Chemistry

Project
THE POLYMERS

SUBMITTED BY
NAME: GIBIN CIJO BABY
CLASS: XII SCIENCE
 INDEX
1. INTRODUCTION
2. ACKNOWLEDGEMENT
3. CONTENT
• CLASSIFICATION OF POLYMERS
• PROCEDURES
• PREPARATIONS
• SYNTHESIS
• MECHANICAL PROPERTIES
• TRANSPORT PROPERTIES

• APPLICATIONS
• CHARACTERIZATION

4. REFERENCE

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 INTRODUCTION
WHAT ARE POLYMERS?

A polymer is a substance or material consisting of very large molecules,

or macromolecules, composed of many repeating subunits. Due to
their broad spectrum of properties, both synthetic and natural
polymers play essential and ubiquitous roles in everyday life. Polymers
range from familiar synthetic plastics such as polystyrene to natural
biopolymers such as DNA and proteins that are fundamental to
biological structure and function. Polymers, both natural and synthetic,
are created via polymerization of many small molecules, known as
monomers. Their consequently large molecular mass, relative to small
molecule compounds, produces unique physical properties including
toughness, high elasticity, viscoelasticity, and a tendency to form
amorphous and semi crystalline structures rather than crystals. The
term "polymer" derives from the Greek word πολύς (polus, meaning
"many, much") and μέρος (meros, meaning "part"), and refers to large
molecules whose structure is composed of multiple repeating units,
from which originates a characteristic of high relative molecular mass
and attendant properties. The units composing polymers derive,

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actually or conceptually, from molecules of low relative molecular
mass. The term was coined in 1833 by Jons Jacob Berzelius, though
with a definition distinct from the modern IUPAC definition. The
modern concept of polymers as covalently bonded macromolecular
structures was proposed in 1920 by Hermann Staudinger, who spent
the next decade finding experimental evidence for this hypo synthesis.
Polymers are substances composed of macromolecules, very large
molecules with molecular weights ranging from a few thousand to as
high as millions of grams/mole. The IUPAC gold book definition of a
macromolecule is: “A molecule of high relative molecular mass, the
structure of which essentially comprises the multiple repetitions of
units derived, actually or conceptually, from molecules of low relative
molecular mass.” Natural polymers include protein, starch, cellulose,
DNA and make up most of the structures of living tissue. Synthetic
polymers now constitute one of the most successful and useful classes
of materials and possess a broad range of physical properties. Today,
synthetic polymers are being used to emit light, act as semiconductors
in low-cost printable devices, as light weight materials for bullet proof
vests (where the fibres are stronger than steel), in medicine to deliver
drugs, as artificial skin and for many other applications that were not
imagined just a few years ago. Rapid advances in polymers are enabling
the nanotechnology revolution. For example, in microelectronics
polymers make possible circuits of a few 10s of nanometres, that is,

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less than 1/1000th the size of a human hair. Natural polymers have
been used by man since prehistory and have been modified and
processed empirically over many centuries for various applications, for
example, textiles for clothing and papyrus. Most of the early
modifications still in use today stem from developments in the 19th
century or the beginning of the 20th century and relate to cellulose and
natural rubber.

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ACKNOWLEDGEMENT
I would like to express my special thanks of gratitude to my teachers,
Mayasree ma’am and Dhanya ma’am for giving me an opportunity to
do the project titled the polymers.

It helped me in doing lot of research and I came to know about so

many new things. I am really thankful to them.

Secondly, I would also like to thank my parents and friends who helped
me a lot in finalizing thin project within the limited time frame.

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 CONTENT
CLASSIFICATION OF POLYMERS:
Polymers are made up of large no of macromolecules. The single unit
of a polymeric chain is called a monomer. This process of formation of
polymers from respective monomers is called polymerization.

Natural polymers- These polymers are found in plants and animals.

Examples are proteins, cellulose, starch, resins and rubber.
Semi-synthetic polymers- Cellulose derivatives as cellulose acetate
(rayon) and cellulose nitrate, etc. are the usual examples of this sub
category.
Synthetic polymers- A variety of synthetic polymers as plastic
(polythene), synthetic fibres (nylon 6, 6) and synthetic rubber (Buna – S)
are examples of man-made polymers extensively used in daily life as
well as in industry. There are three different types based on the
structure of the polymers.
Structural polymers- Linear polymers on Structure: - These
polymers consist of long and straight chains. The examples of Polymers
are high density polythene, polyvinyl chloride, etc. These are

represented as Branched chain polymers. These polymers contain

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linear chains having some branches, e.g., low density polythene. These
are depicted as follows:
 Cross linked or Network polymers- These are usually formed from
bi-functional and tri-functional monomers and contain strong
covalent bonds between various linear polymer chains, e.g.
bakelite, melamine, etc. These polymers are depicted as follows:
 Addition polymers: - Addition polymers are formed from repeated
units of monomer units possessing double and triple bonds.
Polymers formed by addition of two different polymers are called
co-polymers. E.g.: -Condensation polymers: The condensation
polymers are formed by repeated condensation reaction between
two different bi-functional or tri-functional monomer units. In
these polymerization reactions, the elimination of small molecules
such as water, alcohol, hydrogen chloride, etc. take place. The
examples are Terylene (Dacron), nylon 6, 6, nylon 6, etc. For
example, nylon 6, 6 is formed by the condensation of
hexamethylene diamine with adipic acid. Classification of
polymers based on molecular forces:
A large number of polymer applications in different fields depend on
their unique mechanical properties like tensile strength, elasticity,
toughness, etc. These mechanical properties are governed by
intermolecular forces, e.g., van der Waals forces and hydrogen bonds,
present in the polymer. These forces also bind the polymer chains.
Under this category, the polymers are classified into the following four
sub groups on the basis of magnitude of intermolecular forces present
in them.

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  Elastomers: - These are rubber–like solids with elastic properties.
In these elastomeric polymers, the polymer chains are held
together by the weakest intermolecular forces. These weak
binding forces permit the polymer to be stretched. A few
‘crosslinks’ are introduced in between the chains, which help the
polymer to retract to its original position after the force is
released as in vulcanised rubber. The examples are buna-S,
bunaN, neoprene, etc.
 Fibres: - Fibres are the thread forming solids which possess high
tensile strength and high modulus. These characteristics can be
attributed to the strong intermolecular forces like hydrogen
bonding. These strong forces also lead to close packing of chains
and thus impart crystalline nature. The examples are polyamides
(nylon 6, 6), polyesters (Terylene), etc.
 Thermoplastic polymers: - These are the linear or slightly
branched long chain molecules capable of repeatedly softening on
heating and hardening on cooling. These polymers possess
intermolecular forces of attraction intermediate between
elastomers and fibres. Some common thermoplastics are
polythene, polystyrene, polyvinyl, etc.
 Thermosetting polymers: - These polymers are cross linked or
heavily branched molecules, which on heating undergo extensive
cross linking in moulds and again become infusible. These cannot
be reused. Some common examples are bakelite, urea
formaldehyde resins, etc.
Classification based on growth polymers:

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There are two broad types of polymerization reactions, i.e., the
addition or chain growth polymerization and condensation or step
growth polymerization.
Addition Polymerization or Chain Growth Polymerization: - In this type
of polymerization, the molecules of the same monomer or different
monomers add together on a large scale to form a polymer. The
monomers used are unsaturated compounds, e.g., alkenes, alkadienes
and their derivatives. This mode of polymerization leading to an
increase in chain length or chain growth can take place through the
formation of either free radicals or ionic species. However, the free
radical governed addition or chain growth polymerization is the most
common mode.

PROCEDURES:
• Free radical mechanism: - The polymerization of ethene to
polythene consists of heating or exposing to light a mixture of
ethene with a small amount of benzyl peroxide initiator. The
process starts with the addition of phenyl free radical formed by
the peroxide to the ethene double bond thus generating a new
and larger free radical. This step is called chain initiating step. As
this radical reacts with another molecule of ethene, another
bigger sized radical is formed. The repetition of this sequence
with new and bigger radicals carries the reaction forward and the
step is termed as chain propagating step. Ultimately, at some

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 stage the product radical thus formed reacts with another radical
to form the polymerized product.
• Chain terminating step: - For termination of the long chain, these
free radicals can combine in different ways to form polythene.
One mode of termination of chain is shown as under:
Preparation of important addition polymers:
Polytetrafluoroethene (Teflon) - Teflon is manufactured by
heating tetrafluoroethene with a free radical or
persulphate catalyst at high pressures. It is chemically inert
and resistant to attack by corrosive reagents. It is used in
making oil seals and gaskets and also used for non–stick
surface coated utensils.
Polyacrylonitrile- The addition polymerization of acrylonitrile
in presence of a peroxide catalyst leads to the formation of
polyacrylonitrile. Polyacrylonitrile is used as a substitute for
wool in making commercial fibres as orlon or acrilan.
• Condensation polymerization or step growth polymerization: -
This type of polymerization generally involves a repetitive
condensation reaction between two bi-functional monomers.
These polycondensation reactions may result in the loss of some
simple molecules as water, alcohol, etc., and lead to the
formation of high molecular mass condensation polymers. In
these reactions, the product of each step is again a bi-functional
species and the sequence of condensation goes on. Since, each
step produces a distinct functionalized species and is independent
of

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 each other; this process is also called as step growth
polymerization. The formation of terylene or dacron by the
interaction of ethylene glycol and terephthalic acid is an example
of this type of polymerization.
• Polyamides: - These polymers possessing amide linkages are
important examples of synthetic fibres and are termed as nylons.
The general method of preparation consists of the condensation
polymerization of diamine with dicarboxylic acids and also of
amino acids and their lactams.

PREPARATIONS:
 PREPARATION OF NYLONS:
Nylon 6, 6- It is prepared by the condensation polymerization of
hexamethylenediamine with adipic acid under high pressure and at
high temperature. It is used in making sheets, bristles for brushes and
in textile industry. Nylon 6- It is obtained by heating caprolactum with
water at a high temperature. It is used for the manufacture of tyre
cords, fabrics and ropes.

 PREPARATION OF POLYESTERS:
These are the polycondensation products of dicarboxylic acids and
diols. Dacron or terylene is the best known example of polyesters. It is
manufactured by heating a mixture of ethylene glycol and terephthalic
acid at 420 to 460 K in the presence of zinc acetate antimony trioxide

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catalyst as per the reaction given earlier. • Dacron fibre (terylene) is
crease resistant and is used in blending with cotton and wool fibres and
also as glass reinforcing materials in safety helmets, etc.

 PREPARATION OF PHENOL:
Also called formaldehyde polymer (Bakelite and related polymers)
Phenol – formaldehyde polymers are the oldest synthetic polymers.
These are obtained by the condensation reaction of phenol with
formaldehyde in the presence of either an acid or a base catalyst. The
reaction starts with the initial formation of o-and or p-
hydroxymethylphenol derivatives, which further react with phenol to
form compounds having rings joined to each other through – CH2
groups. The initial product could be a linear product – Novolac used in
paints. Novolac on heating with formaldehyde undergoes cross linking
to form infusible solid mass called bakelite. It is used for making combs,
phonograph records, electrical switches and handles of various utensils.

SYNTHESIS OF POLYMERS:
Example of chain polymerization: Radical polymerization of styrene, R.
is initiating radical, P. is another polymer chain radical terminating the
formed chain by radical recombination

Polymerization is the process of combining many small molecules

known as monomers into a covalently bonded chain or network. During
the polymerization process, some chemical groups may be lost from

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each monomer. This happens in the polymerization of PET polyester.
The monomers are terephthalic acid (HOOC—C6H4— COOH) and
ethylene glycol (HO—CH2—CH2—OH) but the repeating unit is —OC—
C6H4—COO—CH2—CH2—O—, which corresponds
to the combination of the two monomers with the loss of two water
molecules. The distinct piece of each monomer that is incorporated
into the polymer is known as a repeat unit or monomer residue.

Synthetic methods are generally divided into two categories,

stepgrowth polymerization and chain polymerization.[20] The essential
difference between the two is that in chain polymerization, monomers
are added to the chain one at a time only, such as in polystyrene,
whereas in step-growth polymerization chains of monomers may
combine with one another directly, such as in polyester. Step growth
polymerization can be divided into polycondensation, in which
lowmolar-mass by-product is formed in every reaction step, and
polyaddition.

MECHANICAL PROPERTIES:
The bulk properties of a polymer are those most often of end-use
interest. These are the properties that dictate how the polymer actually
behaves on a macroscopic scale.

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Tensile strength

The tensile strength of a material quantifies how much elongating

stress the material will endure before failure. This is very important in
applications that rely upon a polymer's physical strength or durability.
For example, a rubber band with a higher tensile strength will hold a
greater weight before snapping. In general, tensile strength increases
with polymer chain length and cross linking of polymer chains.

Young's modulus of elasticity

Young's modulus quantifies the elasticity of the polymer. It is defined,

for small strains, as the ratio of rate of change of stress to strain. Like
tensile strength, this is highly relevant in polymer applications involving
the physical properties of polymers, such as rubber bands. The modulus
is strongly dependent on temperature. Viscoelasticity describes a
complex time-dependent elastic response, which will exhibit hysteresis
in the stress-strain curve when the load is removed.

Dynamic mechanical analysis or DMA measures this complex modulus

by oscillating the load and measuring the resulting strain as a function
of time.

TRANSPORT PROPERTIES:

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Transport properties such as diffusivity describe how rapidly molecules
move through the polymer matrix. These are very important in many
applications of polymers for films and membranes.

The movement of individual macromolecules occurs by a process

called reputation in which each chain molecule is constrained by
entanglements with neighboring chains to move within a virtual tube.
The theory of reputation can explain polymer molecule dynamics and
viscoelasticity.

APPLICATIONS:
Nowadays, synthetic polymers are used in almost all walks of life.
Modern society would look very different without them. The spreading
of polymer use is connected to their unique properties: low density,
low cost, good thermal/electrical insulation properties, and high
resistance to corrosion, low-energy demanding polymer manufacture
and facile processing into final products. For a given application, the
properties of a polymer can be tuned or enhanced by combination with
other materials, as in composites. Their application allows to save
energy (lighter cars and planes, thermally insulated buildings), protect
food and drinking water (packaging), save land and reduce use of
fertilizers (synthetic fibres), preserve other materials (coatings), protect

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and save lives (hygiene, medical applications). A representative, non-
exhaustive list of applications is given below.

• Clothing, sportswear and accessories: polyester and PVC clothing,

spandex, sport shoes, wetsuits, footballs and billiard balls, skis and
snowboards, rackets, parachutes, sails, tents and shelters.

• Electronic and photonic technologies: organic field effect transistors

(OFET), light emitting diodes (OLED) and solar cells, television
components, compact discs (CD), photo resists, holography.

• Packaging and containers: films, bottles, food packaging, barrels.

• Insulation: electrical and thermal insulation, spray foams.

• Construction and structural applications: garden furniture, PVC

windows, flooring, sealing, pipes.

• Paints, glues and lubricants: varnish, adhesives, dispersants,

antigraffiti coatings, antifouling coatings, non-stick surfaces,
lubricants.

• Car parts: tires, bumpers, windshields, windscreen wipers, fuel tanks,

car seats.

• Household items: buckets, kitchenware, toys (e.g., construction sets

and Rubik's cube).

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• Medical applications: blood bag, syringes, rubber gloves, surgical
suture, contact lenses, prosthesis, controlled drug delivery and
release, matrices for cell growth.

CHARACTERIZATION:
Polymer characterization spans many techniques for determining the
chemical composition, molecular weight distribution, and physical
properties. Select common techniques include the following:

• Size-exclusion chromatography (also called gel permeation

chromatography), sometimes coupled with static light scattering, can
used to determine the number-average molecular weight,
weightaverage molecular weight, and disparity.

• Scattering techniques, such as static light scattering and small-angle

neutron scattering, are used to determine the dimensions (radius of
gyration) of macromolecules in solution or in the melt. These
techniques are also used to characterize the three-dimensional
structure of micro phase-separated block polymers, polymeric
micelles, and other materials.

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• Wide-angle X-ray scattering (also called wide-angle X-ray diffraction) is
used to determine the crystalline structure of polymers (or lack
thereof).

• Spectroscopy techniques, including Fourier-transform infrared

spectroscopy, Raman spectroscopy, and nuclear magnetic resonance
spectroscopy, can be used to determine the chemical composition.

• Differential scanning calorimetry is used to characterize the thermal

properties of polymers, such as the glass-transition temperature,
crystallization temperature, and melting temperature. The
glasstransition temperature can also be determined by dynamic
mechanical analysis.

• Thermogravimetry is a useful technique to evaluate the thermal

stability of the polymer.

• Rheology is used to characterize the flow and deformation behavior. It

can be used to determine the viscosity, modulus, and other
rheological properties. Rheology is also often used to determine the
molecular architecture (molecular weight, molecular weight
distribution, branching) and to understand how the polymer can be
processed.

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REFERENCE
• WWW.WIKIPEDIA
• GOOGLE
• CHROME

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