Topic: Polymers

Submitted to: Dr. Asad

Submitted by: Anam Shahzadi
Program: BS-Chemistry
Semester: 4th (Evening)
Roll no: BSF-1702168
Subject: Industrial Chemistry
 Polymers
Introduction and Its Scope:
The word polymer is derived from Greek words, poly= many and mers = parts or
units of high molecular mass each molecule of which consist of a very large number of
single structural units joined together in a regular manner. In other words polymers
are giant molecules of high molecular weight, called macromolecules, which are
build up by linking together of a large number of small molecules, called monomers.
The reaction by which the monomers combine to form polymer is known as
polymerization. The polymerization is a chemical reaction in which two or more
substances combine together with or without evolution of anything like water, heat or
any other solvents to form a molecule of high molecular weight. The product is called
polymer and the starting material is called monomer. Polymers form a very important
class of materials without which the life seems very difficult. They are all around us in
everyday use; in rubber, in plastic, in resins, and in adhesives and adhesives tapes.

Historical Development of Polymers:

Polymers have existed in natural form since life began and those such as DNA, RNA,
proteins and polysaccharides play crucial roles in plant and animal life. From the
earliest times, man has exploited naturally-occurring polymers as materials for
providing clothing, decoration, shelter, tools, weapons, writing materials and other
requirements. However, the origin of today’s polymer industry is commonly accepted
as being the nineteenth century when important discoveries were made concerning
the modification of certain natural polymers. In eighteenth century, Thomas Hancock
gave an idea of modification of natural rubber through blending with ceatrain
additives. Later on, Charles Goodyear improved the properties of natural rubber
through vulcanization process with sulphur. The Bakelite was the first synthetic
polymer produced in 1909 and was soon followed by the synthetic fibre, rayon, which
was developed in 1911. The systematic study of polymer science started only about a
century back with the pioneering work of Herman Staudinger. Staudinger has given a
new definition of polymer. He in1919 first published this concept that high molecular
mass compounds were composed of long covalently bonded molecules.
Structures of Polymers:
 Linear Polymers
 Branched Polymers
 Cross- Linked Polymers

Linear Polymer:
If the monomer units are joined in a linear fashion, polymer is said to be linear
polymer.

X X X X Y X
Linear Homopolymer Linear Copolymer

Branched Polymer:
If the monomer units are jointed in branched fashion, then polymer is called branched
polymer.

X X X Y X Y
X X X X
Branched Homopolymer Branched Copolymer

Cross Linked Polymer:

A polymer is said to be a cross linked polymer, if the monomers are joined in a chain
fashion. In cross linked polymers, the straight chains are interconnected with each
other in network form.

X X X X Y X Y X
X X X X
X X X X X Y X Y
Cross Linked Homopolymer Cross Linked Copolymer
 Classification of Polymers:
Polymers can be classified according to the followings:

 On The Basis Of Origin:

 Natural
 Semi- Synthetic
 Synthetic

Natural Polymers:
The polymers, which occur in nature are called natural polymer also known as
biopolymers. Examples of such polymers are natural rubber, natural silk, cellulose,
starch, proteins etc.

Semi –Synthetic Polymers:

They are the chemically modified natural polymers such as hydrogenated, natural
rubber, cellulosic, cellulose nitrate, methyl cellulose, etc.

Synthetic Polymers:
The polymer which has been synthesized in the laboratory is known as synthetic
polymer. These are also known as manmade polymers. Examples of such polymers are
polyvinyl alcohol, polyethylene, polystyrene, polysulfide, etc.

 On The Basis Of Thermal Response:

 Thermoplastic Polymers
 Thermosetting Polymers
Thermoplastic Plastics:
They can be softened or plasticized repeatedly on application of thermal energy,
without much change in properties if treated with certain precautions. Examples of
such polymers are Polyolefin, nylons, linear polyesters and polyether, PVC, sealing wax
etc.
Thermosetting Polymers:
Some polymers undergo certain chemical changes on heating and convert themselves
into an infusible mass. The curing or setting process involves chemical reaction leading
to further growth and cross linking of the polymer chain molecules and producing giant
molecules. For example, Phenol, resins, urea, epoxy resins, dyne rubbers, etc.

 On The Basis Of Tacticity:

Tacticity is the stereo-chemical arrangement of units in the main chain of the
polymer.

 Isotactic
 Syndiotactic
 Atactic

Isotactic Polymer:
The geometry in which characteristic groups are arranged on the same side of main
chain.

Isotactic Polypropylene

Syndiotactic Polymer:
Polymer is said to be a syndiotactic polymer, if the side groups are arranged in an
alternate fashion.
 Atactic Polymer:
If the characteristic groups are arranged in a irregular fashion around the main
polymer chain, polymer is called atactic polymers.

 On the basis Of Chemical Structure:

 Homopolymer
 Copolymer
 Terpolymer
Homopolymer:
A polymer having single types of monomers in a polymer chain is known as
homopolymer.

X X X X
Copolymer:
A polymer having two different types of monomers in a polymer chain is known as
copolymer.

X Y X Y
Terpolymer:
A polymer having three different monomers in a polymer chain is known as
terpolymer.

X Y Z X Y Z
 On The Basis Of Molecular Forces:
 Elastomer
 Plastics
 Fibre

Elastomers:
Rubber is high molecular weight polymer with long flexible chains and low
intermolecular forces. They exhibits high tensile strength in the range of 300-3000
Psi and elongation at break ranging between 300-1000%.
Examples are natural and synthetic rubbers.

Plastics:
Plastics are relatively tough substances having high molecular weight that can be
moulded with the help of heat. These are usually much stronger than rubbers.
They exhibit tensile strength ranging from 4000-15000 psi and elongation at break
ranging at 20-200% or even higher. Examples are polyethylene, polypropylene,
PVC, polystyrene etc.

Fibres:
Fibres are long chain polymers characterized by highly crystalline regions resulting
from secondary forces. They have a much lower elasticity than plastics and
elastomers. They also have high tensile strength ranging between 20000-150000
psi. They are light weight and possess moisture absorption properties.

Examples are nylon, polyester, rayon etc.

Methods of Synthesis:

 Additional Polymer
 Condensation Polymers
 Additional Polymers:
Addition polymers are formed when individual molecules, known as
monomers, join to form long chains. These chains are called polymers. The
reaction is known as an addition reaction because the monomers join together
to form one big molecule, the polymer, without any atoms or groups of atoms
being either eliminated or substitute. The addition polymers, which are formed
by addition reactions that link together monomers containing multiple bonds.
These polymers usually form via a free-radical mechanism in which the
multiple bonds is homolytically cleaved by light, heat or with the assistance of
a radical initiator. Generally:

Condensation Polymers:
A large number of important and useful polymeric materials are not formed by
chain-growth processes involving reactive species such as radicals, but proceed
instead by conventional functional group transformations of poly-functional
reactants. These polymerizations often (but not always) occur with loss of a small
by-product, such as water, and generally (but not always) combine two different
components in an alternating structure.
Description of Synthetic Polymer:
Polyvinyl Chloride:
It is an addition polymer obtained by polymerizing vinyl chloride at 58C and 9
atmospheric pressure.

Addition of the plasticizer improves the flexibility of the polymer. It is widely used
in floor covering, in pipes, in gramophone recorder, etc.

Polystyrene:
It is an additional polymer and is obtained by the polymerization of styrene in
the presence of catalyst.
Polystyrene is used in the manufacture of food containers, cosmetic bottles, toys
and packing material etc.

Polyvinyl Acetate:
PVA is a colourless, non-toxic resin. It is supplied in a numbers of grades differing
in the degree of polymerization. The resin has a characteristics odour.

It is mostly used as an adhesive material and as a binder for emulsion paints.

Acrylic Resins:
These are closely related to the vinyl resins. The most important monomers of
acrylic resins are methylmethacrylate, acrylic acid and butyl acrylate. The acrylic
fibres are based largely on acrylonitrile.

Acrylic resins are used in the manufacture of plastics, paints of car industry and
weather resistant paints.

Polyester Resins:
Polyesters resins are the products of the reaction of an alcohol (ethane 1, 2 diol)
and aromatic bi-functional acids (benzene 1, 4 dicarboxylic acid).
This product has a number of uses in clothing. Polyester is often blended with
cotton or wool for summer and winter clothing. Polyester resins are also used for
making water tanks etc.

Polyamide Resins:
These polymers are formed by the polymerization of polyamines with aliphatic
dicarboxylic acids. One of the most important condensation polymers discovered
is Nylon. Nylon 6, 6 is the most important polyamide. It is obtained by heating
adipic acid (hexanedioic acid) with hexanethylene diamine. Nylon 6, 6 derives its
name its starting materials adipic acid and hexamethylene diamine, both of which
have six carbon atoms.

Nylon is mainly used as a textile fibre. It has a combination of high strength,

elasticity, and toughness and abrasion resistance.

Biopolymers:
 Carbohydrates
 Proteins
 Lipids
 Enzymes
 Nucleic Acid

Uses of Polymers:
Questions to be asked:
 Difference between addition and condensation polymers?
 Which is the most important polyamide?
 What are the monomer units of nylon6,6?
 What are block and graft polymers?

References:
 Billmeyer Textbook of Polymer Science.2nd edition John Wiley and
Sons. (1971).
 Handbook of Chemistry and Physics. 65th edition.CRC Press (1985).
 Modern Plastics, Encyclopaedia. Mid-October 1990 Issue, Volume 67,
Number 11, McGraw Hill, Inc., Hightstown, NJ (1990).
 Polymer Chemistry, American Chemical Society (1986).
 Chemistry FSC Part II of Punjab Curriculum and Textbook Board.