POLYVINYL CHLORIDE ( PVC) Polyvinyl Chloride (PVC) is an odorless and solid plastic.

The basic structure of this polymer is (C2H3Cl)n. The degree of polymerization varies from 300 to 1500. 1) MONOMERS of PVC Vinyl chloride monomer (VCM) is the key material which PVC is made. ( CH2 = CH Cl ) a)Source of VCM Vinyl chloride monomer does not occur naturally in the environment. It is manufactured by the chemical industry (manufacture of polyvinyl chloride, ethylene dichloride, methyl chloroform (1,1,1 trichloroethane), caprolactam, vinyl acetate, and vinylidene chloride) and the plastics industry.Landfills containing vinyl chloride or other chlorinated hydrocarbons may release vinyl chloride monomer. The treatment of wastewater containing vinyl chloride or chlorinated hydrocarbons may release vinyl chloride. b)Manufacturing of VCM 1- Production from Acetylene Acetylene reacts with anhydrous hydrogen chloride gas over a mercuric chloride catalyst to give vinyl chloride: C2H2 + HCl CH2=CHCl The reaction is exothermic and highly selective. Product purity and yields are generally very high. This was the most common industrial route to VCM, before ethylene became widely distributed. When VCM producers shifted to using the thermal cracking of EDC described above, some used byproduct HCl in conjunction with a colocated acetylene-based unit. The hazards of storing and shipping acetylene meant that the VCM facility needed to be located very close to the acetylene generating facility. 2- Production from Ethylene There are two ways to manufacture VCM from ethylene (obtained from thermal cracking); the direct chlorination method and oxychlorination method: Direct chlorination The production of vinyl chloride from 1,2-dichloroethane (EDC) consists of a series of well-defined steps. EDC is prepared by reacting ethylene and chlorine. In the presence of iron(III) chloride as a catalyst, these compounds react exothermically:

CH2=CH2 + Cl2 ClCH2CH2Cl This process is very selective, resulting in high purity EDC and high yields. However any dissolved catalyst and moisture must be removed before EDC enters the VCM production process. Thermal cracking When heated to 500 C at 1530 atm (1.5 to 3 MPa) pressure, EDC vapor decomposes to produce vinyl chloride and anhydrous HCl. ClCH2CH2Cl CH2=CHCl + HCl The thermal cracking reaction is highly endothermic, and is generally carried out in a fired heater. Even though residence time and temperature are carefully controlled, it produces significant quantities of chlorinated hydrocarbon side products. In practice, EDC conversion is relatively low (50 to 60 percent). The furnace effluent is immediately quenched with cold EDC to stop undesirable side reactions. The resulting vapor-liquid mixture then goes to a purification system. Some processes use an absorber-stripper system to separate HCl from the chlorinated hydrocarbons, while other processes use a refrigerated continuous distillation system. Oxychlorination Modern VCM plants use recycled HCl to produce more EDC via oxychlorination, which entails the reaction of ethylene, oxygen and hydrogen chloride over a copper(II) chloride catalyst to produce EDC: CH2=CH2 + 2 HCl + O2 ClCH2CH2Cl +H2O. The reaction is highly exothermic.Due to the relatively low cost of ethylene, compared to acetylene, most vinyl chloride has been produced via this technique since the late 1950s. This is despite the lower yields, lower product purity and higher costs for waste treatment. By-products of the oxychlorination reaction, may be recovered, as feedstocks for chlorinated solvents production. One useful byproduct of the oxychlorination is ethyl chloride, a topical anesthetic.

Figure 1 : Notation of direct chlorination, oxychlorination and cracking c) Physical properties of VCM VCM is a colourless gas with a molecular weight of 62.5 and boiling point of -13.9C, and hence has a high vapour pressure at ambient temperature. , it is extremely flammable and unstable. It has a mild, sweet odour. The threshold for detecting odour is 3000 parts per million. VCM is soluble in many organic solvents but is not soluble in water It is therefore manufactured under strict quality and safety control.. Specific gravity: 0.9106 Melting Point: -153.8 Relative vapour density: 2.2 Flash point: -77.8

d) Manufacturers of VCM Global capacity for VCM was about 76 billion pounds (35 million metric tons) in 2005. The Dow Chemical Company and its consolidated subsidiaries (Dow) are one of the largest producers of VCM in the world. Dow has VCM manufacturing facilities in Freeport, Texas, Plaquemine, Louisiana, and Schkopau, Germany. A VCM manufacturing facility located in Fort Saskatchewan, Alberta, Canada, was shut down in 2006. Dow has roughly 5.1 billion pounds (2.4 million metric tons) of VCM capacity at the remaining facilities.

Table 1: VCM capacity and production trends (in thousand metric tonnes) Region North Am.a Annual Capacity, 1992 6540 W. Europe 6315 2485 Japan Other Asia b 7860 (rest of world) Annual Capacity, 1996 Operating rate 1996 Actual Consumption 1996d Regional Avg. Growth 1996-2001 (%) 4.0 2.0 -0.5 9.5 6.5 5.0 92% 6723 89% 5266 88% 2486 91% 4877 70% 3462 87% 22814 8027 6420 3189 4236 4461 26333 23200 Otherc Total

e) VCM production in TURKEY Vinyl chloride monomers are manufactured in PETKM petrochemical holding in Turkey. PETKM has a capacity of VCM 142000 tons/years. 2) SYNTHESIS MECHANISMS of PVC This is the case for PVC, which is made from vinyl chloride monomer known usually by its initials VCM through polymerisation. The process of `polymerisation' links together the vinyl chloride molecules to form chains of PVC. The PVC produced in this way is in the form of a white powder. This is not used alone, but blended with other ingredients to give formulations for a wide range of products. VCM is polymerized via free-radical methods . VCM has a liquid density at normal polymerization temperature between 0.85-0.9 g/cm. The polymer has a density of 1.4 g/cm3 which is a sign of the large shrinkage during polymerization.

Figure 2 : Free radical mechanism of PVC . 3) MANUFACTURING of PVC There are four polymerization routes for the manufacture of PVC. They are as follows : Process Route a. Suspension Polymerization b. Emulsion Polymerization c. Bulk or Mass Polymerization d. Solution Polymerization % of World Production 80 10 8-10 0-2

First, the raw material VCM is pressurised and liquefied, and then fed into the polymerisation reactor, which contains water and suspending agents in advance. Through high-speed agitation within the reactor, small droplets of VCM are obtained. Next, the initiator for polymerisation is fed into the reactor, and PVC is produced by reaction under a few bar at 40 - 60C.?PVC obtained through suspension polymerisation is suspended in water as particles of 50~200 ?m diameter (in slurry form). Thereafter the slurry discharged from the polymerisation reactor is stripped of residual monomer, dehydrated, dried and the particle size controlled by screening to yield PVC in the form of a white powder. The un-reacted VCM is entirely recovered through the stripping process, and after purification, recycled as raw

material for reuse in this process. PVC resin produced via this suspension process is referred to within the industry using the abbreviation S-PVC. Emulsion polymerisation and bulk polymerisation are alternative, much less extensively employed, technologies to manufacture PVC. Emulsion polymerisation produces finer resin grades having much smaller particles, which are required by certain applications. This type of resin is sometimes called paste PVC and referred to within the industry using the abbreviation P-PVC to distinguish it from S-PVC. Kinetic features of manufacturing proceses: The following significant features are common for bulk-, suspension- and emulsion polymerization. 1. The reaction is autocatalytic from the on set of reaction. 2. The reaction order, with respect to the initiator, is close to 0.5. 3. Molecular weight does not depend upon the conversion or the initiatorconcentration. Molecular weight and molecular weight distribution are similar for bulk and emulsion polymerization.

4) PROPERTIES OF POLYVINYL CHLORIDE Polyvinyl chloride has a chemistry and a physical structure that makes it broadly unique in the polymer world. PVC (often referred to vinyls or vinyl resins) is made commercially at several molecular weights, depending on the intended applications: from Mw = 39000 g/mol, to Mw = 168000 g/mol Chemical structure of PVC Polyvinyl Chloride is similar in structure to polyethylene, but each unit contains a chlorine atom. The chlorine atom renders it vulnerable to some solvents, but also makes it more resistant in many applications. PVC has extremely good resistance to oils (except essential oils) and very low permeability to most gases. Polyvinyl chloride is transparent and has a slight bluish tint. Narrow-mouth bottles made of this material are relatively thin-walled and can be flexed slightly. When blended with phthalate ester plasticisers, PVC becomes soft and pliable, providing the useful tubing to be found in every well-equipped laboratory.

Physical properties of PVC PVC has an amorphous structure with polar chlorine atoms in the molecular structure. Having chlorine atoms and the amorphous molecular structure are inseparably related. Although plastics seem very similar in the context of daily use, PVC has completely different features in terms of performance and functions compared with olefin plastics which have only carbon and hydrogen atoms in their molecular structures. Chemical stability is a common feature among substances containing halogens such as chlorine and fluorine. This applies to PVC resins, which furthermore possess fire retarding properties, durability, and oil/chemical resistance. PVC Strenght PVC is extensively used for municipal water supply/sewage pipes, spouts, profiles, etc., since its mechanical properties such as tensile strength and tensile modulus are better than those of other general purpose olefin plastics, and these products are robust and durable. When plasticisers are added, PVC shows rubber-like elasticity with high tensile strength and fatigue strength, and can be used for industrial hoses, gaskets, automobile parts, and electric cable covering. Tensile strength Figure shows the comparison of tensile strength of PVC products with other plastics. The tensile strength is expressed in terms of the maximum stress per unit area of the cross section when the test piece breaks by applied loads to both ends of the test piece. (An index to show the magnitude of force at break, when both ends of the test piece are pulled apart)

--Tensile strength of various plastics

Tensile modulus Figure shows the comparison of tensile modulus of PVC products with other plastics. The tensile modulus is also known as the Youngs Modulus, which is expressed in terms of the ratio between the tensile stress per unit area of the cross section and the elongation in the direction of the tensile stress. Plastics possessing large tensile modulus have a small stress-strain ratio. In other words, the tensile modulus is an index showing the magnitude of elongation, when a test piece is pulled apart. It is the equivalent of the spring constant.

--Young's modulus of various plastics Bending strength Figure shows the bending strength of PVC products in comparison with other plastics. It is expressed in terms of the maximum stress upon break of the test piece, where the test piece is supported at two points apart and a vertical stress load is applied at the centre. (An index to show the magnitude of force at break, when the test piece is bent).

--Bending strength of various plastics

Impact strength The glass transition temperature (second order transition point) of PVC is over 70C. The result is low impact strength at room temperature, which is one of the disadvantages of PVC. There are many ways to measure impact strength. Figure shows the results of energies absorbed by test pieces when they are fixed and hammered to break (impact failure). Higher values show higher impact strength.

Creep properties Plastic products are said to show a creep behaviour, where the product is deformed at room temperature as time elapses when an external force is applied continuously.

--Creep properties of various thermoplastics The phenomenon is also known as cold flow. When plastics are used for construction or industrial applications, cold flow is an especially important point to be considered. Under normal environmental conditions, rigid PVC products show very little creep and are superior in comparison with other plastic products such as PE or PP. Therefore, PVC is used in various interior and exterior construction materials (e.g., ducts, panels, window frames and decks) and electric or machine parts. Plasticising PVC is a polar polymer with strong intermolecular forces, therefore it is rigid at room temperature. On the other hand, when a plasticiser is added upon fabrication, flexible PVC products are obtained. This versatility is a major advantage of PVC.PVC products without any plasticisers are called rigid PVC products, while PVC products that include plasticisers are called flexible PVC products. The softness of the flexible PVC products is obtained as a result of plasticisers coming between molecules to separate them, reducing intermolecular forces. Chemical Resistance Since the main chain of the polymer is made by single bonds of carbon atoms, PVC has excellent chemical resistance, as with other general-purpose plastics such as PE, PP, or PS.

The chart shows the chemical resistance of PVC in comparison with other plastics. Some of the engineering plastics and specialty resins are susceptible to acid or alkali, and some plastics have excellent chemical resistance properties, such as polyfluorocarbons. PVC has excellent chemical resistance together with good mechanical properties, therefore is used for chemical storage tanks, plastic valves/flanges, drainage/sewage pipes, and plant piping.

5) OVERWEV of PAST,CURRENT and FUTURE CAPACITY in the PVC INDUSTRY Polyvinyl chloride plastics are the second largest class of theromoplastics in the world, after the polyethylenes. Global PVC production capacity amounted to approximately 26 million metric tons (57 billion lbs.) in 1997 and is expected to increase by approximately 5.5% per year through the year 2002. Thus, world PVC production capacity is expected to reach 34 million metric tons (75 billion lbs.) by the year 2002. From 1992 to 1997, PVC production capacity rose an average of 2% per year, actually going down in Europe. Regions of greatest PVC capacity growth into the next millennium include Asia, Eastern Europe, the Middle East, and South/Central America. Per capita PVC consumption in these areas is in the range of 2 kg compared to 6-8 kg in North America, Western Europe and Japan. These three countries/regions account for approximately 60% of PVC production. To satisfy quickly growing demand in Asia, Latin America and Eastern Europe, mainly due to large investments in construction and infrastructure, 3.4 million metric tons of capacity are expected to be added in developing countries by 2001. Capacity in Asia (except for Japan) is expected to almost double by the year 2002.

Table 2 :Regional PVC Capacity and Expected Expansions (in thousands of metric tons per year) Region North America Western Europe Japan Other Asia Other regions 9620 (all other regions) Africa Middle East South America Eastern Europe Oceania Total 23540 200 26032 200 34187 0 5.5 370 940 1240 840 370 1095 1550 2380 0 3 4.5 23 1992 5210 (only U.S.) 6335 2375 1997 7730 6185 2772 5755 2002 9350 6320 2772 10150 Avg. Annual growth % 4 0.5 0 12

(Source: SRI International)

PVC is currently produced by approximately 150 companies in 50 countries. Table 3 shows that PVC production is highly concentrated in a few large companies, with the top 10 PVC producing companies amounting for more than 40% of global capacity. Formosa Plastics (Taiwan) accounts for approximately 8% of global PVC production capacity. Operating rates (actual production/capacity) range from 90% in North America to 70% in other regions. With the exception of Shin-Etsu (Shintech), all of the largest PVC producers have captive sources of VCM (Shin-Etsu purchases theirs from Dow, though the proposed Shintech plant in Louisiana would have a captive source of chlorine and VCM).

Consumption of PVC in the world Global consumption of PVC reached a level of about 31 million tons in 2005. PVC is a matured polymer with average growth rate less than World GDP, but is seeing good growth in Asia due to more emphasis on infrastructure and construction. In fact, markets indicate that the power of business in PVC and related sectors are surely shifting to Asia, where PVC is growing at about 7% or almost at the same rate as Asia's GDP growth. North America as well as Europe are both matured markets for PVC. These regions are expected to grow at less than 3% in the coming five years. Asia is therefore expected to have a larger share in PVC consumption as compared to Europe and North America by 2010. The global plastics additives market was about 9.9 million tons in 2004, valued at US$19 billion. Overall, the additives market is expected to grow at 4% AAGR from 2004 to 2009. While Europe, North America and Asia-Pacific (excluding China) are growing at about 3%, China is predicted to grow at 8-10%. The other smaller market regions are also poised to grow at 5-6% through 2009. India could be the next big growth area. PVC consumes more than 65% of the total volume of 9 million tonnes of additives, with major portion of this volume arising from plasticizers. Additives for PVC excluding plasticizers, amount to a volume of over 2 million tons. The regional distribution of additives in 2005 has reached a level of 23% in Asia. Europe continues to be the largest region with almost 25% of the total global consumption currently. PVC wire and cable sector also consumes lead stabilizers and will continue to use them because of inherent advantages offered by lead in terms of superior electrical resistance. While wire and cable sector constitutes only about 23% of the total PVC consumption, it requires heavy dosage of lead stabilizer at about 2-3% level. Lead stabilizers are being phased out in Europe. It is expected that by 2010, lead will be replaced by lighter metals like calcium or zinc, as well as organic stabilizers. Most of the replacement of lead will take place in pipe sector. The wire and cable sector is expected to stay with lead stabilizer longer until a suitable alternate is developed matching technical performance of lead. All the developments in this area still continue to be deficient. PVC melt gets stuck on hot metal during processing. It therefore requires higher level of lubricants that prevent sticking of PVC melt to hot metal. In addition, improving flow by addition of PVC compatible additives called internal lubricants are also used. Lubricants of all types are added at about 0.5-1% levels. Obviously 15% of the PVC additives comprise of lubricants. PVC requires the largest dosage among all other polymers. Antioxidant is generally used by polyolefins, but PVC is quite resistant to oxidative degradation. However the dosage of antioxidant is lower than 0.2% compared to average 2-3% of heat stabilizer used in PVC. Antioxidant therefore has only has 1% share of the global additive consumption by volume.

PVC manufacturing in TURKEY PVC is manufactured in PETKM holding in Turkey which has the capacity of 150000 tons/years. 6) PVC and THE ENVIRONMENT Because of its extraordinary stability, PVC is difficult to dispose of. It is not biodegradable and unlike polyethylene and many other plastics it is only very slowly decomposed by exposure to the sun. When PVC is burned it gives off hydrochloric acid and some of the chlorine combines with other material to form very toxic and stable organochlorine compounds such as dioxins. See also Introduction (Persistent Organic Pollutants).In some countries the use of building materials containing PVC is prohibited, mainly because of the very toxic fumes which are formed when there is a fire. In Australia, some local councils are promoting the use of alternatives to PVC pipe, such as aluminium and clay.It is possible to recycle PVC by melting and remoulding it, but there is little recycling of PVC in Australia; the recycling code number for PVC is 3. Health effects When the monomer is polymerised to form the plastic it is no longer toxic, but a very small amount of the monomer remains in the product. PVC intended for use with food is made to very stringent specifications and, in Australia, must not contain more than five ppm of vinyl chloride monomer. It is important that only 'food-grade' PVC be used with food as ordinary PVC may contain much more of the toxic monomer. This can diffuse out of the plastic into the food, particularly if the food is oily or strongly acid or alkaline. For example, do not use garbage cans for making fruit drinks or pickled cabbage, or for storing edible oil. 7) USES of PVC PVC is used extensively within the construction industry for the following products: * Pipes and fittings * Siding * Windows * Flooring * Fencing * Decking * Roofing * Wall coverings * Wire and cable products * Transport and packaging materials * Medical supplies * Consumer products (such as credit cards and toys)

8) REFERENCES - Allen, D. T. "Chapter 4 - Industrial Ecology". Green Engineering. United States Environmental Protection Agency. - Chemical Economics Handbook Report Vinyl Chloride Monomer (VCM), SRI Consulting, July 2006, pages 4, 10, 11, and 20. - faculty.ksu.edu.sa/alhajali/ChE534_CourseNotes/PVC.pdf - aquaticpath.umd.edu/appliedtox/wendy.pdf - www.npi.gov.au/substances/vinyl-chloride-monomer/index.html - www.pvc.org/en/p/vinyl-chloride-monomer-vcm - earth911.com/recycling/construction/pvc/facts-about-pvc/ - www.vinylchem.com/news.html - www.safersolutuions.org.au/a/180?task=view

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