ENR116 – Mod. 4- Slide No.

Polymer chemistry
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Intended Learning Outcomes

At the end of this section, students will be able to:-

• Identify the general structural characteristics of polymers.

• Understand how these structures are chemically

characterised.
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Polymers

What is a polymer?
Poly mer
many repeat unit

repeat repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Adapted from Fig. 14.2, Callister & Rethwisch 8e.

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Natural polymers

Wood – composed of cellulose fibres and lignin.

Proteins - composed of a various

amino acids which are bonded
together via covalent peptide bonds.

Natural rubber:
Latex from the
Para rubber tree
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Polymer composition

Most polymers are hydrocarbons i.e. made up of H and C.

Saturated hydrocarbons (alkanes, paraffin compounds) - each

carbon bonded to four other atoms.

CnH2n+2 H H H H

H C C C C H
H H
H H H H H
C C
Butane
H H Ethane
H
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Unsaturated hydrocarbons

• Contain double and/or triple bonds.

• Relatively reactive - can form new bonds.

Double bond (alkenes) - ethylene or ethene - CnH2n

H H
C C
H H
Triple bond (alkynes) - acetylene or ethyne - CnH2n-2

H C C H

Unsaturated - carbon is not bonded to four other atoms.

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Common polymer classes (groups)

R-OH

OH
R-C
O

R and R’ represent organic

groups such as CH3, C2H5, and
C6H5 (methyl, ethyl, and
phenyl).
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Isomerism
Isomerism: Two compounds with same chemical composition
can have quite different structures, Example C8H18

n-octane
H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H

H3C ( CH2 ) CH3
6

2-methyl-4-ethyl pentane (isooctane)

CH3
H3C CH CH2 CH CH3
CH2
CH3
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Synthesis of polymers

Free radical polymerization:

HH HH H H H H
R + C C R C C initiation
R + CC RCC initiation
H H H H H H H H
R + C C R C C initiation HH HH free radical monomer
H H H H free radical monomer (ethylene)
free radical monomer
(ethylene)
(ethylene)
H H H H H H H H
H H H H H H H H
HH HH HHHH R C C + C C R C C C C propagation
R C C + C C R C C C C propagation
H H H H H H H H
H H H H H H H H RCC + CC RCCCC propagation
dimer
dimer
HH HH HHHH
H H H H H H H H
dimer
R + C C R C C initiation R + C C R C C initiation
H H H H H H H H
free radical monomer free radical monomer
(ethylene) (ethylene)

H H H H H H H H H H H H H H H H
R C C + C C R C C C C propagation R C C + C C R C C C C propagation

H H H H H H H H H H H H H H H H
dimer dimer

Initiator: Example - benzoyl peroxide

H H H
C O O C X 2 C O = 2R
H H H
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Addition (radical) polymerization

Radical polymerization is used in the synthesis of polyethylene,
polypropylene, poly(vinyl chloride), and polystyrene, as well as
many of the copolymers.
Initiation:

Propagation:

Termination:

or

Disproportionation Combination
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Polycondensation (step)
polymerization
Monomers containing functional groups
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Polymer molecules
Homopolymer – composed of the same repeat unit.

Co-polymer – composed of two or more different repeat units.

Functionality – the number of bonds that a given monomer

can form

Bifunctional

Trifunctional Phenol-formaldehyde (Bakelite)

Can make three dimensional structure

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Bulk or commodity polymers

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Bulk or commodity polymers

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Bulk or commodity polymers

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Molecular weight

Number-Average molecular weight: Obtained by dividing the

chains into a series of size ranges and then determining the
number fraction of chains within each size range.

Lower M higher M Adapted from Fig. 14.3,

Callister & Rethwisch 8e.

M n  xi M i

Mi represents the mean molecular

weight of size range i, and xi is the
fraction of the total number of chains
within the corresponding size range.
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Number average molecular weight

Example

Ni Mi xi Mixi Mean mass of range

Mass Range Mean Mass
8,000-16,000 12000 0.05 600
16,000-24,000 20000 0.16 3200
24,000-32,000 28000 0.24 6720 M n   xi Mi
32,000-40,000 36000 0.28 10080
40,000-48,000 44000 0.2 8800
48,000-56,000 52000 0.07 3640

Mn Mean mass,
33,040 multiplied by
number fraction
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Molecular weight
Weight-Average Molecular weight: Is based on the weight
fraction of molecules within the various size ranges.

Adapted from Fig. 14.3,

Callister & Rethwisch 8e.

M w  wi M i

Mi represents the mean molecular

weight of size range i, and wi denotes
the weight fraction of molecules
within the same size interval.
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Molecular weight

Distribution of molecular weights for a typical polymer.

Mw is more sensitive to
higher molecular weights.

Close to 1 – little variation in

chain length across sample

Adapted from Fig. 14.4, Callister & Rethwisch 8e.

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Degree of polymerization, n

n = number of repeat units per chain

H H H H H H H H H H H H
H C C (C C ) C C C C C C C C H n=6
H H H H H H H H H H H H

Mn m – the molecular weight

DP  n 
m of a repeat unit in a chain

With increasing Mn melting temperature increases:

Up to 100 g/mol – liquid
Up to 1000 g/mol – wax
Above 1000 g/mol – solid
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Molecular shape
polyethylene

Adapted from Fig.

14.1, Callister &
Rethwisch 8e.

109o 0.154 nm
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Molecular shape
Conformation: Molecular orientation can be changed by
rotation around the bonds. Note: no bond breaking is needed.
Adapted from Fig.
14.5, Callister &
Rethwisch 8e.

Segments are free to rotate against each other.

The degree of rotation depends on both the chemistry and

repeat unit structure.

C=C makes segment rigid.

Bulky or side groups also restrict mobility.

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Molecular structures
Linear polymers: Those in which the repeat units are joined
together end to end in single chains.

Chains are flexible.

Van der Waals forces act between

the chains.

Examples - polyethylene, poly(vinyl chloride), polystyrene,

poly(methyl methacrylate), nylon, and the fluorocarbons.

Adapted from Fig.

14.7, Callister &
Rethwisch 8e.
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Molecular structures
Branched polymers: Contain side-
branch chains which are connected
to the main ones.

Branches are considered to be

part of the main-chain molecule.

Reduced chain packing efficiency

- lower density. Adapted from Fig.
14.7, Callister &
Rethwisch 8e.

Examples - Low density polyethylene (LDPE) contains

short chain branches.
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Molecular structures
Cross-linked Polymers: Adjacent
linear chains are joined one to
another at various
positions by covalent bonds.

Adapted from Fig.

14.7, Callister &
Rethwisch 8e.

Rubber is usually cross-linked elastic materials

(vulcanization).
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Molecular structures
Network Polymers: Multifunctional monomers forming three or
more active covalent bonds.

Highly cross-linked polymers

may also be classified as a
network polymers.

These have distinctive mechanical and Adapted from Fig.

14.7, Callister &
thermal properties. Rethwisch 8e.

Examples: epoxies, polyurethanes, and phenol-formaldehyde

resins.
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Molecular structures
Polymer chain configurations and strength:

secondary
bonding

Linear B ranched Cross-Linked Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister & Rethwisch 8e.

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Molecular Configurations

Molecular configuration describes:

• The direction in which monomers are linked together

H CH
H 3 H CH
H 3 H CH H 3 H H H HH CH
H 3 H CH H 3 CH
H 3 H CH
H 3 CH H 3H H H H H H
H C C ( C C ) C C C C C C CH CC HC ( C C ) C C C C C C C C
H H H H H H H H H H H HH H H H H H H H H H H H
Head-tail Head-head

• The order in which monomers are joined together (for

copolymers)

The configuration is fixed during synthesis, and cannot be

changed without breaking and reforming bonds.
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Tacticity

Tacticity: Stereoregularity of the chains.

H H H H H H H H
Isotactic - all R groups on
C C C C C C C C
same side of chain.
H R H R H R H R

H H H R H H H R
Syndiotactic - R groups
C C C C C C C C
alternate sides.
H R H H H R H H

H H H H H R H H
Atactic - R groups random.
C C C C C C C C
H R H R H H H R
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cis/trans isomerism

Possible within repeat units having a double bond between

chain carbon atoms.
CH3 H CH3 CH2
C C C C
CH2 CH2 CH2 H
cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same bulky groups on opposite
side of chain sides of chain

Conversion of trans to cis, or vice versa, is not possible by a

simple chain bond rotation because the chain double bond is
extremely rigid.
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Summary

• Most polymers are composed of repeat units of very long

molecular chains of carbon covalently bound with other
elements.

• Polymers are synthesized by addition or stepwise

polymerisation.

• The average molecular weight of a polymer is defined as

number average molecular weight or weight average
molecular weight.

• The structure of the molecular chain has a strong

influence on the final physical structure of the polymer.