22CT104 - ENGINEERING CHEMISTRY

UNIT-1: POLYMER TECHNOLOGY

Prof. Koya Prabhakara Rao

HoD, Department of Chemistry
E-mail:[email protected]
Prof. K. P. Rao 0
Prof. K. P. Rao 12
Prof. K. P. Rao 13
Prof. K. P. Rao 14
 Unit1: POLYMER TECHNOLOGY
Introduction,
classification,
Polymerization techniques,
Preparation, properties and applications of PE, Nylon-6,6;
Elastomers-Natural rubber and properties, vulcanization,
synthetic rubbers-Buna N and S; Introduction to conducting
polymers (polythiophene).

Prof. K. P. Rao 15
 Introduction
History

•The first synthetic organic polymer polyvinylchloride was

synthesized in 1838 by accidentally. Later, polystyrene was
discovered in 1839.

• Origin of polymer industry started in the 19th century, where most of

the works were done on natural polymers or naturally derived
polymers (Semi Synthetic).

• Leo Baekeland’s Bakelite (Phenol-Formaldehyde Resin) was the first

fully synthetic polymer synthesized in 1910 and commercialized for
its insulating property.

• Following this, first synthetic rubber was manufactured during world

war 1 using 2,3-dimethylbutadiene called as Methyl Rubber.

Prof. K. P. Rao 16
 Introduction
 What is a “Polymer”?
The name Polymer was derived from ancient Greek word πολύς (polus, meaning "many or much") and
μέρος (meros, meaning "parts").

- A polymer is a large molecule built by the linking of a large number of small molecules (called
monomers)

Monomers Polymer

nCH2 = CH2 -CH2 – CH2 - CH2 - CH2 - CH2 - CH2 -

(Ethylene) (Polyethylene)
(Monomer) (Polymer)

Prof. K. P. Rao 17
Monomer:

Monomer is defined as a simple molecule with two or

more binding sites through which it forms covalent
linkages with other monomer molecules to form the
macromolecule/polymer.

Polymerization: The process of joining of more number of monomers to form a polymer is called
polymerization.
Polymerization
nCH2 = CH2 -CH2 – CH2 - CH2 - CH2 - CH2 -
CH2(Ethylene) (Polyethylene)
(Monomer) (Polymer)

Prof. K. P. Rao 18
 Degree of Polymerization (DP):

Degree of polymerization is defined as the number of repeating units present in a polymer molecule.

n CH2 = CH2 --[-- CH2 - CH2 ---]n---

In this, n is a whole number and it is called the degree of polymerization.

 Depending on the DP, macromolecules are termed as oligomers and polymers.
 Polymer molecules with Mwt <1000 are called oligomers and their DP will be less
 Polymer molecules with Mwt >1000 are real polymers with high DP.

Prof. K. P. Rao 19
 Functionality:
Functionality of a monomer can be defined as the number of bonding sites or reactive sites in
monomer.
Reactive Functionality / Possible reactive
S.No Name Chemical Formula Polymer formed
functional group linear or branch groups
OH, NH2, RX Polymer will not
1 Acetic Acid CH3-COOH -COOH 1
(X=halogens) be formed
OH, NH2, RX Polyester,
2 Malonic Acid COOH-CH2-COOH -COOH 2 / Linear
(X=halogens) polyamide, etc.
-COOH, RX Polyester,
3 Ethylene glycol HO-CH2-OH -OH 2 / Linear
(X=halogens) Polyether
-COOH, RX Polyester,
4 Penta erythritol C(CH2-OH)4 -OH 4 / Branched
(X=halogens) Polyether
Hexa methylene
5 H2N(CH2)6NH2 0 2 / Linear -COOH Polyamide
diamine
-OH, -COOH,-OH, - Polyester,
6 Lactic Acid CH3-C(OH)-COOH 2 / Branched NH2, RX Polyamide,
-COOH
(X=halogens) Polyether
7 Styrene CH2=CH-C6H5 CH2=CH 2 / Linear CH2=CH Polystyrene
Prof. K. P. Rao 20
 Depending on the number of functionality over the monomer, it can be ascertained whether the formed
polymer will be linear or branched or crosslinked.
 For e.g., If the monomer is bifunctional, i.e. having two reactive sites at two ends, they will form linear or
straight chain polymers.
 If the monomers have tri functionality or more, they will end up in branched side chain polymers or 3D
crosslinked polymers.

Prof. K. P. Rao 21
 Classifications of Polymers
1. Origin
2. Monomer
3. Thermal Response (molecular forces)
4. Mode Of Formation
5. Chain Structure
6. Tacticity

By Origin
1. Natural or Biopolymers as found in nature in
animals and plants

Prof. K. P. Rao 22
 2. Synthetic Organic Polymers from
petroleum crude like Polyethylene,
prolypropylene, polystyrene, etc.

3. Inorganic Polymers like polysiloxanes

and polyphosphazines

Prof. K. P. Rao 23
 By Monomers
1. Homopolymer: Composed of single monomer, E.g. Polyethylene
Polymerization
nCH2 = CH2 -CH2 – CH2 - CH2 - CH2 - CH2 -
CH2(Ethylene) (Polyethylene)
(Monomer) (Polymer)

2. Hetero or Copolymer: Composed of two or more different monomers.

Nylon 6,6-structure

Prof. K. P. Rao 24
 Based on Thermal Response
1. Thermoplastic polymers are linear, long chain polymers, which can be softened on heating
and hardened on cooling reversebly. Thus they can be processed again and again.

For example: polyethylene, polypropylene, polystyrene, and poly vinyl chloride

2. Thermosetting polymers: are those polymers which during moulding get hardened and once
they have solidified, they cannot be softened, i.e. they are permanent setting polymers.

Thermoplastic polymers Thermosetting polymers

Prof. K. P. Rao 25
 Based on Structure
S.N Thermoplastics Thermosetting
o
1 They are formed by They are formed by
either addition or condensation
condensation polymerization
polymerization
2 They have either They have three
linear or branched dimensional, cross
structures linked structures
3 Adjacent polymer Adjacent polymer
chains held together chains held together by
by weak strong covalent bonds
intermolecular forces called cross links
4 They soften on They do not soften on
heating and stiffen heating
on cooling
5 They can be They can not be
remoulded reshaped, remoulded reshaped, re
re used used
6 Ex: PE, PVC, PTFE, Ex: Bakelite,Urea
Nylons formaldehyde
Prof. K. P. Rao 26
 Based on Mode of Formation
1. Addition polymers:
They are formed by the addition of olifinic monomers without the elimination of bye products.
Polymer is exact multiple of monomer.

For example: polyethylene, polypropylene, polystyrene, and poly vinyl chloride

2. Condensation polymers:
In condensation polymerization during formation of polymer some of the atoms of monomers are
released as small molecules (like water, HCl, NH3 etc)

For example: nylon, Bakelite, polyester.

Prof. K. P. Rao 27
 Based on Structural Orientation or Tacticity
• Atactic: side groups are randomly distributed on both the sides of the polymer backbone.

• Syndiotactic: Side groups are distributed alternatively on both the sides of the polymer
backbone.

• Isotactic: side groups are distributed only on one side of the polymer backbone

Prof. K. P. Rao 28
 Types of polymerisation
1. Addition (Chain-growth) polymerisation
A chemical reaction in which unsaturated monomers are added to each other to form long-
chain molecules (polymers) in presence of light, heat, pressure and catalyst without any by-
products or without elimination of any simple molecules. The molecular weight of the
polymer so formed is thus the total of the molecular weights of all of the combined monomer
units.
Ex: PE,PVC,PTFE
• Polymerisation occurs by addition of unsaturated molecule to an active site or a growing
chain.

• The active site will be carried by the growing chain and addition of subsequent molecules
occurs until all the monomers are consumed.

• Classified into three types, Free radical, Ionic, Coordination/insertion.

Prof. K. P. Rao 30
 Addition (Chain-growth) polymerisation

Characteristic features of Chain growth polymerization :

• Growth is by the addition of the monomer at the end of the

chain

• At any point of time, the reaction mixture will contain,

polymer, unreacted monomer and active growing chains.

• The molecular weight of the polymer increases rapidly

• The polymerization rate initially increases and then

become constant

• An initiator is required to start the reaction

Prof. K. P. Rao 31
 Radical polymerisation
Mechanism: Three stages are involved in the mechanism of Chain polymerization reaction for all
the three types of polymerisation. They are:

a.Initiation
b.Propagation
c.Termination.

Prof. K. P. Rao 32
Prof. K. P. Rao 33
2. Condensation (Step-growth) polymerisation
The intermolecular combination between simple polar group containing monomers to form a
polymer with the elimination of small molecules like water, HCl.This reaction takes place between
the monomers having affinity with each other.

Ex: Hexamethylenediamine and Adipic acid condense to form a polymer called Nylon 6.6

Nylon 6.6

Prof. K. P. Rao 34
 Polyethylene (PE)
It is the simplest homoploymer.
It is prepared by the addition polymerization of ethylene by using oxygen as initiator. The
reaction takes place at 1500 atm pressure at 150-250 °C.

Ethylene Poly ethylene

Properties:
 Polythene is a rigid, waxy, white, translucent, non polar material, exhibiting considerable chemical
resistance to strong acids, alkalis and soft solutions at room temperature.
 It is good insulator of electricity.
 However it is swollen and permeable to most oils and organic solvents, particularly kerosene.

Prof. K. P. Rao 35
 There are two types of polyethylene:
i. Low density polyethylene ii. High-density polyethylene

Low density polyethylenes (LDPE)

LDPE is manufactured by addition polymerization of ethylene gas at 350 0C at a pressure of

1000-1500 atm in the presence of O2 or peroxide as catalyst.

High density polyethylenes (HDPE)

HDPE is manufactured by the coordination polymerization of ethylene in a hydrocarbon solvent using

Zeigler Natta catalyst (Heterogeneous supported catalysts based on titanium compounds are used in
polymerization reactions in combination with cocatalysts, organoaluminum compounds such as
triethylaluminium, Al(C2H5)3. used in the synthesis of polymers of 1-alkenes) or ionic catalyst.

Prof. K. P. Rao 36
 Property LDPE HDPE

Structure Branched Linear polymer

Softening point 110 0C 135 0C

Low 0.912-0.925 High 0.941-0.965
Density
gCm-3 gCm-3
Tensile strength Low High
Chemical
Low High.
resistivity

In films, sheets, In molded articles,

Application
pipes for irrigation. House hold articles.

Prof. K. P. Rao 37
 Applications:

 For making high frequency insulator parts

 Bottle caps, kitchen and domestic appliances.

 Toys

 Sheets for the packing materials, chemical plants, tubes, pipes, coated-wires and cables,
bags for packing.

Prof. K. P. Rao 38
 Nylon 6,6

 Synthetic polymers called polyamides with an amide linkage with spacer from linear
hydrocarbons. Dupont researchers led by Dr. Wallace Carothers invented nylon, in 1930s
 Commercial use of nylon in US began in early 1940’s when the material was used to produce
stockings for women. During WWII to increase the production of nylon, new materials with
stronger properties were designed and thus came the other varieties like nylon 6 and 6,6
which are far more durable than the nylon used for stockings.
 Nylon 6,6 is one among the large group of polycondensate products of diacid and diamine
with fiber forming property. Nylon 6,6 (poly hexamethylene diamine adipamide) formed from
adipic acid and hexamethylene diamine by poly condensation. The resulting product can be
extruded into a wide range of fibers. The numbering comes from the number of carbon atoms
used in diamine and diacid.

Prof. K. P. Rao 39
Synthesis:
Equimolar amounts of Adipic acid and hexamethyl
diamine undergoes condensation polymerisation in
presence of acid to form Nylon 6,6. Since the
reaction is an amidation reaction, there is an equal
chance of the water to hydrolyze the amide to form
the starting materials. But this can be avoided by
removing the formed water and shifting the
equilibrium towards product formation. Since the
polymerization happens at the interface where the
two reactants meet as both the reagents are no
miscible with each other it is also called interfacial
polymerisation.

Prof. K. P. Rao 40
 Equimolar amounts of Adipic acid and hexamethyl diamine undergoes condensation
polymerisation in presence of acid to form Nylon 6,6. Since the reaction is an amidation reaction,
there is an equal chance of the water to hydrolyze the amide to form the starting materials. But
this can be avoided by removing the formed water and shifting the equilibrium towards product
formation. Since the polymerization happens at the interface where the two reactants meet as
both the reagents are no miscible with each other it is also called interfacial polymerisation. The
formed molten nylon 6,6 can be either extruded and granulated or directly spun into fibers by
extrusion through a spinneret.

Adipic acid O

HO
n OH O
O
O
H
- H2O N
HN N
H n-1
O
NH2
H2N
n Nylon 6,6
Hexamethyl diamine

Prof. K. P. Rao 41
 Properties:
 Melting point of Nylon 6,6 is 270 C.
 Thermoplastic polymer and can be processed to complex thin walled components to large thick-walled
housings.
 Polymer exhibits excellent resistance to heat, wear, tear and chemicals, which makes them the
unanimous choice for making bearing, battery modules, luggage and conveyor belts.
 The polymer shows high strength, ductility and stiffness making a suitable candidate for metal
replacement applications.
 Semi crystalline polymer with high mechanical strength and toughness.
 Polymer shows good sliding property, good electrical insulating property with resistance to high energy
radiations such as (gamma and X-ray)
 Some of the properties of nylon can be enhanced by modifying the polymer with fillers, fibers, internal
lubricants and impact modifiers.
 When compared to nylon 6, nylon 66, shows superior stability through highly hydrogen bonding and
shows low absorption.
Uses:
 Large quantity of Nylon 6,6 is used in producing tyre cord.
 Used to make monofilaments and ropes

Prof. K. P. Rao 42
 Rubbers
 High molecular weight polymers, which can be stretched at least twice of their length and
return to their original form after removing the stretched force. Because the carbon chains
are not in straight chained they are in the form of coils.

 Rubber is used to describe a material with elastic properties. It can be both natural and
synthetic.

 Elastomers due to inter molecular forces attains a coiled amorphous structure, when a stress
is applied, deformation starts by breaking the weak inter molecular force and attains a linear
ordered structure. When the stress is taken back, the material regains the coiled structure
and becomes amorphous once again.

Prof. K. P. Rao 43
  Synthetic rubbers were generally referred as elastomers. Basically an elastomer is a polymer
with very weak inter molecular network structure / polymers that are joined by chemical bonds
with slightly crosslinked structure.

 Natural rubber is thermoplastic and it becomes thermoset and elastomeric depending on the
extent of crosslinking (Vulcanisation).

Prof. K. P. Rao 44
 Natural rubber is present in (basic material) latex, which is a dispersion of isoprene. During the
treatment. these isoprene molecules polymerize to form, long – coiled chains of cis- isoprene.

 Commercial source of natural rubber is from the latex of para rubber tree – Hevea Brasiliensis.
The main constituent of the rubber latex will be poly cis-1,4 isoprene which will be around 30%-
40% in the form of colloidal solution in water. Rubber is nothing but polymer of cis-1,4 isoprene
units

 It is an addition polymer, addition between molecules of isoprene takes place by 1,4 addition
and one double bond shifts between 2&3 positions.

Prof. K. P. Rao 45
 The rubber from Havea Brazilians tree is cis isomer
 In nature, the trans form of isoprene is obtained from Gutta-percha tree (trans-1,4-
polyisoprene). Unlike the cis isomer, they will not be amorphous. They are crystalline due to the
trans methyl groups. This gives them the rigidity and strength.

n
Natural Rubbers CIS POLY ISOPRENE
TRANS POLY ISOPRENE
 First, removal of rubber from the latex mixture, by coagulating with acid
(Acetic acid or Formic acid). Acid neutralizes the charge between the particles
and forms a homogeneous precipitate.
 The coagulated rubber will be a soft white mass, which undergoes creeping
process to be transformed into sheets of rubber with specific dimension.
 These sheets will be dried under smoke or 40-50°C or dried under sun, which
transform the color of the sheet from white to amber. This process also
makes the rubber to have long life and degradation against microorganism.
This will be further processed to have better elastic and better abrasion
characteristics by vulcanization.
Prof. K. P. Rao 46
 Properties of Natural Rubbers Drawbacks of Natural Rubbers
1. Crude rubber is a tough and an elastic solid. It 1. It is plastic in nature: It becomes soft at
becomes soft and sticky as the temperature high temp and is too brittle at low temp so it
rises.
can be used in the temperature range of 10-
2. The most important property of natural rubber 600C only
is its elasticity. 2. It is weak: its tensile strength is only
200kg/cm2
3. Raw natural rubber has elasticity over a
narrow range of temperature from 10 to 60°C. 3. It has large water – absorption capacity
Because of this, articles made of raw natural 4. It is not resistant to non-polar solvents like
rubber don't work well in hot weather. vegetable oils, benzene .
5. It has little durability.
4. Raw natural rubber has low Chemical
resistance, tensile strength and abrasion 6. It is attacked by oxidizing agents like nitric
resistant. acid, concentrated sulphuric acid.
7. When stretched to greater extent it suffers
5. It absorbs large quantities of water. from permanent deformation
 Vulcanization of Natural Rubbers
 To overcome the drawbacks of natural rubber a process called Vulcanisation was introduced by
Goodyear.

 It is a process in which raw rubber is treated with Sulfur. Technically, the sulfur reacts with the
double bond of rubber and forms crosslinked structures, which prevents the deformation at
high elasticity, gives high tensile strength and increases the resistance to abrasion.

 Raw dry rubber is heated with sulfur (5-8% based on the requirement), zinc oxide (a filler, 5%)
and accelerator (0.5% -1%) at 100-140°C depending on the application.

 As the sulphur quantity increases, the rubber becomes tougher. >30% sulphur gives ebonite
(vulcanite).
 When rubber is heated with Sulphur. Its tensile strength, and resistance to swelling are
Increased tremendously. This process is known as vulcanization

 The Sulphur atoms forms cross covalent bond with the double bond of the isoprene units
bringing about excellent resistance to temperature chemical, oxidation process.
Prof. K. P. Rao 48
  The extent of stiffness of vulcanized rubber depends on the amount of Sulphur added for
example a tyre rubber may contain 3-5% Sulphur, but a battery case rubber may contain as
much as 30% Sulphur.

 Vulcanite or ebonite or Hard rubber: Contains about 32% Sulphur. It possesses no elasticity
because of the cross – links. Vulcanite is tough, high abrasion-resistant and has extremely
good electrical insulation properties.
Vulcanisation can be carried out using different sources
 Sulfur (S8)- this reacts with the double bond and forms crosslinks.
 Crosslinks can also be formed without affecting the double bonds by eliminating hydrogen sulfide gas.
(H2S)
 Disulfur dichloride can also be used to form crosslinks. Here the liberated sulfur will be used for further
crosslinking.
 Sulfur compounds like thioacids, mercaptans add on to the double bonds and increases the crosslink
density.
 Vulcanisation of synthetic rubbers is also possible by the same means.
 Other methods which don’t involve sulfur also exist, they are using metal oxides like ZnO2 and
peroxides.

Prof. K. P. Rao 49
 Advantages of vulcanization:
 Possesses low water absorption
capacity.
 Good tensile strength and extensibility-
2000kg/cm2
 Has higher resistance to oxidation and
to abrasion
 Is better electrical insulator
 Resistant to organic solvents
 Useful temperature range-40 0 to 100 0C

Vulcanized natural rubber

 Possess low elasticity.

Raw natural rubber  It has good resilience

Prof. K. P. Rao 50
 Synthetic Rubber
 A synthetic rubber is manmade rubber
which can be stretched twice its original
length and returns to its original length as
the stretching force is relieved.

 Main constituent of synthetic rubber will be

butadiene, which has the same backbone
structure of the natural rubber.

 Two isomers exists for butadiene, it can be

either 1,2 or 1,3 butadiene.

 To have improved properties than natural

rubber, butadiene is copolymerised with
other comonomers from styrene,
Acrylonitrile, etc.

Prof. K. P. Rao 51
 Styrene rubber (Buna-S or GR-S)
 It’s a random copolymer of Butadiene and Styrene in presence of Na as catalyst. The DP of
Butadiene and Styrene will be 75 and 25 respectively. With increasing styrene ratio, the stiffness
gets increased and becomes harder and less rubbery.
 Butadiene can be polymerized by two techniques, Emulsion and Solution polymerisation.
Emulsion polymerisation, proceeds by free radical polymerisation. By solution polymerisation,
the mechanism of polymerisation will be by anionic initiated by alkyl lithium compound. The
carbanion formed will initiate the polymerisation and propagates until monomers are there.

Prof. K. P. Rao 52
Properties: Uses:
 It resembles natural rubber in its
characteristics and also in the  Mainly used for the manufacture of
quality of finished products. motor tyres

 It possess high load bearing  Used in floor tiles

capacity.
 Shoe soles, footwear components
 High abrasion resistance and high
resilience  In making Gaskets

 It gets readily oxidized in presence  In Wire and cable insulations

of traces of ozone.
 As carpet backing
 It can also be vulcanized as that of
natural rubber, but It requires less  In adhesives
sulphur for vulcanization.

Prof. K. P. Rao 53
 Nitrile rubber (Buna-N or GRA)
 It’s a copolymer of Butadiene (1,2 and 1,3) and Acrylonitrile.
 If the nitrile composition is higher, resistance to oils will be higher with the loss of flexibility
compared to natural rubber. This rubber has the ability to withstand a range of temp from -40 to
108°C, making them useful in the field of aeronautical applications. Synthesized by Emulsion
polymerisation using peroxide or redox initiators.
N

Catalyst / 30-40C
N
Emulsion Polymerisation *
Acrylonitrile 1,3-butadiene Buna N rubber

Prof. K. P. Rao 54
 Properties: Applications:

 It is Heat resistant  For making conveyer belts.

 Resistant to sunlight and  High altitude aircraft

oils components

 Resistant to salts and acids  Oil resistant foams

 Less resistant to alkalis  In automobile parts

because of cyano groups
 In making of printing rollers
 With increase in proportion
of acrylo nitrile there is  In adhesives
increase of heat resistance
but suffers from less  In tank linings.
resilience

Prof. K. P. Rao 55
 Conducting polymers
 Conducting polymers are set of organic polymers which can conduct electricity.
 Polymers are known to have good insulating properties
 Polymers are one of the most used materials in the modern world. Their uses and application
range from containers to clothing.
 They are used to coat metal wires to prevent electric shocks.

Prof. K. P. Rao 56
 Conducting polymers
Polyacetylene was the first conductive polymer that actually launched this new field of research.
Polyacetylene is an organic polymer with -(C2H2)n repeating monomer carbon atoms with
alternating single and double bonds between them each with one hydrogen atom. Double bonds
can have either cis or trans geometry. The cis form will be in copper color and the trans form will
be in silver colour.

H H H H
C C C C I2

C C C C
H H H H
= I3-

H H H H
C C C C
C C C C
H H H H
trans-Polyacetylene Cis-Polyacetylene
x+
CH n 3/2 x I2 CH n x I3-
Prof. K. P. Rao 57