CO-4: Polymers & Plastics

Department of Chemistry
​ oneru Lakshmaiah Education Foundation (KLEF)
K
 What are Polymers?
The term polymer refers to chemical compounds consisting of
large molecules/macromolecules which are constructed from
repeating subunits that are linked by numerous intertwined
links.
There are two types of polymers.
Natural Polymers: Wool, cotton, DNA, proteins.
Synthetic polymers : Teflon, Polyethylene, Nylon, polyester.
 What are Monomers?
Monomers: The individual small and simple molecules from
which the polymer is formed. They are joined together by
chemical bonds.

Examples: Vinyl chloride, ethylene, propylene etc.

 Polymerization

Polymerization is a process of reacting monomer molecules

together in a chemical reaction to form polymer chains or
three-dimensional networks.
 Degree of polymerization (DP)

Degree of polymerization is 5

Classification based on DP

Oligo polymers: they have a low degree of polymerization, with

mol. wt. ranging from 500-5000.

High polymers: they have a high degree of polymerization, with

mol. wt. ranging from 10,000-20,000.
 Basics of polymers

Polymers: Complex and giant molecules, made from joining

many small and simple molecules by primary valency linkage.
Monomers: The individual small and simple molecules from
which the polymer is formed.
Polymerization: The process by which monomer molecules are
linked to form a big polymer molecule
Functionality: The no. of bonding sites or active sites in a
monomer.
Degree of polymerization: Number of monomeric units forming
the polymer chain.
Tacticity: spatial arrangement of pendant groups of successive
stereocenters (asymmetric carbon) in the main chain.
 Classification of polymer
Polymers can be classified into various types depending on their category.

Based on origin:
Natural & synthetic polymers.

Based on constituent groups:

Organic & inorganic polymers.

Based on applications:
Plastics, elastomers, fibres, liquids, & resins.
Based on mechanism of formation:
Addition polymers/condensation/chain-growth/step-growth
polymers.
 Types of polymers-based on monomer units

Examples: polyethylene, polystyrene,

polyacrylamide, etc
Ex.; poly(vinyl chloride-co-vinyl acetate).
 Tacticity
 Tacticity refers to the orientation or arrangement of functional
groups in a polymer with respect to the main chain.

FG arranged on
the same side of a
FG arranged on
polymer chain
the randomly of
a polymer chain

FG arranged in alternative
manner of a polymer chain
 Types of polymers-based on tacticity
Isotactic polymer: all functional groups are on the same side of
the polymer chain.

Alternating/Syndiotactic polymer: all functional groups are

arranged alternatively on either side of the polymer chain in a
regular fashion.

Random or Atactic polymer: all functional groups are arranged

randomly on both sides of the polymer chain.
 Types of polymers-based on applications

• A polymer that can be reshaped into hard and tough utility

articles by applying heat, pressure or both is said to be a
plastic. Ex: Polystyrene, Poly(vinyl chloride), Poly(methyl
methacrylate), polyester etc.
• A polymer that shows good strength and elongation upon
chemical treatment is called an elastomer. Ex: Polyisoprene,
polyisobutylene, etc.
• A polymer that can be drawn into a long filament-like
material, whose length is at least 100 times its diameter is
called a fibre. Ex: Nylon, terylene, polyester, polyacrylonitrile,
etc.
• A polymer used as adhesives, potting compounds, sealants
etc., in a liquid form is called as liquid resin. Ex: Epoxy
adhesives, poly sulfides, sealants, etc.
Classification of polymers-based on chain configurations

E.g., High density polyethylene, PVC. E.g., Low density polyethylene.

E.g., a rubber band is a collection of flexible E.g., Bakelite, melamine etc.,

polymer chains cross-linked with sulfur, it is
a single molecule, vulcanized rubber, urea-
formaldehyde resins.
 Classification of polymers-based on the method of
synthesis
Addition Polymers
Condensation Polymers
Classification of polymers-based on molecular forces
Classification of polymers-based on molecular forces
Thermoplastic polymers
 Linear polymers with long chains that soften
on heating and harden on cooling reversibly.
 These are solid at room temperatures and
viscous liquids when heated. So, they are
shaped by extrusion, molding or pressing.
 They can be recycled and reused several
times by heating and cooling.
 These plastics will return to its original
shape, unless damaged due to overheating
or overstretching; this property is called
plastic memory. E.g., polystyrene,
polyethylene, PVC, PTFE.
 Applications: Milk jugs, soft drink bottles, etc.
Classification of polymers-based on molecular forces
Thermoplastic polymers
 They are synthesized by addition polymerization
 They are straight chain or slightly branched No links b/w polymers
chains helps movement
polymers, held together by weak van der Waal’s
forces of attraction.
 Molecules of thermoplastics are linear, or long
chains with very few entanglements.
 So, when heat is applied, molecules move apart
and disentangle, causing them to soften, making Monomers
them malleable to reshaping.
 On cooling, the molecules regain their original
positions, making the plastic stiff and hard again.
This process of heating and cooling can be
repeated several times.
 They are generally soluble in organic solvents.
Classification of polymers-based on molecular forces
Thermosetting polymers
 Thermosetting polymer or resins, also called Links b/w polymers
thermoset, is a polymer that is irreversibly chains stops
hardened by curing from a soft solid or viscous movement b/w them
liquid prepolymer or resin
 Various polymer chains are cross-linked three
dimensionally using strong covalent bonds or
cross links.
 They are prepared by condensation Monomers
polymerization.
 They resist heat softening and solvent attack.
 Once set after curing, they cannot be softened
and recycled. E.g., polyester resins like fiber
glass; polyurethanes: mattresses, coatings,
adhesives; vulcanized rubber; bakelite: phenol-
formaldehyde resin.
Classification of polymers-based on molecular forces
Classification of polymers-based on molecular forces
Classification of polymers-based on molecular forces
Elastomers
o Elastomer is a polymer with viscoelasticity (i.e., both
viscosity and elasticity) and weak intermolecular forces and
low Young’s modulus.
o Elastomers can be stretched to at least thrice its length but
returns to its original shape and dimensions when the
stretching force is released.
o They exist in the form of a coil in the normal state, and hence
can be stretched like a spring.
o The elasticity is caused by lengthening and shortening of their
polymeric chain springs. E.g., rubber, latex
 Addition Polymerization- Mechanism

1. Chain initiation:-
a) Formation of free radicals from the initiator.

b) Addition of free radicals to monomer to form a free radical intermediate.

 Addition Polymerization- Mechanism

2. Chain propagation:-
Here addition of monomer molecules to the intermediate takes place one by one
leads to the formation of macro-radicals.

3. Chain termination:-
The growing polymer chain is terminated by many ways.
a) Recombination:-
Combination of two free radicals leads to termination.
 Addition Polymerization- Mechanism

b) Disproportionation:-
Transfer of ‘H’ atom from one radical to another leads to formation of two macro
molecules, one of them with a double bond.

Cationic polymerization:-
Anionic polymerization:-
Monomers with electron releasing groups (-
Monomers with electron withdrawing
OCH3, -OC2H5 & -C6H5 etc) undergo cationic
groups (-CN, CH3COO- and C6H5 etc)
polymerization in the presence of Lewis acids
undergo anionic polymerization in presence
like AlCl3, BF3, SnCl4 etc. Cationic
of sodium or potassium amide.
polymerization takes place with higher rates
even at low temperature.
 Classification of polymers-based on the method of
synthesis
Condensation or step-growth polymerization

Polymerization occurs stepwise by reaction between reactive

functional groups, followed by elimination of small molecules
such as water, ammonia, HCl, etc.
Diacid + Diamine Polyamide
 Classification of polymers-based on the method of
synthesis
Chain growth polymers

Successive addition of monomeric units to the growing chain.

 Individual polymers
Preparation of Poly vinyl chloride

Polyvinyl chloride is prepared by heating a water emulsion of

vinyl chloride in presence of benzyl peroxide or hydrogen
peroxide in autoclave under pressure.
 Properties
Polyvinyl chloride is
Colourless
Odourless
Non-inflammable
Chemically inert
Soluble in hot ethyl chloride
Uses
Used for the preparation of
Safety helmets

Light fittings
Tyres, cycles
Refrigerator components

Sheets, which are employed for tank

linings
 Phenol formaldehyde resins :Bakelite
Preparation
These are formed by the poly condensation between phenol and
formaldehyde.
The reaction is catalysed by acid or base
 Steps in synthesis of Bakelite
I. Methylolation
• In this step, mono, di and tri methylol phenols are
synthesized from phenol and formaldehyde

II: Formation of novolac resins

• Monomethylol phenols condense together to form novolac
resins as shown below
 Steps in synthesis of Bakelite
III: Formation of bakelite
• Novolac is heated further in the presence of HCHO
producer, i.e., hexamethylene tetraamine (curing agent) at
high temperature and pressure to form cross-linked
polymers, bakelite.
 Properties of Bakelite
These are
Rigid
Hard , resistant to heat
With stand to high temperature
Good insulator
Uses of bakelite
Used for the preparation of
Electrical insulator parts like

Switches
 Plugs

Handles

Moulded articles like

Telephone parts

Cabinets for T.V

Cabinets for radio

 Polyethylene
Preparation of LDPE
LDPE is prepared by heating ethylene at 1000C-3000C under high
pressure 1500-3000 atm in presence of benzoyl peroxide(initiator)
and benzene(solvent).

Ethylene Polyethylene
 Properties
 Density range from 918-935 kg/m3
 Very tough
 Flexible

Uses

Domestic ware
Squeeze bottles

Tubing

Cold water tanks

 Preparation of HDPE
HDPE is prepared by heating ethylene at 3000C under 1 atm
pressure in presence of aluminum based oxide(catalyst) and
paraffin (diluting agent).

Properties
 Density range from 935-965 kg/m3
 Stronger
 Stiffer
Uses
⌛ Dustbins
⌛ Bottle crates

⌛ Pipes

⌛ Fluid containers
 Teflon (poly tetra flouro ethylene ,PTFE) or Fluon

Preparation

Poly tetra flouro ethylene is prepared by polymerisation of

a water emulsion of tetra flouro ethylene in presence of
benzoyl peroxide under pressure.
 Properties

1. Due to presence of highly electro negative fluorine atom,

very strong attractive forces between different chains.
2. Due to strong attractive forces

Teflon is extreme tough

High softening point ( >3500 )
High chemical resistance towards all chemicals
Except hot alkali metal and hot fluorine
 Uses:
Used as

Insulating material for motors, cables

Coatings
 Impregnating glass
Asbestos fibre

Clothes

Wires

Fittings
 Poly Carbonates
Polymers of containing –o-co-o- functionality
Preparation
By the treatment of bisphenol-A with phosgene in presence of
sodium hydroxide.
 Properties
Polycarbonates
• Good electrical insulators
• Heat and flame resistance
• Easily soluble in organic solvents and alkali
solvents
• Undergo large plastic deformation without
cracking
• Highly transparent to visible light
• Low scratch resistance
 Uses
Used in

Preparation of Compact disc, DVD’S

Construction industry

Automotive components
  Manufacture of lenses like
sunglasses, eyeglasses

 Aircraft components
 Conducting Polymers

o A conducting polymer is an organic based polymer that can

act as a semiconductor or a conductor.
o The most widely studied organic polymers are

 Polyacetylene
 Polyaniline (PANI)
 Polypyrroles
 Polythiophenes
 Polyphenylene vinylenes
 Conducting Polymers
o Conducting polymers (CPs) are extensively conjugated
molecules: they have alternating single and double bonds. In
these molecules, electrons can move from one end of the
polymer to the other through the extended p-orbital system.
o Hence CPs are known to be either semiconductors or
conductors giving themunique optical and electrical
properties.
o Most polymers are poor conductors due to non-availability of
large number offree electrons in the conduction process.
o However, conducting polymers possess electrical
conductivity like metalconductors
Different types
 Intrinsically conducting polymers (ICP)
 Doped conducting polymers
 Extrinsically conducting polymers (ECP
 Conducting Polymers

 Density of charge carriers

 Their mobility
 The direction
 Presence of doping materials
 Temperature
 Intrinsically Conducting Polymers (ICPs)
 Alternating single and double bonds is called conjugated double
bonds.
 In conjugation, the bonds between the carbon atoms are
alternately single and double. Every bond contains a localized
“sigma” (σ) bond which forms a strong chemical bond.
 In addition, every double bond also contains a less strongly
localized “pi” (π) bond which is weaker.
 Conjugation of sigma and pi-electrons over the entire backbone,
forms valence bands and conduction bands. Eg: Poly-acetylene
polymers like poly-p-phenylene, polyaniline, polypyrrole.
 Doped Conducting Polymers
 It is obtained by exposing a polymer to a charge transfer
agent in either gas phase or in solution.
 ICPs possess low conductivity (10-10/Ohm.cm), low
ionization potential and high electron affinity.
 So, they can be easily oxidized or reduced.
Doping
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 .
The polymer structure is disturbed - either by removing electrons
from (oxidation) or inserting them into (reduction) the material.
Types of materials
❑ Oxidation with halogen (or p-doping).
❑ Reduction with alkali metal (called n-doping)
 Intrinsically Conducting Polymers (ICPs)
 It involves treating an intrinsically conducting polymer with a
Lewis acid which leads to oxidation process and positive
charges on the polymer backbone
 Some of the p-dopants are I2,Br2,AsF5,PF5 etc.

N-doping
 It involves treating an ICP with a Lewis base which leads to
reduction and negative charges on the polymer backbone.
 Some of the n-dopants are Li, Na, Ca, FeCl3, naphthylamine
etc.
 Extrinsically Conducting Polymers (ICPs)
 These are those polymers whose conductivity is due to the
presence of externally added ingredients in them.
(1) Conductive element filled polymer:
 It is a resin/polymer filled with carbon black, metallic fibers,
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 element filled polymer:

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.
 Applications of conducting polymers

 As sensors into clothing

 Conducting polymer textiles as a camouflage for defense
machinery. Since the textiles have no sharp edges, they
absorb more than 50%of the incident microwave
radiation.
 In LEDs
 In controlled drug release applications etc.
 Applications of conducting polymers

Group 2
Group 1 Molecular electronics
Electrical displays
Electrostatic materials Chemical & thermal sensors
Conducting adhesives Rechargeable batteries
Drug release systems
Artificial nerves Optical computers
Antistatic clothing Ion exchange membranes
Piezoceramics Electromechanical actuators
Active electronics:
The first group utilizes their conductivity as its main property.
The second group utilizes their electroactivity.
 Conducting Polymers
•Polymers that can conduct electricity are called conducting polymers.
Ex: Poly acetylene, poly aniline, poly pyrrole, poly thiophene, poly quinolene
etc.
On the basis of their conduction properties conducting polymers are classified into
two types
 Conducting Polymers
Intrinsically Conducting Polymers
Conjugation
•These polymers contain conjugated or delocalized  - e- pairs in the back
bone responsible for conduction.
•The orbital’s of conjugated  - e- form valency band as well as conduction
band and they are extended over the entire polymer molecule.
•When current is passed electrons enter conduction band due to shifting of
 - e-.
•Ex; Conduction of poly acetylene due to conjugation.
•When current is passed into poly acetylene, the electron enters the
unhybridised P-orbital of carbon atom and moves through the C – C bonds.
 Conducting Polymers

Doped conducting polymers

•Polymers can conduct due to doping and by using doping agents or dopants.
•Doping of conducting polymers can be two different types.
 p-Doping (or) Oxidative Doping
 n-Doping (or) Reductive Doping
 Conducting Polymers

P-Doping (or) Oxidative Doping:

•In this method the polymer is treated with an oxidizing agent like Lewis acid
which acts as a dopant.
•Examples of dopants used: FeCl3, I2 etc.

Mechanism of P-Doping:
•During this process, oxidation of polymer takes place due to dopant and forms a
cation called Polaron.
•On further oxidation of polymer results in the formation of a dication or
bipolaron.
 Conducting Polymers
•The charges get separated by forming a soliton pair.
•The cation occupies the band gap between valency band and conduction band,
thereby creating a conducting path.
• So electrons move through this path.
 Conducting Polymers
n-Doping (or) Reductive Doping:
• In this method, the polymer is treated with a reducing agent like a Lewis
base which acts as a dopant.
• Ex; Sodium Naphthalide Na+ (C10H8)-

Mechanism of n-Doping:
•During this process, reduction of polymer takes place due to dopant and forms an
anion called Polaron.
•On further reduction of polymer results in the formation of a dianion or
bipolaron.
 Conducting Polymers
•The charges get separated to form a soliton pair.
•The anions occupy the band gap between valency band and conduction band
thereby creating a conducting path.
• So that electrons move through this path.
 Conducting Polymers
Extrinsically Conducting Polymers
•Some of the polymers conduct electricity due to externally added ingredients to them.
•They are of two types.
• Polymers with conductive elements filled
• Blended conducting polymers

Polymers with conductive elements filled

•In these polymers, the polymer acts as a ‘binder’ and holds the conducting element
added so that the polymer becomes a conductor.
•Examples of conductive elements are carbon black, metallic fibers, metallic oxides etc.
•Minimum concentration of conductive element to be added so that the polymer
becomes a conductor is called percolation threshold.
•The conductive elements added to create a conducting path in the polymer.
 Conducting Polymers
Blended conducting polymers
•These polymers are obtained by blending a conventional polymer with a
conducting polymer.
•The polymer thus obtained has good chemical, physical, electrical properties
and mechanical strength.
Ex; 40% pyrrole when blended with a conventional polymer, the combination
gives conducting polymer with good impact strength.
 What is nano?

The prefix ‘nano’ is derived from the Greek word for dwarf. One
nanometre (nm) is equal to one-billionth of a metre, 10–9m

Nano can refer to technologies, materials, particles, objects – we

are focusing on nanomaterials as these are already being used in
workplaces more widely

A sheet of paper is about 100,000 nm thick, a human hair is around

80,000 nanometers wide, a red blood cell approximately 7000nm
wide
 At the nanometer scale, materials may behave
differently.
 We can harness this new behavior to make new
technologies.
 How Big is a Nanometer?
To cover a football field with a 1nm thick layer of paint, you
would need just 1 teaspoon of paint!
 Did Scientists “Create” Nano?

• No, it was already in nature!

centimeters to micrometers
micrometers
1) Wing and wing scale
2) Wing scale
3) Scale ridge, ridge microrib, chitin fibrils and
nanometers
molecules
An Interdisciplinary Endeavor

Chemistry Biology Physics Engineering

Nanoscience
& Nanotechnology

Medicine Materials Science

Biotechnology Information Technology

 Actual physical dimensions relevant to
Nanosystem

Nanoscience

0.1nm 1nm 10nm 100nm 1m 10 m

Size and shape dependent

properties

Nanometer scale : The length scale where corresponding

property is size & shape dependent.
Types of nanomater-
ials
Classes of nanomaterials
 Why are nanomaterials used?
• At nano-scale,
• The material properties change -
melting point, fluorescence, electrical
conductivity, and chemical reactivity
• Surface size is larger so a greater
amount of the material comes into
contact with surrounding materials and
increases reactivity
• Nanomaterial properties can be ‘tuned’ by
varying the size of the particle (e.g.
changing the fluorescence colour so a
particle can be identified)
• Their complexity offers a variety of
functions to products
 Introduction to Carbon Materials

Diamond Graphite Amorphous Carbon

Fullerene SWCNT MWCNT Graphene

 The advantages of carbon materials include low cost, wide potential window and
electrocatalytic activity for a variety of redox reactions.
Single-Wall Nanotube (SWNT)
Multi-Walled Nanotubes (MWNT)

• Multiple rolled layers of

SWCN sheets
• More resistant to chemi-
cal changes than SWNTs
 Why Should We Care of these materials ?
Thermal
Mechanical
Properties
Properties
• Unique properties
• Material of the future
• Seemingly infinite ap-
plications
• Possible health issues

Strong Like Steel

Light Like Aluminum
Elastic Like Plastic