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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

ethylene is further processed to separate it from the co-products.

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

production. Three different electrolysis processes are currently in use:

c ercury cell

c ëiaphragm cell

c embrane cell

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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

ethylene dichloride (1,2-dichloroethane).

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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, these compounds react exothermically:

CH2=CH2 + Cl2 ĺ ClCH2CH2Cl

This process is very selective, resulting in high purity ëCA and high yields. However any dissolved

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

vinyl chloride and anhydrous HCl.

ClCH2CH2Cl ĺ 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, 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

use a refrigerated continuous distillation system.

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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:

CH2=CH2 + 2 HCl + ½ O2 ĺ ClCH2CH2Cl + H2O.

The reaction is highly exothermic.

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

chloride, a topical anesthetic

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Acetylene reacts with anhydrous hydrogen chloride gas over a mercuric chloride catalyst to give vinyl

chloride:

C2H2 + HCl ĺ 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 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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Physical ëescription: Colorless gas

olecular weight: 62.50

Vapour pressure: 2530 mm Hg (20°C)

Specific Gravity: 0.9106 @ 20/4 C

Autoignition temperature 472°C (882°F)

Explosive limits: 3.6 to 33%

ëensity: 0.91 g/ml

elting Point: -154 C

Boiling Point: -13.9 C

Solubility in Water: 2.7 g/L (0.0432 mol/L)

Hap Weighing Factor: 10 [713]

Stability: Vinyl chloride should be protected from light and heat.

Uses: Vinyl chloride is used in the plastics industry as monomer of PVC, as refrigerant, and as an

intermediate in organic synthesis.

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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:

where n is the degree of polymerization.

"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

mechanism is a step-growth polymerization.

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]

c a polymer only (addition)

c a polymer and a molecule with a low molecular weight (condensation)

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]

c by functional groups (step-growth polymerization)

c by free-radical or ion (chain-growth polymerization)

The main characteristics are:

c polymerization process takes place in three distinct steps:

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-

), or peroxide (-O-O-). Two examples are benzoyl peroxide and AIBN.

2.c chain propagation

3.c chain termination, which occurs either by combination or disproportionation. Termination, in

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,

and chain transfer to polymer.

c unlike condensation polymerization (also known as step-growth polymerization):

—c high molecular weight polymer is formed at low conversion

—c no small molecules, such as H2 O, are eliminated in this process

c new monomer adds on the growing polymer chain via the reactive active centre which can be

—c free radical in free radical addition polymerization

—c carbocation in cationic addition polymerization

—c carbanion in organometallic complex in coordination polymerization

c the monomer molecule can be a

—c unsaturated compound like ethylene or acetylene which make them reactive, see vinyl

polymer

—c Alicyclic compound, see ring-opening polymerization

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

polymerisation of VC using initiators, such as organic peroxides, in thick-walled, high-pressure

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

ultimate application and the economics of the process.

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

temperature. Stirring conditions also infl uence the process.

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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

weight and the molecular weight distribution (Wë).

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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Suspension-polymerised PVC (S-PVC) is manufactured when VC is polymerised in large-scale

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.

Other additives are chain-transfer/chain-extending and chain-terminating agents, antioxidants, pH

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

coated with an anti-fouling agent.

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

to those of the emulsion polymerisation process.

icrosuspension-polymerised PVC is used for producing plastisols and paste in combination with

emulsion-polymerised PVC.

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Emulsion-polymerised PVC (E-PVC) is produced in an autoclave when VC is polymerised in the

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

and the latex withdrawn from the bottom.

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

are also known as dispersion resins.

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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

world PVC production.

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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.

olecular structures of general purpose plastics

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.

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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

strength as new pipes

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

properties with new products

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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

construction, bottles, tubes and hoses.

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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),

Vol.10, No.1 (1998)


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ëue to PVC properties, as described

above, around 50% of PVC (or vinyl)

manufactured is used in construction

replacing other materials such as wood

or glass. Cheap, resistant, good weatherabiligy, ect.

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

make it ideal for cabling applications.

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

systems, wallpaper, etc.


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PVC has been widely used for surgery, pharmaceuticals, drug delivery

and medical packaging. Some products include blood bags, medical

containers, fluid bags, tubing, heart and lung bypass sets, masks,

gloves, bottles and jars, drainage systems, ducting, etc.

The reasons to use it in the medical sector is its safety and chemical stability and bio-

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

protective strips, anti-stone damage protection, etc. Brakes

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PVC can be used for manufacturing toys, packaging, electric and electronic

equipment, household goods, coating, plastic parts in motor

vehicles, office supplies, insulation and adhesive tapes,

furniture, etc.

For consumers in shoe soles, children's toys, handbags, luggage, seat

coverings, etc.

Industrial sectors for conveyor belts, printing rollers.

Electric and electronic equipment such as circuit boards, cables, electrical boxes, computer

housing.

l




c Practical Guide to Polyvinyl Chloride

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