Department of Chemistry

19CYE101 – ENGINEERING CHEMISTRY

(FOR I YEAR, I SEM – B.E. – COMMON TO ALL BRANCHES)

ACADEMIC YEAR 2020 - 2021

P.THANGARASU, ASP/Chemistry
SEC
 UNIT II POLYMER CHEMISTRY
2.1 INTRODUCTION
 The word “Polymer” is derived from two Greek words,
“Poly” means many and “meros” means parts.
 Polymer exist in nature, typical examples being starch and
cellulose of plants consisting of thousands of glucose molecules.
Polymers are found abundant on the surface of earth, either in
nature or artificially prepared.
 We use plastic bags,cards,paper,wood,any type of clothing,
paints and endless items that have the basic chemical structure
of a polymer. Human body is made up of protein. Proteins are
also polymers with α-amino acids as repeating units.
 Polymers
• Polymers are macromolecules of higher
molecular weight formed by the repeated
linking of large number of small molecules
called monomers.
• Example: Polyethylene (polymer) is produced
from ethylene (monomer).
 CLASSIFICATION OF POLYMERS
Based in the source, polymers are broadly classified
into two types
• Natural Polymers.
• Synthetic Polymers.
 NATURAL POLYMERS
• The polymers obtained from nature (plants and animals) are
called natural polymers.
Example of natural polymers
 Starch
It is a polymer of glucose. It is a chief food reserve of plants.
 Cellulose
It is also a polymer of glucose. It is a chief structural material of
the plants.
Both starch and cellulose are produced by plants during
photosynthesis.
 Proteins
These are polymers of α-amino acids. They have generally 20 to
100 α-amino acids joined together in a highly organized
arrangement. These are building block of animals.
 SYNTHETIC POLYMERS
 The polymers which are prepared in the laboratories
are called synthetic polymers. These are called man-
made polymers.
 Examples. PVC, polyethylene, nylon, Teflon, Bakelite,
terylene, etc.,
 PLASTICS
• Plastics are high molecular weight organic materials,
that can be moulded into any desired shape by the
application of heat and pressure in the presence of a
catalyst.
Advantages of plastics over other materials
• They are light in weight
• They possess low melting point
• They can be easily moulded and have excellent
finishing
• They possess very good strength and toughness.
• They are corrosion resistant and chemically inert
 Disadvantages of plastics
They are highly soft.
They undergo embrittlement at low
temperature.
Combustibility is high.
They undergo degradation upon exposure to
heat and UV-radiation.
They are Non bio-degradable.
 Classification of Plastics
• Based on the structure and type of resin used
for the manufacture of plastics,plastics are
classified into two main types.
1.Thermoplastic
• Thermoplastics can be softened on heating and
hardened on cooling. They are straight chain
(or) slightly branched polymers and various
chains are held together by weak vanderwaal’s
forces of attraction.
• Examples: Polyethylene, Polyvinyl chloride.
 2.Thermosetting plastic
• Thermosetting Plastics get harden on heating
and once harden, they cannot be softened
again. Various polymer chains are held together
by strong covalent bonds (called crosslink’s).
• Examples: Bakelite, Polyester.
 FUNCTIONALITY
Functionality is defined as the number of
reactive sites or functional groups present in a
monomer.
• Examples
 Significance
1. Bifunctional monomers
If a monomer is Bifunctional, then a linear or
straight chain polymer can be produced.
Each monomeric unit in the linear chain is
linked by strong covalent bonds, but the
different chains are held together by weak
Vander Waals forces of attraction.
This linear type of polymers has less strength
and is soft, flexible and soluble in organic
solvents.
 2.Trifunctional monomers
• When a small amount of trifunctional monomer
is mixed with a bifunctional monomer, they
form branched chain polymer.
 3.Polyfunctional monomer
• Polyfunctional monomer form cross-linked
polymer. All the monomers in the polymer
connected to each other by strong covalent
bonds. This type of polymers are hard and
brittle, high strength, insoluble in organic
solvents.
 POLYMERISATION
Polymerisation is a process in which large number of small molecules(called
monomers) combine to give a big molecules (called a polymer) with or without
elimination of small molecules like water.

Degree of polymerisation
 The number of repeating units (n) in a polymer chain is known as the degree
of polymerization. It is represented by the following relationship.

Degree of polymerization (n) = Molecular weight of the polymeric network

Molecular weight of the repeating unit
5 CH2 = CH2 → ….CH2 –CH2–CH2 –CH2– CH2 –CH2–. CH2 –CH2-CH2 –CH2–

 In this example, five repeating units are present in the polymer chain. So, the
degree of polymerisation is 5.
 Oligo Polimers
• Polymers with low degree of polymerisation
are known as Oligo polymers, their molecular
weight ranges from 500-5000.

High Polimers
• Polymers with high degree of polymerisation
are known as high polymers, their molecular
weight ranges from 10,000 – 2,00,000.
 Types of Polymerisation
• Polymers can also be classified on the basis of mode
of polymerization into three groups.
1.Addition Polymerisation
• It is a reaction that yields a polymer, which is an
exact multiple of the original monomeric molecule,
usually, contains one or more double bonds. In this
addition polymerization there is no elimination of
any molecule.
• Example: Polyethylene is produced from ethylene
 2.Condensation Polymerisation
 It is a reaction between simple polar
groups containing monomers with the
formation of polymer and elimination of
small molecules like H2O, HCl, etc.

• Example: Hexamethylene diamine and

adipic acid condense to form a polymer,
Nylon 6:6
 3.Copolymerization
• It is the joint polymerization in which two (or)
more different monomers combine to give a
polymer.
• Example: Butadiene and Styrene copolymerize
to give GR-S rubber.
 PROPERTIES OF POLYMER
1.Glass Transition Temperature
Definition
When an amorphous polymer is heated, the
temperature at which it changes from a glassy state to
the rubbery form is called the glass transition
temperature, Tg.
The factors affecting or influencing glass
transition temperature of a polymer:
1.The presence of bulky side groups: Presence
of bulky side group hinders the free rotation
about the c-c bond of polymer chain and hence
increases the Tg.
 2.Intermolecular Forces: Presence of large
number of polar groups in the polymer chain
increases intermolecular forces of attraction,
which restrict the mobility. This leads to an
increase in Tg.
•
3.Molecular weight of polymer: Tg is directly
proportional to the molecular weight of the
polymer.
4.Density of branches in the polymer chain
raises Tg.
5.Cross-linking: The presence of cross-links
between chains restricts rotational motion and
raises Tg.
6.Plasticizers: Plasticization also decreases the
Tg, since plasticizer molecules cause separation
of the chains and increase their mobility.
 2.Tacticity (Stereospecfic Polymers)
Definition
 The orientation of monomeric units or functional groups in a
polymer molecule can take place in an orderly or disorderly
manner with respect to main chain is known as tacticity.
Types of Tacticity
1. Isotactic polymer
 If the functional groups are arranged on the same side of the
main chain, the polymer is called isotactic polymer.
 Example: Isotactic polystyrene
 2. Syndiotactic polymer
 If the functional groups are arranged in an
alternating fashion, the polymer is called
syndiotactic polymer.
Example: Syndiotactic polystyrene
 3.Atactic polymer
 If the functional groups are arranged randomly,
the polymer is called atactic polymer.
• Example: Atactic polystyrene
 3.Molecular weight
When we speak molecular mass of a polymer, it is
quite different from that applied to small sized
compounds. Polymers are poly dispersed and
heterogeneous in molecular mass.
In other words polymers are mixtures of molecules of
different molecular masses. So, it is necessary to take
average molecular mass.
The three main types of molecular mass of a polymer
are
• i) Number average molecular mass
• ii) Weight average molecular mass
 i) Number average molecular weight
Number average molecular weight is the total
mass of all the molecules in a polymer sample
divided by the total number of molecules
present.
 ii) Weight average molecular weight
Weight average molecular weight is
mathematically defined as,
 POLYVINYL CHLORIDE (PVC)
Preparation of PVC involves the following two
steps.
I- step: Vinyl chloride is prepared by treating
acetylene with HCl at 60-800C in the presence of
metal chloride as catalyst.
II- step:
PVC is obtained by heating water emulsion of
vinyl chloride in presence of H2O2 under
pressure
 Properties
 It is colourless, odourless, non-inflammable and chemically
inert.

 It is insoluble in inorganic acids and alkalis but soluble in hot

chlorinated hydrocarbons such as ethyl chloride.

 It undergoes degradation in the presence of heat (or) light.

 Pure resin possesses a high softening point (1480C) and a
greater stiffness and rigidity compared to polyethylene, but is
britle.

 It has glass transition temperature of 810C.

 Uses
It is used in the production of pipes, cable
insulations, table covers and rain- coats, etc.
It is also used for making sheets, which are
employed for tank- linings, light fittings,
refrigerator components, etc.

NYLON 6:6 (POLYAMIDES)

Preparation
 Nylon – 6:6 is obtained by the polymerisation of adipic acid with
hexamethylene diamine.
 Among the different nylons, nylon 6:6 is important for fibre. The
number indicates number of carbon atoms in the monomer
from which it is made.
 Properties
 Nylons are translucent, whitest, horny and high melting
polymers.
 They possess high temperature stability and good abrasion-
resistance.
 They are insoluble in common organic solvents and soluble in
phenol and formic acid.
Uses
 Nylons are used for making filaments for ropes, bristles for
tooth-brushes and films, etc.
 Nylon is mainly used for moulding purposes for gears, bearings,
etc.
 Nylon 6:6 is used for fibres, which is used in making socks,
dresses, carpets, etc.
 POLYETHYLENE
Preparation
• It is obtained by the polymerisation of ethylene.
The gas is first liquefied under high pressures
and then pumped into a heated pressure
vessel, maintained at 150 to 2500C.
 Properties
 It is a rigid,waxy,white and translucent material.
 It is chemical resistance to strong acids.
 It is good insulator of electricity.
 It is swollen and permeable to most oils and organic

solvents, particularly kerosene.

Uses
It is used for making high frequency insulator parts,
bottle caps, flexible bottles.
It is used for kitchen and domestic appliances.
It is used for the packing materials, chemical
plants,tubes,pipes,coated-wires and cables, bags for
packing.
 RUBBERS OR ELASTOMERS
Rubbers (or) elastomers are non-crystalline high
polymers (linear polymers), having elastic and
other rubber- like properties.
Structure of rubber
 Types of rubber
There are two types of rubbers,
• Natural rubber
• Synthetic rubber
1. Natural rubber
• Natural rubber is obtained from nearly five
hundred different plants. It consists of basic
material latex, which is a dispersion of
isoprene.
• During the treatment, these isoprene molecules
polymerize to form, long-coiled chains of cis-
polyisoprene.
2.Synthetic rubber
Synthetic rubber is a vulcanizable,man-made
rubber like polymer and stretchable to 2-3
times its length, It is better to term it artificial
rubber as it is not chemically identical with
natural rubber.
Examples
 Silicone rubber
 Polyurethanes
 Nitrile rubbers
 SBR (or) Styrene Butadiene rubber
 Vulcanization of Rubber

Drawbacks of raw rubber

 The raw rubber obtained is of little use as such because it has

very undesirable properties. They are
 It is plastic in nature: It becomes soft at high temperature and is
too brittle at low temperature. So it can be used in the
temperature range of 10 to 600C only.
 It has a low tensile strength and poor resistance to abrasion.
 It has large water absorption capacity.
 It has little durability.
 It is attacked by oxidizing agents like nitric acid, chromic
acid,etc.,
 Vulcanization
• To improve the properties of rubber, it is compounded
with some chemicals like sulphur,hydrogen
sulphide,etc., Most important is addition of sulphur.
Objectives of vulcanization
• The raw rubber obtained from trees are having poor
tensile strength, high water absorbing property, very
high elasticity and very poor chemical resistance
because of its uncross linked structure.
• The cross linking and good properties are achieved by
vulcanization of rubber.
 Process of Vulcanization
 Charles Spencer Goodyear was the first
American scientist discovered the
vulcanization process in 1839 and
patented on June 15,1844.
 He observed that when rubber is heated
with sulphur, its tensile strength, elasticity
and resistance to swelling are increased
tremendously.
 Definition
“The process of heating the raw rubber with
sulphur to 100-1400C to improve the tensile
strength, resistance to swelling and etc., called
as vulcanization of rubber”.
Vulcanization brings about a stiffening of the
rubber by restricting intermolecular movement
of the rubber springs. This is due to the
chemical combination of the sulphur at the
double bonds of different rubber springs and
providing cross-linking between the chains.
 Advantages of Vulcanization
• Vulcanized rubber has good tensile strength
and extensibility, when a tensile force is
applied.
• It has excellent resilience, i.e., article made
from it returns to the original shape, when the
deforming load is removed.
• It possesses low water-absorption tendency.
• It has higher resistance to oxidation and to
abrasion.
• It is a better electrical insulator.
 MOULDING CONSTITUENTS OF A PLASTIC
It is unusual for a finished high-polymer article
to consist solely of high-polymeric material alone.
 Usually,the high-polymer material is mixed with
4 to 10 ingredients, each of which either
discharges a useful function during moulding or
imparts some useful property to the finished
artifact. This is called a mix.
The main types of compounding ingredients
and their functions are described below.
 1.Resin
• Resin is the binder, which holds the different
constituents together.
2.Plasticizers
• Plasticizers are materials that are added to resins to
increase their plasticity and flexibility. Their action is
considered to be the result of the neutralization of
part of the intermolecular forces of attraction
between macromolecules of resins.
• Most commonly used plasticizers are vegetable
oils,camphor,esters and some phosphates(like
tricresyl phosphate,triphenyl phosphate).
 3.Fillers
Fillers are added to give to the final plastic
better hardness, tensile strength,opacity,finish
and workability.sometimes,fillers are added to
impart special characters to the products.
For example, barium salts as are added to
make the plastic impervious to X-rays.
Most commonly used fillers are etc., wood-
flour,asbestos, chine clay,talc,gypsum,saw-
dust
 4.Lubricants
• Lubricants like waxes,oils,stearates,oleates and soaps
are employed to make the moulding of plastic easier
and to impart a glossy finish to the products.
Lubricants prevent the plastic material from sticking to
the fabricating equipment.

5.Catalysts or accelerators
• Catalysts or accelerators are added only in the case of
thermosetting plastics with the object of accelerating
the polymerization of fusible resin, during moulding
operation, into cross-linked infusible form.
 6.Stabilizers
• The purpose of adding stabilizers is to improve the
thermal stability during processing.
• For example, vinyl chloride and vinylidene chloride
polymers show a tendency to undergo decomposition
and discoloration at moulding temperatures.
• Stabilizers commonly used are
• Opaque moulding compounds like salts of
lead,e,g.,white lead, lead chromate,litharge,red lead,
lead silicate and lead naphthenate.
• Transparent moulding compounds like stearates of
lead, cadmium and barium.
 7.Colouring materials
• Colour appeal is soften of prime
importance in high-polymer artifacts. The
main colorings materials are organic
dyestuffs and opaque inorganic pigments.
 MOULDING OF PLASTICS INTO ARTICLES
o Many methods of fabricating plastics into
desired-shape articles are employed.
o The methods,usually,depend upon the type of
resins used,ie.,whether thermosetting or
thermoplastic.
o Commonly used plastic fabrication methods are
described below:
 1.Compression moulding
 It is a method applied to both thermoplastic and
thermosetting plastics. The predetermined quantity of
plastic ingredients in proper proportions get filled
between the two half-pieces of mould, which are
capable of being moved relative to each other.
 Heat and pressure are then applied according to
specifications. The cavities get filled with fluidized
plastic.
 Two halves are closed very slowly.Finally,curing is done
either by heating or cooling. After curing, the
moulded article is taken out by opening the mould
parts.
 2.Injection moulding
 It is applicable mainly to thermoplastic resins. In this,
the moulding plastic powder is fed into a heated
cylinder, from where it is injected at a controlled rate
into the tightly-locked mould by means of a screw
arrangement or by a piston plunger.
 The mould is kept cold to allow the hot plastic to cure
and become rigid.
 When the material have been cured sufficiently, half of
the mould is opened to allow the injection of the
finished article without any deformation. etc., Heating
is done by oil or electricity.
 3.Blow Molding
• This is the most common method for
manufacturing hollow articles from
thermoplastics .
• The most simple products and articles that are
made by blow molding are bottles, ventilation
ducts, suit cases and fuel tanks for
automobiles.
• Two processes are generally followed for blow
molding
 a. Extrusion Blow Molding :
 An extruded tube or parison is elongated to reach the
required length . The parison is then enclosed by the
mold , which is then cut by a blade. It is then conveyed
to the blowing station.
 In the blowing station, a blow mandrel is inserted into
the mould and the actual process is subsequently
carried out. It is then cooled and the finished product
is removed by opening the mould. The open mould is
then transferred to the position below the extrusion
die in order to receive a new parison. The process then
continues
 b .Stretch Blow Molding :
 This is a special form of blow molding in which the
mechanical properties are considerably improved.
 A high degree of orientation is introduced in the
plastics by drawing near the glass transition
temperature or crystalline melting points. The molding
material is drawn not only in the circumferential
direction, but also in the machine direction.
 A mechanical ram is used for drawing in the
longitudinal direction. The process is carried out under
low temperature with the application of high
deformation forces.
 PVC, polypropylene and poly ethyl terephthalate are
some of the materials for use with this process.
 BIODEGRADABLE POLYMER
• These are those polymers which get
decomposed under aerobic or anaerobic
conditions, as a result of the action of
microorganism/enzymes.
• The materials develop it like starch, cellulose,
and polyesters. Aliphatic polyesters are the
most commonly used polymers of this type.
 Examples of Biodegradable Polymers
Poly β-hydroxybutyrate –
co-β-hydroxyvalerate (PHBV):
• It is derived by combining 3-hydroxy butanoic
acid and 3-hydroxy pentanoic acid, in which
monomers are cross-linked by an ester
linkage. It decomposes to form carbon dioxide
and water. It is brittle in nature, and it can be
used in the production of drugs and
manufacturing of bottles
 CONDUCTING POLYMERS
• Most polymeric materials are poor conductor of
electricity, because of the non-availability of large
number of free electrons in the conduction process.
• Within the past several years, polymeric materials has
been synthesized which possess electrical
conductivities on par with metallic conductors. Such
polymers are called conducting polymers.
• Conductivities as high as 1.5 X 107 ohm-1 m-1 have
been attained in these polymeric materials. On a
volume basis, this value is equal to one-fourth of the
conductivity of copper, or is twice its conductivity on
the basis of weight.
 Different types of conducting polymers are discussed below:
1.Intrinsically conducting polymer (ICP) or conjugated π-
electrons conducting polymer
• It is a polymer whose backbones or associated groups consist of
delocalized electron-pair or residual charge. Such polymers
essentially contain conjugated π-electrons of the polymer get
excited, thereby can be transported through the solid polymeric
material.
• Overlapping of orbital’s (of conjugated π-electrons) over the
entire backbone results in the formation of valence bands as
well as conduction bands, which extends over the entire
polymer molecule. Presence of conjugated π-electron in a
polymer increases its conductivity to a larger extent.
• Important commercially produced conducting
polymers:
Polyacetylene polymers e.g. poly-p-phenylene,
polyphenylene-co-vinylene, poly-m-phyenylene
sulphide, etc.
With condensed aromatic rings, e.g.,
polyaniline,polyanthrylene,polyphenarnthrylene,etc.
With aromatic heteroaromatic and conjugated
aliphatic units, e.g., polypyrrole, polythiophene,
polyazomethine, polybutadienylene, etc.
 Doped conducting polymer
• It is obtained by exposing a polymer to a charged
transfer agent in either gas phase or in solution.
Intrinsically conducting polymers possess low
conductivity (10-10 Ω-1 cm-1), but these possess low
ionization potential and high electron affinities, so
these can be easily oxidized or reduced.
• Consequently of ICP can be increased by creating
either positive or negative charges on the polymer
backbone by oxidation or reduction. This technique,
called doping (an analog with semiconductor), is two
types:
• P-doping involves treating an intrinsically
conducting polymer with a lewis acid, thereby
oxidation process takes place and positive
charges on the polymer backbone are created.
Some of the common P-dopant used are I2, Br2,
AsF5, PF6, naphthylamine, etc. used for
example:
• N- doping involves treating an intrinsically
conducting polymer with a lewis base thereby
reduction process takes place and negative
charges on the polymer backbone are created.
Some of the common N- dopant used are Li,
Na, Ca, tetrabutyl ammonium, FeCl3, etc. For
example
 3.Extrinsically conducting polymers
 These polymers whose conductivity is due to the
presence of “externally” added ingredient in them.
These are of the following two types:
Conductive element – filled polymer is a resin or
polymer filled with conducting elements such as
carbon black, metallic fibres, metal oxides, etc.
In this, the polymer acts as the binder to hold the
conducting elements together in the solid entity.
These polymers possess reasonably good bulk
conductivity; and are, generally, low in cost, light in
weight, mechanically durable and strong, and easily
processable in different forms, shapes and sizes..
 4.Coordination conducting polymer (inorganic
polymer)
• It is a charge transfer complex containing
polymer obtained by combining a metal atom
with a polydentate ligand.
• Although the degree of polymerization in such
polymers is small (≤ 18), yet they exhibit
corrosion characteristics, and are usually in
doubtable in most solvents.
 Applications
• Conducting polymers are finding increased use
because they are light weight, easy to process
and have good mechanical properties. Some of
the important applications of conducting
polymers are:
 In wiring in aircrafts and aerospace components.
 In telecommunication systems.
 In antistatic coatings for clothing.
 In electromagnetic screening materials.
 In electronic devices such as transistors and diodes.
In solar cells, drug delivery system for human
body, etc.
In photo voltaic devices, e.g., A1 / polymer / Au
photovoltaic cells.
In non-linear optical materials.
In molecular wires and molecular switches.