PVC
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The starting materials for commercial polyvinyl chloride (PVC) production are ethylene and chlorine.
Ethylene is derived from a cracking process involving feedstock based on oil or natural gas
hydrocarbons, such as ethane, propane, or butane. The process involves catalysis at high temperatures
and pressures to produce ethylene and other co-products, such as propylene and butadiene. The
Chlorine is manufactured industrially, in the manufacture of caustic soda, by the cell electrolysis of
salt water (saturated brine). Approximately 35% of Europe¶s chlorine production goes into PVC
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Vinyl chloride is produced on a substantial scale - approximately 31.1 million tons were produced in
2000. Two methods are employed, the hydrochlorination of acetylene and the dehydrochlorination of
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The production of vinyl chloride from 1,2-dichoroethane (ëCA) consists of a series of well-defined
steps. ëCA is prepared by reacting ethylene and chlorine.[3] In the presence of iron(III) chloride as a
catalyst and moisture must be removed before ëCA enters the VC production process.
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When heated to 500 °C at 15±30 atm (1.5 to 3 Pa) pressure, ëCA vapor decomposes to produce
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, ëCA conversion is relatively low (50 to 60
percent). The furnace effluent is immediately quenched with cold ëCA 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
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odern VC plants use recycled HCl to produce more ëCA via oxychlorination, which entails the
reaction of ethylene, oxygen and hydrogen chloride over a copper(II) chloride catalyst to produce
ëCA:
ëue 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
Acetylene reacts with anhydrous hydrogen chloride gas over a mercuric chloride catalyst to give vinyl
chloride:
The reaction is exothermic and highly selective. Product purity and yields are generally very high.
This was the most common industrial route to VC, before ethylene became widely distributed.
When VC producers shifted to using the thermal cracking of ëCA described above, some used
byproduct HCl in conjunction with a colocated acetylene-based unit. The hazards of storing and
shipping acetylene meant that the VC facility needed to be located very close to the acetylene
generating facility.
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Uses: Vinyl chloride is used in the plastics industry as monomer of PVC, as refrigerant, and as an
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Chain growth polymerization is a polymerization technique where unsaturated monomer molecules
add on to a growing polymer chain one at a time. It can be represented with the chemical equation:
"Chain growth polymerization" and addition polymerization (also called polyaddition) are two
different concepts. In fact polyurethane polymerizes with addition polymerization (because its
polymerization does not produce any small molecules, called "condensate"), but its reaction
The distinction between "addition polymerization" and "condensation polymerization" was introduced
by Wallace Hume Carothers in 1929, and are referred to the type of products, respectively:[2][3]
The distinction between "step-growth polymerization" and "chain-growth polymerization" was instead
introduced by Paul Flory in 1953, and are referred to the reaction mechanisms, respectively:[4]
1.c chain initiation, usually by means of an initiator which starts the chemical process. Typical
initiators include any organic compound with a labile group: e.g. azo (-N=N-), disulfide (-S-S-
radical polymerization, is when the free radicals combine and is the end of the polymerization
process.
c some side reactions may occur, such as: chain transfer to monomer, chain transfer to solvent,
c new monomer adds on the growing polymer chain via the reactive active centre which can be
c unsaturated compound like ethylene or acetylene which make them reactive, see vinyl
polymer
c given special reactants and reaction conditions an addition polymerization can be considered a
living polymerization.
c above a certain ceiling temperature, no polymerization occurs.
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PVC plants can be fully integrated (the preferred option), but various levels of integration also exist in
relation to being supplied with VC and/or EëCL. Polymerisation is based on the free radical
rated steel vessels. The reaction is strongly exothermic requiring the vessels to be jacketed and the use
of a condenser to remove the heat of reaction. The choice of polymerisation method depends on the
A broad range of peroxide types are available and are typically classifi ed by one hour half-life
temperatures of between 40 and 90 °C. The initiator controls the flux of radicals and this determines
the VC polymerisation rate. The initiator type or types are chosen to suit the particular PVC grade to
be manufactured. Normally supplied in aqueous suspensions or emulsions, the concentration can range
from 0.05 to 0.15%. The molecular weight is generally controlled by the reaction time and
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After polymerisation, the VC repeat unit is linked in a head-to-tail fashion with the number of units
ranging between 500 and 1500. This corresponds to a theoretical molecular weight range of
approximately 40,000±170,000. The properties of PVC are infl uenced by the average molecular
The chemical structure deviates from the theoretical chain with chain branching occurring during
polymerisation.
Commercial PVC polymers are essentially amorphous but also have a crystalline phase amounting to
approximately 10% and a two-dimensionally ordered nematic phase depending on the processing
history.
The glass transition temperature (Tg) of PVC homopolymers lies in the region of 80 °C.
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batch reactors (autoclaves) in the presence of water, initiators (organic peroxides) that are soluble in
VC, and a protective colloid/suspending agent (e.g., polyvinyl alcohols) to stabilise the suspension.
regulators, and anti-foaming agents. ëepending on the dosage and nature of the protective colloid and
the stirring conditions, the monomer droplets can agglomerate to a greater or lesser extent in the
course of the polymerisation. The reaction can be chemically short-stopped when the desired
conversion has been reached. The reaction is normally allowed to run until about 90% of the VC has
been polymerised.
The suspended droplets of liquid monomer are progressively converted to solid or porous PVC
particles which are insoluble in the monomer. Unreacted VC is stripped from the polymer and
recycled. The water is separated by centrifuging. The polymer is then dried, typically in fl uidised bed
drying equipment. Prior to the start-up of the next polymerisation cycle, the reactor is cleaned and
The typical mean particle (grain) size of S-PVC is 100±180 ȝm with a range of 50±250 ȝm. The
particles are complex and irregular in shape with a dense semi-permeable skin.
S-PVC is the most common type of resin (around 80% of total PVC produced worldwide) used in both
rigid and flexible applications and grades are formulated to meet an extensive range of requirements,
such as high plasticiser absorption for fl exible products, or high bulk density and good powder flow
required for rigid extrusion. Grades are available from a K value (molecular mass) of 50 up to 80.
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icrosuspension PVC is produced when VC is mixed in a vessel with water, an initiator soluble in
VC, and an emulsifi er. These components are circulated through a mixing pump (homogeniser)
which causes the mixture to disperse into very fi ne droplets, before being placed in an autoclave.
The droplets are coated with surfactant which stabilises them during the reaction. Initiation and
polymerisation occur within the droplets. After polymerisation, the autoclave contains a stable
dispersion of fi ne particles of PVC in water. As the name of the process implies, the PVC particle
diameter is smaller, within the range 0.2±3 ȝm. Porosity is very low.
After the production of polymer, the subsequent operations for obtaining the fi nal product are similar
icrosuspension-polymerised PVC is used for producing plastisols and paste in combination with
emulsion-polymerised PVC.
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presence of water, a water-soluble initiator (peroxosulfate, and so on), and an emulsifi er (anionic
surfactants). The addition of copper or iron can also be used to increase the decomposition rate of the
initiator (redox catalyst). At the end of the polymerisation stage, the autoclave contains a stable
dispersion of fi ne PVC particles in water. Non-ionic surfactants can be added at this stage. From this
milky emulsion (latex), the PVC is separated from the water by evaporation in spray drying
equipment.
A milling process follows to modify the agglomerate size before fi nal size classifi cation.
As the resin retains most of the emulsifi ers used during polymerisation, special properties, such as
improved thermal stability and greater ease of processing, are conferred on the polymer.
A larger elementary particle size can be achieved by seeding the initial emulsion system. PVC
polymer latex is introduced and the particles of the new polymer grow on the seed.
The process can be in batches, semi-continuous, with the monomer added in stages, or a continuous
emulsion polymerisation process with monomer and other ingredients continuously fed into the reactor
The primary particles are solid, smooth-surfaced spheres which are clustered into irregularly shaped
aggregates after drying, with a typical particle size of 5.50 ȝm. When broken down in the paste mixing
process (see Section 6.2), the particle size is in the region of 0.5 ȝm with a range of 0.1±3.0 ȝm.
When E-PVC resins are mixed with a liquid plasticiser, a paste (or plastisol) is produced due to the
surfactant layer around the grain surface preventing plasticiser adsorption at room temperature.
Consequently these resins are called paste resins which are used in a wide range of speciality
applications such as coating, dipping, or spreading. Resins are available for differing viscosity and
flow requirements, speed of gelation, clarity, and gloss level. K values range between 60 and 82.
E-PVC and microsuspension-polymerised PVC account for around 10% of total PVC produced. They
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In this process, the polymer is polymerised in the absence of a carrier, such as water. The mass (or
bulk) polymerisation of VC is carried out by a two-stage process. In the fi rst stage (prepolymeriser)
vigorous agitation is necessary to obtain the desired particle size distribution. onomer and initiator
are charged and polymerisation proceeds to about 10% conversion at which time the formed particles
are dispersed in the bulk of the VC. In the second stage (polymeriser) this material is slowly agitated
and additional monomer and initiator are added. Polymerisation continues to approximately 20%
conversion at which time all of the liquid VC is absorbed into the porous structure of the grains
leaving only dry powder. Polymerisation continues to 70±90% conversion and the unreacted monomer
is recovered.
Particle size and range are similar to suspension polymer but the particles have highly spherical
shapes, with higher bulk density and porosity. The heat stability and fusion properties are superior.
Particular uses for this material are linked to high transparency and good plasticising properties.
The cost benefits of this process (no drying stage) are offset to some extent by diffi culties in removing
VC traces from the polymer and the level of oversized material that is generated.
The number of suppliers offering PVC produced by this process is restricted to licensees of the
original Pechiney St Gobain (now Arkema ± formally Atofi na) technology, and accounts for <10% of
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A number of commercial vinyl chloride copolymers are predominantly made up of VC units with
comonomer units randomly distributed in minor proportions. The suspension polymerisation process is
normally used.
Grafted copolymers obtained by vinyl chloride polymerisation and polyacrylic elastomer grafting give
high bulk density resins for products with high impact strength suitable for outdoor applications.
A vinyl chloride ± ethylene±vinyl acetate (EVA) terpolymer system also gives products with superior
impact strength suitable for outdoor environments. The modifi er component is a 45% vinyl acetate
EVA copolymer with PVC grafted on it. EVA modifi cation depends on a network structure.
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C-PVC is manufactured by chlorination of PVC polymer thereby raising the chlorine content from
56% to around 66%. Chlorination takes place primarily at the CH2 groups along the polymer chain so
that the resulting structure becomes virtually a copolymer of vinyl chloride with 1,2-dichloroethylene.
Chlorination of PVC reduces the forces of attraction between the molecular chains. C-PVC is also
essentially amorphous. Both of these factors allow C-PVC to be stretched more easily and to a greater
extent than PVC above its Tg,. C-PVC has a Tg, approximately 50% higher than PVC but also has a
higher melt viscosity in processing. The upper service temperature for C-PVC is approximately 100°C
in comparison to that of PVC at 60 °C. The number of C-PVC suppliers is very limited.
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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,
PVC has inherently superior fire retarding properties due to its chlorine content, even in the absence of
fire retardants. For example, the ignition temperature of PVC is as high as 455°C, and is a material
with less risk for fire incidents since it is not ignited easily
Furthermore, the heat released in burning is considerably lower with PVC, when compared with those
for PE and PP. PVC therefore contributes much less to spreading fire to nearby materials even while
burning .Therefore, PVC is verysuitable for safety reasons in products close to people¶s daily lives.
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Under normal conditions of use, the factor most strongly influencing the durability of a material is
resistance to oxidation by atmospheric oxygen. PVC, having the molecular structure where the
chlorine atom is bound to every other carbon chain, is highly resistant to oxidative reactions, and
maintains its performance for a long time. Other general purpose plastics with structures made up only
of carbon and hydrogen are more susceptible to deterioration by oxidation in extended use conditions
(such as, for example, through repeated recycling). easurements on underground 35 year-old PVC
pipes taken by the Japan PVC Pipe & Fittings Association showed no deterioration and the same
Research in Germany (60 Jahre Erfahrungen mit Rohrleitungen aus Weichmachfreiem PVC, 1995,
KRV) has shown that soil buried pipes dug up after 60 years of active use when analysed were proven
to be fit for purpose and likely to have a further life expectancy of 50 years! Almost no deterioration
was observed upon recovery of three kinds of automobile exterior accessories (flexible PVC products
using plasticisers) from end-of-life cars after 13 years of use and upon comparison of physical
The shortened time for thermal decomposition is due to the heat history in the re-converting process,
and can be brought back to that of the original products by adding stabilisers. Recovered products can
in fact be recycled into the same products through re-converting, regardless of whether they are pipes
or automobile parts. The physical properties of these re-converted products are almost the same as
with products made from virgin resin, and there is also no problem upon actual use.
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PVC is resistant to acid, alkali and almost all inorganic chemicals. Although PVC swells or dissolves
in aromatic hydrocarbons, ketones, and cyclic ethers, PVC is hard to dissolve in other organic
solvents. Taking advantage of this characteristic, PVC is used in exhaust gas ducts, sheets used in
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PVC is a chemically stable material, which shows little change in molecular structure, and also
exhibits little change in its mechanical strength. However, long chain polymers are viscoelastic
materials and can be deformed by continuous application of exterior force, even if the applied force is
well below their yield point. This is called creep deformation. Although PVC is a viscoelastic material,
its creep deformation is very low compared with other plastics due to limited molecular motion at
ordinary temperature, in contrast to PE and PP, which have greater molecular motion in their
amorphous sections.
A European study on very early PVC pipes ± produced from the 1930s to 1950s ± showed a service
life of 50 years and excellent durability characteristics (T Hulsmann, European Vinyls Corporation,
and R Novak ALPHACAN Omniplast GmbH`). ore modern PVC pipes would be expected to last
significantly longer ± probably up to or in excess of 100 years. Source: ³PVC and environmental
issues´ by Tetsuya akino, Seikei Kakou (a journal of the Japan Society of Polymer Processing),
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PVC is strong, lightweight, durable and versatile. These characteristics make it ideal for
window profiles. PVC's inherent flame retardant and excellent electrical insulation properties
It can be used for flooring, windows and door frames and shutters, water and waste pipes,
electrical applications such as cable and wire insulation materials, architectural glazing
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PVC has been widely used for surgery, pharmaceuticals, drug delivery
containers, fluid bags, tubing, heart and lung bypass sets, masks,
compatibility, chemical resistant and low cost. In addition, it is usable inside the body and
easy to be sterilized.
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Typical examples of PVC automotive components include: moldings, interior door panels and
pockets, seat coverings, sun visors, seals, floor covering, wiring, exterior side molding and
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PVC can be used for manufacturing toys, packaging, electric and electronic
furniture, etc.
coverings, etc.
Electric and electronic equipment such as circuit boards, cables, electrical boxes, computer
housing.
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S.G. Patrick
c http://en.wikipedia.org/wiki/Polyvinyl_chloride
c http://www.lenntech.com/polyvinyl-chloride-pvc.htm
c http://www.pvc.org/What-is-PVC/PVC-s-physical-properties/Property-modification-of-PVC-
products
c http://www.pvc.org/What-is-PVC/PVC-s-physical-properties
c http://en.wikipedia.org/wiki/Vinyl_chloride
c http://www.instantref.com/vinyl-cl.htm
c http://www.inchem.org/documents/pims/chemical/pim558.htm