Polymer Chemistry

Polymers
(Poly) Many + (meros) Parts
This name hints at how polymers are made.

mers are the macromolecules (giant molecules of higher mas

-up by the linking together of a large number of small molec
ed monomers).

monomers

Polymers
The word, polymer, implies that polymers are
constructed from pieces (monomers) that can be
easily connected into long chains (polymer).

Polyester
Polyester is used to make bottles and fabrics.

Polyester fabrics were "drip-dry" also called wash and wear,

meaning they were quick to wash, quick to dry, and no ironing
needed.

Another polymer, which is almost the same as

polyethylene, is PolyVinyl Chloride or PVC.
The difference is that every other hydrogen is
replaced with a chlorine atom.
PVC pipes are used in our homes
and they are even handy for making
a table or chair. PVC is also used as
insulation around electric wires in the
home and the automobile. PVC is
quite safe until it burns.

Monomers and polymers

Monomer
CH2

CH2

CH2

CHCl

Polymer

CH2CH2

CH2CH2
Cl

O
H2C

CH2

CH2CH2O

HOCH2CH2OH

CH2CH2O
O

HO

CO2H

Functionality: A substance to act a

monomer, it must have at least two reactive
sites or bonding sites. The number of
bonding sites in a monomer is referred to as
its functionality.

For e.g. Ethylene is considered to be

bifunctional
H

C
H

C
H

Definitions
According to the amount of repeating units
monomer : one unit
oligomer : few unit
polymer : many unit (poly many, mer part)
telechelic polymer : polymer containing reactive end
group

(tele = far, chele = claw)

telechelic oligomer : oligomer containing reactive end

group
macromer(=macro monomer) : monomer containing
long chain

Definitions
DP : Degree of polymerization
The total number of repeating units contained
terminal group in a polymer

A polymer may consist of identical monomers or

monomers of different chemical structure and
accordingly
they
are
called
Homopolymer,
copolymers terpolymers.
-A-A-A-A-A-A-A-AThe kinds of applied monomers

One
kind
Homopolymer

Two
Copolymer

kinds

A-B-A-B-A-B-A-B-

Types of polymer

Homopolymer : -A-A-A-A-A-A-A-ARandom copolymer : -A-B-B-A-B-A-A-BAlternating copolymer : -A-B-A-B-A-B-A-BBlock copolymer : -A-A-A-A-B-B-B-BGraft copolymer : -A-A-A-A-A-A-A-AB-B-B-B-B-

Tacticity

ntation of monomeric units in a polymer can take place in orderly or diso

with respect to the min chain. The differences in configuration of polyme
a tacticity.
ic polymer: If the arrangement of all functional groups are at the same
n chain known as a isotactic polymer.
polymer: if the arrangements of functional group are at random aroun
ain, it is called atactic polymer.
tactic polymer: if the arrangements of functional group is in alternative
ed syndiotactic polymer.

Classification of polymers

mer can be classified in a number of ways:

ssification on the basis of sources

Natural polymer: which are found in nature in animals and plants etc. like cellul
Protein, nucleic acids, natural rubber.

nthetic polymer (man made polymer) like polyethylene, polypropylene, polyvin

rene, nylon, etc
H

ssification on the basis of structure:

r polymer in which monomeric units are joined in the form of long straight chain
xample: nylons, polyester etc. these polymer possess high density , m.p. and ten
gth due to close paking of polymer

(a) linear

nched chain polymer are mainly liner in nature, but also posses branches alon
ain. f. g. low density polyethene. These polymers possess low m.p. density and
strength as compared to the liner polymer

(b) Branched

nsional network polymers contain monomers molecules connected to each o

nt bond. They are giant molecules in which movement of individual monomeric
ed by strong cross links. Therefore, they are rigid, hard and brittle and do not me

(c)network

Classification on the basis of molecular force

(i) Thermoplastic polymer: these polymer are
linear, long chain, which can softened on
heating and hardened on cooling reversibly i.e.
their hardness is a temporary properties. For
e.g. polythene, PVC, polystyrene
(ii)Thermosetting polymer: these polymer get
hardened during moulding and once they have
solidified, they cannot be softened. So, these
polymer once moulded cannot be reprocessed.

(iii) Elastomer: polymer which can be stretched

to at least thrice its length, but it returns to its
original shape and dimensions as
soon as
stretching force is released.
(iv) Fibers: fibers are those polymers whose
chains are held by strong intermolecular forces
like hydrogen bonding.
TheyH are crystalline in
H2
2
nature .
N C
C
C
N C
H

H2
C

H2
C

ypes of polymerization reactions

1)Addition (or chain growth) polymerization

2)Condensation (or step growth) polymerization
In addition polymerization, the polymer is formed from
the monomer, without loss of any material, and the
product is exact multiple of the original monomeric
molecule.
Example:
Ethylene -> Polyethylene, Styrene-> Polystyrene

pes of polymerization reactions

(1) Addition (or chain growth) polymerization
reactions:
Addition or chain polymerization is
reaction, which is an exact multiple of the original
monomeric
molecules.
The
monomeric

molecules usually have one or more

double
bond
which
by
intermolecular
rearrangement, may make the molecule bifunctional.
The addition polymerization must be instigated by the
application of heat, pressure or catalyst etc. for
H
H
H
breaking
bond of monomers.
H
H down the doubleHcovalent
n

light, heat, pressure

C

Ethene

bifunctional molecules

polythene

Addition is a reaction in which elements are added to the

starting material.

ree redical polymerization mechanism:

(i) Initiation step is considered to involve two
reactions. The first step is the production of free
radicals by homolytic dissociation of an initiator to
yield pair of radicals.(benzoylperoxide, tertbutylperoxide, AIBN)
I

2R

(Initiator)

Free radicals
Azobisisobutyronitrile

The second part of the initiation steps involves

the reaction of this radical with first monomer
unit (M) to produce chain initiating species
R + M
monomer

M1

O
O

O
O

pagation step consists of the growth of M1 free radical by successive reaction

mbers of monomers molecules

M1 + M
monomer

M2

M2 + M
monomer

M3

M3 + M
monomer

M4

Mn + M
monomer

Mn+1

In general

Termination steps

Termination by coupling.
Termination by disproportionation.

Termination by coupling

Termination by disproportionation

Ionic polymerization
In ionic polymerization, the active centres initiating the
chain reaction are ions. Ionic polymerization proceeds
due to the presence of catalysts and hence it is called
catalytic polymerization. Depending upon the charge of
the ion formed, the polymerization may be cationic or
anionic.

Cationic polymerizationis a type ofchain growth

polymerizationin which a cationic initiator transfers
charge to amonomerwhich becomes reactive. This
reactive monomer goes on to react similarly with other
monomers to form a polymer.
Protonic acids

Lewis acids

Carbenium ion
salts

Propagation

Anionic polymerizationis a form ofchain growth

polymerizationoraddition polymerizationthat involves
the polymerizationof vinyl monomers with strong
electronegative groups.This polymerization is carried out
through acarbanion active species.Like all chain-growth
polymerizations, it takes place in three steps:chain
initiation,chain propagation, andchain termination.

dination polymerization (Ziegler-Natta catalysts)

Coordination polymerisationis a form ofaddition
polymerizationin
whichmonomeradds
to
a
growingmacromoleculethrough anorganometallicactive
center.The development of this polymerizationtechnique
started in the 1950s withheterogeneousZiegler-Natta
catalystsbased
ontitanium
tetrachlorideand
analuminiumco-catalyst. Coordination polymerization
has a great impact on the physical properties ofvinyl
polymerssuch
aspolyethyleneandpolypropylenecompared to the same
polymers prepared by other techniques such asfree
radical polymerization. The polymers tend to be linear
and not branched and have much highermolar mass.
Coordination type polymers are alsostereoregularand
can beisotacticorsyndiotactic instead of justatactic.
Thistacticityintroducescrystallinityin
otherwiseamorphouspolymers. From these differences in

Ziegler-Natta catalysts

Cl C H
2 5

Cl

TiCl4 + Al(C2H5)3

Ti

C2H5

Al

Cl

Cl

C2 H5

C2 H5
CH2
H
Cl C2
Cl

Ti

Cl

Cl

CH2

Cl

Ti

Al

C2H5
C2H5

(CH2-CH2)n C2H5

Al
Cl

Ti

Cl
Cl
H2C CH2

C2H5

H
Cl C2
Cl

Cl

C2 H5

Al

Cl C H
2 5

Cl H

C2H5

Cl

Ti

Cl

C2H5

H2C CH

Al
Cl

C2 H 5
C2H5

(CH2-CH2)n C2H5

BULK POLYMERIZATION
The simplest method of polymerization where the
reaction mixture contains only the monomer and a
monomer soluble initiator. The process generally
carried out in the by a continuous process, which
involves two stages:First Stage
Pre polymerization is carried out in nitrogen
atmosphere in in a reaction vessel , which is heated by
hot jacket and monomer and initiator is added
continuously with stirring at certain rate. The
monomer is polymerized to about 30%.

Second Stage
The polymerization mixture is highly viscous and clear,
is fed into the upper end of vertical reactor, divided
into zones, each kept at desired temperature except
the lowest one. The highest conversion of
polymerization is carried out in the lowest zone. The
resulting molten polymer is taken out with the help of

ADVANTAGE
Advantage of the high concentration
of monomer result in
High rates of polymerization
High degree of polymerization
High purity of product
High molar mass polymer are
produce

Limitations:
Difficulty in removing the last traces
of monomer
The problem of dissipating heat
produced during the polymerization

In practice, heat dissipated during bulk

polymerization can be improved by
providing special baffles.

Emulsion Polymerization
The monomers are dispersed as fine droplets
(d=~1mm) in large amount of water and then
emulsified by the addition of emulsify agents
(soaps, detergent).
Then initiator is added which are usually water
soluble or monomer soluble. Very often
persulphates are used.
These ion radicals react with monomer in
emulsion form and polymerization occurs.
Finally the polymer emulsion is may be broken
by adding electrolyte followed by washing,
drying etc. of coagulated polymer.
For example PVC etc.

Emulsion Polymerization

Advantages of emulsion polymerization

include:
High molecular weight polymers can be made
at fast polymerization rates.
The continuous water phase is an excellent
conductor of heat and allows the heat to be
removed from the system, allowing many
reaction methods to increase their rate.
The final product can be used as it is and does
not generally need to be altered or processed.

Emulsion Polymerization
Disadvantages of emulsion polymerization
include:
For dry (isolated) polymers, water removal
is an energy-intensive process
Emulsion polymerizations are usually
designed to operate at high conversion of
monomer to polymer. This can result in
significant chain transfer to polymer.

Suspension
Polymerization
In this methods monomer is dispersed as relatively
large droplets (10-100 mm) in water.
It is kept in suspension by mechanical agitation.
The catalyst is then added and imitation take places.
As the polymerization will proceeds, the viscosity will
of dispersed drops increases and become sticky.
At this stage suspension is stabilize by small amount
of suspension stabilizer.
When the reaction is complete, the reaction products
(in form of pearl) is washed dried and used.

Advantages of Suspension Polymerization

Process is economical since it involves only water
instead of costly solvents.
Agitation and thermal control are easy
Product isolation is easy since the product is insoluble
in water and involves only filtration, washing and
drying.
Polymer obtained is small granular form which is
convenient and easily handled at high temperature.

Disadvantages
The method can be adopted for only water insoluble
polymers
It is difficult to control the particle size
Yield per reaction value is low.

sliquid transition(orglass transition) Tg

Theglassliquid transition(orglass transitionfor
short) is the reversible transition inamorphousmaterials
(or in amorphous regions withinsemicrystallinematerials)
from a hard and relatively brittle state into a molten
orrubber-like state.
Despite the massive change in the physical properties of a material
through its glass transition, the transition is not itself aphase
transitionof any kind; rather it is a laboratory phenomenon extending
over a range of temperature and defined by one of several
conventions.Such conventions include a constant cooling rate (20
K/min)and a viscosity threshold of 1012Pas, among others. Upon
cooling or heating through this glass-transition range, the material
also exhibits a smooth step in thethermal-expansion coefficientand
in thespecific heat, with the location of these effects again being
dependent on the history of the material.However, the question of
whether some phase transitionunderliesthe glass transition is a
matter of continuing research.
Theglass-transition

temperatureTgis

always

lower

than

Factors affecting Tg
Upon heating through the glass transition temperature,
the amorphous solid polymer transform from a rigid to a
rubbery state and the molecules which are virtually
frozen in position below Tg begin to experience rotational
and translational motions above Tg
1) The presence of bulky side groups increase Tg.
2) Polar side atoms or groups of atoms increase Tg.
3) Double chain bonds and aromatic chain groups which
tend to stiffen the molecular backbone increases T g.
4) Increase in the molecular weight also tends to raise
the glass transition temperature.
5) A small amount of branching will tend to lower Tg; on
the other hand , a high density of branches reduces
chain mobility, and elevates glass transition

Molecular Weight of Polymers

Unlike small molecules, polymers are typically a mixture of differently
sized molecules. Only an average molecular weight can be defined.

Number Average Molecular Weight: It is determined by

the measurement of the colligative properties (such as freezing
point depression, boiling point
elevation, lowering of vapors pressure etc.) which counts the
numbers of
molecules in a given volume or mass. Hence this methods
depends on the
Ni M i
M
=
n presents.
number of molecular
N
i

Where Ni is number of molecules of molecular weight M i

Average Molecular Weight: It is obtained When the molecul

ged according to the weight of the molecules of each types. I

ned by the light scattering methods.

Mw

Ni
M2i Ni Mi

Consider a polymer sample containing 50 molecules of

molecular weight 10000, 35 molecules of molecular
weight 12000 and 15 molecules of molecular weight
14000.
Determine Number Average Molecular
Weight and Weight Average Molecular Weight. If
the polymer is
polypropylene, what will be the
degree of polymerization?

Number Average Molecular Weight

Mn

Ni M i
Ni

Weight Average Molecular Weight:

Mw

Ni
M2i Ni Mi

The didispersity index, or formerly

polydispersity index (PDI)= Mw Mn

Unlike simpler pure compounds, most polymers are

not composed of identical molecules. The HDPE
molecules, for example, are all long carbon chains,
but the lengths may vary by thousands of
monomer units. Because of this, polymer molecular
weights are usually given as averages. Two
experimentally determined values are common:Mn,
the number average molecular weight, is
calculated from the mole fraction distribution of
different sized molecules in a sample, andMw, the
weight average molecular weight, is calculated
from the weight fraction distribution of different sized
molecules. These are defined below. Since larger
molecules in a sample weigh more than smaller
molecules, the weight average, Mw is necessarily
skewed to higher values, and is always greater

+ (35x 12000) + (15x14000)

=
Mn (50x10000)
(50+35+15)

Ans. =11,300 (Number Average Molecular Weight )

Mw

2
2
2
50(10000)
+
35(12000)
+
15(14000)
=

(50x10000)+(35x12000)+(15x14000)

Ans. =11,486.7 (Weight Average Molecular Weight )

Mn

DP=
Molecular weight of monomer
Ans. = 269 (DP)

tetrafluoroethylene (TEFLON) or FLUON (PTFE)

F

benzoyl peroxide
C

Tetrafluoro ethene

Polytetrafluoroethene (PTFE)

roperties of TEFLON:

hey are extreme tough, high softening point, exceptionally high

chemical-resistances towards all chemicals, high density, waxy touch.
can be punched, machined and drilled

Uses

s a insulating materials (for motors, transformers, cables, wires, fitting)

or making gaskets, packing, pump parts, tank, chemical-carrying pipe lin
or coating
non-lubricating bearing and non-sticking stop-cocks.

Nylon:
A man-made polymer
Nylon is used in
clothes, shoes, jackets,
belts, Tires, ropes and
various accessories.

lons are used for fibers, use in making cloths, carpets etc.
ey are used for moulding purposes for gears, bearing, electrical equipme
ey are also used for making filaments for ropes, for tooth brushes and fil

(2) Condensation or step polymerization: A

reaction between polar group containing monomer units to yield
polymer and elimination of small
molecules (like H2O, HCl, NH3 etc).
For example hexamethyl diamine and adipic acid condense to form a
polymer known as nylon 6:6

roperties of Nylons

hey
hey
hey
hey

are high melting point (160 to 264C) whitish polymer.

possess high temperature stability and good abrasion-resistances.
are insoluble in common organic solvents like benzene acetone
have self lubricating properties.

Phenolic resins ( PF Resins)

condensation polymerization products of phenolic derivatives (p

l) with aldehydes (formaldehyde).

sis of the Bakelite from phenol: it is prepared by condensing phenol u

ehyde in presence of acid or base

OH

HCHO
CH2OH

CH2OH
OH
OH

roperties of Bakelite:

hey are rigid, hard, scratch-resistant, infusible, water resistant, insoluble

esistant to non-oxidizaing acids, salts and many organic solvents.
hey are attacked by alkalis
hey possess excellent electrical insulting character

Uses

For making electric insulators parts like switches, plugs, switch

board, heater-handles etc.
For making moulded articles like telephone parts, cabinets for
radio and television.
For impregnating fabrics, woods and paper
As adhesives (binder) for grinding wheels.
In paints and varnish
As hydrogen exchanger resins in water softening

Epoxy resins

ared by the condensation polymerization of bisphenol and epicho

operties of Epoxy resins:

Due to the presences of stable ether linkage, epoxy
resins are high chemical resistances towards water,
many solvents, acids, alkalis and other chemicals
high flexibility
Tough materials and heat resistances due to cross links
Excellent adhesion quality due to the presences of polar
functional groups
Uses
As surface coating , adhesive like ardilite (for glass and
metals)
For skid-resistant surfaces for highways
Components for automobile and aircrafts
Applied on cotton, rayon and bleached fabrics to impart
crease-resistances and shrinking control.
As laminating materials used in electrical equipment.

Rubbers (Elastomers)
Highly amorphous
Highly random
orientation
Elastic properties

Stressed
In tension

No Stress

Natural Rubber
Natural rubber is cis-1,4-polyisoprene, a polymer
of isoprene (2-methyl-1-3- butadiene). It is a
stereo regular polymer with all the pendent
methyl groups in the linear polymer chain lying in
one side.

H
H

H
C

H
C

C
H

C
H

Cis-polyisoprene

Raw material extracted from

Natural rubber is obtained from the exudates of

the rubber trees in the form of a milky colloidal
solution called latex containing 25-45% of rubber
dispersed in a watery medium with small
amounts of protein and other materials. The latex
is tapped by cutting through the bark of the tree
and the liquid that comes out is collected in
containers.
The latex is processed either by i) coagulation by
acid or by heat and processed further or ii) mixed
with compounding materials and precipitated
directly from the solution.

awback of raw rubber

It is plastic in nature: It becomes soft at high

temperature and
is too brittle at low temperature. So it can be used in
temperature range between 10 to 60C only
weak: tensile strength is only 200kg/cm 2
has large water absorption capacity
n-resistant to non polar solvents like vegetable and m
s attacked by oxidizing agent
ells in organic solvent and gradually degrade
t has little durability

Vulcanization
Vulcanization is a process, through which elasticity of the rubbers
increases and reduces plasticity by the formation of a crosslinked
molecular network.
Vulcanizationisdonebyheatingtherubberwithsulfurorother
vulcanizingagentsunderpressure

Charles Goodyear (December 29, 1800 July 1, 1860) was an American

inventor who developed a process to vulcanize rubber in 1839a
method that he perfected while living and working in Springfield,
Massachusetts in 1844, and for which he received patent number 3633
from the United States Patent Office.

Tetramethylthiuram disulfide

Compounding of Rubber
Compoundingismixingoftherawrubber(syntheticornatural)with
othersubstancessoastoimparttheproductspecificpropertiessuitable
forparticularjob.
(1)Softener and plasticizers are added to give the rubber greater tenacity
and adhesion. For e.g. vegetable oil, waxes, stearic acid.
(2) Vulcanizing agents: sulfur, sulfur monochloride, benzoyl chloride etc.
(3) Accelerators: These materials drastically shorten the time required for
vulcanization. 2-mercaptol, Benzothiazole etc.
(4) Antioxidants: Natural rubbers has a tendency to perish due to the
oxidation. For this reason antioxidants are required, such as complex
amine, phosphites etc.
(5) Reinforcing fillers: theses materials gives strength and rigidity to the
rubber products. For e.g. CaCO3, ZnO etc.
(6) Colouring agents

Comparison of condensation and Addition Polymerization

Condensation/StepReaction
Growth occurs throughout matrix by
reaction between monomers, oligomers,
and polymers
DPa low to moderate

Addition/ChainReaction
Growth occurs by successive addition of
monomer units to limited number of
growing chains
DP can be very high

Monomer consumed relatively slowly, but

molecular weight increases rapidly
molecular weight increases slowly
Initiation and propagation mechanisms different
No initiator needed; same reaction
Usually chain-terminating step involved
mechanism throughout
Polymerizaion rate increases initially as
No termination step; end groups still reactive initiator units generated; remains relatively
Polymerization rate decreases steadily as
constant until monomer depleted
functional groups consumed
Monomer consumed rapidly while

DP, average degree of polymerization.

Some examples:
A polymer made
form just one
monomer is
polyethylene. It
is the most
common plastic
you see.
It is used for
bottles, buckets,
jugs, containers,
toys, even
synthetic
lumber, and
many other
things.

Polyethylene

city:

The orientation of monomeric units in a polymer molecule

aces in an orderly or disorderly fashion with respect to the main
fferences in configuration is known as tacticity.

head-to-tail configuration, in which the functional groups are all on the same sid
hain is called isotactic polymer

e arrangement of functional groups are at random around the main chain, is calle
ctic polymer e.g. polypropylene

rangement of the side groups is in alternating fashion, it is called syndiotactic

ta percha