Polyvinyl Chloride

Introduction
n CH2=CH Polymerization
CH2-CH
n
Cl Cl
 Polyvinylchloride (PVC) is the world’s most versatile
thermoplastics with a wide range of applications than any
other plastics.
 It plays an important role in every field such as
agriculture, electrical, irrigation, house roofs, shoe soles
and many other fields .
 It is having limited thermal stability.

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 Polyvinyl Chloride
Introduction

 Vinyl Chloride was first synthesized and reported by

Reghawlt in 1835 .
 The first report of polyvinyl bromide was published by
Hoffmann in 1860.
 The full scale commercial production of PVC resin began in
1931 in Germany.
 In India the manufacturing of PVC began in 1961 when
Calico started its plant in Mumbai.

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 Preparation of Monomer
Commercial Method
- Vinyl chloride monomer is prepared by cracking 1,2-dichloro
ethane.
CH2-CH2 CH2=CH + HCl
Cl Cl Cl

- Vinyl Chloride may be produced by the addition of HCl to

acetylene.

HC CH + HCl CH2=CH + 95.5 KJ/mol

Cl

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 Polymerization

 Suspension Polymerization
 Emulsion Polymerization

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 Suspension Polymerization
 About 85% of the world’s PVC production are by
suspension polymerization.
 Dr. Berg at Wacker-Chemie Polymerization developed
this technique in 1935.
 Vinyl chloride is dispersed in water with stirring.
 Monomer soluble organic peroxides are used as initiators.
 Protective collides such as Cellulose ethers are added to
prevent the monomer droplets from coalescing.
 After the polymerization reaction, unreacted vinyl chloride
is removed and is passed to monomer recovery plant.
 The polymer is then centrifuged to remove free water and
resulting wet polymer is dried by hot air.
 The particle size of PVC resin is about 100-150µm.
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 Suspension Polymerization

Water
Vinyl chloride
monomer

Polymerization Stripping Centrifuging Drying

Water PVC
Vessel
Suspending
agent Water

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 Emulsion Polymerization
 The system consists of the monomer- water containing
emulsifier and water soluble initiator.
 In presence of the emulsifier, agitation of the charge in the
autoclave disperse the monomer into very fine droplets.
Initiator starts polymerization.
Packing

Final Size
Classification

Monomer-Water containing
Emulsifier Conc(2-3%)
Autoclave Grinding
Water soluble initiator

Drying

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 Structure Property Relationship
CH2-CH
n
Cl
- PVC is polar in nature due to presence of C-Cl dipole.

- Resistant to non- polar solvents.

- Flame retardant and self extinguishing.

- Presence of chlorine atom causes an increase in inter

chain attraction and increase hardness and stiffness of
polymer.

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Properties of PolyVinyl Chloride
Name Value Unit
Specific gravity 1.18-1.70 --

Tensile Strength 5.5-26.2 MPa

Tensile modulus 4.8-12.4 MPa
Flexural modulus 30 MPa
Elongation at break 150-450 %
Hardness A85 ---
Glass transition temperature 80-85 °C
Dielectric Strength 9.9-15.8 KV/mm

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 Dilute Solution Viscosity
(K Value Of PVC)

 PVC is heat sensitive material and therefore instead of

melt flow index, K-value is calculated.

 The K-values of PVC for processing lie between 55

and 60.

 Higher K-values lead to better mechanical and

electrical properties of the moulded material at the
cost of decreasing processibility.

 Optimum results can be achieved in each type of

processing using products of suitable K-value.
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 Dilute Solution Viscosity
(K Value Of PVC)
The value of ‘k’ is calculated by the relationship

Log10 ηrel = 75 k2 x 10-6 + (k x 10-3) C

1+ 1.5 kc x 10 -3
ηrel = relative viscosity = η/ ηo
k = k-value
C= concentration in gm/ml.
From K-value one will know the grade of PVC material
K-Value 60-65 Injection Moulding
65-67 Extrusion Process
67-70 Calendaring Process
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Additives and Compounding

A PVC compound may contain the following ingredients.

- Polymer
- Stabilizers
- Plasticizers
- Polymeric Processing Aids
- Impact Modifiers
- Fillers
- Pigments
Some other miscellaneous materials include flame (fire)
retardants, optical bleaches and blowing agents.

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Stabilizers

- Heating of PVC at temperature above 70°C has a

number of adverse effects on the properties of the
polymers. Sufficient degradation may take place
during standard processing operations (150-200°C)
making the product useless.Therefore to avoid
degradation ‘stabilizers’ are found useful.

- The compounds of Cd, Ba, Ca and Zn are

prominent as PVC stabilizers.

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Plasticizers

Plasticizers are used

- For reducing processing temperature of polymer
below the decomposition temperature.
- To modify the properties of finished products such as
flexibility.
- To modify processability.

All PVC plasticizers have a solubility parameter to that of PVC.

Di-iso-octyl phthalate (DIOP) and di – ethyl
hexylphthalate (DEHP) are most important plasticizers
used in PVC.
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 Extenders
- Sometimes plasticizers are not found useful in PVC
because of their limited compatibility with the polymer.

- When mixed with ‘true plasticizer’ (commercially called

extenders), a reasonable compatibility is acquired.

- Extenders are cheaper than ‘plasticizers’.

- Plasticizers can often be used along with ‘Extenders’
without any adverse effects on the properties of
compound.
Commonly used extenders in PVC are
- Chlorinated paraffin waxes
- Chlorinated liquid paraffin fraction
- Oil extracts
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 Lubricants
- Two types of lubricants are generally used in PVC
- internal lubricants and external lubricants.

- External lubricants prevent sticking of the compound to

the processing equipments by forming a film
between the bulk of the compound and the metal
surface of the processing equipment.

- Internal lubricants improves flow behaviour of the

materials.

- Calcium Stearate, normal Lead Stearate, Dibasic Lead

Stearate, Graphite are employed to improve flow
properties.
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 Fillers
Fillers are commonly employed in order to reduce cost.
They may also be incorporated for technical reasons
such as;
 To increase the hardness of a flooring compound,
 To reduce tackiness of highly plasticized compounds,
 To improve electrical insulation properties
 To improve the hot deformation resistance of cables.

For electrical insulation, china clay is commonly

employed while various carbonates are used for general
purpose work.

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Pigments

To add a pigment, firstly the following facts are to be

considered
- Will it decompose, fade or plate out?
- Will the pigment adversely affect the
functioning of stabilizer and lubricant.
- Will it fade, bleach out or will it bleed.
- Will the pigment adversely affect properties that are
relevant to the end usage (because many pigments
will reduce the volume resistivity of a compound).

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 Polymeric Impact Modifiers & Processing Aids
- Unplasticized PVC has a high melt viscosity leading to
some difficulties in processing. The finished product is also
too brittle for some applications. In order to overcome
these problems ‘impact modifiers’ are generally added.

- Impact modifier are semi-compatible and often somewhat

rubbery in nature.

- Examples for Impact modifier are ABS graft copolymers,

Methacrylate – butadiene - styrene (MBS) terpolymers,
Chlorinated Polyethylene, EVA-PVC graft polymers.

- Chlorinated Polyethylene is being widely used as an

‘impact modifier’ particularly where good aging properties
are required.

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 Formulations

The formulation given below is intended as a

general guide but not for a specific application
(Flexible Pipe).
Suspension polymer ( K- 65) 100
DIOP 40
Trixylyl Phosphate 20
China clay 20
Tribasic lead sulphate 7.0
Stearic Acid 0.5
Pigment 2.0

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 Compounding of PVC
 This is the most important operation in the PVC
processing where the PVC resin is formulated into
a compound with the desired properties with
respect to processing and end product by addition of
selected additives. Adding and mixing additives into
plastics is an integral part of a much broader operation
called compounding in which ingredients including the
colorants are intimately mixed together into a
nearly homogenous mass.

Compounding operation can be classified into following two

Categories;

 Melt blending , where the mix is fluxed or fused.

 Dry blending, where the resultant compound is a dry

relatively free flowing powder containing the liquid
ingredients absorbed on the polymer particles.
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Melt compounding
 In this process a premix is prepared which is then
fluxed.

 The fluxed mixture is made into pallets and fed to

process equipment.

 Simple mixers like ribbon or tumble blenders are used

for the preparation of premix of the ingredients.

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Dry Blending
The dry blending process constitutes the following steps

 Addition of polymer to blender and heating it at a

temperature of 80-105°C.
 The premixed and heated plasticizers are added to
blender through a spray spread over a period of 10-20
minutes.
 The stabilizer, pigments are added.
 Other compounding additives are added and the
mixture is allowed to dry up.
 The lubricants dissolved in the plasticizers are added
and the mixer is agitated thoroughly.
 The mixture is then cooled to below 60°C, screened
and transported to storage.
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 Processing Considerations
 Polymer lacks thermal stability and degradation is rapid
during processing evolving hydrochloric acid. All the
metal surfaces that come in contact with the melt should be
resistant to this acid. Good ventilation of the working area
is also essential.

 Polymer doesn’t absorb water but some plasticizers may do

so.

 uPVC melts are viscous and typical flow path ratio is in the
order of 60 : 1 viscosity of plasticized PVC depends on
plasticizer level.

 Polymer is amorphous in nature so that shrinkage is low.

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 Processing Techniques
Injection Moulding
Typical Injection Moulding Conditions

 Recommended melt temperatures are 180-200 °C for

uPVC and 150-190 °C for PPVC.

 Mould temperature is 20-60 °C.

 Injection pressures are in the range of 100-175 Mpa for

uPVC and 80 – 120 Mpa for PPVC.

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 Extrusion
Typical Extrusion conditions are

 Temperature profile is 150-180°C for uPVC and 140-

175°C for PPVC.

 Recommended screw L/D ratio 14:1 to 17:1 for uPVC

and 17:1 to 20:1 for PPVC.

 Recommended compression ratio is 2:1

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 Blow molding

- UPVC has a much lower average specific heat between

the processing temperature and room temperature than
polyethylene.

- Because of this much less heat is removed on cooling of

mouldings and hence very short cycle times are possible.

- Blow molding is confined to UPVC using general

conditions given under extrusion.

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 Calendaring
 Calendaring is an important process for making UPVC film
or sheet.

 High molecular weight PVC is compounded and partly

agglomerated in an extruder mixer.

 The heated mix is then fed to an L- type calendar mixer.

The hot calendar rolls simply partly consolidate the
granules so that the resulting film or sheet is strong enough
to be drawn over a train of heated drums which are well
above the fluxing temperature of the compound.

 The PVC is therefore subjected to only a very short but

intense heating process. The resulting films with the high
mechanical properties are used for packaging applications.
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 PVC Plastisol and Organosol
 Plastisol and organosol are pastes types obtained when the
voids between particles are completely filled with a plasticiser
so that the polymer particles are suspended in it.

 A typical plastisol includes paste making polymer, plasticizer,

small mount of stabilizer and filler.

 Organosols are distinguished by the presence of volatile

diluent used for reducing the paste viscosity.

 Most PVC pastes are used in the manufacture of leathercloth.

 Coating of objects are also done by pastes.

 Rotational casting , paste injection moulding processes have

been developed forCORPORATE
makingTRAINING
flexible products.
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 Trade names
IPCL, India - Indovin
Reliance, India - Relcair
Mitsubishi gas Ind, Japan - Vinylfoil
Mitsui toatsu chemical, Japan - Vinychol
B.F. Goodrich, US - Vynaloy
Goodyear, US - Vycell
ICI - Vynide
Solvay - Benvic

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 Applications of PVC
Automotive
 PVC is widely used in air filters, boat bumpers, mats,
seat belts, head and arm rests, spark plug covers, seat
covers, transmission covers.

Agriculture
 PVC is used in manufacturing of irrigation pipes and
profiles, pipe fittings, drip irrigation systems, reservoir
liners, horticultural and green house irrigation system,
sprinkler system fittings.

Building
 Floor tiles & covering, fencing, wall coverings, furniture
covers, sofa seats, house sidings, windows, doors, cabinets,
swimming pool liners, carpet backing, heat seal adhesives,
foil coatings.
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 Electrical/ Electronics
 Pipe and profiles, wire extrusions, cable insulation, TV
back, cable fittings, wire sacks, electrical parts, plating
racks, tool handles.

Industrial
 PVC is used in manufacturing of film, fittings, printing
plates, screens, steel strip coatings, profiles, printing
inks, conveyor belting, battery separators, storage tanks,
gloves.

Medical
 PVC is used in medical sector to manufacture of blood
bag, glucose bag, urine bag, syringes, infusion set, tubing,
catheter tubes.
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 Applications of PVC

Vinyl records PVC flexible blood bag

PVC Automobile interiors PVC wire and cable

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Poly Vinylidene Chloride (PVDC)
Introduction
Polymerization
n CH2=Cl2 CH2-Cl2
n
 Vinylidene Copolymers were first commercialized by
R.M. Wiley and J.H.Reily in 1933 and PVDC was
commercialized in 1939.
 Packaging materials with good oxygen and water
vapour barrier properties were made by the films and
coatings of PVDC.

 VDC is prepared by pyrolysis of trichloro ethane at

400°C.
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 Polymerization
- Vinylidene Chloride can be polymerized by bulk,
emulsion and suspension techniques but suspension
technique is very common in industries.

- In suspension process, glass-lined reactor with a water

jacket for temperature control is used.

- In this process, comonomers, water, a methocel

cellulose and free radical initiator ( like Benzoyl
peroxide) are loaded and heated in a sealed reactor.The
polymer precipitates and crystallizes giving a hard,
porous bead.

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 Structure Property Relationship
Cl
(—CH2—C—)n
Cl
 Molecules of PVDC are extremely regular, thus
capable in crystallization.

 Close packing of molecules results in higher

specific gravity, low permeability of vapour and gases.
 Due to presence of chlorine atom, it is self extinguishing.

 Copolymerization with vinyl chloride will reduce

regularity and increase molecular flexibility.
Vinylidene dichloride - vinyl chloride copolymer is
self extinguishing in nature.

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 General Properties
 Mechanical properties of Vinylidene Chloride copolymers
depend on
Co-monomer type.
Degree of crystallinity.
Orientation.
Plasticizer level.

 Semi crystalline copolymers having high tensile modulus

and less elongation at break. Reinforced polymer is having
high impact strength.

 Vinylidene Chloride homopolymer has glass transition

temperature around –12°C. Copolymers have higher Tg.

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 General Properties
 Vinylidene Chloride homopolymer has crystalline melting
point at about 200°C. Copolymers have in the range of 130-
180°C.

 Clear and high gloss.

 Resistant to solvents and chemicals.
 Excellent barrier resistance to oxygen, water vapour
and carbon dioxide.

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 Processing Considerations
 Vinylidene Chloride copolymers are thermally sensitive.

 Overheating during processing evolves HCl.

 Processing of Vinylidene Chloride copolymers require

careful control of the melt temperature and minimum melt
residence time.

 In processing of VDC copolymers, materials feeding is

accomplished by air venting or by gravity feed.

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 Applications of PVDC
- Copolymers may be used in the manufacturing of
extruded pipe and moulded fittings and in chemical plants.
- Copolymers are used in the manufacture of filament
which may be extruded from steam heated extruders with
L/D ratio 10:1 and compression ratio 5:1 into a quench
bath. These filaments are used for deck chair fabrics, car
upholstery, decorative radio grills, dolls hair, filter
brushes.

- Biaxially oriented film is used in packaging for

exceptional clarity, brilliance, toughness, and water and
gas impermeability.

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