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Plastics are everyday materials in modern life, and are often used in disposable applications, such as packaging. This is the origin of a serious pollution problem, more so if these materials are disposed of irresponsibly.

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Malaysia - transformation from agricultural country to urban environment Our habits have changed : solid waste generated increase in quantity and in complexity. Towards a society of convenience = throwaway-society - items we buy wrapped in fanciful packaging, resulting in more things to throw into our environment.

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A shift of the waste from biodegradable to non-biodegradable items, such as from paper to plastic wrappingsdisposable plastic food containers, spoons and forks.

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Solid waste management has been around since the existence of local municipalities. Complaints are generally directed towards the collection services whenever it is not made regularly and piles of rubbish start accumulating at the doorstep.
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Like many other countries, Malaysia is also facing an escalating problem of environmental pollution by plastic waste.. Generally these plastics are inert to microbial degradation. There has been increasing public concern over the harmful effects of petrochemical-derived plastic materials in the environment.

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What happens after the waste is collected is generally not the concern of the public because the problem has been taken away from his doorstep.

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In the past, solid waste management = collection + disposal. (No consideration about pollution, energy conservation and recycling) Recent years - vast amounts of money and effort are being spent to manage the problems associated with solid waste. Growing concern about the effect of discarded plastics on the quality of life in Malaysia.
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Land filling accounts for more than 95% of municipal waste in Malaysia. Careful control of this process is required in order to protect the site and its surroundings from problems of odor, fire and vermin. Sanitary landfill method - Wastes brought to disposal site - tractors used to level the wastes workers spray disinfectant and insecticide.[ Mixture of Izol, gamaxene and antimalarial oil or Dipthrox has been commonly used as the disinfectant/ insecticide] - The waste covered with one layer of sand. Plastics as part of the municipal waste are thus disposed at the landfill. Overall, plastics in landfills are fairly inert. The majorities of common polymers is not biodegradable SCES2434- Module 8 12
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Land filling space is dwindling By contrast, the amount of plastic waste is growing. Polymers have lower density, consequently plastic waste takes up a larger volume for relatively little mass as compared to the other household and industrial wastes.
Table 1 Plastic contents in wastes from a few locations in Selangor
Location Plastic content in waste By weight Kumpung Tunku Section 17 Sg Way Low Cost PKNS Low Cost 7.5% 8.1% 6.6% 4.8% By volume 16.7% 18.1% 14.7% 10.7%
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> 30% of all synthetic polymers used in packaging Plastic packaging is not always disposed of responsibly. Significant amounts are not dumped in appropriate places. A large amount of plastic waste finds its way into the waterways, including streams, rivers and the sea. The variety of items is enormous: plastic bottles, shopping bags cups, plates, Styrofoam etc. Polymers usually in the form of pellets for fabrication into plastic articles - During transportation or careless handling in the factory, the palletized polymers may be accidentally spilled, thereby releasing the materials into the environment
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Several hundred thousand tons of discarded plastics find their ways into the waterways (rivers, streams, ponds, oceans).

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Many birds mistake plastic pellets for food and could lead to fatal consequent as the indigestible polymers clogs their intestines. The effect on marine life by polymer pollutants is also significant. For example, sea turtles may mistake plastic pellets for food. After filling their bellies with these pellets, the turtles become too buoyant to dive for proper food and consequently die.
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Soft drink industry as an illustration.

Plastic bottles, which are lighter and cheaper than those made of glass, have already superseded the traditional materials in all sectors of the modern drink industry. In Malaysia millions of plastic bottles are used a year, which contribute significantly to serious environmental problems. For instance, plastic bottles dumped in the wrong place tend to collect rainwater and become breeding grounds for mosquitoes.

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Difficulties in recycling plastic bottles

They cannot be reused because of the need for sterilization process that is done at high temperatures, which could cause softening or melting of the plastics.
Previously, soft drinks were in glass bottles most of that were returnable to the traditional sundry shops. With the growing role of supermarkets as the main outlet for bottled beverages, the use of returnable glass bottles has declined. The problem of returnable bottles is CLEARLY not just a technical one and could be overcome through educating the suppliers and consumers. For example, the supermarkets in Germany, France and Spain have encouraged the users to return bottles in exchange for discount coupons, and because of this customers have happily continued to use and return their empty bottles. SCES2434- Module 8 18
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Table 2 Estimated waste for major polymers Polymer % discarded per year 65.5 38.1 27.5 17.9

Polyethylene (LLDPE,LDPE) Polystyrene Polypropylene Poly(vinyl chloride)

Figures taken from the Encyclopedia of Polymer Science and Engineering, vol 5, 105, John Wiley SCES2434- Module 8 Copyright sngan 19

Table 3 Plastic waste generation classified by end use End use Approximate life /years Packaging Transport Furniture & housewares Electrical appliances Building and construction 1 5 10 10 50 100 20 10 10 2 % Discards

Encyclopedia of Polymer Science and Engineering, vol 5, p 105, John Wiley, 1986

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Plastics have become materials widely used in packaging

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RECYCLING OF POLYMERS Recovery and reuse of synthetic polymers is ideally the best way in solving the problem of plastic waste. In principle, polymers can be recycled without significant loss of their properties. Plastic bottles may not be reusable as bottles, but the polymers can be recycled. For example, PET bottles can be recycled to give an acceptable grade of PET resin for carpet fiber, furniture stuffing or insulation. Currently there is growing interest in chemically converting the PET into polyols for the manufacture of polyurethane foams. Waste nylon can also be recycled profitably.
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Containers made from high-density polyethylene (HDPE) are widely used for detergents, lubricant oil, printing inks, antifreeze and other chemicals, and enormous amounts are used in disposable applications. The recycled HDPE could be remolded for making drainpipes, flowerpots, dustbins and plastic crates.
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Current problem with recycling is economics It is not cost effective to recycle the common polymers such as PE, PS because the recovered material has a low intrinsic value. The fact is that the original polymers are easily produced cheaply. The challenge is how to organize the collection of waste materials, followed by separation and reprocessing, in a way that is economically viable !!

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Recycle Code

Plastic coding system has been introduced for easy identification and separation of plastics (for recycling)
= PVC

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POLYMERS AND ENERGY

Table 4 - Calorific value of different constituents Material type Vegetable Paper Textile Plastic kJ/kg 5700 14168 15525 38000
The Institution of Municipal Engineers

kcal/kg 1370 3393 3718 9100

Source: The recovery of useful materials from refuse, Monograph No.27,

Under circumstances where recycling is not a feasible option the use of these plastics in wastederived fuels may be an acceptable conservation measure. These materials are potentially useful as fuels, and burying them simple wastes their SCES243426 potential in this respect. Module 8
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BIODEGRADABLE POLYMERS

Not all synthetic materials are worth recovering. For example plastic items such as grocery bags and shampoo bottles, fishing nets and food wrappers are generally difficult to recover. If the degradation products of these plastics are harmless to environment, then using degradable polymers to make these items certainly could solve the pollution problem.
In designing synthetic polymers to become biodegradable, we often make use of functional groups that are susceptible to enzymatic actions, hydrolysis and oxidation. These include aliphatic polyesters, polyurethane, poly(vinyl alcohol) and 27 poly(vinyl acetate). SCES2434- Module 8
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BIOPOLYMERS
Natural polymers from animal or plant sources are biodegradable. The degradation processes by microorganisms, either bacteria or fungi, and are generally complex. Natural macromolecules such as cellulose or proteins are generally degraded in biological systems by hydrolysis followed by oxidation. Scientists are also trying to synthesize biopolymers from various microorganisms through biotechnology : PHBs, PHAs and PLA (some of them have been produced and used in commercial scale)
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SOME WORKS AT UM
Postgraduates:
K.Sudesh Kumar, Production of PHAs by P.putida PGA1 from palm oil and palm kernel oil, M.Biotech, August 1995. Ghufran Redzwan,Occurrence of PHAs in local bacterial isolate, M.Biotech, July 1996 Theanmalar Masilamani,Studies of some conditions on PHAs accumulation in P.putida grown with palm kernel oil derivatives, M.Biotech, July 1996. Ho Yen Him , Degradability in river water of bacterial PHA produced from SPKO , M.Biotech, Oct. 1999. Shaza Eva bt Mohamad, Degradability in garden soil of bacterial PHA produced from SPKO , M.Biotech, Oct. 1999. Lim Siew Ping, "Degradation of medium chain length polyhydroxyalkanoates PHAMCL in mangrove and forest soils, M.Sc., March 2003. Tan Ai Lian,Production of lactic acid by fermentation of effluents from palm oil, rubber and sago mills, M.Sc., Nov 2003

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Some publications:
Tan, Irene K.P., K.Sudesh Kumar, M.Theanmalar, S.N.Gan and B.Gordon III, 1997. Saponified palm kernel oil and its major free fatty acid as carbon substrates for the production of polyhydroxyalkanoate in Pseudomonas putida PGA1, Appl-Microbiol-Biotechnol. 47(3) P 207-211. Redzwan,G., S.N.Gan and I.K.P.Tan. 1997. Short Communication: Isolation of polyhydroxyalkanoate-producing bacteria from an integrated-farming pond and palm-oil mill effluent ponds, World Journal of Microbiology & Biotechnology, 13, 707-709. Ho,Y.H., S.N.Gan and Irene K.P.Tan, 2002. Biodegradation of a Medium-Chain-Length Polyhydroxyalkanoate in Tropical River Water, Applied Biochemistry and Biotechnology, vol. 102-103, no. 1-3, pp. 337-348(12) Gan, S.N. 1997. Research works on biodegradable polymers at University of Malaya.1st Biodegradable Plastics Colloquium, USM, Penang, 27 Nov. Ho Y.H., S.N.Gan and Irene K.P.Tan, 2000. Degradation in River Water of Bacterial Polyhydroxyalkanoates (PHA) Produced from Saponified Palm Kernel Oil. Proceedings in 12th National Biotechnology Seminar, Damai Laut Country Resort, Lumut,12-15th November Lim S.P., Irene K.P.Tan and S.N.Gan. 2001. Degradation of bacterial polyhydroxyalkanoates in forest soil, Proceedings of National Symposium on Polymer Materials 2001, 2-3 October, UKM, Bangi. P 1-5 Lim S.P., Irene K.P.Tan and S.N.Gan. 2001. Degradation of bacterial PHAs in Mangrove Soil. p 169, Proceedings of 13th National Biotechnology Seminar, 10-13th November, pp169-. Bayview Beach Resort, Penang. Sidik, M., Irene K.P.Tan, S.N.Gan and K.B.Ramachandran, 2003. Production of medium chain length polyhydroxyalkanoates (PHAMCL) in fermenter using saponified crude palm oil (SCPO) and saponified crude palm kernel oil (SCPKO) as carbon sources. International Conference on Chemical and Bioprocess Engineering, 27-29th August,Universiti Malaysia Sabah, Kota Kinabalu, Sabah. Sidik, M,, Irene K.P.Tan, S.N. Gan and K.B.Ramachandran, Production of medium chain length polyhydroxyalkanoates from oleic acid using Pseudomonas putida PGA1 by fed batch culture, the 17th SOMChE symposium (SOMChE 2003) will be held in Penang, from 29-30th December 2003.

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DURABLE POLYMERS
In many applications besides packaging, we might actually want the materials to be more durable. This would range from the very high-end polymeric composite materials used in space ships and airplanes.. to the common plastic items such as wire covers, electrical switch boxes, water pipes, and even cushions, carpets and furniture. The more durable polymers could ensure better safety and cost effectiveness of these applications.

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Many of these high performance polymers are produced from petrochemicals derived from crude oil and coals, both of which are diminishing natural resources. The production of petroleum-based monomers, very often, requires the use of organic solvent, high energy and could be accompanied by toxic by-products.

There is a need to look into alternative replacements - preferably from renewable resources.
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Better to use renewable alternatives The use of plant resources, such as castor oil to produce PUR adhesives and coatings is not new. More recently, refined palm oil, palm olein, palm kernel oil and fish oil have been chemically converted to polyols. These could provide the alternative choice to replace the petroleumbased polyols with those made from renewable resources.
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Natural rubber (particularly after vulcanization) may not be readily biodegradable The production of natural rubber from the rubber trees is certainly less polluting than the production of synthetic rubber from petrochemicals. IT IS A RENEWABLE RESOURCES
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CONCLUSIONS
One solution to the growing problem of plastic waste is to control the use of these materials in packaging. This has already happened in the United States, when in 1989 the Suffolk County of New York State banned the use of PE bags, PS hamburger boxes and other disposable plastic packaging through the countys restaurants and grocery shops. This kind of intervention by national authorities, through the recommendation of local consumer associations, is likely to become more common in the future.

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If the well-informed individuals choose to avoid items that use certain polymers wrongly, the manufacturers could be forced to change accordingly. For example, through the consumer preference, the shampoo bottles in Germany must be made of biodegradable plastics. The production of synthetic polymers itself could be a polluting industry. Whenever possible, we should look at increasing the use of natural polymers such as natural rubber rather than to increase the production of more synthetic rubbers.

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Biopolymers or other synthetic film forming polymers that are biodegradable could replace synthetic polymers such as PE and PP. Plastics cannot be completely banned, and it is not necessary that they should be. Their usage will have to be carried out more thoughtfully in the future than it has been in the past.

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