• What are some of the polymers that you encounter every day?

Sandwich bags, carpets, nylon stockings, stackable chains, milk cartons,

etc.

• Why do different polymers have different properties?

They have different chemical compositions (different monomer units),
different structures, different ways of being fabricated, etc.

• Imagine samples of LDPE (sandwich bag, squeeze bottle) and HDPE

(milk jug, grocery bag). What are some of the differences in the physical
properties of these substances?
LDPE – more transparent, flexible, waxy
HDPE – more opaque, rigid, non-waxy
 POLYMERS
DEFINITION:
The word polymer is derived from the two greek words

poly and mers

many parts or units

e.g.
mer mer mer
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 CH 3 H CH 3 H CH 3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Polymers are macro molecules formed by linking smaller

molecules repeatedly, called monomers.
Examples:
Polyethylene is formed by linking a large number of
ethylene molecules
H H
H H
n C C Polymerisation
C C
H H n
H H
Ethylene polyethylene

polystyrene is formed by linking styrene molecules

H H H
H
n C C Polymerisation
C C
H n
H
styrene polystyrene
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.
Classification of Polymers:
1. Based on origin:

A. Natural Polymers

These occur in nature in plants and animals and are very essential for life. For
e.g., proteins, nucleic acids, Starch, cellulose, protein, silk, wool and natural
rubber are some natural polymers.

B. Synthetic Polymers

Synthetic polymers are man-made polymers which include fibers like teflon and
dacron, synthetic rubbers, Polyethylene, Polystyrene, polyvinylchloride, nylone,
polyester
Homopolymer is a polymer made up of only one
type of monomer
( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n
Teflon Polyethylene Cl
PVC

Copolymer is a polymer made up of two or more

monomers

(CH CH2 CH2 CH CH CH2 )n

Styrene-butadiene rubber
Copolymers

two or more monomers polymerized together

A B

Alternating A and B alternate in polymer

chain

Block large blocks of A units alternate

with large blocks of B units

Random A and B randomly positioned

along chain

Graft chains of B units grafted onto

A backbone
Tacticity : the orientation of monomeric units in a polymer molecule
It affects the physical properties of polymers.

R groups on same
side of chain
Isotactic

R groups alternate
from side to side
Syndiotactic

R groups disposed
at random
Atactic
3. Based on thermal behavior
The response of a polymer to mechanical forces at elevated temperature is
related to its dominant molecular structure.
Thermoplastics and Thermosets are the 2 categories.

1. A thermoplastic is a polymer that turns to a liquid when heated and

freezes to a very glassy state when cooled sufficiently. Thus thermoplastics
can be moulded on heating. Most thermoplastics are high-molecular-weight
polymers whose chains associate through weak Van der Waals forces
(polyethylene); stronger dipole-dipole interactions and hydrogen bonding
(nylon).
These polymers have no cross-linking between chains. Examples:
Polyethylene, polystyrene etc.

2. Thermosetting polymers
Thermosetting polymers made from relatively low molecular mass semi-fluid
polymers which when heated in a mould forms an insoluble hard mass which
is infusible. This is due to extensive crosslinks between the different polymer
chains forming three dimensional network of bonds.
16
 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 thermoplastic polymer.
 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’).
2. based on polymerization reactions:

Based on the mode of polymerization, polymers are

classified as:

1. Addition polymers
2. Condensation polymers
Addition polymers
Addition polymers are formed when monomer units are separately added to form long chains without
elimination of any by-product molecules. These polymers are formed by reactions between monomer
molecules possessing multiple bonds.
Example: Ethylene undergoes polymerization to form polythene.

The empirical formula of the monomer and polymer are the same. Other examples:
Polypropylene is an addition polymer of propylene.

Styrene-butadiene rubber is an addition polymer formed by addition reactions between butadiene and
styrene.
Condensation polymers
Condensation polymers are formed when the monomers containing active functional groups (generally
two), which react together with the elimination of a small molecule like water, ammonia, alcohol etc.

Examples: Nylon-66, polyester, Bakelite etc.Nylon-66 is formed by condensation between

hexamethylene diamine and adipic acid as shown below:
Functionality

The number of bonding sites in a monomer is referred

as its functionality

Bifunctional: eg. alkene

Trifunctional: eg. Monomethylsilicon trichloride (MeSiCl3)

Polyfunctional: eg. Silicon tetrachloride (SiCl4)

 Functionality

the number of reactive sites or bonding sites

Some mono functional hydrocarbons

Alcohols Methyl alcohol

Ethers Dimethyl Ether

Aromatic
hydrocarbons Phenol
Some bi-functional hydrocarbons

Terephthalic acid

Adipic acid (hexanedioic acid)

Ethylene glycol

1,6-hexanediamine
Ethylene is considered to be bifunctional

H H H H

C C C C

H H H H

H H

C O C O

H H
General method of polymerization
Two major methods generally used for preparing polymers:

1. Addition polymerization

2. Condensation polymerization

Addition Polymerization
It is a reaction that yields a product, which is an exact multiple of the original monomeric molecule. Such a
monomeric molecule usually contains one or more double bonds, which by intermolecular rearrangement
may make the molecule bifunctional. The addition polymerization reaction must be instigated by the
application of heat, light, pressure or a catalyst for breaking down the double covalent bonds of monomers.

Condensation polymerization
May be defined as a reaction occurring between simple polar-group-containing monomers with the formation
of polymer and elimination of small molecules like water, HCl etc.

Examples: Nylon-66, polyester, Bakelite etc. Nylon-66 is formed by condensation between hexamethylene
diamine and adipic acid as shown below:
Mechanism of addition polymerization:

1. Free radical polymerization

2. Cationic polymerization

3. Anionic polymerization

4. Coordination polymerization or Ziegler-Natta

polymerization
Free 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, tert-butylperoxide, 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

O
R + M M1
O
monomer O
O
(ii) Propagation step consists of the growth of M1 free radical by successive reaction of
large numbers of monomers molecules

M1 + M M2
monomer

M2 + M M3
monomer

M3 + M M4
monomer

In general
Mn + M Mn+1
monomer
Termination steps
a)Termination by coupling
b) Termination by disproportionation

Termination by coupling

Termination by disproportionation
 IONIC CHAIN POLYMERIZATION
Ionic polymerization is more complex than free-radical 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.

Cationic initiation is therefore usually limited to the polymerization of monomers

where the R group is electron-donating This helps stabilize the delocalization of
the positive charge through the p orbitals of the double bond

Anionic initiation, requires the R group to be electron withdrawing in order to

promote the formation of a stable carbanion

Using catalyst, not initiator

Highest reaction rate

Termination step is just disproportionation

Environment must be pure

Ionic Polymerization
 A). Anionic Polymerization
Involves the polymerization of monomers that have strong electron-withdrawing
groups, eg, acrylonitrile, vinyl chloride, methyl methacrylate, etc.

typical catalyst include KNH2, n-BuLi, and Grignard reagents such as alkyl magnesium
bromides

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.

Steps of polymerization
i) Initiation: KNH2 initiates the reaction and carbanion is formed

ii) Propagation

iii) Termination
 B) Cationic Polymerization
• Involves the polymerization of monomers that have strong electron-
donating groups, eg, propylene etc.

• Typical initiators (catalysts) are compounds with electron acceptor

properties eg. AlCl3, SnCl4, TiCl4, and BF3

• Steps of polymerization
i) Initiation : AlCl3 initiates the reaction and carbocation is formed

ii) Propagation

iii) Termination
Coordination polymerization (Ziegler-Natta catalysts)
Coordination polymerisation is a form of addition polymerization in
which monomer adds to a growing macromolecule through
an organometallic active center.
The development of this polymerization technique started in the
1950s with heterogeneous Ziegler-Natta catalysts based on titanium
tetrachloride and an aluminium co-catalyst (TiCl4 + R3Al)
Coordination polymerization has a great impact on the physical
properties of vinyl polymers such
as polyethylene and polypropylene compared to the same polymers
prepared by other techniques such as free radical polymerization.
The polymers tend to be linear and not branched and have much
higher molar mass. Coordination type polymers are
also stereoregular and can be isotactic or syndiotactic instead of
just atactic. This tacticity introduces crystallinity in
otherwise amorphous polymers.
From these differences in polymerization type the distinction
originates between low-density polyethylene (LDPE), high-density
polyethylene (HDPE) .
Mechanism: Coordination polymerization

Initiation

Propagation

Termination
 Cl C H
2 5
Cl C2H5
TiCl4 + Al(C2H5)3 Ti Al
Cl Cl C2H5
C2H5
CH2

H Cl C H
Cl C2 2 5
Cl C2H5
Cl C2H5 Ti Al
Ti Al Cl Cl C2H5
Cl Cl C2H5 H2C CH2

CH2 (CH2-CH2)n C2H5

H
Cl C2 Cl H
Cl C2H5 Cl C2H5
Ti Al Ti Al
Cl Cl Cl
C2H5 Cl C2H5

H2C CH (CH2-CH2)n C2H5

 CONDENSATION POLYMERIZATION

Minumum two functional groups required

Usually linear Molecular weight increases
slowly at low conversion
High extents of reaction are required to obtain
high chain length
Step-growth polymerization refers to a type of polymerization mechanism in which
bi-functional or multifunctional monomers react to form first dimers, then trimers,
longer oligomers and eventually long chain polymers. Many naturally occurring and
some synthetic polymers are produced by step-growth polymerization, e.g. polyesters
polyamides, polyurethanes, etc.
Due to the nature of the polymerization mechanism, a high extent of reaction is
required to achieve high molecular weight. The easiest way to visualize the mechanism
of a step-growth polymerization is a group of people reaching out to hold their hands to
form a human chain — each person has two hands (= reactive sites). There also is the
possibility to have more than two reactive sites on a monomer: In this case branched
polymers are produced.

A generic representation of a step-growth

polymerization. (Single white dots represent
monomers and black chains represent oligomers
and polymers)
 Differences between step-growth polymerization and chain-growth
polymerization

Step-growth polymerization Chain-growth polymerization

Growth throughout matrix Growth by addition of monomer only at
one end of chain
Rapid loss of monomer early in the Some monomer remains even at long
reaction reaction times
Same mechanism throughout Different mechanisms operate at different
stages of reaction (i.e. Initiation,
propagation and termination)
Average molecular weight increases Molar mass of backbone chain increases
slowly at low conversion and high extents rapidly at early stage and remains
of reaction are required to obtain high approximately the same throughout the
chain length polymerization
Ends remain active (no termination) Chains not active after termination
No initiator necessary Initiator required
Glass transition temperature: (Tg)

• At low temperatures, all amorphous polymers are stiff and glassy

• On Warming, polymers soften in a characteristic temperature range known as the

glass-rubber transition region.

• The glass transition temperature (Tg), is the temperature at which the amorphous phase of the polymer is
converted between rubbery and glassy states.

• Tg constitutes the most important mechanical property for all polymers. In fact, upon synthesis of a new
polymer, the glass transition temperature is among the first properties measured.

So, the glass transition temperature can be defined as the temperature below
which an amorphous polymer is brittle, hard and glassy and above the
temperature it becomes flexible, soft and rubbery.

Glassy state rubber state

(Hard brittle plastic) (soft flexible)

In the glassy state of the polymer, there is neither molecular motion nor segmental motion.
To become more quantitative about the characterization of the liquid-glass transition
phenomenon and Tg, we note that on cooling an amorphous material from the liquid
state, there is no abrupt change in volume such as occurs in the case of cooling of a
crystalline material through its freezing point, Tf. Instead, at the glass transition
temperature, Tg, there is a change in slope of the curve of specific volume vs.
temperature, moving from a low value in the glassy state to a higher value in the
rubbery state over a range of temperatures. This comparison between a crystalline
material (1) and an amorphous material (2) is illustrated in the figure below. Note
that the intersections of the two straight line segments of curve (2) defines the
quantity Tg.
 Factors affecting Tg

Crystalline polymers have higher Tg s than amorphous polymers

Effect of Side Groups-the bulky groups on chain, increases the Tg of the polymer

Polyethylene
Tg = -110 0C

Polypropylene
Tg = 90 0C

Polystyrene
Tg = 100 0C
Intermolecular Forces-The presence of H-bonds between the polymer molecules
increases the Tg

• e.g., the Tg of nylon 6,6 (Tg = 50 0C) is higher than PE (Tg = -110 0C)

H  O H  O
H H
nylon 6,6  |  ||  | 
 
||
polyethylene
− N − C  − N −C − C  − N −C −
−C− C−
   
| | | | | H H
H H  6 H H  H
4
+ +
+ + + +
Hydrogen Van der Waals
+ +  + +

bonds + bonds
+
H H
H  O H  O
  ||  |  || −C− C−
|
   
− N − C  − N −C − C  − N −C − H H
   
| | | | |
H H  6 H H  H
4


 With H-bonds vs vdW bonds, nylon is expected to have (and does) higher Tg.
The Tg of a polymer is influenced by its molecular weight
With increase in molecular mass, the Tg increases

e.g.,
PE (low Mw) -110 0C

PE (high Mw) - 90 0C

Stereo-regularity-Tg increases with stereo regularity

The presence of a plasticizer reduces the Tg of a polymer

The plasticizers are usually dialkyl phthalate esters, such as dibutyl

phthalate, a high boiling liquid.

O
C
O CH2CH2CH2CH3
O CH2CH2CH2CH3
C
O dibutyl phthalate

The plasticizer separates the individual polymer chains from one another.
It acts as a lubricant which reduces the attractions between the polymer
chains.
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 Tg.
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 temperature.
Which polymer more likely to crystallize? Can it be decided?

alternating random
Poly(styrene-Ethylene) poly(styrene - ethylene) copolymer
Copolymer

• Alternating co-polymer more likely to crystallize than random ones, as they are
always more easily crystallized as the chains can align more easily.
 Molecular Weight of Polymers

The molecular weight of a polymer can only be viewed statistically and expressed as some
average of the Mol. Wt.s contributed by the individual molecules that make the sample
the molecular weight of a polymer can be expressed by two most and experimentally
verifiable methods of averaging

(i) Number – average

(ii) weight – average

Number average molecular mass of a polymer can be defined as the total mass of all the
molecules in a polymer sample divided by the total number of molecules present

The molecular mass of a polymer can use either number fractions or the weight fractions of the
molecules present in the polymer

In computing the number average molecular mass of a polymer, we consider the number
fractions
 Molecular weight distributions
The molecular weight distribution can be shown graphically by plotting the number of molecules
against the molecular weight. It is worth noting that these plots are sometimes shown with
molecular weight decreasing along the x-axis.

The distribution may be relatively simple, such as:

Polymers: Molecular Weight
Ni: no. of molecules with degree of polymerization of i
Mi: molecular weight of i

number average, Mn

• weight average, Mw The dispersity index, or formerly

polydispersity index (PDI)= Mw Mn
The number-average molecular mass (Mn) is determined by the
measurement of colligative properties such as

Lowering of vapour pressure

Osmotic pressure
Depression in freezing point

Elevation in boiling point

The weight-average molecular mass (Mw) is determined by

Light scattering

Ultra-centrifugal techniques
The degree of polymerization (DP or Xn) is defined as the
number of monomer units in the polymer. It is calculated as
the ratio of molecular weight of a polymer and molecular
weight of the repeat unit.

where Mw is the average molecular weight of the polymer and

Mo is the molecular weight of the repeating unit or monomer.
 Numerical

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?
 (50x10000) + (35x 12000) + (15x14000)
Mn =
(50+35+15)

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

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

Mw =
(50x10000)+(35x12000)+(15x14000)
Ans. =11,486.7 (Weight Average Molecular Weight )

Mn 11300
DP = =
Molecular weight of monomer 42
Here polypropylene is the monomer having mol. weight = 42
Ans. = 269 (DP)
A polymer sample analysis indicated presence of 20 % (by weight) of
macromolecules of molecular weight 2000, 30 % (by weight) of
macromolecules of molecular weight 3000 and 50% (by weight) of
macromolecules of molecular weight 5000. Calculate the number average
and weight average molecular weight of the sample.
162 gram of poly 1,3-butadiene was treated with sulphur (S) to get a modified
polymer. Calculate the amount of sulphur required to get the modified polymer.
(Atomic weight of S is 32)
 Calculate the degree of polymerization of vinyl chloride
if the number average weight of polymer is 1.31 x 105 g/mol
 Polytetrafluoroethylene (TEFLON) or FLUON (PTFE)

F F F F F F
benzoyl peroxide
n C C n C C C C

F F F F F F
n
Tetrafluoro ethene Polytetrafluoroethene (PTFE)
Properties of TEFLON:

• They are extreme tough, high softening point, exceptionally high

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

Uses
• As an insulating materials (for motors, transformers, cables, wires, fitting)
• For making gaskets, packing, pump parts, tank, chemical-carrying pipe lines, tubing
• For coating
• In 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.

Polyamides are synthetic polymers, which have recurring amide

groups. Nylons, used mostly for making fibers, belong to
polyamides.

Nylon 6:6
Nylon 6
Nylon 11
Nylon 6:10
Nylon 6:6

Nylon 6:6 is obtained by the polymerization of adipic acid with

hexamethylene diamine.
Nylon 6: Nylon-6 is produced by the following two methods:

1. Self-condensation of 6-aminohexanoic acid (ε-aminocaproic

acid)
2. Ring opening polymerization of a caprolactum:

Heat
Nylon-11

Nylon-11 is made by self condensation of 11-aminoundecanoic

acid.
Nylon 6:10

Nylon 6:10 is obtained by the polymerization of Decanedioyl

dichloride with hexamethylene diamine.
Properties of Nylon:

1. One of the very strong fibers. Extremely resistant to abrasion and flexing.
2. The specific gravity is 1.14 Very light, i.e., 80% of that of silk fibers, and 70% of
that of cotton fibers.
3. Since nylon fibers absorb little water even though they are wetted., they dry fast
and simple in laundering.
4. Excellent in elasticity and resistant to wrinkle.
5. Resistant to chemicals and oil. Non-attackable by sea water.
7. Non-attackable by molds and insects.

Uses:

1. Nylon-6:6 is primarily used for fibers, which find use in making socks, under-
garments, dresses, carpets etc.
2. Nylon -6 and nylon-11 are mainly used for moulding purposes for gears,
bearings etc. Nylon bearing and gears work quietly without any lubrication.
3. They are also used for making filaments for ropes, bristles for tooth brushes
and films, tyre-cords etc.
Polyethylene (PE)

Polyethylene (PE)is obtained by polymerization of ethylene.

Properties:
1) Polyethylene is a rigid , waxy, white translucent, non polar
material.
2) Polyethylene exhibits considerable chemical resistance to
strong acids, alkalis and salt solutions at room temperature.
3) It is good insulator of electricity.
4) It is swollen and permeable to most oils and solvents.
HIGH-DENSITY POLYMERS
Linear polymers with chains that can pack closely together. These polymers are often quite rigid.

LOW-DENSITY POLYMERS
Branched-chain polymers that cannot pack together as closely. There is often a degree of cross-linking.
These polymers are often more flexible than high-density polymers.
Low-density polyethylene (LDPE)

Low-density polyethylene (LDPE) is a linear polymer with

branching. It is manufactured under high pressure (1000-3000
atm) and in the temperature range of 80-350oC using initiators
such as benzoyl peroxide or oxygen.
Method: free radical polymerization.
Properties of LDPE
1)LDPE is defined by a density range of 0.910–0.925 g/cm3.
2) It is not reactive at room temperatures, except by strong
oxidizing agents, and some solvents cause swelling.
3)It can withstand temperatures of 80 °C continuously and 95 °C
for a short time.
4)Made in translucent or opaque variations, it is quite flexible,
and tough but breakable.
5) LDPE has more branching than HDPE.
6)Since its molecules are less tightly packed and less crystalline
because of the side branches, its density is lower. LDPE
contains the chemical elements carbon and hydrogen.
Uses of LDPE

LDPE is widely used for manufacturing various containers,

dispensing bottles, wash bottles, tubing, plastic bags for computer
components, and various molded laboratory equipment. Its most
common use is in plastic bags. Other products made from it
include:

1)Trays and general purpose containers.

2)Corrosion-resistant work surfaces.
3)Parts that require flexibility, for which it serves very well
4)Juice and milk cartons are made of liquid packaging board, a
laminate of paperboard and LDPE (as the water-proof inner and
outer layer), and often with of a layer of aluminum foil (thus
becoming aseptic packaging)
5) Parts of computer hardware, such as hard disk drives, screen
cards, and optical disc drives
High-density polyethylene (HDPE)

High-density polyethylene (HDPE) is a linear polymer with little or

no branching. It is manufactured under low pressure and below
100oC using Ziegler Natta catalyst (Et3Al and TiCl4) by
coordination polymerization or using metal oxide catalyst by
Phillips process.
Properties of HDPE

1)HDPE is known for its large strength to density ratio.

2)The mass density of high-density polyethylene can range from
0.941 to 0.97 g/cm3.
3) Although the density of HDPE is only marginally higher than
that of low-density polyethylene, HDPE has little branching, giving
it stronger intermolecular forces and tensile strength than
LDPE.The difference in strength exceeds the difference in density,
giving HDPE a higher specific strength.
4) It is also harder and more opaque and can withstand somewhat
higher temperatures (120 °C/ 248 °F for short periods, 110 °C
/230 °F continuously). High-density polyethylene, unlike
polypropylene, cannot withstand normally required autoclaving
conditions. The lack of branching is ensured by an appropriate
choice of catalyst (e.g., Ziegler-Natta catalysts) and reaction
conditions.
HDPE is resistant to many different solvents and has a wide
variety of applications, including:

3-D printer filament

Banners
Bottle caps
Chemical resistant piping systems
Food storage containers
Fuel tanks for vehicles
Electrical and plumbing boxes
Folding chairs and tables
 P – F Resins

These are formed by condensation polymerization and are thermosetting

polymers

There are two important commercial PF resins: Novolacs and Resoles

Both novolacs and resoles are linear, low molecular weight, soluble and
fusible prepolymers

The nature of the product formed depends largely on the molar ratio of
phenol to formaldehyde and also on the nature of the catalyst
During moulding operations, these two undergo extensive branching leading
to the formation of highly cross linked, insoluble, hard, rigid and infusible
products
The phenol ring has three potential reactive sites while the formaldehyde
has two reactive sites

The polycondensation reaction between these two are catalyzed by either

acids or alkalies
 Novolacs
When P/F molar ratio is > 1 and the catalyst used is an acid, low mol. wt. polymers
formed are called Novolacs

The first step in the reaction is the addition of formaldehyde to phenol to form ortho or para
methylol phenols

OH
H
+
C=O
H
Phenol (excess) H+ formaldehyde

OH OH

CH2OH
and

o-methylol phenol CH2OH

p-methylol phenol
These methylol phenols condense rapidly to form Novolacs

OH
OH

CH2OH
or
CH2OH
o-methylol phenol OH
p-methylol phenol

OH H2 H2 OH H2 H2 OH
C C C C

HO OH

Novolacs
 These novolacs are linear and low mol. wt. polymers. They are soluble and fusible. About 5
– 6 phenol rings per molecule are linked through methylene bridges
Since they contain no active methylol groups, they themselves do not undergo cross linking.
However, when heated with formaldehyde or hexamine, they undergo extensive cross linking,
resulting in the formation of infusible, insoluble, hard and rigid thermosetting product
OH H2 H2 OH H2 H2 OH
C C C C

HO OH
Novolacs (prepolymer) Curing with
Formaldehyde or
hexamine
Resoles

When the molar ratio of P/F is < 1 and the catalyst used is a base, the polymer formed are called
Resoles
The first step in the reaction is the formation of mono, di and trimethylol phenols. They
undergo condensation to form resoles

The resoles in which phenols are linked through methylene bridges are soluble
and fusible
Since they contain alcoholic groups, further reaction during curing leads to
cross linking, resulting in a network, infusible and insoluble product
OH
H
+
C=O
H
Phenol Formaldehyde
OH-- (excess)
 OH OH OH OH
CH2OH + CH2OH HOH2C CH2OH
+ +

CH2OH CH2OH CH2OH

o-methylol phenol p-methylol di methylol tri methylol phenol
phenol phenol
Curing
 Properties of Bakelite:
• They are rigid, hard, scratch-resistant, infusible, water resistant, insoluble
solid.
• Resistant to non-oxidizaing acids, salts and many organic solvents.
• They are attacked by alkalis
• They 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
 ELASTOMERS

Elastomer is defined as a long chain polymer which under stress undergoes

elongation by several times and regains its original shape when the stress is
fully released

Stretched

Returned to
randomization
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.
Natural rubber is an addition polymer formed from the monomer called isoprene
i.e., 2-methyl-1,3-butadiene

The average D.P. (n) of rubber is around 5000

Addition between molecules of isoprene takes place by 1,4 addition and one
double bond shifts between 2nd and 3rd positions
Drawback 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 60˚C only

➢ It is weak: tensile strength is only 200kg/cm2

➢ It has large water absorption capacity
➢ It is non-resistant to non-polar solvents like vegetable and mineral oil
➢ It is attacked by oxidizing agent
➢ It swells in organic solvent and gradually degrade
➢ It 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.
Vulcanization is done by heating the rubber with sulfur or
other vulcanizing agents under pressure

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

American inventor who developed a process to vulcanize rubber
in 1839—a 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.
e.g., a tyre rubber may contain 3 to 5% sulphur, but a battery case rubber may contain as
much as 30% sulphur
H H H

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

C C C C C C
C C
C C C C

H H H H H H

+S+
H H H H H H

C C C C C C

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

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

H H H
 H H H

HH H HH H HH H
C H C H C H
H H H

C C C C C C
C C C C
C C

H H H H H H

S S
H H H H H H

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

H C HH H C HH H C HH

H H H
Advantages of vulcanization:-

(i) The tensile strength increase

(ii) Vulcanized rubber has excellent resilience. It has better resistance to
moisture, oxidation & abrasion
(iii) It is resistance to organic solvents like CCl4, Benzene petrol etc.
(iv) It has only slight thickness
(v) It has low elasticity
 Applications

(i) The major application of natural rubber is in the manufacture of tyres.

(ii) In heavy duty tyres, the major portion of the rubber used is natural rubber.
(iii) The tank linings in chemical plants where corrosive chemicals are stored
are prepared from rubber.
(iv) To reduce machine vibrations, rubber is used for sandwiching between two
metal surfaces.
(v) Foam rubber is used for making cushions’, matrices, padding etc. toys and
sports items are manufactured from natural rubber
162 gram of poly 1,3-butadiene was treated with sulphur (S) to get a modified
polymer. Calculate the amount of sulphur required to get the modified polymer.
(Atomic weight of S is 32)
 Compounding of Rubber
Compounding is mixing of the raw rubber (synthetic or
natural) with other substances so as to impart the product
specific properties suitable for particular job.

(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
 Synthetic Rubber:

Styrene rubber or Buna-s-Rubber:-

It is a copolymer of butadiene (75%) and styrene (24%). In the early days of

its synthesis sodium was used as the catalyst. Hence the name bu
(butadiene), na (symbol Na for sodium) and S (for styrene). It is also called
GRS (government rubber styrene) or SBR (styrene butacliene Rubber). The
Buna-S-Rubber is the first synthetic rubber developed during the second time
of world war by US in order to overcome the scarcity of natural rubber. It is
prepared by the copolymerization of butadiene & styrene.
 Styrene rubber (GR-S or Buna-S or SBR)

Preparation
This is produced by copolymerization of butadiene (about 75% by wt.)
and styrene (about 25% by wt.)

H2C CH

n x H2C CH CH CH2 + n

H2C CH CH CH2 H2C CH

x
n
 Styrene-butadiene copolymer

Styrene domains act as

anchors or junctions

Butadienes provide
flexible linkages

The desire to maximize the ways you can arrange the flexible
links is what causes rubbers to return to given shapes
Properties:-

(1) It is a strong & tough polymer.

(2) The rubber can be vulcanized similar to natural rubber using
either sulphur ot sulphur mono chloride.
(3) It is a good electrical insulator.
(4) It possess excellent abrasion resistance
(5) It is resistance to chemicals but swell in oils and attacked by
even traces of ozone present in the atmosphere
(6) It possess high load bearing capacity and resilience
 Buna-N( Nitrile rubber)
Buna –N is copolymer of butadiene and acrylonitrile rubber.
 Properties of Buna-N

It possesses excellent resistance to heat, sunlight, oils, acids and

salts, but less resistant to alkalis than natural rubber, because of
presence of cyano (-CN) groups. As the proportion of acrylonitrile
is increased, the resistance to acids, salts, oils, solvents increases
but the low temperature resilience suffers. Vulcanized nitrile
rubber is more resistant to heat and ageing than natural rubber.

Uses:

For making conveyer belts, high altitude aircraft components, tank

lining, hoses, gaskets, printing rollers, adhesives, oil resistant
foams and automobile parts.
 Thiokol rubber (or) poly sulphide rubber (or) GR-P:-

Thiokol is prepared by the condensation polymerization of

sodium poly sulphide (Na2Sx) and ethylene dichloride (Cl CH2
CH2 Cl). In these elastomers, sulphur forms a part of the
polymer chain.

Cl – CH2 – CH2 – Cl + Na – S – S – Na + Cl – CH2 – CH2 – Cl

Polymerization

(CH2 – CH2 – S – S – CH2 – CH2 )n + NaCl

Properties:-

(1) These rubbers possess strength and impermeability to gases.

(2) This rubber cannot be vulcanized because its structure is not
similar to natural rubber and it cannot form hard rubber.
(3) It possesses extremely good resistance to mineral oils, fuels,
oxygen, solvents ozone & sunlight.
Properties:

1. PET can exist both in amorphous and semicrystalline form

2. It has high mechanical strength and dimension stability and is stable over temperature range
of -40 oC to 100 oC.
3. It shows creep and abrasion resistance and good electrical insulating properties.
4. At room temperature, it is resistant to water, dilute acids, salts, aromatic and aliphatic
hydrocarbons and alcohols.

Applications:
1. It is used for making video and audio tapes.
2. It is commonly used in making clear bottles for foods and beverages.
3. It is used to make films for shrink packaging.
4. As an electrical insulator, it is used for making molds for electrical appliances.
5. The synthetic fibers can be woven to make fabrics, upholstery, artificial grass etc.
6. The fiber may be blended with wool and other natural fibers.
7. The films may be combined with paper or other polymeric films to form multilayer materials.
8. It can be used to produce injection molded articles, such as switches, valves etc.
Some Numericals
A polymer sample analysis indicated presence of 20 % (by weight) of
macromolecules of molecular weight 2000, 30 % (by weight) of
macromolecules of molecular weight 3000 and 50% (by weight) of
macromolecules of molecular weight 5000. Calculate the number average
and weight average molecular weight of the sample.
 4.46 x 103
3.75 x 103
1.19

A polymer has the following composition 100 molecules of

molecular mass 1000g/mol, 200 molecules of molecular mass
2000g/mol, 500 molecules of molecular mass 5000g/mol,
calculate number average and weight average molecular
weight.
Calculate the maximum percentage of sulphur that can be present in vulcanized
rubber
260 grams of butadiene is copolymerized with 104 gram of styrene what is the
molecular formula of the copolymer?
If average degree of polymerization of polypropylene
is 2X 104, calculate the weight average molecular weight
One mole of any substance contains 6.022 × 1023 molecules