Engineering Chemistry

Unit 1: Specialty Polymers for Engineering

Applications
 What are Polymers

A Polymer (Greek, Poly - many and meros –

parts or units) is a large molecule,
or macromolecule composed of many
repeated subunits (Monomer).
 Classification of polymers
Based on Types

Occurrence a. Natural Polymers b. Synthetic or organic polymers

Structure of a. Linear Polymers b. Branched Polymers c. Cross linked

monomer chains polymers

Stereochemical a. Isotactic b. Syndiotactic Polymers c. Atactic Polymers

orientation

Repeating units a. Homopolymers b. Co-polymers

Synthesis a. Addition Polymers b. Condensation Polymers

Thermal a. Thermoplastic polymers b. Thermosetting or thermoset

Behavior polymers
 Classification of Polymers based on the occurrence
Natural Polymers
They occur naturally and are found in plants and animals.
Ex: Proteins, Starch, Cellulose, Natural rubber,
biopolymers. Semi-synthetic Polymers
They are derived from naturally occurring polymers and
undergo further chemical modification.
• Ex: Cellulose nitrate and cellulose acetate.
Synthetic Polymers
These are human-made polymers. Plastic is the most common
and widely used synthetic polymer. It is used in industries and
various dairy products.
Ex: Nylon, Polythene, Polyvinyl chloride etc.
Based on the structure of the Monomer Chain
Linear Polymers
The structure of polymers containing long and
straight chains
falls into this category.
HDPE,PVC etc.
Branched Polymers
When linear chains of a polymer form branches, then
such polymers are categorised as branched chain
polymers.
LDPE
Cross-linked Polymers
They are composed of bifunctional and trifunctional monomers.
They have a stronger covalent bond in comparison to other
linear polymers.
Bakelite,Melamine Formaldehyde etc.
 Based on stereo chemical orientation
a.Isotactic Polymers: In this type of polymers all
the functional groups are present on the same side of
the chain ie:Ordered orientation.
Ex: Polypropylene
b.Syndiotactic Polymers: If the arrangement of
functional group is in alternating fashion around the main
chain, it is called syndiotactic polymers
Ex:Natural rubber
c.Atactic Polymers: In this type of polymers the
arrangement of the functional groups are at random
around the main chain
Ex: Polystyrene
 Based on synthesis/polymerization
Addition Polymerization:
Polyethylene, Teflon, Polyvinyl
chloride (PVC) etc.
Condensation Polymerization:
Nylon 6,6,Polyesters,Polycarbonates
etc.
Based on repeating units
Homomer: In this type, a single type of monomer unit
is present.
Ex: Polythene, Polypropylene, Polyvinyl chloride etc.
Heteropolymer or co-polymer: In this type,
different types of monomer units.
Ex: Nylon 6,6, Styrene Butadiene Rubber etc.
Based on thermal behaviour of polymers

Thermoplastics polymers: These polymers are flexible,

linear chain molecules which once shaped or formed can
be soften by the application of heat & can be reshaped
repeatedly.
Ex:PE,PVC etc.

Thermosetting polymers: These are rigid & 3D

polymeric network, which once shaped or formed can’t
be soften by the application of heat.
Ex: Bakelite, Thermoset resins, Melamine formaldehyde
resins etc.
 Classification based on thermal behaviour of polymers
Sr. No. Description Thermoplastic polymers Thermosetting polymers

1 Monomer Unsaturation Functional group

2 Reaction Addition Condensation
3 Mechanism Chain growth Step growth

4 Mol. weight Low or medium High

5 Structure Linear or branched (small Highly branched or

branches) crosslinked

6 Solubility Soluble in some organic Insoluble

solvents

7 Action of heat Reversible Irreversible

8 Reshaping Shapes can be changed Once shaped, reshaping is

many times impossible
9 Reclaimed Reclaimed from waste Not possible
10 Examples PE, PP, PVC, PS etc Urea formaldehyde, Melamine
formaldehyde, Bakelite etc.
 Polymerization

 Addition polymerization
 Condensation polymerization
 Reactions of Polymerization

Carothers in 1929 – classified polymers on the basis

of compositional difference
Addition polymerization
Condensation polymerization
 Addition Polymerization
• A polymer formed by direct addition of repeated
units of monomer is called addition polymerisation
• eg – PE, PP, PVC, PS etc.
 Addition Polymerization

 Monomers polyfuctionality - unsaturation

 Polymerization by addition reaction
 Polymers with low or medium molecular weight
formed at once
 Fast
 High yields
 Elemental composition of monomer is retained in
polymer
 Ex:PE,PP,PVC etc.
 Condensation Polymerization

A polymer formed by condensation of two same

or different monomers with the liberation of by-
product is known as condensation polymers
Ex: Nylon 6,6,Polyester,Kevlar etc.
 Condensation Polymerization

 Monomers polyfunctionality - functional group

 Polymerization by condensation reaction
 Elimination of small molecule
 New functional group linkage in polymer
 Name of polymer involves name of new functional
group linkage
 Elemental composition of monomer not retained
in polymer
 Molecular weight increases steadily
 Ex: Nylons, Polyester, Polycarbonate etc.
 Polymerization Mechanism
Classification based on polymerization mechanism
1. Chain polymerization
2. Step polymerization
 Chain Growth Polymerization

Steps of polymerization:
 Chain initiation – Catalyst or initiator to generate
chain initiating species (free radical, cation or
anion)
 Chain Propagation – Accounts for growth
of polymer
 Chain termination – Active polymer chain
get terminated
Free radical chain mechanism
 Molecular weight of polymers
 Molecular weight of a polymer is defined as sum of

the atomic weight of each of the atoms in the

molecules, which is present in the polymer.
 It indicates the average length of the bulk resin's
polymer chains.
 All polymer molecules of a particular grade do not
have exactly same molecular weight.
 There is a range or distribution of molecular
weights.
 Number-average molecular weight (Mn)
• Total mass (M) of all the polymer molecules in a
polymer sample, divided by the total number
of polymer molecules in the sample.
 Weight-average molecular weight (Mw)
Weight-average molecular weight (Mw) is defined as
the total weight (w) of all the molecules in a polymer
sample divided by the weight-fraction of
molecules present.
• The ratio Mw/Mn is called the molar-mass dispersity
index often called Polydispersity (PDI) .
• If all the polymer chains are exactly the same, then
the number average and weight average
molecular weights are exactly the same and the
PDI is 1
 Viscosity average molecular weight
 The average molecular weight is related to the
viscosity of the polymer under specific conditions.
 In the case of solution viscosity, the weight
dependence of the viscosity can be described by the
well-known empirical Mark-Houwink relation;
 [η] = Kmηα
 Where [η] is the intrinsic viscosity, and α, K are the
Mark-Houwink parameters.
 Glass Transition Temperature (Tg)

Tg

Amorphous solid Melting state

• Hard • Soft
• Brittle • Soft flexible state
• Glassy • Rubbery or viscoelastic
state
 Glass Transition Temperature (Tg)

• Tg - Temperature below which polymers exist as

hard and brittle (glassy state) and above
which they exist as soft and elastic
(rubbery state)
• Tm -Temperature above which polymer exist as
molten mass.
 Factors affecting Tg
• Presence of Bulky Side Group slows down C-C bond rotation
(Steric crowding).
• Polystyrene has more Tg than Polyethylene because of bulky
side
group
 Factors affecting Tg
 Nylon-6,6 has hydrogen bonding causing Tg to higher side.

 Addition of plasticizer reduces intermolecular forces and

increase flexibility and hence decreases Tg.
 Polymer has more crystalline (A rgular chain geometry)
leads to tight close packing leading to higher Tg
 Branching reduces spacing among polymer chain by
increasing free volume in polymer chain and decreases
Tg
 Cross linking will make polymer chain tight and hence
Tg
 TECHNIQUES OF POLYMERISATION
1.BULK
POLYMERISATION:-
 Monomer (Liquid State)+ Initiator →
Homogeneous mixture.
 The mixture is constantly agitated (Stirring) & heated to
polymerization temperature
 Once the reaction starts, heating is stopped, since the
reaction is exothermic
 The polymer is usually removed in molten state
otherwise it is difficult to remove the polymer from
reactor
 Viscosity increases dramatically during conversion
ADVANTAGES:-Since only monomer, initiator are taken
in the reactor obtained polymer is pure
 There is no solvent contamination in the product
 It does not require any isolation
 Percent conversion of monomer to polymer is high
 Purity of the product is high
 Method gives high yield of the product
 DISADVANTGES:-
 As polymerization proceeds, viscosity increases rapidly,
and stirring becomes difficult
 Reaction is exothermic
 Adopted to produce PS,PVC,PMMA etc.
 SOLUTION POLYMERISATION
 In this method monomer, initiator are dissolved in solvent to
form homogeneous mixture.
 After the reaction, the polymer used as in the form of solution.

 ADVANTAGES:-The solvent allows for easy stirring as it

decreases the viscosity of reaction mixture.
 Solvent also helps for the removal of polymer from the
reactor.
 The polymer used in solution form, directly for used
as adhesive, coating material.
 Disadvantages:-

 To get the pure polymer evaporation of solvent is

required
 The method becomes costly since it uses costly
solvent
 This technique gives smaller yield

 The purity of the product is also not so high

 Applications:-This method is used to produce

Polyacrylonitrile, Polyacrylic acid, Polyisobutylene,
Polybutadiene etc.
 SUSPENSION POLYMERISATION
 Monomers used as water insoluble.
 Initiators used are monomer soluble.
(Dibenzoyl Peroxide)
 Initiator is dissolved in monomer, then monomer is
dispersed in the form of droplets in water.
 The reaction mixture contains two phases- A liquid
matrix and monomer droplet
 The monomer & initiator are insoluble in the liquid
phase, so they form drops within the liquid matrix
 The polymerization takes place inside the droplet, the
formed product being insoluble in water.
 The product, separated out in the form of spherical
pearls/beads of polymer
 Hence this technique is called pearl/granular/bead
polymerization.
 Advantages:- Isolation of product is easy since the
product is insoluble in water.
 Purity of the product is high.

 The process is more economical; water is used as

solvent.
 Disadvantages:- Applicable only for the water insoluble
monomers, difficult to control the particle size.
 Applications:- Used for the production of
Polyvinylchloride, Polyvinyl acetate, Polystyrene ,
Poly(styrene-divinyl benzene) co-polymer used for the
ion exchange resins.
 EMULSION POLYMERISATION
 The system consists of water insoluble monomer,
dispersion medium water, emulsifying agent/surfactant
(Soaps/detergents), water soluble initiator (Potassium
per sulphate/H2O2.
 To bring the monomer & initiator into close proximity
and to initiate polymerisation, surface active agents
(surfactant) are added & the mixture is continuously
stirred.
 The emulsion of monomer is stabilised by a surfactant

 A surfactant has a hydrophilic & hydrophobic end

in its structure.
 When it put into a water, the surfactant molecule gathers
in to aggregates called micelles.
 The hydrocarbon tails (hydrophobic) orients inwards
& heads (hydrophilic) orient outward into water.
 The monomer molecule diffuse from monomer droplet to
water & from water to the hydrocarbon center of
micelles.
 Advantages:- High molecular weight polymer is
obtained, there is continuous supply of monomers,
viscosity build up is less.
 Disadvantages:- This method requires rapid stirring,
difficult to remove the emulsifier.
 Applications:- It is used in the preparation of water-
based paints, adhesives.
 Used in the preparation of SBR,
Polychloroprene(Neoprene) etc.
 Solution Suspension Emulsion
Feature Bulk Polymerisation
Polymerisation Polymerisation Polymerisation

Monomer droplets in
Monomer droplets in
Medium Pure monomer Monomer + solvent water (with emulsifier +
water (with stabiliser)
initiator in water)

Low (solvent lowers Low (dispersed

Viscosity High (processing difficult) Low (discrete droplets)
viscosity) micelles)

Easier (but chain

Molecular Weight
Difficult transfer to solvent Easier Very good
Control
possible)

Very high (no solvent, no Lower (needs solvent High (polymer beads Lower (emulsifier
Purity of Polymer
additives) removal) contain few residues remain)
impurities)
Polymer Requires solvent Polymer beads filtered Requires coagulation &
Direct (no separation step)
Recovery removal or precipitation & dried drying

Excellent heat control,

Good heat control, low Easy heat control,
Simple, pure product, low high polymerisation
Advantages viscosity, directly produces bead polymer,
cost rate, fine particle
usable solution easy handling
dispersion

Heat control issues, Surfactant

Expensive solvent Stabiliser contamination
Disadvantages autoacceleration contamination,
recovery, lower purity possible
(Trommsdorff effect) separation needed

Polystyrene, PMMA, Coatings, adhesives, PVC, styrene polymers, Synthetic rubbers,

Applications
engineering plastics PAN, PVAc ion-exchange resins paints, latex products
 Epoxy Resins
 These polymers are given epoxy name
because the monomer & polymer
(before cross linking ) contains epoxide
groups.
 The epoxy polymer is obtained by
condensation reaction between an epoxide
group & phenolic –OH group
 Epoxy resins are prepared by epichlorohydrin
& bis phenol A (Di-phenylol propane)
 Epichorohydrin is prepared by chlorination
of propene
 CH H2 O
H C
3 OH+ Cl C C
CH2
O CH H
Bisphenol
3
Epichlorohydrine(Excess)
A

O CH H2 H H2 H2 O
H2
H2 C C C
3 O C C C C C CH2
C O n H
O CH
H 3
OH
Epoxy
resins
 Properties
 Due to stable ether linkage-high resistance
to water
 Due to polarity in molecules-Shows excellent
adhesive property
 Resistant to heat & chemicals
Applications
 Used in surface coating material,in
lamination, skid resistant material,
Electrical equipments etc.
 Synthesis
• It is synthesized from acrylonitrile,
butadiene
and styrene.
Acrylonitrile-
• The scheme is as follows:
Butadiene-
Styrene
Application
 Safety helmets
 Pipes
 Telephone bodies
 Furniture
 Car components

• High impact strength

• Good chemical resistance
 Synthesis
• It is synthesized by the polymerisation
Polypropylene propylene using of famous Ziegler-Natta
catalysts. the
Application • The monomer, propylene is obtained
 Carpets,mats as a
 Pipes byproduct from gasoline refineries.
 Ropes
 packaging, and storage
boxes.
 Bottles

• High impact strength

• Good chemical resistance
 SPECIALITY OF POLYMERS
CONDUCTING POLYMERS
 Bad conductor of electricity—No free electrons
 Intrinsically Conducting Polymers ICP –
Conjugated pi-electron system
 Electric field Applied-Pi-electrons delocalized,
get excited
 Electron transported through the resonance
 Increase in conjugation – Increases the
conductivity in large extent
 e.g. Polyacetylene, Polyaniline, Polypyrrole,
Polythiophene, Poly(3,4-ehtylenedioxythiophene)
etc.
Structural requirements –
Conjugation
Hetero atom containing Lone pair of electrons
Planarity
 DOPING
 Intrinsically Conducting Polymers (ICP)
Conductivity can be improved by creating positive
or negative charge on the polymer chain by
oxidation or reduction this technique is called
DOPING.
 P-Doping:- It includes doping of ICP with a
Lewis acid - Electron pair acceptor - (I2, Br2,
PF6, FeCl3)
 Oxidation — Removal of electrons —
Positive charge will develop.
 N-Doping
 It includes doping of ICP with a Lewis base –
Electron pair donor (Li, Na, Naphthyl amine)
 Reduction - Addition of electrons —Negative
charge will develop
 Application:-
 In rechargeable light weight batteries
 In electronic devices such as transistors,
photodiodes, LED, sensors, actuators etc.
 LIQUID CRYSTAL POLYMERS-LCP

 Solid- Mesomorphic or Liquid crystal phase

– Liquid.
 A polymer that under suitable conditions of
temperature, pressure & concentrations, exist
as liquid crystals.
 LCP are of two types;
 Thermotropic LCPs:- Obtained by increase in
temperature/heating.
 Lyotropic LCPs:- Obtained by dissolving a
polymer in solvents.
 There are three forms of Liquid
Crystals Structures;
 i) Smectic State:- Arranged in parallel
and lateral order
 ii) Nematic State:- Arranged as parallel but
not in lateral order
 iii) Cholesteric State:- Oriented parallel to
one another but the direction vary from one
layer to another layer
 Properties:
 Good thermal stability
 Electrical properties at high temperature
 High resistance to chemicals etc.

 Applications:-
 In electronic & electrical equipment's ,
switches, fiber optic cables, In data storage
discs etc.
 Televisions, computer monitors, laptops,
smartphones, digital cameras, portable gaming
devices, e-readers etc.
 LCP-KEVLAR
 Kevlar is an aromatic polyamide (Aramid)
chemical composition of Kevlar is poly-para
phenylene terephthalamide (PPTA)
 It is prepared by terephthalic acid dichloride &
P- Phenylene di-amine

 Properties:- High strength, thermally

stable
 Applications:-Air craft body, high
performance race cars, vehicle tyres etc.
 Bio based-BIODEGRADABLE POLYMERS
 Biodegradation of polymers is a process
carried out by biological systems (usually
bacteria or fungi) wherein a polymer chain is
cleaved via enzymatic activity
 Various factors are responsible for
biodegradation of polymers like;
Microorganisms, environment, nature of
polymer.
 Structural requirement for biodegradable
polymers tend to consist of ester, amide, or
ether bonds.
 Biopol
Poly( hydroxybutyrate, hydroxyvalarate ) PHBV
 PHBV stands for Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
 It is a copolymer
 PHBV undergoes bacterial degradation in the environment

 Polyhydroxybutyrate (PHB)-
 PHB is produced by the fermentation of glucose by the bacteria
Alcaligenes eutrophus

 Polyhydroxyvalarate (PHV)-
 PHV can be prepared by glucose with Alcaligenes eutrophus or
Pseudomonas oleovorans
 Features of biodegradable
polymer
 Naturally occurring polymers are biodegradable

 Synthetic addition polymers with only C atom

chain are not biodegradable

 Synthetic polycondensation polymers are

generally biodegradable

 Amorphous nature of polymer accelerate

degradation

 Lower molecular weight polymers undergo

biodegradation easily

 Applications:
Hydrophilic polymers degrade faster than
 As packaging
hydrophobic material, Medical field, Agriculture etc.
polymer
 Limitations of
biodegradable polymer
They can not be manufactured on large scale

They are costly

They do not possess required high mechanical

strength

They have low shelf life

Chemical structures of PHB, PHV and their copolymer PHBV
ELECTROLUMINESCENT POLYMERS
 Electrolumincent Polymers
• EL is in which a material emits light in
response to the passage of an electric
current or strong electric field.
• EL was first reported by using
poly(phenylene vinylene) PPV
• In PPV the electrical conductivity increases by
doping with iodine,ferric chloride,alkali
metals
• PPV is water insoluble.It gives bright
yellow- green fluorescence on application of
electric field.
 PROPERTIES OF PPV
Diamagnetic material

Low intrinsic electrical conductivity

Water insoluble

Gives yellow-green fluorescence

• Applications:
• It is used as light emitting diode(LED),Organic light
emitting diode (OLED) Solar cells etc.
Smart Polymers
 Smart Polymers
• The smart polymers are of two categories:

• Active polymers that respond to input stimuli such

as pH, magnetic field and light. Eg. PAC
(Polyanionic cellulose)
• Electro-active polymers that respond to the
change of electrical input
 Example Smart Polymers
• Azobenzene
hν, 300-400 nm

> 400 nm

• Response to light due to azobenzene groups, contain

N=N double bonds.
• Trans form Cis Form
• Thermally relax to the stable Trans form
• Photoisomerization