Properties and Types of Polymers

Prof. Dr. F.
Nawaz Khan, VIT

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Prof. Dr. F. Nawaz Khan, VIT
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oPolymers are macromolecules with high molecular
weight.
oPerformance, reliability and cost make the polymeric

materials useful for a wide variety of applications.
oThey can operate in a variety of environments without

deforming or degrading.
oThey can be converted into articles having

complicated shapes and reproducible dimensions.
o”
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o
Terminology: mer: a unit
Monomer : one unit (A)

Dimer : two units (A-A)
Trimer : three units (A-A-A)
Tetramer : four units (A-A-A-A)
Polymer : many units (-A-A-A-A-A-A-A-A-A-A-A-)n
o Poly means many and mers means units in Greek.
o Eg. Polyethylene formed by linking large no. of ethylene

monomer units: Heat/Pressure
H 2C CH2 Catalyst ( CH2 CH2 )n
Monomer Polymer
o The no. of repeating units is called the “Degree of
Polymerization”
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o Polymers 1. Natural - Eg. Rubber, Wool etc.,
2. Synthetic - Eg. PE, PVC etc.,

o Classification based on application:
1. Plastics
2. Fibres
3. Elastomers
o Classification based on structure:

1. Homochain polymers
2. Heterochain polymers
o Classification based on mechanism of polymerization:
1. Addition polymerization : Eg. PE, PS etc.,
2. Condensation polymerization : Polyester, Polyamide
3. Co-polymerization giving
copolymers : Eg. Polybutadiene styrene
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o Homochain polymers :
Polymers containing the same species of atoms throughout the
chain are called homochain polymers.
Eg. Polyethylene, Polyvinyl chloride

-C–C–C–C–C-
o Heterochain polymers :
Polymers containing different species in the main chain are

called heterochain polymers.
Eg. Terylene, Nylon 6,6

-C–C–O–C–C–O–C–C-

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1. Homopolymer :
o Polymers containing same type of monomer units repeating
are called homopolymers.
-M–M–M–M–M–
2. Heteropolymer (or) copolymer:
o Polymers containing more than one type of monomer are

called copolymers.
- M1 – M2 – M1 – M2 – M1 –
o Homopolymers are subdivided into:

a) Linear homopolymers
b) Branched homopolymers and
c) Cross linked homopolymers
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-M –M – M – M – M – M – M –
Linear homopolymer
-M – M – M- M – M – M
-M–M–M–M–
Branched homopolymer
-M – M – M- M – M – M
-M–
-M – M – M- M – M – M
-M–
-M – M – M- M – M – M Cross linked homopolymer

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Copolymers are further divided into :
1. Random copolymers : M1 – M2 – M2 – M1 – M1 – M2 –
2. Alternating copolymers : M1 – M2 – M1 – M2 – M1 – M2 –
3. Block copolymers:
- M1 – M1 – M1 – M2 – M2 – M2 – M1 – M1 – M1-
4. Graft copolymers: - M1 – M1 – M1 – M1 – M1 – M1 – M1 –
-M2 – M2 – M2 –
-M2 – M2 – M2 –
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o Tacticity is based on the geometrical arrangement of functional
groups in a polymer.
Three main kinds of arrangements exist:

i) Isotactic
ii) Atactic &
iii) Syndiotactic
i) Isotactic: functional groups are arranged on the same side of
the backbone.
H H H H H
- CH2 – C – CH2 – C – CH2 – C – CH2 – C – CH2 – C -
CH3 CH3 CH3 CH3 CH3
Isotactic polypropylene
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ii) Atactic polymers: Functional groups are arranged randomly
H CH3 CH3 H CH3
CH3 H H CH3 H
iii) Syndiotactic polymers: Functional groups are arranged in alternating fashioni
H CH3 H CH3 H

CH3 H CH3 H CH3
Eg. PP exists as isotactic and syndiotactic forms

PMMA exists as syndiotactic and isotactic forms
PBD exists as syndiotactic and isotactic forms
PP exists as atactic and isotactic forms

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Functionality of a polymer:
o Functionality is defined as the number of reactive sites that the monomer
possesses. H H
Bifunctionality of ethylene: C=C
-C–C-
H H
For a monomer, minimum two reactive sites are necessary to
polymerise. Such monomers are known as bifunctional monomers.
The monomer units are held by covalent bonds while different chains
are held by weak van der Waals forces. This gives possibility of chain
movement.
Bifunctional polymers are usually linear polymers.
o Mixtures of bifunctional and trifunctional polymers are branched

polymers as well as cross linked polymers.
In branched chain and three dimensional network polymers, strong cross-

linking exists between the chains and hence the movement is prevented by the
cross links
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1. Addition polymerization
Eg. PE, PVC, PTFE, PVA etc.
2. Condensation polymerization
Eg. Nylon, Bakelite, urea formaldehyde, melamine
formaldehyde etc.
o Addition polymerization is a process where monomer

units join together by the application of heat, light,
pressure or catalyst.
o Condensation polymerization is a reaction occuring

between simple polar groups containing monomers
with the elimination of small molecules like HCl, H2O
etc. University
i). Addition or Chain polymerisation
• It is a reaction that yields a polymer, which is an exact multiple of the

original monomeric molecule.
• The original monomeric molecule, usually, contains one or more
double bonds.
• In this addition polymerisation there is no elimination of any molecule.
Heat / pressure )
n CH2 = CH2 n - CH2 - CH2 - - CH2 - CH2)-
Catalyst n
Ethylene Bifunctional monomer Polyethylene (PE)
Cl Cl
Cl
Heat / pressure )
n CH2 = CH n - CH2 - CH - CH2 - CH -)
Catalyst n
Vinyl Chloride Bifunctional monomer Polyvinylchloride (PVC)
CN CN
CN
Heat / pressure )
n CH2 = CH n - CH2 - CH - CH2 - CH -)
Catalyst n
Acrylonitrile Bifunctional
Prof. Dr. F.monomer
Nawaz Khan, VIT Polyacrylonitrile (PAN)
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Addition (Chain-Growth) Polymerization:
Typical Addition Polymerization

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3. Types of Polymerization (Chain & Step growth)
Condensation (Step-Growth) Polymerization:
Some of the earliest useful polymeric materials, the Bakelite resins formed from the
condensation of phenol and formaldehyde, are examples of step-growth processes.
In general, step-growth polymers such as polyesters and polyamides possess

more robust mechanical properties, including toughness, stiffness, and higher
temperature resistance, than polymers from addition polymerization processes
such as polyolefins and other vinyl-derived polymers.
Some naturally occurring polymers such as cellulose, starch, wool, and silk are
classified as condensation polymers
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Condensation (Step-Growth) Polymerization:
Typical Condensation Polymerization

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o Plastics are made of polymeric materials by mixing resins, fillers, plasticizers,
pigments, lubricants and catalysts along with them.
o Plastic have different applications because of their unique properties .
o Plastics are classified based on the constituents used and the method of
manufacturing.
Advantages of Plastics:
o Light weight, good thermal and electrical insulation, corrosion resistance, easy
workability and mouldability, adhesiveness, low fabrication cost, decorative
surface effects, chemical inertness, transparency, low maintenance cost, low
softening points, high refractive index, good shock absorption capacity, high
abrasion resistance, dimensional stability, water resistance, good mechanical
strength, toughness, vibration absorption, good finish etc.
o Disadvantages of plastics:
High cost, combustibility, poor ductility, softness, deformation under load,
embrittlement at low temperatures, low heat resistance etc.

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Plastics are classified as
a) thermoplastics & b) thermosetting plastics
Thermoplastics Thermosetting plastics
1. They soften on heating They do not soften on heating;
On prolonged heating they burn
2. They consist of long chain They have three dimensional network
linear polymers joined by strong covalent bonds
3. They are formed by addition They are formed by condensation
polymerization polymerization
4. They can be softened on They can not be softened on heating ;
heating and reused for they crumble on excessive heating
moulding
5. They are soft, weak and less They are hard, strong and more brittle
brittle
6. They can be reclaimed from They can not be reclaimed from
wastes wastes
7. They are usually soluble in They are insoluble in organic solvents
organic solvents since they have strong cross linking
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Important thermoplastic resins:
1. Cellulose derivatives
a) cellulose acetate
b) cellulose nitrate
2. Polyethylene or vinyl resins:
a) polyethylene (LDPE, HDPE)

b) polyvinyl chloride (PVC)
c) polystyrene (PS)
d) polytetrafluoroethylene (PTFE – Teflon)
3. Polyamides:
a) nylon 6,6
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iii) Polyvinyl chloride (PVC):
H Cl
C C
H H n
Preparation & Properties:
It is a colourless, odourless, non inflammable material, - resistant

to light, atmospheric oxygen, inorganic acids and alkalis but
soluble in chlorinated hydrocarbons, - possesses high softening
point (148oC), -high stiffness, - it is brittle.
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Applications of PVC:
Unplasticised PVC (rigid PVC) is used for making - sheets, - tank
linings, light fittings, - safety helmets, - refrigerator components, -
tyres, - cycle and motorcyle mudguards, - tubes etc.
Plasticised PVC is used for making - sheets, - rain-coats, table cloths

and curtains, - insulating covering for electrical appliances, - toys,
Tool handles, - radio components, - chemical containers, - conveyor
Dibutyl phthalate, dioctyl phthalate, tricresyl
belts.
phosphate Prof. Dr. F. Nawaz Khan, VIT
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vi) Teflon (Polytetraflouroethylene – PTFE):
F F
C C
F F
n
Properties of Teflon:
The strong electronegative ‘F’ atom results in very strong attraction between the
different chains results in excellent properties for TEFLON which makes the
material suitable for several applications.
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o Teflon is extreme tough, has high softening point (350oC), has
exceptionally high chemical resistance towards all chemicals, has
high density, has low coefficient of friction, has extremely good
electrical and mechanical properties.
o It can be machined, punched and drilled.
o The only disadvantage is that it cannot be dissolved in any solvent.
o At 350oC, it becomes a viscous liquid and can be moulded into
certain forms by applying high pressure.
Applications of TEFLON:
o As insulating material for motors, transformers, cables, wires and
fittings,
o For making gaskets, packings, pump parts, tank linings, chemical
pipes, tubings and tanks etc.
o For coating glass fibres, asbestos fibre and cloth.
o In non lubricating bearings and non-stick cookware, stop cocks for

burettes etc.
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Acrylonitrile butadiene styrene(ABS)
ABS is a ter-polymer
It is polymerized by the polymerization of acrylonitrile, butadiene

and styrene
It is an amorphous and thermoplastic polymer
Mainly ABS can be prepared in two different grades: 1. for extrusion

and 2. for injection moulding.

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Acrylonitrile butadiene styrene (ABS)
Properties of ABS:
• Cost effective
• Good Impact Strength
• Good Chemical Resistance
• High Gloss Surface Finish
• Good Flexural Properties
• Can prepare in different grades as per the requirement
• musical instruments (recorders, plastic clarinets, and piano movements)

• automotive trim components, automotive bumper bars
• medical devices for blood access
• White-water canoes
• buffer edging for furniture and joinery panels
• luggage and protective carrying cases
• small kitchen appliances
• Keyboard keycaps
• toys, including Lego and Kre-O bricks
• golf club heads (because of its good shock absorbance)
• Household and consumer goods
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b) Themosetting plastics:
i) Phenol-formaldehyde (Bakelite)
ii) Urea formaldehyde (amino resin)
i) Phenol-formaldehyde resin : (Bakelite)
OH OH OH
CH2 CH2 CH2 -Prepared by condensing

Phenol with formaldehyde in
the presence of acid /base
CH2 catalyst
CH2
During moulding, hexa-
methylenetetramine is added
CH2 CH2 CH2 to help in cross-linking and
fusing the polymer into a
OH OH OH
hard cross-linked structure.
Cross-linked polymer - Bakelite
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Bakelite :
Properties:
o Rigid, hard, scratch-resistant, infusible
o Water-resistant, insoluble solid
o Resistant to non-oxidising acids, salts and many organic solvents
o Electrical insulating properties
o Non-suitable to alkalis due soluble nature in alkali
Applications:
o Making electrical insulators like switches, plugs, switch-boards,
heater-handles
o Making moulded articles like telephone parts, cabinets for radio
and TV
o Impregnating fabrics, wood and paper
o As adhesives for grinding wheels
o In paints and varnishes
o As hydrogen-exchanger resins in water softening
o Making bearings used in propeller shafts for paper industry and
rolling mills
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o Plastics are prepared by adding the polymeric resin along with
plasticizer, fillers, lubricants, stabilizers, colouring materials.
o After preparing the plastic, different methods of moulding are

used for conversion into articles:
a) Compression moulding
b) Transfer moulding
c) Injection moulding
d) Extrusion moulding
e) Blow moulding
o The moulding method depends on what type of resin is being used

i.e., thermoplastic or thermosetting plastic.

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Compression moulding
o The process of moulding a material in a confined shape by applying pressure and
usually heat.
o Almost exclusively used for thermoset materials. But can also be used for
thermoplastics
o Used to produce mainly electrical products.
Process:
 The mould is made up of two halves, the upper and the lower halves.
 The lower half usually contains a cavity in the shape of the article to be moulded.
 The upper half has a projection, which fits into the cavity when
 the mould is closed.
 •Pre-weighed plastic material is filled between the two half pieces of the mould.
Heat and pressure are applied as per pre-set parameters.
 the mould is heated to 100-200o C and simultaneously high pressure (100-500 kg/cm2) is
applied on the top of the mould.
o The cavities in the mould get filled with fluidized plastic.
o The mould is closed slowly.
o Finally curing is done either by heating (thermosetting) or by cooling
(thermoplastic).
o After curing, the moulded article is taken out by opening the mould.
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Hand made compression mould for a hand held mirror
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Transfer moulding
o Used for thermosetting plastics.

o First of all all ingredients are preheated in a heated chamber.
o When the moulding powder begins to become plastics the
plastic material is forced to inject through a orifice into the
mould by using a plunger working at a high pressure.
o When the moulding plastics pass through the orifice at high

pressure the temp. rises to a great extent causing liquefaction
of the plastic and it flows quickly into the mould.
o Then heated to the curing temperature required for setting.

o The moulded article is taken out/ejected by mechanical
means.
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o Used for thermoplastics resins.
o The compound plastic resin in the form of powder, granules

or pellets is fed into the horizontal cylinder through the
hopper.
o Temp. is applied to melt the plastic material.
o Then using a piston plunger or a screw arrangement molten

plastic resin is pushed into the mould fitted at the end of
the injection mould through a nozzle, Cooled by cold water
or by cold air circulation or by any other means for curing
o Finally mould is opened to eject the article
o The whole process is done automatically

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Advantages:
o High speed production
o Low mould cost (since fewer cavities needed)
o Very low loss of materials
o Low finishing cost
Disadvantages:
o Too Large no of cavities can not filled simultaneously.
o Article design with large no of difficult profiles is not

suitable for moulding.

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Injection moulding machine

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Extrusion Moulding
o For continuous molding of thermoplastic materials into articles

of uniform cross-section like tubes, rods, strips, insulated
electric cables.
o Heated to plastic is pushed by means of a screw conveyor into

a die having the outer shape of the article to be manufactured.
o Curing takes place automatically by normal atmospheric air or

by an air jets.
o A long conveyor carries away continuously the cooled product.

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Extrusion Moulding

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Extrusion Moulding

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o Polymers, particularly those with a conjugated p-bond structure often
show higher conductivity when doped with conductive materials.
o Conducting polymers (CPs) are extensively conjugated molecules: they have
alternating single and double bonds. In these molecules, electrons are able to
move from one end of the polymer to the other through the extended p-orbital
system.
o But the use of conductive polymers is limited since they have poor
mechanical strength.
o Hence, a combination of mechanical and electrical properties can only

find good applications in conductive polymers area.
o Conductive polymers can be made using simple procedures like melt

blending, solution blending etc.
o Sometimes, in a polymer blend, a bifunctional linker is doped to increase

the conductivity of Polyaniline (PANi)
Prof. Dr. F. andVIT
Nawaz Khan, polycaprolactum (PCL).
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 Optical and electronic applications
 Batteries, displays, plastic wires, optical signal
processing , information storage, solar energy
conversion, etc

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Polymer consisting of alternating single and double bonds
called conjugated double bonds.
In conjugation, the bonds between the carbon atoms are

alternately single and doubled. Every bond contains a localised
“sigma” (σ) bond which forms a strong chemical bond.
In addition, every double bond also contains a less

strongly localised “pi” (π) bond which is weaker.
Conjugation of sigma and pi-electrons over the entire

backbone, forms valence bands and conduction bands.
In these molecules, electrons are able to move from one end

of the polymer to the other through the extended p-orbital
system.
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The conductivity of ICP can be increased by creating positive charges
(oxidation) or by negative charges (reduction) on the polymer
backbone. This technique is called DOPING .
There are two types of doping:
1. Oxidation with halogen (or p-doping).
2. Reduction with alkali metal (called n-doping).

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 It involves treating an intrinsically conducting polymer with a
Lewis acid which leads to oxidation process and positive charges
on the polymer backbone are created.
 Some of the p-dopants are I2, Br2, AsF5, PF5 etc.

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 It involves treating an ICP with a Lewis base
which leads to
 reduction process and negative charges on the
polymer backbone are created.
 Some of the n-dopants are Li, Na, Ca, FeCl3,
naphthylamine etc.

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 Three types of polymers
 Electron conducting polymer- Polyacetylene
First synthesized conducting polymer
 Shirakawa (nober prize 2000)
 Due to the asymmetry of poly acetylene ground state, two
equivalent polyene chains R and L are interconveted through the
intervention of a mobile charge carrier, a soliton. The soliton is a
mobile charge or neutral defect, or a kink in the polyacetylene
chain that propagates down the chain and thus reduces the barrier
of interconversion
 Proton conducting polymer

 Ion conducting

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Factors that affect the conductivity
1-Density of charge carriers.

2- Their mobility.
3-The direction.
4-presence of doping materials (additives
that facilitate the polymer conductivity)
5-Temperature.

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R form
L
L form
Soliton

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+
A-

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Extrinsically Conducting Polymers
These are those polymers whose conductivity is due to the presence of
externally added ingredients in them.
Two types:
(1)Conductive element filled polymer:
It is a resin/polymer filled with carbon black, metallic fibres, metal
oxides etc. Polymer acts as a binder to those elements.
These have good bulk conductivity and are low in cost, light weight,
strong and durable. They can be in different forms, shapes and sizes.
(2) Blended Conducting Polymers:

It is product obtained by blending a conventional polymer with a
conducting polymer either by physical or by chemical change.
Such polymers can be processed and possess better physical, chemical
and mechanical strength.

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Eg. PANi and PCL are blended together and p-hydroxybenzene
sulphonic acid (PHBSA) is used as dopant which serves as a
bifunctional linker and increases the conductivity of the polymer
blend.
o PANi has a conjugated double bond structure, benzenoid amine
and quinoid imine.
quinoid imine.
Structural formula of undoped polyaniline

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PANi exists in three forms:
- Leucoemeraldine (fully reduced or only benzenoid structure)
- Emeraldine (neutral or partially reduced and partially oxidised)
- Pernigraniline structure (fully oxidised or only quinoid imine)
o Out of these, the emeraldine based form of PANi is the only conductive
polymer and also the most stable form.
o PANi is doped with PHBSA in a 1:2 ratio to increase the conductivity of the
polymer blend by two to three fold.
o Doping increases the concentration of the charge carriers and hence the
conductivity of the polymer blend increases.
o When PANi is doped with PHBSA, the polymer blend of PHBSA and PCL, PANi
will attain Bipolaron structure.
o Bipolaron structure of PANi though is less stable, has high energy .
o Hence it will transform itself into Polaron structure which has lower energy
and higher stability.
o The hydrogen bonding between PANi and PCL in the presence of PHBSA
ensures that the blend is conductive.

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H H
NH N N
+ +
n
Bipolaron structure of PANi EB
H H H
NH N N N
+/- +/-
n
Polaron structure of PANi EB

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+ +
NH NH NH PANi
n
Ionic interactions
SO3 SO3
PHBSA
HO Hydrogen HO
bonds
O O
C C C C C C O C C C C C C O PCL
Structure of doped PANi and PCL Blend

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o Polymers are made conductive by adding fillers such as carbon
black, metal coated fibres, metal flakes etc.
- used in high voltage electric cable shielding, electromagnetic
shields, antistatic conductive flooring etc.
o Polymers are converted to their salts to make them conductive.

Eg. Polyacetylene is reacted with iodine to convert to salt which is
conductive.
o Polymers doped with oxidising or reducing chemicals such as

iodine, lithium, potassium, arsenic trifluoride.
- These dopants make the polymer either by addition or removal of

electrons.
- These find applications as electrodes in rechargeable batteries,
contact bridge switches etc.,
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Properties and Types of Polymers

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Properties and Types of Polymers

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Prof. Dr. F.

Nawaz Khan, VIT

oPerformance, reliability and cost make the polymeric

oThey can operate in a variety of environments without

oThey can be converted into articles having

Monomer : one unit (A)

o Poly means many and mers means units in Greek.

o Eg. Polyethylene formed by linking large no. of ethylene

2. Synthetic - Eg. PE, PVC etc.,

o Classification based on structure:

Eg. Polyethylene, Polyvinyl chloride

Polymers containing different species in the main chain are

Eg. Terylene, Nylon 6,6

Prof. Dr. F. Nawaz Khan, VIT

o Polymers containing more than one type of monomer are

o Homopolymers are subdivided into:

-M – M – M- M – M – M Cross linked homopolymer

Three main kinds of arrangements exist:

- CH2 – C – CH2 – C – CH2 – C – CH2 – C – CH2 – C -

CH3 CH3 CH3 CH3 CH3

H CH3 CH3 H CH3

- CH2 – C – CH2 – C – CH2 – C – CH2 – C – CH2 – C -

- CH2 – C – CH2 – C – CH2 – C – CH2 – C – CH2 – C -

Eg. PP exists as isotactic and syndiotactic forms

Prof. Dr. F. Nawaz Khan, VIT

Bifunctional polymers are usually linear polymers.

o Mixtures of bifunctional and trifunctional polymers are branched

In branched chain and three dimensional network polymers, strong cross-

o Addition polymerization is a process where monomer

o Condensation polymerization is a reaction occuring

• It is a reaction that yields a polymer, which is an exact multiple of the

Prof. Dr. F. Nawaz Khan, VIT

In general, step-growth polymers such as polyesters and polyamides possess

Prof. Dr. F. Nawaz Khan, VIT

Prof. Dr. F. Nawaz Khan, VIT

2. Polyethylene or vinyl resins:

a) polyethylene (LDPE, HDPE)

Preparation & Properties:

It is a colourless, odourless, non inflammable material, - resistant

Plasticised PVC is used for making - sheets, - rain-coats, table cloths

o In non lubricating bearings and non-stick cookware, stop cocks for

It is polymerized by the polymerization of acrylonitrile, butadiene

It is an amorphous and thermoplastic polymer

Mainly ABS can be prepared in two different grades: 1. for extrusion

Prof. Dr. F. Nawaz Khan, VIT

• musical instruments (recorders, plastic clarinets, and piano movements)

i) Phenol-formaldehyde resin : (Bakelite)

CH2 CH2 CH2 -Prepared by condensing

o After preparing the plastic, different methods of moulding are

o The moulding method depends on what type of resin is being used

Prof. Dr. F. Nawaz Khan, VIT

o Used for thermosetting plastics.

o When the moulding plastics pass through the orifice at high

o Then heated to the curing temperature required for setting.

o The compound plastic resin in the form of powder, granules

o Temp. is applied to melt the plastic material.

o Then using a piston plunger or a screw arrangement molten

o Finally mould is opened to eject the article

o The whole process is done automatically

o Too Large no of cavities can not filled simultaneously.

o Article design with large no of difficult profiles is not

Prof. Dr. F. Nawaz Khan, VIT