POLYMER

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 Intended Learning Outcomes
The students should be able to:
• Identify the composition of polymer
• Explain different polymerization processes
• Determine the various application of polymers

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What is a polymer?

• A long molecule made

up from lots of small
molecules called
monomers.
• Very large organic
compounds made of
repeating units
 Polymer

A molecule of high Molecular weight, structure of which

comprises of multiple repetition of units derived from
molecules of low relative Molecular weight (monomers)
 Polymers
Macromolecules formed by the covalent
attachment of a set of small molecules termed
monomers.
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 7e.

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chemistry: polymer structure connected by covalent bond

kinetic: produced from chemical reaction of small units,

called “monomer”

property: - high strength, with Tg and rubber elasticity,

- high viscosity in melt or

solution states
The kinds of applied monomers
One kind : Homopolymer
Two kinds : Copolymer
Three kinds : Terpolymer

POLYMER CHEMISTRY
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Types of copolymer

Homopolymer : -A-A-A-A-A-A-A-A-

Random copolymer : -A-B-B-A-B-A-A-B-

Alternating copolymer : -A-B-A-B-A-B-A-B-

Block copolymer : -A-A-A-A-B-B-B-B-

Graft copolymer : -A-A-A-A-A-A-A-A-

B-B-B-B-B- POLYMER CHEMISTRY

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Representation of polymer types

(a) linear (b) branch

(c) network

POLYMER CHEMISTRY
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Polymers are classified as:

(1)Biological polymer that are found in nature.

DNA, proteins, carbohydrates

(2)Man-made or synthetic polymers that are

synthesized in the laboratory
nylon, poly-ethylene, poly-styrene

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Biopolymers

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Representation of the constitution of a protein

Amino acids polymers (Proteins)

Structural strength and catalysis: Proteins

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One strand unwinds to
duplicate its
complement via a
polymerization of the
monomers
C, G, A and T

Nucleic acid polymers (DNA, RNA)

Genetic information for the cell: DNA

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Sugar polymers (Carbohydrates)

Energy source: Carbohydrates

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Originally natural polymers were used
– Wood – Rubber
– Cotton – Wool
– Leather – Silk

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POLYMER COMPOSITION

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Most polymers are HYDROCARBONS
which are an organic compounds made
up of C and H

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• A polymer chain is built on a Carbon backbone
• A monomer unit consists of a small carbon
chain attached to a specific type of functional
group
• The functional group is what gives each
polymer chain its individual characteristics
 ALKANES

• Hydrocarbons which contain only single

bonds are called alkanes (paraffins).
• They are called saturated hydrocarbons
because there is a hydrogen in every
possible location.
• This gives them a general formula CnH2n+2.
• Saturated hydrocarbons
– Each carbon bonded to four other atoms

H H
H
C C

H H
H CnH2n+2
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 Alkanes

H H H H H H H H H H H H H H H
H C H H C C H H C C C H H C C C C H H C C C C C H
H H H H H H H H H H H H H H H

methane ethane propane butane pentane

CH3 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3
 Naming Alkanes
Prefix for number of carbons listed below and suffix – ane
are used.
Number of Carbons As Prefix Name
1 Meth - Methane
2 Eth- Ethane
3 Prop- Propane
4 But- Butane
5 Pent- Pentane
6 Hex- Hexane
7 Hept- Heptane
8 Oct- Octane
9 Non- Nonane
10 Dec- Decane
 Hydrocarbons
ex: Alkanes

• 1 – Meth-
• 2 – Eth-
• 3 – Prop-
• 4 – But-
• 5 – Pent-
• 6 – Hex-
• 7 – Hept-
• 8 – Oct-
• 9 – Non-
• 10 – Dec-
• 11 – Undec-
• 12 – Dodec-
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 Hydrocarbons
at Room Temperature

• Gas  Liquid  Waxy • Plastic

– Methane 20 to 40 40 or more
– Ethane 5 to 19 Carbons Carbons
– Propane
Carbons
– Butane
• Alkanes are obtained from the fossil fuel
resource
• Alkane derivatives are used in hundreds of
products such as plastics, paints, and other
materials.
• Some alkanes are highly combustible and
are valuable as clean fuels, burning to form
water and carbon dioxide.
• Methane, ethane, propane and butane are
gases and used directly as fuels.
• Alkanes from pentane up to around C17H36
are liquids.
 Melting Point

• As the length of hydrocarbons get longer, the

Melting Point grows Higher.
Melting and Boiling Temperatures of Alkanes
600

500

400
Boiling Point (˚C)
Tempurature (˚C)

300

200 Melting Point(˚C)

100

-100

-200

-300
0 5 10 15 20 25 30 35 40 45
Number of Carbons
UNSATURATED HYDROCARBON

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 Classes of Unsaturated
Hydrocarbons
• 1. Alkenes – An acyclic hydrocarbon
with one or more carbon-carbon
double bonds (with one double bond : C H )
n 2n

• 2. Alkynes – An acyclic hydrocarbon

with one or more carbon-carbon
triple bonds (with one triple bond : C H )
n 2n-2

• 3. Aromatic – A cyclic hydrocarbon

six*-carbon (usually) ring containing
three carbon-carbon double bonds.
* known as a benzene ring (C6H6).
 Unsaturated Hydrocarbons
Physical properties – Similar to saturated
hydrocarbons
Chemical properties -
1.More reactive than saturated hydrocarbons
2.The carbon-carbon double or triple bonds
are the reactive sites
(In most cases we will be working with double bonds)

So, common reactive sites are:

Multiple bond sites
Functional group sites
 UNSATURATED HYDROCARBONS

Alkenes (Olefins)
• Contains double bond
• General formula: CnH2n
• End in ene
 ALKENES

– Double bond – ethylene or ethene - CnH2n

H H
C C
H H

• 4-bonds, but only 3 atoms bound to C’s

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 Alkenes
• An alkene can be formed by removing a
hydrogen atom from two adjacent
carbons in a carbon chain.
– Ex: Hexane -C—C—C—C—C—C-
becomes
– Hexene -C—C—C=C—C—C-
(3-Hexene)

– Ex: Ethane -C-C- becomes

– Ethene -C=C-
(also known as ethylene)
 ALKENE

H 2C CH 2 H 3C CH CH 2
Ethene Propene
 Example of polymers
• Polythene – plastic bags, bottles, bowls
Very cheap and strong. Easily moulded.

• Polypropene – crates, ropes, carpets.

Forms strong fibres. Has high elasticity.

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 Chemistry of Polymers
Adapted from Fig.
14.1, Callister 7e.

Note: polyethylene is just a long HC

- paraffin is short polyethylene
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 ALKYNES (Acetylenes)
• General Formula: (CnH2n-2)
• Aliphatic hydrocarbons with one triple bond
between carbons are called alkynes.
• They follow the naming convention of the
alkanes except that the suffix -yne is used
instead of -ane.
 ALKYNES
• Alkynes are unsaturated hydrocarbons and are
generally very reactive.
• Typical reactions involve the addition of
hydrogens or halogens.
 Alkynes
• Formation is similar to that of alkenes (more
hydrogens are removed; higher temp.)
– Ethyne = Acetylene
• Naming: same rules as for alkenes
• Isomerism: cis-trans NOT possible
– Linear geometry around the triple bond
• Properties & Reactions are similar to those of
alkenes
 Unsaturated Hydrocarbons

– Triple bond – acetylene or ethyne - CnH2n-2

H C C H

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H C C H H 3C C C H
Ethyne Propyne
(acetylene)
 Ethyne
• The simplest of the alkynes series, it is
commonly called acetylene.
• It is often used as a fuel for welding torches
since it produces a large amount of heat upon
combustion.
• Oxyacetylene welding uses compressed
acetylene and compressed oxygen for mixing
in the torch flame.
 Unsaturated Hydrocarbons
• 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

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 Aromatic Hydrocarbons
• Have ring structure with multiple bonds.
• Benzene (C6H6) is the simplest aromatic.

H
H C H
C C
C C
H C H
H
 Unsaturated Hydrocarbons
• Benzene, C6H6, is the simplest and first
recognized aromatic hydrocarbon

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 Drawing polymers – shorthand formulae
Polymers contain thousands of molecules, so how can their
structures be easily drawn?

Part of the polymer molecule can be drawn:

A better way is to show a shorthand formula:

The ‘n’ means that the polymer

contains a very large number of the
repeating unit shown in the brackets.
 Isomerism
• Isomerism
– two compounds with same chemical formula can have
quite different structures/atomic arrangement
Ex: 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
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CH3
Bulk or Commodity Polymers

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SYNTHETIC POLYMERS

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 Range of Polymers
• Traditionally, the industry has produced two
main types of synthetic polymer – plastics and
rubbers.
• Plastics are (generally) rigid materials at
service temperatures
• Rubbers are flexible, low modulus materials
which exhibit long-range elasticity.

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Range of Polymers

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 PROPERTIES OF PLASTICS
 they do not conduct electricity and are poor
conductors of heat
 they are unreactive – most are not affected
by water or air, and many are not affected by
chemicals.

Why is the unreactivity of plastics both useful

and problematic?
Their unreactivity makes plastics durable and
able to safely contain and protect many
substances. However, it also means that they
persist in the environment for a long time.
 What makes plastics different?
The properties of plastics depend greatly on how the
polymer chains are arranged:
 branching chains
make plastics
light, soft and
easy to melt
(e.g. low-density
polyethene)

 lined-up chains
make plastics
dense, rigid and
harder to melt
(e.g. high-density
polyethene).
 Changing the properties of plastics
What factors might determine the properties of a plastic?

Factor Effect
reaction Temperature, pressure and catalysts
conditions affect the length and branching of the
polymer chain.
monomer The type of monomer used affects the
type of forces between polymer chains.
additives Additives can ‘lubricate’ polymer
chains, join them together with cross-
links, or preserve them from decay.
 Range of Polymers
• Plastics are further subdivided into
thermoplastics and thermosets

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 Uses of thermosoftening plastics
Thermosoftening plastics (also called ‘thermoplastics’) do not
contain cross-links.
This means they are flexible, stretchy and have a low melting
point. It also means they can be moulded and shaped after
they have been made, many times.
What are some examples of thermoplastics?

polyethene natural rubber

 What are thermosoftening plastics?
What do polymer chains and spaghetti have in common?
Cooked spaghetti is solid when cold, but soft when warm.
The strands can slide past each other. It is the same with
many polymers.
weak
intermolecular
forces –
these let the
chains slide past
each other

Plastics made of these polymers are stretchy and have a

low melting point. They are called thermosoftening plastics.
 What are thermosetting plastics?
Some polymer chains cannot slide past each other.

strong
intermolecular
forces
(cross-links) –
these hold the
chains firmly in
place

Plastics made of these polymers cannot be stretched, are

rigid and have a high melting point. They are called
thermosetting plastics (or ‘thermosets’).
 Uses of thermosetting plastics
Thermosetting plastics contain cross-links. This means
that they:
 are rigid
 will break when bent
 have a high melting point (they char rather than
melt)
 must be moulded into shape when they are being
made,

What type of objects might you make from thermosetting

plastics?
 uPVC chains
uPVC is perfect for window
frames as it is strong, light
and durable.

The ‘u’ stands for

unplasticized, and means
the polymer is rigid.

chains packed
tightly together
 Oiling the chains?
Adding a plasticizer lets the chains slide.

plasticizer

How will the plasticizer change the polymer’s properties?

The polymer will be flexible, not rigid.
Polymers, plastics and properties
 Range of Polymers
• Another way of classifying polymers is in
terms of their form or function

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Synthesis of
Polymers
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 Synthesis of Polymers
• There are a number different methods of
preparing polymers from suitable monomers,
these are
– step-growth (or condensation) polymerisation
– addition polymerisation
– insertion polymerisation.

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 Types of Polymerization
• Chain-growth polymers, also known as
addition polymers, are made by chain
reactions

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 Synthetic Addition Polymers
• Addition Polymerization: a polymerization in
which monomer units with unsaturated carbon-
carbon bonds are joined together without loss
of atoms. For example:
nCH2 = CH2 catalyst
CH2 CH2
n
Ethylene Polyethylene

• The properties of polymers are dependent on

the type of functional group attached to the
monomer.
 Types of Addition
Polymerization
• Free Radical
• Cationic
• Anionic

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 Free Radical Polymerization
• Usually, many low molecular weight alkenes
undergo rapid polymerization reactions when
treated with small amounts of a radical
initiator.
• For example, the polymerization of ethylene

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 Addition polymerization
Polyethene (sometimes called polythene) is a polymer made
from ethene.
The process by which polyethene and other polymers is
made is called addition polymerization. This is because
many monomers (ethene molecules) are added together.

monomers  addition polymerization

polymer
• Free radical polymerization
H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer
• Initiator: example - benzoyl peroxide
H H H
C O O C 2 C O =2R
H H H
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Free Radical Polymerization

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Free Radical Polymerization

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Free Radical Polymerization

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 Ionic Polymerization
• Ionic polymerization is more complex than
free-radical polymerization

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 Ionic Polymerization
• Whereas free radical polymerization is non-
specific, the type of ionic polymerization
procedure and catalysts depend on the nature
of the substituent (R) on the vinyl (ethenyl)
monomer.

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 Ionic Polymerization
• Cationic initiation is therefore usually limited
to the polymerization of monomers where the
R group is electron-donating
• This helps stabilise the delocation of the
positive charge through the p orbitals of the
double bond

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 Ionic Polymerization
• Anionic initiation, requires the R group to be
electron withdrawing in order to promote the
formation of a stable carbanion (ie, -M and -I
effects help stabilise the negative charge).

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Ionic Polymerization

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Ionic Polymerization

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 Ionic Polymerization
• M is a Monomer Unit.
• As these ions are associated with a counter-
ion or gegen-ion the solvent has important
effects on the polymerization procedure.

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 Ionic Polymerization
(ii) Chain Propagation depends on :
• Ion separation
• The nature of the Solvent
• Nature of the counter Ion

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 Anionic Polymerization
• Involves the polymerization of monomers that
have strong electron-withdrawing groups, eg,
acrylonitrile, vinyl chloride, methyl
methacrylate, styrene etc. The reactions can
be initiated by methods (b) and (c) as shown
in the sheet on ionic polymerization

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 Anionic Polymerization
• eg, for mechanism (b)

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 Anionic Polymerization
• The gegen-ion may be inorganic or organic
and typical initiators include KNH2, n-BuLi,
and Grignard reagents such as alkyl
magnesium bromides

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 Anionic Polymerization
• If the monomer has only a weak electron-
withdrawing group then a strong base initiator
is required, eg, butyllithium; for strong
electron-withdrawing groups only a weak base
initiator is required, eg, a Grignard reagent.

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 Anionic Polymerization
• Initiation mechanism (c) requires the direct
transfer of an electron from the donor to the
monomer in order to form a radical anion.
• This can be achieved by using an alkali metal
eg.,

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Anionic Polymerization of Styrene

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Anionic Polymerization of Styrene

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Anionic Polymerization of Styrene

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Cationic Polymerization

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 Cationic Polymerization
• (ii) PropagationChain growth takes place
through the repeated addition of a monomer
in a head-to-tail manner to the ion with
retention of the ionic character throughout

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Cationic Polymerization

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 Cationic Polymerization
(iii) Termination
Termination of cationic polymerization
reactions are less well-defined than in free-
radical processes. Two possibilities exist as
follows:

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Cationic Polymerization

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 Cationic Polymerization
• Hydrogen abstraction occurs from the growing
chain to regenerate the catalyst-co-catalyst
complex.
• Covalent combination of the active centre
with a catalyst-co-catalyst complex fragment
may occur giving two inactive species.

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 Cationic Polymerization
• The kinetic chain is terminated and the
initiator complex is reduced - a more effective
route to reaction termination.

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Cationic Polymerization

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 Types of Polymerization
• Step-growth polymers, also called
condensation polymers, are made by
combining two molecules by removing a small
molecule

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 Condensation Polymerization
Water is “Condensed out”
during polymerization of Nylon

• Some of the original monomer’s materials are shed

(condensed out) during polymerization process
• Process is conducted in the presence of a catalyst
• Water, CO2 are commonly condensed out but other
compounds can be emitted including HCN or other acids
 Synthetic Condensation Polymers
• Condensation polymerization: a polymerization
in which chain growth occurs by a condensation
reaction (removal of water) between
difunctional monomers
• Polyesters: A polymer formed by a
condensation reaction that results in ester
linkages between monomers.
• Polyamides: a polymer formed by condensation
reactions resulting in amide linkages between
monomers.
 Polyesters
• Poly(ethylene terephthalate) (PET) is fabricated
into plastic beverage containers
O O
nHOC COH + nHOCH2 CH2 OH heat
1,4-Benzenedicarboxylic 1,2-Ethanediol
acid (Ethylene glycol)
(Terephthalic acid)
O O
C COCH2 CH2 O + 2 nH2 O
n
Poly(ethylene terephthalate)
(Dacron, Mylar)
 Polyamides
• Nylon 66 (from two six-carbon monomers)
O O
heat
nHOC(CH 2 ) 4 COH + nH 2 N(CH 2 ) 6 NH2
Hexanedioic acid 1,6-Hexanediamine
(Adipic acid) (Hexamethylenediamine)
O O
C(CH 2 ) 4 CNH(CH 2 ) 6 NH + 2 nH2 O
n
Nylon 66
during fabrication, nylon fibers are cold-drawn to
about 4 times their original length, which increases
crystallinity, tensile strength, and stiffness
 Polyamides
• Kevlar is a polyaromatic amide (an aramid)
O O
nHOC COH + nH2 N NH2
1,4-Benzenedicarboxylic 1,4-Benzenediamine
acid (p-Phenylenediamine)
(Terephthalic acid)
O O
C CNH NH + 2 nH2 O
n
Kevlar

• cables of Kevlar are as strong as cables of

steel, but only about 20% the weight. Kevlar
 Cross-Linking
• Some monomer functional groups have the ability to
form cross-links.
• Cross-linking is bonding of adjacent polymer strands
• As a general rule, the more cross-linking present the
more rigid and inflexible the polymer becomes.
• Dienes (monomers with 2 unsaturated bonds) form
strong cross-links
• Sulphur is also used to create cross-links due to the
fact it is able to form two covalent bonds.
(vulcanization)
 Cross links

Primary bonding occurs with cross linking of adjacent

molecules. This results in a rigid, non-reversible
structure.
 Condensation polymerization
Condensation polymerization: the polymer grows from monomers by
splitting off a small molecule such as water or carbon dioxide.

Example: formation of amide links and loss of water

Monomers

First unit of polymer + H2O

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Rembember from GChem?

Nylon is a condensation polymer

made of the monomers adipic acid
and hexamethylene diamine.

O OH
O

OH
Q uickTim e™ and a
Phot o - JPEG decom pr essor
ar e needed t o see t his pict ur e.

They're nylons, Benjamin.

adipic acid
+
NH2
H2N

hexamethylene diamine

nylon
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 Hydrogen bonds between chains

Supramolecular
Structure of nylon

Intermolecular hydrogen
bonds give nylon
enormous tensile
strength

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 Fabrication
Methods
1

1
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