Lecture 1 PDF

CHPE4102-Polymers
Text Book:
Joel R. Fried, “Polymer Science and
Technology”, Prentice Hall Ltd., Third
Edition, 2014.
POLYMERS
Ancient Polymers
Originally natural
polymers were used:
– Wood
– Rubber
– Cotton
– Wool
– Leather
– Silk
Oldest known use: Rubber balls used by Incas
3
Naturally occurring polymers
•Proteins
•Nucleic acids
•Cellulose
•Rubber
Synthetic polymers
•Nylon
•Dacron
•Lucite
Polymer Building Blocks
• Hydrogen
• Carbon (key)
• Oxygen
• Nitrogen
• Fluorine
• Silicon
• Sulfur
• Chlorine
Polymer Composition
Most polymers are hydrocarbons
– i.e., made up of H and C
• Saturated hydrocarbons
– Each carbon singly bonded to four other atoms
– Example:
• Ethane, C2H6
H H
H
C C
H H
H
6
Unsaturated Hydrocarbons
• Double & triple bonds somewhat unstable
• Thus, can form new bonds
– Double bond found in ethylene or ethene - C2H4
H H
C C
H H
– Triple bond found in acetylene or ethyne - C2H2
H C C H
7
Unsaturated Hydrocarbons
• Benzene, C6H6, is the simplest and first recognized
aromatic hydrocarbon
An aromatic hydrocarbon (abbreviated as AH) or arene is a

hydrocarbon, of which the molecular structure incorporates one or
more planar sets of six carbon atoms that are connected by
delocalised electrons numbering the same as if they consisted of
alternating single and double covalent bonds
Chemistry and Structure of Polyethylene
Adapted from Fig.
Ethylene 14.1, Callister &
Ethene Rethwisch 8e.
Note: polyethylene is a long-chain hydrocarbon
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E. Examples of monomers and polymers
Monomer Polymer
CH2 CH2
CH2CH2
n
CH2 CHCl CH2CH2
Cl
O
H2C CH2 CH2CH2O
HOCH2CH2OH CH2CH2O
HO CO2H O C
Repeating unit ‘n’ For a polymer, if ‘n’ =10000, and molecular wt of one molecule
(monomer ) is 120, then the total molecular wt of this polymer will be 120, 0000
11
Classification of Polymers
1. Thermal Behavior
1. Thermoplastic
2. Thermosets
2. Polymerization Mechanism
1. Addition (Chain) Polymerization
2. Condensation (step) Polymerization
3. Polymer Structure
1. Copolymer
2. HomoPolymer
4. Classification based on Steriochemical
Configurations
1.Isotactic
2.Syndiotactic
3.Atactic
Polymer Types: Based on Thermal Behavior
Thermoplastics
• Those which soften on heating and then harden again on cooling
These are called thermoplastic polymers because they keep their plastic
properties
• These polymer molecules consist of long chains which have only weak
bonds between the chains
• The bonds between the chains are so weak that they can be broken when
the plastic is heated
• The chains can then move around to form a different shape
• The weak bonds reform when it is cooled and the thermoplastic material
keeps its new shape
Polymer Types: Based on Thermal Behavior
Thermosets
• Extensive cross-linking formed by covalent bonds.

• Bonds prevent chains moving relative to each other.
• What will the properties of this type of plastic be like?
• Thermosets are generally stronger than thermoplastics due to this three
dimensional network of bonds (cross-linking)
• Better for high-temperature applications up to the decomposition
temperature.
• Since they are "set" (non-reformable), they tend not to be recyclable.
Classification of Polymers: Polymerization Mechanism
Addition (Chain) Polymerization
An addition polymer is a polymer which is formed by an addition reaction, where
many monomers bond together via rearrangement of bonds without the loss of any atom
or molecule.
Catalyst
– Initiation
– Propagation
– Termination
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Chain –growth: High molecular wt polymers formed in early stage of reaction and % of
monomer conversion increase with time
Some Common Addition Polymers
Classification of Polymers: Polymerization Mechanism
Condensation (Step) Polymerization
condensation polymer is formed by a condensation reaction where a molecule, like
water, is lost during the formation.
Step growth: High-molecular wt polymers yield near the end of

reaction, ~ 98% conversion
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Condensation Reaction
Classification of Polymers: Structures of Polymers
Sequence of monomer linking: Homopolymer and Copolymer
• Polymer chemistry
– If formed from one monomer (all the repeat units are the
same type) – this is called a homopolymer
– If formed from multiple types of monomers (all the repeat

units are not the same type) – this is called a copolymer
Homopolymer and Copolymer
Homopolymer is a polymer made up of only one type of monomer
( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n
Teflon Polyethylene Cl
PVC
Copolymer is a polymer made up of two or more monomers
( CH CH2 CH2 CH CH CH2 )n
Styrene-butadiene rubber
Terpolymer: 3 different unit monomers

Classification of Copolymers Adapted from Fig.
two or more monomers

4.9, Callister &
Rethwisch 3e.
polymerized together random

depending on reactivity
• random – A and B randomly
positioned along chain
• alternating – A and B alternate alternating
in polymer chain
• block – large blocks of A units block
alternate with large blocks of B
units
• graft – chains of B units grafted
onto A backbone
graft
A– B– 24
Classification based on Steriochemical configuration
(how atoms are arranged ?) of Polymers
R groups on same
side of chain
Isotactic
R groups alternate
from side to side
Syndiotactic
R groups disposed at
random
Atactic
cis/trans Isomerism
CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H
cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
H atom and CH3 group on H atom and CH3 group on
same side of chain opposite sides of chain
27
Geometrical Isomerism
Classification scheme for
the characteristics of
polymer molecules
isomerism – different molecular

configurations for molecules (polymers)
of the same composition
Stereoisomerism
Geometrical Isomerism
Molecular configurations
Vs conformation ?
POLYMER MICROSTRUCTURE
• Covalent chain configurations and strength:
Direction of increasing strength
Adapted from Fig. 14.7, Callister 6e.
2
Linear polymers
 polymers in which the monomer units are
connected end-to-end along the whole length of the
chain
 These types of polymers are often quite flexible
• Van der waal’s forces and H-bonding are the two
main types of interactions between chains
• Some examples – polyethylene, teflon, PVC,
polypropylene
Branched polymers
• Polymer chains can branch:
• Or the fibers may aligned parallel, as in fibers and some

plastic sheets.
– chains off the main chain (backbone)
– This leads to inability of chains to pack very closely
together
» These polymers often have lower densities
• These branches are usually a result of side-reactions during
the polymerization of the main chain
• Most linear polymers can also be made in branched forms
Crosslinked polymers
• Molecular structure
– adjacent chains attached via covalent bonds
– Carried out during polymerization or by a non-reversible
reaction after synthesis (referred to as crosslinking)
– Materials often behave very differently from linear polymers
– Many “rubbery” polymers are crosslinked to modify their
mechanical properties; in that case it is often called
vulcanization
– Generally, amorphous polymers are weak and cross-linking adds
strength: vulcanized rubber is polyisoprene with sulphur cross-
links:
Network polymers
– polymers that are “trifunctional” instead of bifunctional
– There are three points on the monomer that can react
– This leads to three-dimensional connectivity of the
polymer backbone
• Highly crosslinked polymers can also be classified as
network polymers
• Examples: epoxies, phenol-formaldehyde polymers

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CHPE4102-Polymers

– Double bond found in ethylene or ethene - C2H4

– Triple bond found in acetylene or ethyne - C2H2

An aromatic hydrocarbon (abbreviated as AH) or arene is a

Note: polyethylene is a long-chain hydrocarbon

• Those which soften on heating and then harden again on cooling

• Extensive cross-linking formed by covalent bonds.

Step growth: High-molecular wt polymers yield near the end of

– If formed from multiple types of monomers (all the repeat

Homopolymer is a polymer made up of only one type of monomer

( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n

( CH CH2 CH2 CH CH CH2 )n

Terpolymer: 3 different unit monomers

two or more monomers

polymerized together random

CH3 H CH3 CH2

isomerism – different molecular

• Covalent chain configurations and strength:

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.

• Or the fibers may aligned parallel, as in fibers and some

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