CHEM-7003

Applied Polymers Dr. Aftab Ahmad

Prepared by
Dr. Aftab Ahmad
Department of Chemistry
University of Sialkot
Email: aftab.ahmad@uskt.edu.pk
Contact: 0334 5544117
 Course contents
Course Title: Applied Polymers (CHEM-7003)
Instructor: Dr. Aftab Ahmad Credit hours: 03

Introduction to polymer chemistry, Free radical addition polymerization, ionic polymerization, coordination polymerization
(Polymerization using Ziegler-Natta catalyst), Step-Growth Polymerization, Stereochemistry of polymers, Stereoregulation and
Streroconformtion of polymers, Synthetic organic addition and condensation polymers, Polymer degradation, Transition of
polymers from high elastic to glassy and viscofluid states, Glass transition temperature and its measurement, Rheological
properties of polymers, Elastomers, Fabrication of polymers, Reactivity of polymers, Testing and characterization of polymers,
Dendrimers and their applications, Liquid crystals and their classification, applications of liquid crystals, Recent advances and
applications of polymers.
RECOMMENDED BOOKS:
i. Polymer Science by V.R Gowariker
ii. Introduction to Polymer Chemistry Charles E. Carraher Jr.
iii. Text Book of Polymer Sciences Fred W. Billmeyer. Jr.
iv. Introductory Polymer Chemistry G. S. Mishra
v. Text Book of Polymer S. Chand, M. S. Bhat Nagar
vi. Principles of Polymer Chemistry Paul J. Flory
 What are polymers?
• “polymer” Greek word poly "many" meres "parts"

• Macromolecules consisting of several monomers that are linked together to form long
chains
• High molecular weight (between 10,000-1000,000 g/mol)
• The number of monomeric units in a polymer is called Degree of polymerization
 History of Polymers
• The history of natural polymers is as old as the formation of earth. Since 4 billion years ago, elements like C, H,
O, N etc. have been combining to form complex molecules to form most intriguing process i.e. life by formation
of various macromolecules (proteins, carbohydrates, lipids etc.)
• In other natural form wood, cotton, cellulose, starch etc.
• Use of animal skin, leaves, trees, wood clubs, weapons for human shelter and survival was also a gift of
polymerization
• In 15th century, Christopher Columbus, noticed the natives of South America playing a bouncing game with a
solid mass collected from exudate of a tree called “weeping wood”. Years later, Joseph Priestly noticed that this
solid mass could rub off pencil marks from paper and hence the material was called rubber to build up a
multi-billion dollar rubber industry to start synthetic polymers
• With the advent of time, natural polymers were replaced by synthetic polymers (animal skin by polyester), but
again the basic need is polymer in whatever form
• Roy J. Plunkett in 1938 accidentally discovered the most stable polymer i.e. Teflon
by keeping the cylinder filled with TFE gas for few days. Later he observed that
volume inside the cylinder was reduced due to polymerization of TFE which was
turned to white waxy material.
 Significance of Polymers
• For many years, people used polymers in their life but they did not know it well almost until
World War II. There were relatively few materials to manufacture the articles needed for a
civilized life. Glass, wood, stone, brick, and concrete for most of the construction and
cotton, wood, jute and a few other agricultural products for clothing or fabric manufacture
were used
• The rapid increase in demand for the manufactured products introduced the new materials.
These new materials are polymers, and their impact on the present way of life is almost
incalculable. Products made from polymers are all around us: clothing made from synthetic
fibers, polyethylene cups, fiberglass, nylon bearings, plastic bags, polymer-based paints,
epoxy glue, polyurethane foam cushions, silicone heart valves and Teflon-coated
cookware, the list is almost endless.
 Significance of Polymers in Research
• Both natural and synthetic polymers are remarkably involved in comfort and facilitation of
human life. They are responsible for life, medication, nutrition, communication,
transportation, irrigation, containers, clothing, recording history, buildings, highways
etc. It is difficult to imagine human society without synthetic and natural polymers.
• It is not surprising that nearly all material scientists and most of chemists and chemical
engineers, a large number of physicists, textile technologists, mechanical engineers,
pharmacists and other scientific groups are involved in research and development projects
related to polymers
• Perhaps polymer chemistry, more than any other research field, crosses over and cuts the
traditional lines of all branches of Chemistry, Biology, Physics, material, engineering,
pharmacy, and even medicine. A newcomer to polymer science requires enough ability to
mix together the vast knowledge from all aforementioned fields
• The knowledge of polymers and related texts provides both the information and insights of
their better understanding in our life
 Desirable properties of polymers
To get strong solid articles, flexible rubber-like masses, soft and resilient foams,
smooth and fine fibers, clean and clear glass-like sheets, and swollen, jelly-like food
materials for multi-purpose applications, some specific properties of polymers are
desirable:
• High strength
• Light weight
• Good flexibility
• Special electrical properties
• Resistance to chemicals
• Amenability for quick and mass production
• Fabrication into complex shapes with a wide variety of colors
Difference in behaviour of polymers and small molecules
It is essentially the “giantness” of the size of the polymer molecule that makes its behaviour different from that of
small molecules
• Melting point: small molecules melt at sharp melting points e.g benzene melts at 5.5 oC to become liquid,
while polymer molecule does not melt at sharp melting point into clean liquid, instead it becomes softer and
ultimately turns into a viscous tacky molten mass. Further heating of this hot viscous molten polymer does not
convert it into gases but it is no longer a polymer
• Solubility: small molecules have specific solubility and dissolve in solvent upto a point (saturation point and
after that point, any further addition does not go into solution but settles at the bottom. But the polymer does not
go into the solution immediately, rather globules of polymer absorb water, swell and get distorted in shape and
after a long time go into solution. A large quantity of polymer can be added into the same quantity of solvent
without the saturation point ever being reached.
• Viscosity: of the saturated solution of small molecule is not very much different from that of solvent. While, as
more and more quantity of polymer is added into solvent, the mix ultimately assumes a soft, dough-like texture
and viscosity increases several time
Small molecules Polymers
Have sharp melting points Do not have sharp melting point and heating at even very high temperature does
not convert them into gases but they no longer remain a polymer

Have specific solubility and saturation point Do not have specific solubility and their saturation point never reaches

Viscosity of their saturated solution is quite similar to that of solvent Their viscosity increases several time with the addition of polymer in mix
 CLASSIFICATION OF POLYMERS
Since Polymers are numerous in number with different behaviours and can be naturally found
or synthetically created, they can be classified in various ways.
1. Classification Based on Source
a. Natural polymers: occur in natural sources like plants and animals. Some common
examples are Proteins (which are found in humans and animals alike), Cellulose and
Starch (which are found in plants) or Rubber (which we harvest from the latex of a
tropical plant ).
b. Synthetic polymers: can be artificially created/synthesized in a lab. These are
commercially produced by industries for human necessities e.g. Polyethylene (a mass-
produced plastic which we use in packaging) or Nylon Fibers (commonly used in our
clothes, fishing nets etc.)
c. Semi-Synthetic polymers: obtained by making modification in natural polymers
artificially in a lab. These polymers formed by chemical reaction (in a controlled
environment) and are of commercial importance. Example: Vulcanized Rubber ( Sulphur
is used in cross bonding the polymer chains found in natural rubber) Cellulose acetate
(rayon) etc.
2. Classification Based on Structure of Polymers
a. Linear polymers: The monomers in these are linked together to form a long chain. These
polymers have high melting points and are of higher density. A common example of this is
PVC (Poly-vinyl chloride). This polymer is largely used for making electric cables and
pipes.
b. Branched polymers: Monomers join together to form a long straight chain with some
branched chains of different lengths. As a result of these branches, the polymers are not
closely packed together. They are of low density having low melting points. Low-density
polyethene (LDPE) used in plastic bags
c. Cross-linked or Network polymers: Monomers are linked together to form a three-
dimensional network. The monomers contain strong covalent bonds as they are composed
of bi-functional and tri-functional groups. These polymers are brittle and hard. e.g
Bakelite (used in electrical insulators), Melamine etc.
 3. Classification Based on Mode of Polymerisation
a. Addition polymers: form when an addition reaction occurs, the monomers rearrange
themselves to form a new structure, but there is no loss of an atom or a molecule. There are
four types of addition polymerizations:
• Free Radical Polymerization: polymer forms by addition of atoms with a free electron in
its valence shells called free radicals which join in a successive chain during free radical
polymerization
• Cationic polymerization: A polymerization where a cation causes a chain reaction. It
results in forming a long chain of repeating monomers
• Anionic Polymerization: Involves the polymerization of particularly vinyl polymers with
a strong electronegative group to form a chain reaction
• Coordination Polymerization: invented by Nobel Prize winners Ziegler and Natta which
polymerizes unsaturated hydrocarbons. It produces a polymer which has more density
and strength
b. Condensation polymers: form from the step growth polymerization where monomers
react to form a bond and replace certain molecules which are the by-product of the reaction
e.g H2O, CO2, NH3 etc.
 ADDITION VS CONDENSATION POLYMERIZATION
• In addition polymerization, monomers only join at the active site of the chain. But in
condensation polymerization, molecules react with where functional groups are present
• In addition polymerization, there are three distinct steps. Initiation, propagation and finally
termination. In condensation polymerization, there is no termination step. The end groups
remain reactive through the entire process
• Addition polymerization results in homo-chain polymers whereas condensation
polymerization results in hetro-chain (co-) polymers
• In addition polymers there is no loss of atom. But in condensation reaction, there is a loss of a
molecule of water, ammonia etc as a by-product
4. Classification Based on Molecular Forces
The properties exhibited by polymers depend largely on the strength of the forces between
these molecules which categorizes the polymers into 4 types:
a. Elastomers: Elastomers are rubber-like solid polymers that are elastic in nature. The
polymer chains are held by the weakest intermolecular forces, hence allowing the polymer
to be stretched, and removing that stress also results in the polymer taking up its original
form. This happens as we introduce crosslinks between the polymer chains which help it
retract to its original position. E.g. car tyres are made of Vulcanized rubber. This is when
we introduce sulphur to cross-bond the polymer chains.

b. Plastics
• Thermoplastics: these are long-chain polymers in which inter-molecular forces (Van der
Waal’s forces) hold the chains together. When they are heated, they soften (thick fluid like)
and hardened when they are allowed to cool down, forming a hard mass. They do not
contain any cross bond and can easily be shaped by heating and using moulds. A common
example is Polystyrene or PVC (which is used in making pipes).
c. Thermosetting: polymers that are semi-fluid in nature with low molecular masses. When
heated, they start cross-linking between polymer chains, hence becoming hard and infusible.
They form a three-dimensional structure upon heating. This reaction is irreversible in nature.
The most common example of a thermosetting polymer is that of Bakelite, which is used in
making electrical insulation.

d. Fibres: are thread-like in nature, and can easily be woven. They have strong inter-
molecular forces between the chains giving them less elasticity and high tensile strength. The
intermolecular forces may be hydrogen bonds or dipole-dipole interaction. Fibres have sharp
and high melting points. A common example is that of Nylon-6,6, which is used in carpets and
apparel.
 CLASSIFICATION OF POLYMERS
Classification Classification based on structure Classification Based on Mode Classification
based on sources of Polymerisation Based on
Molecular Forces
1. Natural polymers 1. Linear polymers 1. Addition polymers 1. Elastomers
(proteins, cellulose, (PVC) • Free Radical Polymerization
starch, rubber) • Cationic polymerization
2. Synthetic polymers • Anionic polymerization
(polyethylene, PVC, • Coordination Polymerization
Nylon fibres) 2. Plastics
3. Semi-Synthetic 2. Branch chain polymers • Thermoplastics
polymers (Vulcanized (LDPE)
Rubber, cellulose acetate
(Rayon )
• Thermosetting
2. Condensation polymers
3. Cross-linked or Network polymers
(Bakelite)

3. Fibres
THANKS FOR YOUR ATTENTION