Classification of Polymers - Lecture 1

Monomer is a small molecule
Polymer is a long chain of monomers
The process by which monomers combine is called polymerization

Hermann Staudinger
(1881 – 1965)
“Father of Macromolecular Chemistry”

1953 Nobel Prize in Chemistry.
German chemist who demonstrated the existence of macromolecules,

which he characterized as polymers.
He postulated that materials such as natural rubber have very high
molecular weights. In a paper, Staudinger presented several reactions
that form high molecular weight molecules by linking together a large
number of small molecules. During this reaction, which he called
"polymerization," individual repeating units are joined together by
covalent bonds.
polyvinylchloride polypropylene
polyethylene polytetrafluoroethylene
Repeating units are a simplified method of drawing a polymer
Polymers consist of repeating molecular units which usually are joined by covalent bonds
A pendant group on a polymer is a small group of atoms (even a small chain sometimes) that hangs off of the main
chain (that is, the backbone of the polymer).
Here are some examples of pendant groups circled in red:

polypropylene polyvinylalcohol polystyrene
Polymers can be classified into several ways:
Based on Structure of Polymers

i) Linear polymers (ii) Branched chain polymers (iii) Cross linked polymers
Based on the Origin of the Polymer

i) Natural polymers (ii) Semi-synthetic polymers (iii) Synthetic polymers
Based on Thermal Processing Behaviour

i) Thermoplastic Polymers (ii) Thermosetting Polymer
Classification Based on Structure of Polymers
Linear Polymer:
Branched Polymer:
Branched polymers are defined as having secondary polymer chains linked to a

primary backbone.
Linear Polymer: Cross-linked Polymer:
Classification Based on the Origin of the Polymer
•Natural
•Semi-synthetic
•Synthetic
Natural Polymers: Polymers in Plants
Cellulose
Cellulose, a linear polymer of D-glucose units (two are shown) linked by

β(1→4)-glycosidic bonds.
While cellulose is a basic structural material of most plant substances, it is
also produced by bacteria. Bacterial cellulose has different properties from
plant cellulose and is characterized by high purity, strength, moldability and
increased water holding ability.
The majority of bacteria synthesize cellulose, which form protective

envelopes around the cells. Many methods are currently being investigated
to enhance cellulose growth from cultures in laboratories as a large-scale
process.
A purified microbial cellulose sample Paper made from bacterial cellulose

Starch
Natural Polymers: Polymers in Animals
Protein
Examples of Proteins:
All enzymes are proteins. Collagen in teehth and bone; keratin in skin, hair and nails.
Chitin
the exoskeletons of crabs,

lobsters and shrimps
(polymer of the N-Acetylglucosamine units)

Semi-synthetic Polymers: Chitosan
obtained from natural polymers by subjecting them to some chemical processes

Synthetic Polymers
Poly(methyl methacrylate) (PMMA) (1935)
PMMA sheet (organic glass) Plexiglass aquarium

Nylon 6,6 (1938)
A 1949 advertisement in Life

Magazine sings the praises of Natural animal bristles were replaced by
nylon products. synthetic fibers, usually nylon, by DuPont
in 1938.
Polyesters (1950)
Recycled PET Fabric
Poly(ethylene terephthalate)-PET bottles

Biodegradable polymers can be consumed or broken down by microorganisms.
They are widely used in the medicine, agriculture and packaging.
Polylactic acid
(PLA) is a
biodegradable
polymer derived
from renewable
resources such as
corn starch.
The concept of biomaterials was introduced soon after World War II
Classification of polymers according to their thermal behaviours:
1) Thermoplastıcs
•Thermoplastic polymers can be repeatedly softened when heated

and hardened when cooled with little change in their properties.
•The softening/melting occurs as the polymer chain move more and

more freely because of absence of cross link.
2) Thermosets
• Thermosets are generally prepared from low molecular mass

semifluid substances. When heated they get highly cross linked to
form rigid and insoluble products. They cannot be dissolved and
melted.
POLYMER CRYSTALLINITY
The glass transition temperature is the

property of the amorphous region of the
polymer, whereas the crystalline region is
characterized by the melting point.
The amorphous nature of polymers is analogous to a plateful of spaghetti --- loose

and randomly coiled.
The crystalline state is more like the uncooked spaghetti in the box --- the chains
are all tightly bundled and ordered in the same direction.
Factors affecting Tm - Intermolecular forces
Factors affecting Tm - Intermolecular forces
*The polar ester groups make for strong

crystals.
*In addition, the aromatic rings like to
stack together in an orderly fashion,
making the crystal even stronger.
Glass Transition Temperature (Tg)
The temperature at which polymers undergo the transition

from glassy to rubbery state.
The value of Tg depends on the mobility of the polymer

chain - the more immobile the chain, the higher the value
of Tg.
Below Tg : Polymers are hard and brittle like glass, due to

the lack of chain mobility.
Above Tg : Polymers are soft and flexible like rubber due
to chain mobility.
Factors affecting Tg - Chain Stiffness
Stiffening groups in the polymer chain reduce the flexibility of the

chain and raise the value of Tg.
poly(ethylene adipate)
Tg = -70oC
poly(ethylene
Tg = 69oC
terephthalate)
poly(ethylene terephalate) is a stiffer molecule than poly(ethylene

adipate) because a benzene ring is not as flexible as a chain of
CH2 groups.
Factors affecting Tg - Intermolecular forces
Stronger intermolecular forces lead to a higher

Tg. PVC has stronger intermolecular forces than
polypropylene because of the dipole-dipole forces
from the C-Cl bond.
Atactic Polypropylene Tg = -20oC
Atactic Poly(vinyl chloride) Tg = 81oC

Factors affecting Tg - Pendant Groups
Flexible pendant groups, such as aliphatic chains, tend to limit how

close chains can pack. This increases rotational motion and lowers
Tg.
Poly(methyl methacrylate) Tg = 105oC
Poly(butyl methacrylate) Tg = 20oC
An aliphatic compound is an organic compound containing carbon

and hydrogen joined together in straight chains, branched chains, or
non-aromatic rings.
MOLECULAR WEIGHT & CRYSTALLINITY
• Molecular weight, Mw: Mass of a mole of chains.
smaller Mw larger Mw
• Tensile strength (TS):

--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.
• % Crystallinity: % of material that is crystalline.
--TS and E often increase
with % crystallinity.
crystalline
region
amorphous
region
3
Adapted from Fig. 14.11, Callister 6e.
For relatively small deformations, the mechanical behaviour at low temperatures may
be elastic; at the highest temperatures, viscous behaviour prevails, for intermediate
temperatures the polymer is a rubbery solid that exhibits the combined mechanical
properties, the condition is termed viscoelasticity.
*The magnitude of Er(t) decreases
with time.
*The curves are displaced to lower
Er(t) levels with increasing
temperature.
≈Glass transition region

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Monomer is a small molecule

Polymer is a long chain of monomers

The process by which monomers combine is called polymerization

“Father of Macromolecular Chemistry”

German chemist who demonstrated the existence of macromolecules,

Repeating units are a simplified method of drawing a polymer

Here are some examples of pendant groups circled in red:

Based on Structure of Polymers

Based on the Origin of the Polymer

Based on Thermal Processing Behaviour

Branched polymers are defined as having secondary polymer chains linked to a

Cellulose, a linear polymer of D-glucose units (two are shown) linked by

The majority of bacteria synthesize cellulose, which form protective

A purified microbial cellulose sample Paper made from bacterial cellulose

the exoskeletons of crabs,

(polymer of the N-Acetylglucosamine units)

obtained from natural polymers by subjecting them to some chemical processes

PMMA sheet (organic glass) Plexiglass aquarium

A 1949 advertisement in Life

Recycled PET Fabric

Poly(ethylene terephthalate)-PET bottles

•Thermoplastic polymers can be repeatedly softened when heated

•The softening/melting occurs as the polymer chain move more and

• Thermosets are generally prepared from low molecular mass

The glass transition temperature is the

The amorphous nature of polymers is analogous to a plateful of spaghetti --- loose

*The polar ester groups make for strong

The temperature at which polymers undergo the transition

The value of Tg depends on the mobility of the polymer

Below Tg : Polymers are hard and brittle like glass, due to

Stiffening groups in the polymer chain reduce the flexibility of the

poly(ethylene terephalate) is a stiffer molecule than poly(ethylene

Stronger intermolecular forces lead to a higher

Atactic Polypropylene Tg = -20oC

Atactic Poly(vinyl chloride) Tg = 81oC

Flexible pendant groups, such as aliphatic chains, tend to limit how

Poly(methyl methacrylate) Tg = 105oC

Poly(butyl methacrylate) Tg = 20oC

An aliphatic compound is an organic compound containing carbon

• Tensile strength (TS):

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