Dr Amal Abd El-Maboud 2 March 2023 1

Dr Amal Abd El-Maboud 2 March 2023 2

1)Classification of polymers based on the
origin
2) Classification of polymers based on nature
of monomer.
3) Classification of polymers based on type of
polymerization mechanism:

a)Addition Polymerization.
b)Condensation Polymerization.
c)Ring opening polymerization.

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4- Classification of polymers based on
thermal behavior.
(a) Thermoplastics.
(b) Thermosetting or Thermosets.
5-Classification Based on Structure
6- Cassification Based on application.

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a)Natural polymers.

These polymers are found in nature

and control the life process in plants and

animals.
The following table represents examples of
natural polymers.

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These polymers are prepared in the
laboratory or man-made polymers, e.g.,
polyolefins, polydienes,Polyamides, resin of
polymers, polyesters, and
plycarbonates(lecture 1 and lecture 2).


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These polymers obtained by making some
modification in natural polymers by artificial
means,

e.g.,
i)semi synthetic cellulose diacetate fibers
are obtained by acetylation of nautural celllose
with acetic anhydride in persence of sulphuric
acid.

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ii)An explosive cellulose nitrate obtained on
nitration of celulose

iii)Vulcanized rubber used for making rubber

tyres

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a) Homo-polymers: A polymer containing
identical monomers. • A-A-A-A

b) Co-polymers are the compounds formed by

two or more different monomers.
For example in polystyrene butadiene.
A-B-A-B-A-A-B

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a)Linear polymers
These are the polymers in which the
monomer units are linked to one
another to form long linear chains

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These linear chains are closely packed in
space.

 Linear polymers have extensive van der

Waals attractions or hydrogen bonding
between the chains, which affects the
strength of the material between the chains.
◦ Examples: polyethylene, polyvinyl
chloride, polystyrene, and nylon.

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The close packing results in high densities,
tensile strength and high melting and boiling
points.

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In such polymers, the monomer units are
linked to form long chains with some branched
chains of different lengths with source.

As a result of branching, these polymers are

not closely packed in space.
Thus, they have low densities, low tensile
strength as well as
low melting and boiling points.

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Some common examples of such polymers are
low density polyethylene, starch.

-Polyethylene may be present as low density

polyethylene(LDPE) or

high density polyethylene(HDPE).

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1-Intermolecular forces between the chains
are strong, enabling the molecules to be tightly
packed.
2-It has a higher degree of crystallinity, a
higher density, a higher melting point, and is
several times stronger than LDPE.

3- Is used in applications where rigidity is

important.

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Low density polyethylene (LDPE) or branched
polyethylene.

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1- Intermolecular forces between the chains
are weak.
2- Characterized by a large degree of
branching.
3- Chains does not packed forming a low
density material.
4-Is soft and pliable
5-Linear polyethylene has a melting point 20oC
higher than that of a branched polyethylene.

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In addition to the bonds which hold monomers
together in a polymer chain, many polymers
form bonds between neighboring
chains(chemical linkages exist between the
chains).

These bonds can be formed directly between

the neighboring chains, or two chains may
bond to a third common molecule.

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-Though not as strong or rigid as the bonds
within the chain, these cross-links have an
important effect on the polymer.
-When the polymer is stretched, the cross-
links prevent the individual chains from
sliding past each other.
-These cross-linked polymers insoluble in any
solvents. Solvents swell these cross-linked
polymers.

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-The tendency to absorb solvents decreases as
the degree of cross-linking is increased WHY?
because the chains cannot move enough to
allow the solvent molecules to penetrate
between the chains.

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Thus,The more cross-links present, the
smaller are the amount of swelling.

If the degree of cross-linking is high enough,

the polymer may be a rigid and high melting

Examples of cross-linking polymers are the

vulcanized rubber and bakelite

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a)Addition polymers :(Chain- growth
polymerization)

The polymers formed by the polymerization of

monomers containing double or triple bonds
(unsaturated compounds). Addition polymers
have the same empirical formula as their
monomers.

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The monomer molecules bond to each other
without the loss of any other atoms.

Alkene monomers are the biggest groups of

polymers in this class.Examples of addition
polymers are polyolefines and polydienes

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Condensation polymerization is a type of
reaction that proceeds through the elimination
of a smaller molecule (ex. H2O, HX, or NH3)
and formation of a bond between two
monomers, each of which contains two
functional groups (ex.–COOH or –OH)

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so that the reaction can occur repeatedly to
yield a polymer. This type of reaction is used
as a basis for the synthesis of many important
polymers such as polyamides, polyesters,
polycarbonates, phenol-formaldehyde,
melamine-formaldehyde and urea-
formaldehyde resins

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Presence of catalysts lead to cleavage of the
ring followed by polymerization to yield high-
molecular weight polymers.
Example :
(i) trioxane can be polymerized to yield
polyoxymethylene.
:

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 O
H O
NH 1. partial hydrolysis
n N
2. heat n
Caprolactam Nylon 6

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(a) Thermoplastics.
(b) Thermosetting or Thermosets
a)Thermoplastics

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These show reversible change on heating i.e

they soften on heating but regain their original

properties on cooling.

They gain or lose hardness with rise or fall in

temperature.

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 Their chemical nature does not get affected

even on repeated heating and cooling, i.e the

changes are more of physical nature.

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1-They are usually formed by addition
polymerization and condensation.

2-They consist of long chain linear polymers

with negligible cross-links.

3-They soften on heating readily, because

secondary forces between the individual chain
can break easily by heat or pressure or both.

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4-By reheating to a suitable temperature they
can be softening, reshaped and thus reused.

5-They are usually soft, weak, and less brittle.

6-They can be reclaimed from waste.

7-They are usually soluble in some organic
solvents.
8-Examples: polyethylene, polypropylene

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They become permanently hard when they
are heated and do not soften as the heating
process continues.

They are harder and stronger than

thermoplastics and have better dimensional
stability.
Most of the crosslinked
and network polymers are in this group.

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1-They are usually formed by condensation
polymerization .

2-They coss-link and bonds retain their

strength on heating and hence they do not
soften on heating.

3- They retain their shape and structure even

on heating .Hence, they cannot be reshaped
and reused.

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4-They are usually, hard, strong and more
brittle.

5-They cannot be reclaimed from waste.

6- Due to strong bonds and cross-links they

are insoluble in some organic solvents.

7-Examples: phenolic resin, polyesters.

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On the basis of applications, polymers can be
further classified as –

a)Elastomers
b)Fibers
c) Plastics
i)Thermosetting polymers
ii)Thermoplastics

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are polymers which possess elastic properties.

The elastic property:

arises from the fact that in an elastomer the
units are not linked in a straight chain but are
arranged in the form of a coil.

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When the deforming stress is released, the
chains go back to their original coiled state.

For example: rubber

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These are the polymers which have strong
intermolecular forces between the chains.

These forces are either hydrogen

bonding (For example nylon )or dipole-dipole
Interactions( as in polyesters).

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-Fall between the elastomers and fibers.
However there is no exact boundary

-They are pliable, that is, they can be

shaped and molded easily

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 i)Thermoplastics: Melt when heated and can be
melted again after cooling

ii)Thermosets: Undergoes crosslinking when

heated, so does not melt again, decomposes if
heated further

Plastics possess plasticity but no elasticity

but
rubbers possess elasticity and no plasticity.

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Plasticity is the property to get deformed on

application of force

and elasticity is the property to regain the

original shape when the deforming force is
removed.

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The physical properties of a polymer, such as its
strength and flexibility depend on:

-Chain length - In general, the longer the chains the

stronger the polymer;

-Side groups - Polar side groups give stronger

attraction between polymer chains, making the
polymer stronger;
-Cross-linking :

If polymer chains are linked

together extensively by covalent bonds, the

polymer is harder and more difficult to melt.

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