POLYMERS

Module: 1: Polymers [4 Sessions] [Knowledge Level]

Introduction, Types of Polymerizations, Thermoplastics & thermosetting polymers.

Preparation, properties, and applications of the Teflon, PVC, Nylon and Phenol
formaldehyde; Elastomers: classification; Natural rubber, Synthetic rubber and
Inorganic rubbers (Silicone Rubber); Conducting polymers

Self learning Vulcanization of rubber, Synthetic rubber and Inorganic rubbers, Polymer

composites- Properties and advantages, Synthesis and applications of Kevlar

CLASS ROOM TEACHING TOPICS: Introduction, Types of
Polymerizations, Thermoplastics & thermosetting polymers. Preparation,
properties, and applications of the Teflon, PVC, Nylon and Phenol
formaldehyde; Elastomers: classification; Natural rubber, Synthetic rubber and
Inorganic rubbers (Silicone Rubber); Conducting polymers
LIMITATION OF CONVENTIONAL MATERIALS
IN ENGINEERING DESIGNS

 Heavy in weight

 Prone to undergo corrosion

 Less flexible

 Cost effective

 Fabrication requires high temperature

 Extraction process is laborious

 ADVANTAGES OF POLYMERS

Polymers or plastics are having attractive properties such as,

▪ Light weight and high tensile strength
▪ Good shock-absorbing capacity
▪ Good thermal resistance
▪ Chemical inertness and high resistance to corrosion
▪ Low electrical conductivity and good insulation properties
▪ High optical clarity and transparency
▪ Good adhesion property
▪ heat and sound dampening property
▪ good scratch resistance
▪ ability to be made in a variety of colors
▪ Fabricate into any desired shape
▪ biocompatible, suitable for medical and biomedical applications
Old CAR made of CAR using Plastic material
conventional material
POLYMERS ARE EVERYWHERE
DEFINITION
The word POLYMER is derived from Greek

POLY= Many; MER= part or unit

These are macromolecules built by linking

together a large number of small repeat units.

The repeated units are called MONOMERS

 What is polymer?

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3. Polymerization: It is the process in which simple
monomers combine together to form a polymer
having high molecular weight with or without the
elimination of by products such as HCl, H2O, etc

Ethylene Polyethylene
(monomer) (polymer)

Vinyl chloride Polyvinyl chloride

(monomer) (polymer)
4. Degree of polymerization (DP): The number of repeating
units present in a polymer is called degree of polymerization.
Molecular weight of the polymer (M)
Degree of polymerization (n) = ----------------------------------------------------
Molecular weight of monomer or
repeating unit (W)
Example: 5 CH2=CH2→ -CH2-CH2-CH2-CH2-CH2-CH2- CH2-CH2-CH2-CH2-
Here, Degree of polymerization = 5
5. Functionality: The total number of bonding sites or
functional groups present in a monomer molecule is called the
functionality of the monomer.
For example, Methanol (monofunctional, can’t undergo
polymerisation), ethylene (bifunctional), adipic acid
(bifunctional), glycerol (trifunctional), etc.

6. Tacticity: Tacticity (from Greek: τακτικός, romanized:

taktikos, "relating to arrangement or order"). The orientation of
monomeric units in a polymer can take place orderly or
disorderly. This is called tacticity of a polymer. This difference
in the orientation can affect the physical properties of the
polymer
The types of tacticity possible are:
(i) Isotactic Polymers
(ii) Syndiotactic polymers
(iii) Atactic Polymers
Isotactic Polymers: In isotactic macromolecules all the substituents are
located on the same side of the macromolecular backbone.
Syndiotactic polymers: In syndiotactic or syntactic macromolecules the
substituents have alternate positions along the chain.
Atactic polymers: In atactic macromolecules the substituents are placed
randomly along the chain.
 Natural
Synthetic
Based on source Linear
Branched
Based on Structure Cross-linked
Atactic
Isotactic
Based on Tacticity
Syndiotactic
Classification
Thermoplasstic
Based on thermal properties
Thermosetting

Homopolymer
Based on type of monomeric units Heteropolymer
(Copolymer)

Addition
Polymerization
Based on type of polymerization

Condensation
polymerization
 CLASSIFICATION BASED ON SOURCE

▪ i) Natural polymers: These polymers are the

naturally occurring polymers or synthesized
by nature, such as Starch, Cellulose, Nucleic acids,
Proteins, Natural rubber, Silk, Wool etc.,

▪ ii) Synthetic polymers: These polymers are

manmade or synthesized polymers such as
Poly Vinyl Chloride (PVC), Bakelite, Nylon,
Polystyrene etc.,
 CLASSIFICATION BASED ON STRUCTURE

Linear Polymers Branched Polymers

High Density Poly Ethylene (HDPE)

Low Density Poly Ethylene (LDPE)

Cross-linked
Polymers

Eg. Bakelite, Vulcanized

rubber, Resin
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 •High Density Poly Ethylene (HDPE)

•Low Density Poly Ethylene (LDPE)

CROSS LINKED POLYMER: BAKELITE
 CLASSIFICATION BASED ON PROPERTIES

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CLASSIFICATION BASED ON PROPERTIES

i) Thermo Plastics:
Polymers that can be melted and re-molded multiple
times without undergoing significant chemical change.
Eg: Polyethylene; PVC; Teflon; Nylon-6,6; etc.

ii) Thermosetting Plastics:

These are polymers which undergo chemical changes and
cross-linking on heating and become permanently hard, rigid
and infusible on cooling.
Eg: Phenol–formaldehyde (Bakelite), Urea–formaldehyde,
Epoxy resin, etc.
Differentiate between thermoplastics and thermosetting polymers
Thermoplastic Thermosetting polymers

They are mostly formed by addition They are formed by condensation

polymerization polymerisation

They consist of linear long chain polymers They consist of three-dimensional network
with cross linking structure

Polymer chains are held together by weak vander Polymer chains are held by strong
Waals forces covalent bonds

They are soft, weak and less brittle They are hard, strong, and more brittle

These polymer are usually soluble in organic They are usually insoluble in organic
solvent as their intermolecular weaker. solvents as their intermolecular stronger and
they are cross-linked.

They can be remoulded and recycled They cannot be remoulded or recycled

There is no changes in chemical composition and They undergo chemical changes, such as
structure during molding process. further polymerisation and cross-linking
during molding process.

They can be softened on heating and hardened on They get hardened on heating and once
cooling reversibly. hardened they cannot be softened by
reheating

Eg: PVC, polyethylene Eg: bakelite, epoxy resin

CLASSIFICATION BASED ON MONOMERIC UNITS
i) Homopolymer:
If the main chain or backbone of a polymer contains the same type of
monomers, it is called homo polymer.

Eg: Polyethylene, Polyvinyl chloride (PVC).

ii) Copolymer (heteropolymer):

If the polymer main chain contains two or more different monomers it is
called Copolymer.

Eg: Nylon 6,6 (acid and amine monomers),

Terylene (alcohol and acid monomers).
Classification based on polymerisation techniques

Types of Polymerization
Addition (Chain-Growth)
Polymerization

Condensation (Step-Growth)
Polymerization
 Addition and condensation
polymerization

Product of addition polymerization

Addition polymerization

Product of condensation
polymerization

Condensation polymerization

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ADDITION (CHAIN-GROWTH) POLYMERIZATION

This is a kind of polymerization in which the polymer

formed is exactly the multiple of its monomer. It is
usually made up of one or more double bonds which,
by intermolecular rearrangement may make the
molecule bifunctional.
Example

1.
2.

3.
CONDENSATION (STEP-GROWTH) POLYMERIZATION

This is a kind of polymerization in which the polymer

formed by the reaction of simple polar-group containing
molecules with the elimination of small molecules like
H2O, NH3 etc.
SYNTHESIS, PROPERTIES & APPLICATIONS
OF TEFLON
Teflon = Polytetrafluoroethylene, PTFE
Discovered in 1938 by a DuPont chemist
Dr. Roy J. Plunkett
Teflon consists of a chain of carbon atoms
completely surrounded by fluorine atoms. Fluorine
atoms shield the carbon chain due to strong bonds
between them. Vinyl monomer undergoes free-radical
polymerization turning into polytetrafluorethylene.

Polymerisation

Tetrafluoroethylene Teflon
 PROPERTIES OF TEFLON
▪ PTFE is a thermo polymers, which is a white solid at room
temperature.
▪ Tensile Strength: 21-34 MPa (high strength, toughness)
▪ Self-lubrication at low temperatures down to -268.15 °C;
and good flexibility at temperatures above 79 °C.
▪ Inert to virtually all chemicals.
▪ It is hydrophobic and high temperature resistant.
▪ It is a good insulator
▪ Lowest dielectric constant of any known plastic (1.89 - 2.1)
which means it can withstand a very high voltage without
discharging.
▪ Easy to mold and spin cast.
APPLICATIONS OF TEFLON

Teflon used in,

▪ coated cookware and bearings
▪ impregnated clothing
▪ wiring in aerospace and computer applications (e.g.
hookup wire, coaxial cables)
▪ cables, printed circuit boards, microwave frequencies
because of its insulating property
▪ infused oils
▪ tubing, specifically for chemistry applications
▪ bench laminates
▪ plastic substitute when harsh chemicals are involved
 SYNTHESIS, PROPERTIES & APPLICATIONS
OF PVC
Polyvinyl Chloride (PVC) is the third
most widely used thermoplastic polymer
after polyethylene and polypropylene

PVC is prepared from Vinyl Chloride.

SYNTHESIS
PROPERTIES OF PVC
1. It is a linear polymer and thermoplastic in nature.
2. It is a white brittle solid, hard, rigid material which tends to
stick to the metallic surface.
3. It is insoluble in all hydrocarbon solvents.
4. It has a melting point of 212℃ and glass transition
temperature (Tg) is 80℃.
5. PVC is resistant to acids, alkalis, and many chemical solvents
6. It has good mechanical strength and dimensional stability.
7. It is a good electrical insulator
 APPLICATIONS OF PVC
# PVC is widely used in the construction sector for pipes, fittings.
# PVC is used in electrical cables due to its excellent electrical
insulating property.
# PVC finds applications in the automotive industry for cable
insulation, seat covers, dashboard covers, and door panel.
# PVC is used in medical tubing, blood bags
# Toys, footwear, and various household items
# Construction for waterproofing roofs, raincoat and other
structures.
SYNTHESIS, PROPERTIES & APPLICATIONS OF
NYLON 6,6
Nylon 6,6 is one of the Polyamide, which is synthetic
polymer have amide groups in the polymer chain.
SYNTHESIS OF NYLON-6,6

Obtained by the condensation polymerization of

hexamethylene diammine and adipic acid
 Two ingredients are mixed and a solid begins to form
at the junction between the two layers of liquid.

Hot nylon spaghetti can be extracted.

We say certain polymers are man-made, but the truth is they

make themselves. Humans only have to get the ingredients
near each other. The chemicals will assemble themselves.
PROPERTIES OF NYLON 6,6

▪ Light weight, high melting polymers

▪ Possess high temperature stability
▪ Insoluble in common organic solvents
▪ Soluble in formic acid and phenol
▪ Behaves as plastic and fibre
▪ Has good mechanical property
▪ Has high strength, elasticity (flexible), toughness and
abrasion resistance
 APPLICATIONS OF NYLON 6,6

▪ Nylon-6,6 is primarily used as fibres which in turn is

used in making consumer goods like brushes, fishing
lines, and nets.
▪ Nylon-6,6 is used in Mechanical Engg. for gears,
bearings, bushes etc.

▪ Electrical insulation

▪ Ropes, watch straps etc.

▪ Used in the production of consumer goods such as
luggage, sportswear, and household items.
THERMOSETTING POLYMERS

Phenol–Formaldehyde
Resins
Urea–Formaldehyde
Some Important Resin
Commercial Amino Resins
Thermosetting Resins Melamine–
Formaldehyde Resin

Silicone Resins
SYNTHESIS, PROPERTIES & APPLICATIONS OF
BAKELITE (PHENOL–FORMALDEHYDE RESIN)

▪ Was developed by a Belgian Chemist Leo

Hendrick Baekeland in 1907.
▪ One of the first plastics made from synthetic
components
▪ It is a thermosetting phenol formaldehyde resin
BAKELITE
SYNTHESIS OF BAKELITE

▪ It is prepared by condensing phenol with

formaldehyde in presence of acidic/alkaline
catalyst

▪ Initial reaction results in the formation of ortho

and para hydroxymethyl phenol, which reacts to
form NOVOLAC, a linear polymer
 SYNTHESIS OF BAKELITE
▪ During moulding of NOVOLAC,
Hexamethylenetetramine is added [(CH2)6N4]. This
converts the soluble and fusible Novolac to a hard
infusible, insoluble, cross-linked polymer, Bakelite.
Synthesis of Bakelite

, (CH2)6N4
PROPERTIES OF BAKELITE

▪ Hard, rigid, scratch resistant

▪ Resistant to water

▪ Resistant to chemicals except alkalies

▪ Electrical insulator

Uses

• Fuses, switches

• Moulded articles like telephone parts

• Paints and varnishes

• Hydrogen exchanger resins in water softening

• Bearings
Elastomers (Rubbers)

Elastomers are polymers which undergo very long

elongation (500–1000%) when subjected to an external
force, but readily regain their original position when
external force is removed. This property of elastomers is
called elasticity.
Silicone Rubber (Polymethyl siloxane) Inorganic polymer
Alternating Si and O atoms . Si has two methyl groups.

Applications:
1. As a sealing material in searchlights and in aircraft engines.
2. For insulating the electrical wiring in ships.
3. As adhesive in electronic industry.
4. For making boots for use at low temperature.
5. For manufacture of tyres for fighter aircrafts.
6. In making artificial heart valves, transfusion tubings and
padding for plastic surgery.
7. In making insulation for washing machines and electric blankets
for iron board covers.
POLYSILOXANES [POLYSILICONES]
Conducting polymers
Organic polymers having electrical
conductance of the order of conductors
with conjugation (presence of alternative
single bond and double bond) in the polymer
main chain are called conducting polymers.
 CONDUCTING POLYMERS
Organic polymers are normally used in electrical and electronic
applications as insulators.
The Nobel Prize in Chemistry 2000,
Highly delocalized pi-electron system having the
electrical conductance of the order of conductors

Conducting Polymers with Conjugated π-Electrons

1. Poly( p-phenylene)

2. Polythiophene

n
3. Poly( p-phenylene vinylene)

n
4. Polypyrrole

5. Trans-polyacetylene

n
6. Polyaniline

n
CRITERIA FOR CONDUCTING POLYMERS

▪ Polymer should have linear structure.

▪ The molecule (polymer) should also have extensive
conjugation (delocalised π-electron) in the polymer
back bone.

Doping : It can be done by,

Oxidation done by halogens (p-type)

Reduction done by alkali metals (n-type)
APPLICATIONS OF CONDUCTING POLYMERS
SELF-LEARNING
TOPICS
 Natural Rubber (NR)

Hevea trees

Cis-polyisoprene Trans-polyisoprene
Processing of Latex
Processing of Latex

Latex is obtained from rubber tree by making a cut in the bark and
tapping.

Crude rubber is obtained by further processing of the latex by any

one of the following steps:

1. Coagulation: Raw rubber can be coagulated by heating or

addition of dilute acid (acetic or formic acid) solution or
potassium alum. The coagulum is washed with water, dried and
rolled into thick sheets which are dried further in smoke from
burning wood.
2. Direct precipitation: Raw rubber can also be precipitated
directly from the emulsion by mixing with compounding
materials and moulded into required shape.
Processes for Improvement of Properties of Natural Rubber

Natural rubber’s principal uses are automotive tyres, tyre tread

and mechanical goods.
Automotive applications are always compounded with carbon
black to impart UV resistance and to increase mechanical
properties.

Latex concentrate is used for dipped goods, adhesives and latex

thread.

Although NR is satisfactory for many applications, its use is limited

by the fact that it is a natural crop produced only in tropical
countries.
The other drawbacks associated with its use are as follows:

1. It becomes hard and brittle at low temperatures and soft

and sticky at high temperatures.
2. It has high water absorption capacity. (it develops bad
odour on storage).
3. It is non-resistant to organic solvents, non-polar solvents
and oxidizing agents.
4. It exhibits very weak tensile strength.
5. It has poor abrasion resistance.
6. It suffers permanent deformation because of the sliding
of molecular chains over each other.
7. It is sensitive to oxidative degradation.
VULCANIZATION

❖ The process of heating and mixing the crude rubber with

sulphur to a definite temperature for a specific time
❖ The Sulphur combines chemically at the double bonds forming
cross-links between different polymer chains.
❖ Cross-linking brings about stiffness
❖ Rubber tyre contains 3 – 5 % sulphur
❖ Highly vulcanized rubber is called ebonite
Properties of vulcanized rubber:

1. It has good tensile strength and extensibility.

2. It has excellent resilience (getting back to original shape)
3. It possesses low water absorption capacity.
4. It has higher resistance to oxidation and to abrasion, wear
and tear resistance.
5. It is resistant to organic solvents such as petrol, benzene, CCl4
and fats and oils. However, it swells in these liquids.
6. It exhibits good electrical insulation property.
7. It has a wide useful temperature range from -40°C to 100°C.
8. It is very easy to tailor make the properties of vulcanized
rubber for the specific needs.
Synthetic Rubbers
Synthetic rubbers have been developed for a wide range of
applications with specific properties as per the use. The advantages
of synthetic rubbers over natural rubber are discussed as follows:

1. It is produced using monomers derived from

petrochemical raw materials.
2. It is more economical than natural rubber.
3. It is superior to natural rubber in certain properties, such
as tensile strength and abrasion resistance.
4. It can be tailor-made to the end properties and use.
5. Synthetic rubbers have low temperature flexibility and high
temperature stability.
 Butyl Rubber (GR-I Rubber)

Polychloroprene (Neoprene or
GR-M Rubber)

Styrene–Butadiene Rubber
(SBR) (Buna-S or GR-S
Some Commercially Rubber)
Important Synthetic
Rubbers Nitrile Rubber (NBR) (Buna-
N or GR-A Rubber)

Polysulphide Rubber

Silicone Rubber
Butyl Rubber (GR-I Rubber)
Polychloroprene (Neoprene or GR-M Rubber)
Styrene–Butadiene Rubber (SBR) (Buna-S or GR-S Rubber)

Properties:
1. It has high abrasion resistance and load-bearing capacity.
2. It has low oxidation resistance and swells in oil and solvents,
like natural rubber.
3. SBR also vulcanizes to produce cold rubber, which has greater
tensile strength and abrasion resistance.
Applications: SBR is used in motor tyres, shoes soles, footwear
components, insulation of wires and cables, carpet backing, gaskets
and adhesives.
Nitrile Rubber (NBR) (Buna-N or GR-A Rubber)

Properties:
1. It has low swelling and low solubility.
2. It has good tensile strength and abrasion resistance even after
immersion in oil.
3. It also possesses good heat resistance.
Applications: Nitrile rubber is used in fuel tanks, gasoline hoses, as
an adhesive and in the form of latex for impregnating paper, leather
and textiles.
POLYMER COMPOSITES

The combination of two or more distinct material to form a new

class of material suitable for functional applications is called as
composites. Polymer composites consists of fillers or reinforcing
agents and a compatible matrix binder in order to obtain specific
characteristic properties. The reinforcing agents prevents slip and
crack propagation of polymer matrix and enhances mechanical
properties of the composite.
Classification of Composites
1. Matrix constituent: Organic matrix composites (OMCs), Metal
matrix composites (MMCs), Ceramic matrix composites (CMCs)
2. Reinforcement form:
• Fiber reinforced composites
• Laminar composites
• Particulate composites
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PROPERTIES OF POLYMER COMPOSITES

Polymer composite,
▪ is a multi-phase material in which reinforcing fillers are
integrated with a polymer matrix, resulting in synergistic
mechanical properties that cannot be achieved from alone
polymer
▪ are light in weight as compared to traditional building materials
such as concrete, metal, and wood.
▪ have high strength per unit of weight.
▪ are highly resistant to heat, chemicals and never rust or corrode.
▪ are non-conductive in nature.
▪ are elastic in nature and hence have higher yield strength,
fracture strength and fatigue life.
▪ offer greater design flexibility.
APPLICATIONS OF POLYMER COMPOSITES

Due to the above properties of polymer composites they are

used,
▪ in making cars, aircrafts and boats
▪ in car leaf springs and in the limbs of archery bows
▪ in making bridges
▪ for thermal insulation and sound absorption
▪ in electronic equipments
▪ in water and sewage pipelines
▪ for making house holds
▪ bullet proof and other defence materials
 Synthesis and applications of Kevlar

Introduction
Synthesis of Kevlar
Fibers of KEVLAR consist of long molecular chains produced from poly-paraphenylene
terephthalamide. The chains are highly oriented with strong inter chain bonding, which
result in a unique combination of properties.
Applications
While Kevlar is probably best known for being used in body armour, this was not what it
was originally designed for.It was initially intended as a high strength fibre to reinforce
tires. Kevlar can be used for a multitude of applications, which include:
•Racing car fuel tanks
•Off-Road vehicle tires
•Linings for clutch and brake pads
•Cables
•Body Armour