Polymers

What is polymer
• A polymer is a material whose
molecules contain a very large
number of atoms linked by
covalent bonds, which makes
polymers macromolecules.
• Polymers consist mainly of identical
or similar units joined together.
• The unit forming the repetitive
pattern is called a "mer" or
"monomer".
• Usually the biggest differences in
polymer properties result from how
the atoms and chains are linked
together in space.
• Polymers that have a 1-D structure
will have different properties than
those that have either a 2-D or 3-D
structure.
Polymers are long chain
molecules
 What is polymer
• Polymers are a very important class of materials.

• Polymers occur naturally in the form of proteins,

cellulose(plants), starch(food) and natural rubber.
Engineering polymers, however, are usually synthetic
polymers.

• The field of synthetic polymers or plastics is currently one of

the fastest growing materials industries.

• The interest in engineering polymers is driven by their

manufacturability, recyclability, mechanical properties, and
lower cost as compared to many alloys and ceramics.
 Degree of Polymerization
• Number of monomer units in the chain
N >> 1.
• For synthetic macromolecules usually
N=102-104
• For natural macromolecules like DNA
N=109-1010
Number of monomers in a chain is
called degree of polymerization (DP).
 Average degree of polymerization
• The degree of polymerization (DP) in a polymer molecule is the
number, n, of repeating units in the polymer chain.
•

• The molecular weight of a particular polymer molecule is a product

of the degree of polymerization and the molecular weight of the
repeating unit.
• For instance a particular polyethylene molecule with DP = 1000 will
have a molecular weight of 28,000.
• Because polymeric materials do not consist of strictly identical
molecules, but instead are a mixture of many species having
different values of DP, the DP of the material only is an average DP
value.
• Hence, measured polymer molecular weights are only average
values.
 What governs physical
properties of polymers
Monomer units are connected in the chain.
They do not have the freedom of independent motion
low number of degrees of freedom
(unlike systems of disconnected particles, e.g. low molecular
gases and liquids).
Polymer systems are poor in entropy.
• Polymer chains are generally flexible.
 Polymer molecular structure

1. Chemistry (Mer composition)

2. Size (Molecular Weight)
3. Shape (Chain twisting, entanglement)
4. Structure- Linear (Isomers-Stereo and Geometrical)
Branched
Cross-linked
Ring
Network
Types of Polymer Molecules (Structure)
1. Homopolymers: all monomer units are the
same.
2. Copolymers : monomer units of different
types.
(for example, proteins - 20 types of units
DNA - 4 types of units ).
Sequence of monomer units along the chain is
called primary structure.
3. Bifunctional (2-D), Chain structure, ethylene
4. Trifunctional (3-D) Network structure, Bakelite
 Different kind of copolymers
• The polymerization of a mixture of two monomers
of suitable reactivity leads to the formation of a
copolymer.
• Random copolymer: A polymer in which two types
of mer units have entered the chain in a more or less
random fashion.
• Alternating Copolymer: both mer units occur
alternately in the structure
• If chains of one homopolymer are chemically joined
to chains of another, the product is called a block
copolymer or a graft copolymer.
 Different kind of copolymer
A-B-A-A-B-B-B
(Random copolymer)
A-B-A-B-A-B-A-B
(Alternating copolymer)
A-A-A-A-A-B-B-B-B-
(block copolymer)
A-A-A-A-A
|
B
|
B
|
B
(Graft polymer)
Branched macromolecule
Ring macromolecules
Polymers are special
 Physical states of Polymer
1.Partially crystalline state
2. Viscoelastic state (polymer melt)
3. Highly elastic state ( e.g. rubbers)
4. Glassy state ( e.g. organic glasses from poly(styrene),
poly(methylmethacrylate), poly(vinyl chloride)).

Polymers are large molecules with strong intermolecular forces and
tangled chains, and do not have a vapor phase - they decompose before
the temperature gets high enough to form a vapor.

The length of polymer molecules also makes it difficult for the large
crystals found in the solid phases of most small molecules to form.

Instead solid polymers can be modeled in terms of two phases - crystalline and
amorphous.

Thus the behavior of polymers can better be understood in term of the three
phases: melt, crystalline, and amorphous.
 Crystaline polymer
Crystalline Polymer
• Highly crystalline polymers are rigid, have high melting point, and
less affected by solvent penetration.
• Crystallinity makes a polymers strong, but also lowers their impact
resistance.
• As an example, samples of polyethylene prepared under high pressure
(5000 atm) have high crystallinities (95 - 99%) but are extremely
brittle.
Amorphous Polymers
• Polymer chains with branches or irregular pendant groups cannot pack
together regularly enough to form crystals.
• These polymers are said to be amorphous.
 Molecular weight of Polymer
• Polymers are different. Imagine polyethylene. If we have a sample of
polyethylene, and some of the chains have fifty thousand carbon atoms in
them, and others have fifty thousand and two carbon atoms in them, this
little difference isn't going to amount to anything.

• To know the truth, one almost never finds a sample of a synthetic

polymer in which all the chains have the same molecular weight.

• Instead, we usually have a bell curve, a distribution of molecular

weights. Some of the polymer chains will be much larger than all the
others, at the high end of the curve. Some will be much smaller, and at
the low end of the curve. The largest number will usually be clumped
around a central point, the highest point on the curve.

• So we have to talk about average molecular weights when we talk about

polymers. The average can be calculated in different ways, and each
way has its own value.
 Different average molecular weights
• The Number Average Molecular Weight, Mn
• The number average molecular weight is not too difficult to understand. It
is just the total weight of all the polymer molecules in a sample, divided
by the total number of polymer molecules in a sample.

• The Weight Average Molecular Weight, Mw

• The weight average is a little more complicated. It's based on the fact that
a bigger molecule contains more of the total mass of the polymer sample
than the smaller molecules do.

• The Viscosity Average Molecular Weight, Mv

• Molecular weight can also be calculated from the viscosity of a polymer
solution. The principle is a simple one: Bigger polymers molecules make
a solution more viscous than small ones do.
• Of course, the molecular weight obtained by measuring the viscosity is a
different from either the number average or the weight average molecular
weight. But it's closer to the weight average than the number average.
Number averaged molecular weight
• Suppose a mixture of polymer molecules with different molecular weights in
which the number of molecules having a particular molecular weight, Mi,
is given by Ni. The "number-average" probability of a given mass being
present is

and the number-average molecular weight is given by the formula

• The number average is the simple arithmetic mean, representing the total
weight of the molecules present divided by the total number of molecules.
• Most thermodynamic measurements are based on the number of molecules
present and hence depend on the number-average molecular weight:
examples are the colligative properties, osmotic pressure and freezing
point depression.
 Weight average molecular weight
• The probability factor in a weight-average emphasizes the mass
of the molecules so that the heavier molecules are more
important.
The weight-average molecular weight formula is

Molecular weight measurements that depend on the contributions

of molecules according to their sizes give weight-average
molecular weights.

Light scattering and ultracentrifuge methods are examples of
this type of technique.
 Measure of Polydiversity
• The weight-average molecular weight is larger than or equal to the
number-average molecular weight.

The ratio of the weight-average and number-average molecular

weights, is a measure of the polydispersity of a polymer mixture .

Signifies how widely distributed the range of molecular weights are

in the mixture.

A ratio that is around 1.0 indicates that the range of molecular

weights in the mixture is narrow

A high ratio indicates that the range is wide. With rare exceptions,
all synthetic polymers are polydisperse.
 Threshold Molecular Weight
• Polymer chemists sometimes refer to the threshold
molecular weight below which an oligomer will not display
the properties needed for a particular application.

• The value of the threshold molecular weight depends on

the application.

• If the polymer is to be used as an adhesive, the required

molecular weight may be relatively low.

• If the polymer is to be used in a trash barrel on the other

hand, a high molecular weight is required.
 Commercial Polymer Range
• Beyond the critical degree of
polymerization, as molecular weight
grows larger polymer strength increases
rapidly. Eventually, as is shown in the
diagram at the right, the strength levels
off.
• The threshold molecular weight is a lower
limit for the molecular weight required
for a given commercial application
• As the molecular weight increases the
chains also entangle more, which
increases the viscosity of the polymer
melt.
• In most industrial applications a polymer
is melted as it is processed so that it will
flow into a mold or through an orifice.
• Eventually the viscosity gets so high that
the polymer cannot be processed easily,
establishing an upper molecular weight
limit beyond which it is prohibitively
expensive to process the polymer.
 Commercial Polymer Range
• For a particular application
only a certain molecular weight
range is practical for a given
polymer.
• This range is a compromise
between optimum properties
and ease of processing.
• Most of the practically useful
polymers have a DP between
200 to 2000, corresponding to a
molecular weight range from
20,000 to 200,000.
 Polymer structures: one
dimensional polymers
• One dimensional polymers are most common.
• They can occur whenever 2 reacting chains join to
make a chain.
• If the long-chains pack regularly, side-by-side, they
tend to form crystalline polymers.
• If the long chain molecules are irregularly tangled, the
polymer is amorphous since there is no long range
order.
• Sometimes this type of polymer is called glassy.
 Polymer structures: Two
dimensional polymers
• Two dimensional polymers are rare, the best
example of one would be graphite.
• It is the structure of graphite which provides its
great lubricating capability.
• The condition to form this planar structure is to
have 3 or more active groups all directed in the
same plane and capable of forming a planar
network.
• This structure offers low shear strength and good
lubricating properties.
 Polymer structures: Three
dimensional polymers
• Crystalline Diamond is an example of the 3-
dimensional crystalline polymer in which carbon is
linked to four corners of the tetrahedra and these
are packed with long range order in space to form a
lattice.
• Diamond has properties which are much more like
ceramics than polymers in terms of mechanical
behavior (high melting point, modulus, hardness,
strength, and fracture behavior)
Classification of polymers-Thermal response
Thermoplastic Polymers
• These are linear, one-dimensional polymers which have
strong intramolecular covalent bonds and weak
intermolecular van Der Waals bonds.
• At elevated temperature, it is easy to "melt" these bonds
and have molecular chains readily slide past one another.
• These polymers are capable of flow at elevated
temperatures, can be remolded into different forms, and in
general, are dissolvable.
• A thermoplastic, under the application of appropriate
heat, can be melted into a "liquid" state.
 Thermosetting Polymers
• These are three-dimensional amorphous polymers which are
highly crosslinked (strong, covalent intermolecular bonds)
networks with no long-range order.
• Thermosetting polymers are those resins which are "set" or
"polymerized" through a chemical reaction resulting in
crosslinking of the structure into one large 3-dimensional
molecular network.
• Once the chemical reaction or polymerization is complete, the
polymer becomes a hard, infusible, insoluble material which
cannot be softened, melted or molded non-destructively.
• A good example of a thermosetting plastic is a two-part epoxy
systems in which a resin and hardener (both in a viscous state)
are mixed and within several minutes, the polymerization is
complete resulting in a hard epoxy plastic.
 Rubbers and Elastomers
• In general, a rubber material is one which can be stretched
to at least twice its original length and rapidly contract to its
original length.
• Rubber must be a high polymer (polymers with very long
chains) as rubber elasticity, from a molecular standpoint, is
due to the coiling and uncoiling of very long chains.
• To have "rubber-elastic properties" a rubber materials' use
temperature must be above its glass transition
temperature and it must be amorphous in its unstretched
state since crystallinity hinders coiling and uncoiling.
• Rubbers are lightly crosslinked in order to prevent chains
from slipping past one another under stress without
complete recovery
 Polymer Synthesis
• There are two major classes of polymer formation mechanisms

– Addition polymerization: The polymer grows by sequential

addition of monomers to a reactive site
• Chain growth is linear
• Maximum molecular weight is obtained early in the
reaction

– Step-Growth polymerization: Monomers react together to

make small oligomers. Small oligomers make bigger ones, and
big oligomers react to give polymers.
• Chain growth is exponential
• Maximum molecular weight is obtained late in the reaction
 Addition Polymerization
A
In* In A* A
Initiation
 Addition Polymerization
Propagation

A
In* In A A* A
Initiation
 Addition Polymerization
Propagation

A
In* In A A A* A
Initiation
 Addition Polymerization
A nA
In* In A A A A* In A A A A A*
Initiation Propagation n

*A A A A A
A *A A A A A m
m

In A A A A A In A A A A A A A A A A
In A A A A A n
n n m

A* Combination
B A A A A
m
Chain Transfer Disproportionation
New reactive site
is produced
Termination
MW Reactive site is consumed

k propagation
MW ∝
k ter mination
0 100
% conversion
 Types of Addition Polymerizations
Anionic

n Li+
Ph Li+ Ph
C4H9 C4H9
C3H7 Li n
Ph Ph Ph
Radical

n
Ph Ph
PhCO2• PhCO2 PhCO2
n
Ph Ph Ph
Cationic

n
Ph Ph
Cl3Al OH2 H H HOAlCl3
n
Ph Ph Ph
HOAlCl3
 Step-Growth Polymerization
Stage 1
n n
Consumption
of monomer

Stage 2

Combination
of small fragments

Stage 3

Reaction of
oligomers to give
high molecular
weight polymer
 Step-Growth Polymerization
• Because high polymer does not form until the end
of the reaction, high molecular weight polymer is
not obtained unless high conversion of monomer is
achieved. 1000

1
Xn =
100
1− p

Xn = Degree of 10
polymerization
p = mole fraction monomer
conversion
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction Conversion (p)
 Polymer synthesis: step growth
Polymerization is the process by which monomers (smaller
chemical units) are combined to form a polymer.
• Step Growth Polymerization
In step growth polymerization or condensation
polymerization, chains of any length x and y combine to
form long chains:
x-mer + y-mer → (x + y)-mer

• The term condensation polymerization is mainly

characterized by the fact that the early reaction yields water.

• More recently it has been found that several other polymer

reaction condense out products such as HCl or will condense
out no products at all.
 Step growth (example)
• An example is the polymerization reaction involving terephthalic acid
and ethylene glycol, both of which are bifunctional.

• Polymer formation begins with one diacid molecule reacting with one
dialcohol molecule to eliminate a water molecule and form an ester.

• The ester unit has an alcohol on one end and acid on the other, which
are available for further reactions
 Step growth (example)
• The eventual result is a polyester called poly(ethylene
terephthalate) or more commonly, PET.

• PET is the plastic in soda bottles. It can be represented with a

shorthand notation.
 Step growth
• Step growth polymerization is used to yield branched
as well as networked polymers.
• true initiator of a network structure lies in a multifunctional
monomer.
• As the length and frequency of branches on the polymer
chain increases so does the probability that the branches will
reach from chain to chain.
• When all the chains are connected together the entire
polymer mass becomes one giant molecule.
• Consider a bowling ball, it has a molecular weight on the order
of 1027 g/mol, and it is one giant molecule.
Crosslinked or network polymers form in one of two ways:
1. Starting with tri functional (or higher) monomers
2. Chemically creating crosslinks from previous linear polymers
 Chain growth/ Addition
polymerization
• Chain growth polymerization involves an active chain site which
reacts with an unsaturated (or heterocyclic) monomer such that
the active site is recovered at the chain end.

• Vinyl polymers were probably the first to be synthesized in this

manner when in 1839 Simon reported the conversion of styrene to
some gelatinous mass.

• In general, high molecular weight species are made by the

successive addition of new monomers to the chain end.
Chain growth
 Chain growth
• Chain-reaction polymerization, sometimes called addition
polymerization, requires an initiator to start the growth of the
reaction.
• The largest family of polymers , vinyl polymers, are produced by
chain polymerization reactions.
• A good example is the free-radical polymerization of styrene, which
is initiated by a free radical (R) that reacts with styrene.
• The compound that is formed still is a free radical, which can react
again.
• This reaction eventually leads to the formation of polystyrene, a portion
of which is shown below. Polystyrene prepared by free-radical
polymerization is

• Polystrene can be represented as

 Chain growth
• There are several different techniques of synthesis
depending on the active site. These are:

Active Site Synthesis Technique

Free Radicals Free Radical
Polymerization
Carbanions Anionic Polymerization
Carbenium Ions Cationic Polymerization

Coordination Bonds Ziegler-Natta

with Transition Metals Polymerization
 Transitions in Polymer: Glass
Transition temperature
• Amorphous polymers exhibit two distinctly different types of
mechanical behavior.
• Some polymers like polymethyl methacrylate and polystyrene
are hard, rigid, glassy plastics at room temperature while
others like polybutadiene and polyethyl acrylate are soft,
flexible, rubbery materials at room temperature.
• There is a temperature, or range of temperatures, below
which an amorphous polymer is in a glassy state and above
which it is rubbery.
• This temperature is called the glass transition temperature, Tg,
and it characterizes the amorphous phase.
• It is especially useful since all polymers are amorphous to
some degree, they all have a Tg.
 Molecular Motions in Amorphous Polymers
• The molecular motions occurring inside an amorphous polymer
influence the glass transition temperature.
• The important motions are:
1. Translation motion of entire molecules (permits flow)
2. Cooperative wriggling and jumping of segments of molecules
(permits flexing and uncoiling leading to elasticity)
3. Motions of a few atoms along the main chain or side groups on the
main chain .
4. Vibrations of atoms about equilibrium position
• The glass transition temperature is the temperature at which there
is only enough energy for motions (3) and (4) to occur.
• Below the glass transition temperature processes (1) and (2) are
frozen out.
• This makes polymer ‘glassy’ below Tg & ‘rubbery’ above Tg.
 Factors Influencing Glass
Transition Temperature
In general the glass transition temperature depends on five other
factors which are:
1. Free volume of the polymer vf, - Volume of the polymer mass
not actually occupied by the molecules themselves. The higher
the vf is, the more room the molecules have to move around
and the lower is Tg. For all polymers the ratio of the free volume
vs the total volume (vf/v) is about 0.025 at Tg.
2. The attractive forces between the molecules. The more strongly
the molecules are bound together , the more thermal energy must
be applied to produce motion and hence more will be Tg
3. The internal mobility of the chains, or their freedom to rotate
about the bonds.
 Factors Influencing Glass
Transition Temperature
4. The stiffness of the chains- Stiff chains cannot easily coil and
fold, causing Tg to be higher for polymers with stiff chains.
Polymers with parallel bonds in the backbone, like polyimides,
and polymers with highly aromatic backbones have extremely
stiff chains and thus high Tg's.
5. The chain length. The glass transition temperature varies
according to the relation:
Tg = Tinf - C/x
where C is a polymer specific constant, Tinf is the asymptotic
value of the glass transition temperature for a chain of length
infinity and x is the length of the chain.
This relationship shows that shorter chains can move easier
than longer chains. For most commercial polymers Tg ~ Tinf,
since x is quite long.
 Relation between chain length and
bond length
• For a linear chain polymer, the chain length

θ
L = N d s in
2
where θ is the angle between adjacent
backbone chain atoms, d is the bond length,
and N is the total number of bonds in the
molecule
 Determination of the Glass Transition
Temperature
• The most common method used to determine Tg is to observe
the variation of a thermodynamic property with T.

• Tg determined in this manner will vary somewhat depending

on the rate of cooling or heating.

• This reflects the fact that long entangled polymer chains

cannot respond instantaneously to changes in temperature.

• At the glass transition temperature a thermodynamic property

will exhibit a discontinuity with temperature.

• A second order thermodynamic transition.

 Crystallinity in polymer
• Crystallinity of a polymer material refers to the degree to
which polymer molecules are oriented into repeating
patterns.
• For same material, density of crystalline polymer is greater
than that of amorphous polymer.
• Chains are more closely packed together for the crystalline
structure.
ρ c ( ρ s − ρ a)
% crystallinity = X 100
ρ s ( ρ c − ρ a)
• Degree of crystalline character of a polymer depends on the
rate of cooling during solidification as well as on the chain
configuration.
• Crystallization easy in linear polymers and branching
(networking) interferes with crystallization.
• Lesser crystallinity in bulkier or larger side groups.
 Electrical properties of polymer
• Most of the polymers are
normally insulators specially polymer Conductivity
when they are in pure form.
in Ω − 1 m −1
• This will be clear from the
following table. Phenol 10-9-10-10
formaldehyde
• But by suitable choice of
doping one can make ionically
conducting and electronically Polymethyl <10-12
conducting polymer. methacrylate
Poyethylene 10-15-10-17
 What is conductivity?
Conductivity can be defined simply by Ohms Law.
V= IR
Where R is the resistance, I the current and V the voltage present in the
material. The conductivity depends on the number of charge carriers
(number of electrons) in the material and their mobility. In a metal it
is assumed that all the outer electrons are free to carry charge and
the impedance to flow of charge is mainly due to the electrons "bumping"
in to each other.

Insulators however have tightly bound electrons so that nearly no

electron flow occurs so they offer high resistance to charge flow. So
for conductance free electrons are needed.
 What makes the material conductive?
Three simple carbon compounds are diamond, graphite and
polyacetylene. They may be regarded as three- two- and
one-dimensional forms of carbon materials .

Diamond, which contains only σ bonds, is an insulator and its

high symmetry gives it isotropic properties. Graphite and
acetylene both have mobile π electrons and are, when doped,
highly anisotropic metallic conductors.
 How can plastic become conductive?
Plastics are polymers, molecules that form long chains, repeating
themselves.
In becoming electrically conductive, a polymer has to imitate a
metal, that is, its electrons need to be free to move and not bound to
the atoms.
Polyacetylene is the simplest possible conjugated polymer. It is
obtained by polymerisation of acetylene, shown in the figure.
 Two conditions to become conductive:
I- The polymer consists of alternating single and double
bonds, called conjugated double bonds.
In conjugation, the bonds between the carbon atoms are
alternately single and double. Every bond contains a
localised “sigma” (σ) bond which forms a strong chemical
bond.
In addition, every double bond also contains a less
strongly localised “pi” (π) bond which is weaker.
2-The second condition is that the plastic has to be
disturbed - either by removing electrons from
(oxidation), or inserting them into (reduction), the
material. The process is known as Doping.

• There are two types of doping

• 1-oxidation with halogen (or p-doping).

3x +
(CH n ) + I → (CH n ) + I 3−
2
2- Reduction with alkali metal (called n-doping).

x−
(CH n ) + xNa → (CH n ) + xNa +
• The game offers a simple model of a doped polymer. The
pieces cannot move unless there is at least one empty
"hole".
• In the polymer each piece is an electron that jumps to a
hole vacated by another one. This creates a movement
along the molecule - an electric current.
Factors that affect the conductivity

1-Density of charge carriers.

2- Thier mobility.
3-The direction.
4-presence of doping materials (additives
that facilitate the polymer conductivity)
5-Temperature.
 Applications
Conducting polymers have many uses. The most documented
are as follows:
• anti-static substances for photographic film
• Corrosion Inhibitors
• Compact Capacitors
• Anti Static Coating
• Electromagnetic shielding for computers
"Smart Windows"
A second generation of conducting polymers have been
developed these have industrial uses like:
• Transistors
• Light Emitting Diodes (LEDs)
• Lasers used in flat televisions
• Solar cells
• Displays in mobile telephones and mini-format television
screens
Shield for computer screen
against electromagnetic smart" windows
"smart" windows
radiation

Solar cell
Photographic Film Light-emitting diodes
 Conclusion
• For conductance free electrons are needed.
• Conjugated polymers are semiconductor materials
while doped polymers are conductors.
• The conductivity of conductive polymers decreases
with falling temperature in contrast to the
conductivities of typical metals, e.g. silver, which
increase with falling temperature.
• Today conductive plastics are being developed for
many uses.