EMISSIONS RESULTING FROM PLASTIC MANUFACTURING

INTRODUCTION:
Plastic products manufacturing involves molding, forming, shaping, or otherwise altering plastic resins or plastic materials to produce an intermediate or final product. This manufacturing industry is also commonly referred to as plastics processing or polymer processing. The manufacture of resins is not a part of plastic products manufacturing; however, some facilities manufacture resins at the same site as where the resins are processed. [1] Volatile organic compounds may be formed and emitted at any stage in the life cycle of a material. VOCs can be produced during: Manufacturing, processing and extruding Treatment (coating, irradiation, etc) Improper or prolonged storage, handling and transportation End-use [6]

EMISSION SORCES:
Emissions from plastic products manufacturing come from a variety of sources and are highly dependent upon the chemical makeup of the raw materials (resins, additives) and types of production processes used. In addition, the diverse nature of these raw materials and manufacturing techniques results in a wide range of potential combinations of emission sources and pollutants. The primary sources of emissions at plastic products manufacturing facilities are the pieces of equipment (e.g., extruder hopper, die head, sander) used to handle raw materials and produce the final product. These are typically the locations where chemical reactions occur, liquid solvents and solvent blends are exposed to the atmosphere, solid resin is heated and melted, and additives are introduced. In addition to emissions generated directly from primary production processes associated with plastic products manufacturing, there may be additional emissions produced by secondary processes at these facilities. Emission sources from these secondary processes include storage tanks, equipment leaks, wastewater treatment, combustion sources, and cleaning and surface coating operations.

There are multiple processes occurring at plastic products manufacturing facilities that give rise to a wide variety of pollutants. Emissions from plastic products manufacturing may be generally classified as follows: Volatile organic compound (VOC) and hazardous air pollutant (HAP) emissions resulting from the volatilization of free monomer or solvent in the primary polymer blend during processing; VOC and HAP emissions that result from secondary process materials, such as blowing agents, additives, and lubricants (mold release compounds); VOC, HAP, and particulate matter (PM) emissions that result from byproducts formed by chemical reactions or formed during heating of resins; and PM emissions generated during raw material handling and finishing operations. The following discussion provides additional information on some of the specific pollutants emitted from plastic products manufacturing facilities and the specific processes giving rise to emissions.

EMISSIONS DURING PROCESSING:

High temperature and high-shear processing of plastics can cause thermal oxidation of the polymer, resulting in scission, crosslinking, and/or oxidation of macromolecules. These changes can affect physical properties, stability during use, suitability for some applications and are often associated with emission of particulates and formation of low molecular weight products. Parameters affecting the nature and extent of volatile emissions during extrusion include: extrusion temperature and rate, extruder size and type, residence time, extrudate surface exposed to air, cooling rate and ofcourse the nature of the raw materials being processed (resin type, its degree of dryness, residual monomer content, level of metal catalyst residues, degree of stabilization, additive package, and processing aids). Volatiles may consist of residual monomers, additives, modifiers, moisture, solvents, residual catalysts, decomposition products of resins and their additives and can be associated with odour and off-taste in packaging foodstuffs. The identification of VOCs generated during polymer processing is thus crucial for safety and health as they relate to potential worker exposure and from an environmental point of view are governed by the new regulations on emissions.

In the US the environmental Protection Agency (EPA) and the occupational Safety and Health Administration (OSHA) have been concerned with potential problems related to emissions in the plastics processing industry whereas the Food and Drug Administration (FDA) is mostly concerned with the suitability of plastic products for food, cosmetics and drug packaging. A wide range of bulk commercial thermoplastic materials have been studied, including polyvinyl chloride (PVC), polyamide 6, acrylonitrite-butadiene-styrene terpolymer (ABS), high impact polystyrene (HIPS), polypropylene (PP), low density polythyelene (LDPE) and high density polythelene (HDPE). From the point of view of odour formation, numerous reports deal with the formation of odorous VOCs produced during manufacturing and processing. Chain scission processes and reaction with oxygen can produce low molecular weight volatile species. Typical carbonyl VOCs causing unpleasant odours or off-flavours were identified such as ketones (e.g., methyl isobutyl ketone, 7-octen-2-one), aldehydes (e.g., heptanal) and carboxylic acids (C2-C5 hydrocarbons). Some hydrocarbons like 2,2,4,6,6pentamethylheptane (PMH) and 2,2,7,7-tetramethyloctane have been claimed to yield a metallic odour. Hexane is said to be characteristic of a weak plastic-like odour. Aromatic compounds like o-xylene also have a typical odour (solvent odour, burned-plastic odour). Finally, some alcohols can cause off-odours, like 2-hepten-4-ol.

EMISSIONS DURING TREATMENT: Volatile chemicals may be produced during the sterilization process and the aseptic packagaing of food, cosmetics and medical products. Most research has been focusing on identifying and quantifying products formed in food contact polymers after exposure to ionizing radiations. A major objective was to determine the potential of volatiles to migrate into food and to allow a better assessment of the risks potentially associated with irradiation. Exposure of polymers to ionizing radiation, particularly at elevated dose levels, may result in crosslinking and scission of the polymer chain, formation of unsaturations in the polymer hydrocarbon chain and formation of volatile odorous products which can cause undesirable organoleptic properties (offodours and off-taste). Increased migration of plastic origin chemicals could be observed under certain circumstances as a consequence of irradiation. For example, increased migration of additives (especially antioxidants) and of their degradation products has been reported.

Numerous parameters may influence radiation-induced changes: the type of polymer, the additives used, processing history, the dose of radiation, the temperature and the irradiation atmosphere. As during processing, irradiation of polymers in the presence of oxygen causes additional chain scission and oxidation, resulting in the formation of various low molecular weight oxygenated compounds (hydroperoxide, alcohol, aldehydes, carbonyl, etc.). Moreover, free radicals created during irradiation may remain trapped in the polymer contributiong to postirradiation ageing. Different polymers (e.g., polyethylene, polypropylene, polyester, ABS, PVC, polyamide, polystyrene foam and ethylene-vinly alcohol copolymer) have been evaluated before and after exposure to different levels of gamma and electron beam (e-beam) radiation. All polymers produce detectable amounts of low-molecular weight degradation products characteristic of each plastic. Sampling of volatile chemicals has been carried out static headspace sampling and dynamic thermal desorption techniques. The thermal desorption spectroscopy (TDS) technique cannot replace toxicity testing of medical products or migration studies of packaging materials but has the advantage of a high sensitivity concentration step (without dilution or loss of volatile compounds). The technique permits identification of unknown products at the trace level (less than 0.1ppm radiolysis product) and provides valuable complementary information to classical tests. Worst-case scenarios could be calculated assuming a total transfer of the substances into any environment (e.g., the human body, a drug solution, or a food stimulant). The approach has been incorporated into a protocol.

FREE MONOMER/SOLVENT
Emissions of free monomer (a single molecule of a chemical used in a polymer) may occur when a solid resin is heated during extrusion, molding, or any of the other processes. For example, one study (Contos et al., 1995) found a monomer (styrene) to be the principle component of the emissions produced during the extrusion of acrylonitrile-butadiene-styrene (ABS) resins. Emissions of free monomer would also be expected from resins used in solvent form. Some resins may be handled using a solvent medium to store and transport the resin prior to processing. In this case, emissions would also come from the solvent used to suspend the resin

prior to the polymerization step. Thermoset resins are often handled in monomer form prior to solidifying under heat or pressure, or reaction with a hardening agent to generate a solid polymer. For example, when curing of thermosets is accomplished during processing or when processing involves polymerization (such as when thermoset polyurethane elastomers are processed using reaction injection molding), substantial emissions of monomers are likely to be generated (Midwest Research Institute, 1993).

REFERENCES: [1] Preferred and alternative methods for estimating air emissions from plastic products manufacturing www.epa.gov/ttnchie1/eiip/techreport/volume02/ii11.pdf [2] Bruno Gervet, The use of crude oil in plastic making contributes to global warming May 2007, Renewable Energy Research Group, Division of Architecture and Infrastructure, Department of Civil and Environmental Engineering, Lule University of Technology, Lule, [3] Plastic grocery bags: The ecological footprint Sara Ellis, Sarah Kantner, Ada Saab, Mary Watson, Geography 214, Dr. Lisa Kadonaga, (December 22, 2005)
www.vipirg.ca/archive/publications/pubs/student_papers/05_ecofootprint_plastic_bags.pdf

[4] Material on Plastic Waste Management Central Pollution Control Board, (June 2012) [5] The Plastic Bag Jessica Standley, Carbon neutrality Unst 421, (spring 2010) [6] Emissions from plastics