Polyvinyl chloride or PVC.

Introduction
PVC is one of the most successful modern synthetic materials. It uses very wisely the
natural resources, has a long lifespan and is characterized by production, use and
Safe disposal. PVC is also suitable for a wide and diverse range of everyday applications. It plays, by
elsewhere, an important role in promoting health and safety.
All these advantages have made PVC the second most important basic plastic (approximately 20% of all plastics just
after the polyethylenes ≈32%) and its demand is only increasing.
In the construction sector, it holds the first place with 55%, followed by polystyrene with 15% and polyethylene with 12%.

PVC manufacturing.
Raw materials.
To manufacture PVC, two chemical species are used, dichlorine Cl.2on one hand and ethylene also called ethylene
CH22on the other hand.

Obtaining dichlorine: this very dangerous yellowish-green gas, emitting a pungent and unpleasant odor, is obtained by
electrolysis of an aqueous solution of sodium chloride Na Cl.
Reaction equation: 2(Na+ + Cl–) + 2 H2O = H2+ Cl2+ 2 (Na+ + HO–)
Note: the electrolysis of sodium chloride is used not only for the preparation of dichlorine, but also for that
sodium hydroxide (Na OH) also known as caustic soda which is notably used in the paper industry,
aluminum and soap, but also in water treatment facilities and the cleaning of glass bottles.

Obtaining ethylene: this colorless gas with a slight odor (apple scent) is mainly obtained by
cracking of light hydrocarbons. We heat various alkanes strongly (t ≈ 800°C) in the presence of steam:
a complex mixture containing various alkenes and other hydrocarbons that are separated by distillation
fractionated.

2. Production of vinyl chloride monomer CH2CHCℓ noted VCM.

The production of VCM, the basic component of PVC, takes place in two stages:

1eraStep: First, we prepare 1,2-dichloroethane, the two most commonly used methods currently being:
the direct chlorination of ethylene by chlorine dichloride catalyzed by iron (III) chloride FeCl3:
C H2=CH2+ Cl2 = CH2Cℓ--CH2Cℓ
the oxychlorination of ethylene by hydrogen chloride and dioxygen carried out on a fluidized bed of catalyst CuCl/
Copper(I) chloride2on Aℓ2O3under a pressure of 0.5 MPa and a temperature of 250°C. This reaction is practically complete.
H2C=CH2+ 2 HCl + O2 = CH2Cℓ--CH2Cl + H2O
2thwe perform a pyrolysis at a temperature of 500°C of 1,2-dichloroethane:
CH2Cℓ--CH2Cℓ = CH2Chlorine gas HCl
Note: the hydrochloric acid produced by this reaction can be reused for the oxychlorination of ethylene.

At atmospheric pressure and ambient temperature, VCM is a toxic gas that must be handled in...
high security conditions.

3. PVC production.
PVC is obtained by polyaddition of VCM: macromolecules are obtained by the addition of a very large
name of VCM. Reaction equation: n CH2=CHCl = 2-CHCln–
The degree of polymerization n, that is to say the number of identical units that a PVC macromolecule contains is
ranging between 750 and 1500.
The methods of manufacturing PVC are numerous, the most common being those of polymerization in
suspension and emulsion.

3.1. Suspension polymerization.

This process, which is discontinuous, lasts between 6 and 8 hours per cycle: reactors, called
autoclaves, water, vinyl chloride monomer, catalysts and various additives, especially initiators of
reactions that are soluble in the monomer.
The polymerization reaction, which is exothermic, takes place in large capacity autoclaves (≈ 120 m)3)
controlled in temperature and pressure and equipped with mechanical agitation devices.
At the end of the polymerization, a suspension in water of PVC grains of about 100 to 150 is obtained. m. On
Then transfer this mixture, called 'slurry', into a degasser to extract the unreacted VCM. This VCM
is recovered and recycled.
Then comes the continuous phase: the 'slurry' is sent to large tanks equipped with a stirring system.
Then it is transferred to centrifuges that allow for the almost complete removal of mother liquors.
After centrifugation, a 'wet cake' is collected and dried in a rotary dryer or in a fluidized bed dryer.
fluidized.
The obtained product, a white powder that resembles sugar, is stored in a silo to be delivered in bulk or is
packed in 25 kg bags.
 3.2. Emulsion polymerization.
Emulsion polymerization occurs according to the same principle as in suspension, but with catalysts and
very different additives, particularly reaction initiators that are soluble in water and surfactants
that improve the formation of the emulsion. The mixture of water and vinyl chloride is stirred so that the chloride
of vinyl is dispersed into very fine droplets (emulsion), then it is brought to the temperature and pressure of
desired polymerization.
At the end of polymerization, the autoclave contains a stable emulsion of fine PVC particles (less than 1 m)
in the water. This milky-looking emulsion, called 'latex', is sent to large tanks and, as in the
suspended process, the continuous phase can begin.
However, spinning is impossible due to the fineness of the latex grains. Therefore, all the water must be evaporated.
which makes the process much more expensive. The PVC particles are indeed separated from the water by spraying the
latex in fine droplets in a stream of warm air. This operation is carried out in large drying towers.
called 'spray dryers'.
Another difference with the suspension lies here: the structure of the product depends not only on what is
passes through the reactor, but also the drying conditions: the spray mode determines the quality of
final product.
At the outlet of the dryer, we obtain PVC grains of small diameter (30 to 50) average men), made up of
The aggregation of PVC particles formed during polymerization. These PVC grains are sifted. In
In certain applications, the product will be used as is, but in the majority of cases, it still needs to undergo an operation.
grinding that brings the particle size of the powder between 10 and 15 m, a product that is then similar to flour.
In the emulsion process, the structure and final characteristics of the product are established based on
client requirements, by acting on the conditions of polymerization, drying, and grinding. This process, which lasts
between 10 and 15 hours per cycle, is much more complex and more expensive but it is used for the development of
qualities of special resins intended for very specific applications because this PVC can be further plasticized
easily (coating, molding, dipping, ...).

4. Formulation of PVC.
PVC owes its versatility to the advantageous properties of the polymer; these properties can be modified by making
vary the production conditions and by adding various substances. It is thus possible to manufacture a large
PVC has a wide range of properties. The mechanical properties of PVC can vary from extreme rigidity
to a very high flexibility through the controlled addition of plasticizers. PVC can be colored by the addition of various
Colorants. Rigid PVC is naturally fire-resistant: it burns when exposed to a flame but does not propagate the
combustion; flexible PVC can also be adapted to environments where there is a fire hazard.
by the addition of fireproof products such as electrical appliances.
The main additives involved in the transformation of PVC are stabilizers, plasticizers, pigments,
charges, lubricants, and possibly flame retardant products.
The stabilizers.
Exposed to high temperatures, oxidizing chemicals or ultraviolet light, plastics
risk becoming damaged and degrading. Stabilizers allow plastics to withstand these conditions. There are
in principle, two types of stabilizers: primary (metallic derivatives) and secondary (non-co-stabilizers)
metallic: products such as organic phosphites, epoxy products, organic antioxidants and polyols). They
represent 2 to 3% of the finished PVC product.
Plasticizers.
Plasticizers are organic products with a high boiling point. The addition of 20 to 50% plasticizer to PVC
makes the plastic more flexible. This results in a plasticized or flexible PVC with a wide range of applications (packaging,
cables, garden hoses, flooring, imitation leather, games, etc.).
Most plasticizers are alcohols based on phthalic acid. Diethylhexyl phthalate (DEHP), better known as
The name DOP (dioctyl phthalate) is by far the most commonly used.
Colored pigments.
Pigments are added to PVC and other plastics at concentrations of 0.1 to 4%. This allows for
obtain PVC in all colors. Many traditional pigments for plastics contain chrome or
lead but they are increasingly being replaced by less harmful organic pigments in case of decomposition of the
PVC by fire for example.
The charges.
Fillers are sometimes used to reduce the production cost of PVC, to increase its fire resistance or to
strengthen certain other physical properties. The most common fillers are chalk (calcium carbonate in
powder), talc (magnesium silicate) and, to a lesser extent, magnesia (magnesium oxide). PVC can
contain up to 50% of fillers. These do not pose any danger to health or the environment.
Lubricants
Lubricants facilitate the processing of PVC and help prevent it from sticking to surfaces.
metallic contacts of machines. These are organic waxes, fatty alcohols, fatty acids, esters, and salts.
metallic. They pose no health risk and only intervene at very low concentrations in PVC.
Fire retardants.
Rigid PVC is fireproof by nature. Flame-retardant substances are added to flexible PVC because
the addition of plasticizers increases its flammability. In applications where fire resistance is a requirement
imperative, substances such as antimony trioxide, aluminum hydroxide, and magnesium oxide are
added to soft PVC formulas; phosphoric acid esters or
chloroparaffin.
– The other additives:
In addition to the aforementioned additives for PVC, other auxiliary materials can also be added in small amounts.
quantities according to the area of application:
the blowing agents, involved in the production of PVC foam layers: these products release a gas, in
general carbon dioxide during heating involved in the manufacturing process and this creates micro bubbles in
the polymer.
fungicidal additives, to protect flexible PVC mainly against attacks from microorganisms. We
use here 10,10-oxybisphenoxyarsine.
antistatic additives, to reduce static charge. For example, glycol derivatives that absorb water from
The atmosphere is well suited for this effect.

Some applications of PVC.

There are two main forms of PVC: the rigid form and the plasticized form (polymer to which additives have been added)
a significant amount of plasticizer that can go up to 50% for very flexible products).
In its rigid form, PVC is widely used for the manufacture of piping, this application being related to its low
cost, its chemical inertia and its very good resistance to aging at room temperature. For some time now
decades, PVC finds many other applications in construction such as frames (doors and
windows, blinds, ...) where it brings its fireproof and unalterable character. PVC fibers are also used to make fabrics.
furniture materials that are rot-proof and self-extinguishing. Finally, the electrical insulating and fire-retardant properties of PVC open up the
market for small electrical equipment.
Plasticized PVC has a production level comparable to that of rigid PVC. It is a completely
different from the previous one; it is widely used for the manufacturing of molded objects that must be deformable or resistant to
chocks. The films produced by calendering have the appearance of leather and compete with it in certain applications.
cheap (furniture, clothing...). It is also very commonly used in construction, particularly for flooring.
plastic tiles, carpets,...) and for wall decoration (vinyl papers,..).

To manufacture PVC objects, or PVC-based objects, various shaping techniques are used, here they are
some of them:
injection molding: molten PVC is injected under pressure into a mold, then after cooling the mold
is open and the piece recovered.
Extrusion molding: involves continuously passing molten PVC through a die with the desired cross-section.
profile to be made. (manufacturing of pipes, profiles for frames, coating of wire for fencing and wires
electric, ...
Processes derived from extrusion such as blow molding are also used for the production of thin films.
or hollow bodies (various bottles).
Calendering: involves passing PVC between different rollers to produce sheets and plates.
(manufacturing of synthetic leathers, floor coverings, certain wall coverings, ... )
Coating: involves covering a textile, paper, or other support with PVC (tarpaulins, fabrics, and plastics papers, ...).
Dipping: consists of covering an object with a layer of PVC. (very commonly used to coat glass bottles)
intended for the packaging of medications and cosmetics)
spinning: allows for obtaining fibers intended for making upholstery fabrics.

All these examples clearly show the great importance of PVC in the modern world: the annual production
The current world total is around 26 million tons.

The SOLVAY site in Tavaux.

The Solvay plant in Tavaux, which was built in 1927, currently has around 1500 employees.

Main activities of this factory:

sodium products: sodium hydroxide and sodium carbonate.
– plastics: PVC, PVDC, and PVDF.
– chlorinated products: dichlorine, hydrochloric acid, sodium hypochlorite (bleach), chlorinated solvents, ...
– peroxide products: hydrogen peroxide, sodium perborate, sodium percarbonate.

In 1999, Solvay and BASF pooled their expertise in the production of PVC and PVDC in the market.
European and created the joint venture SolVin (75% Solvay and 25% BASF).
The Tavaux factory that manufactures approximately tons of PVC per year (90% by the suspension process and 10% by
the emulsion process) uses as raw materials:
the sodium chloride that arrives by pipeline in the form of concentrated aqueous solution from the extraction sites.
Note: the production of chlorine by electrolysis of salt water requires a huge amount of electricity (the site
consumes as much power as the city of Lyon!
Ethylene comes directly from the Feysin refinery south of Lyon via pipeline.

The factory certainly has laboratories for quality control (mechanical resistance, grain size control by
laser diffraction,...), for the development of new PVC formulations as well as their implementation in order to
better adapt the product to customer demand.