Introduction

Polymers are Everywhere!

To get a look at just what this polymer stuff means to you,
and what these things called polymers have to do with your life
Examples
1-Clothing
First of all, these blue jeans and t-shirts are made of cotton, which is
mostly cellulose.
The polymers in clothes can come from plant materials, synthetics, or
even proteins like silk and wool. The one thing that most of the
polymers in clothes have in common is that they are fibers.
Sweaters like these can be made from wool, which is
a protein called keratin. So is your hair and fingernails, by the way.
Sweaters can also be made out of acrylics,
like polyacrylonitrile …….etc
2-Digital electronics
Polymers do abound here, believe it or not. When we think of
electronics we usually are thinking of materials that conduct electricity,
like copper and other metals, or semi-conductors like silicon. Most
polymers are insulators rather than conductors, but that doesn't mean
they don't have a place in the electronics store. The obvious place to
look is on the cables behind any stereo in here. Remember that polymers
tend to be good insulators, so it's natural that these cables should be
insulated with polymers like polyethylene and PVC, or poly(vinyl
chloride). For wires that get really hot we use insulation made from a
fireproof polymer called poly(vinylidene fluoride).
3- Toys
4- Food court
Fast food often comes in boxes made of polystyrene foam.

5-Family Pharmacy
Examples
The diapers themselves are made of polyethylene. They have elastic to
keep them from leaking, and that elastic is made from natural rubber.
But most importantly they're packed with poly(acrylic acid).
Poly(acrylic acid) is a member of the acrylate family of polymers that
absorb lots of moisture. It can absorb many times its own weight in
water, as well as that blue stuff they use in diaper commercials. This
keeps other things away from your baby so he or she won't get a nasty
rash.
Toothbrush bristles were the first
things ever made from nylon.
Toothbrush handles are made of polyester or polypropylene.
Clean hair is a good thing, and clean hair
comes from shampoos, which have
thickeners like hydroxyethyl cellulose. Many
conditioners are made with silicones.
Silicones don't leave a build-up the way some
conditioners do.

6- Eyeball
PMMA, PC,…
7-Paints
.
.etc
Growth in demand for polymers in the UK, 1980–2000
Molecules are compounds that are made of more than one type of atom.
An example of a small molecule is water--it contains three atoms--two
of hydrogen and one of oxygen.
Definition of polymer
A polymer is a large molecule of high molecular weight obtained by the
chemical interaction of many small molecules of low molecular weight
of one or more type. The process of manufacture of a polymer is called
the polymerization.
The word polymer is derived from the Greek root poly-, meaning many,
and mer, meaning part or segment. Many of the same units (or mers) are
connected together to form a long chain or polymer. Because they can be
extremely large, often made up of hundreds of thousands of atoms,
polymers are also referred to as macromolecules.
So, Polymers are macromolecules formed by linking together of a large
number of small molecules called monomers. The polymers are giant
molecules with high molecular masses
So Monomers: Small molecules of low molecular weight, which
combine to give a polymer, are called monomers.
The single repeating unit is called as monomer, and the resultant high
molecular weight compound is called as polymer.
Polymers exhibit diverse characteristics based on their molecular
structure.

For example, the monomer ethylene gets linked with many other
ethylene molecules to form polyethylene, or large number of vinyl
chloride molecules combines to form polyvinyl chloride.
In the following illustrated example, many monomers called styrene are
polymerized into a long chain polymer called polystyrene. The squiggly
lines indicate that the polymer molecule extends further at both the left
and right ends. In fact, polymer molecules are often hundreds or
thousands of monomer units long.

Single chain

Entangled polymer chains

This structure gives polymers some unusual properties, including their
resistance to breakage. In contrast, small molecules like water do not
tend to get tangled with each other; each molecule is separate and
distinct from the other.
Degree of Polymerization (n)
Calculating DP: To find the degree of polymerization, you would first
calculate the total mass of the resulting polymer and the mass of the
monomer unit (ethene). Then, you would apply the formula:
DP=Total Mass of PolyethyleneMass of Ethene
The number of monomers used in the process is called degree of
polymerization
If n= degree of polymerization ≤ 20 it is called oligomer
CLASSIFICATION •
i) Based on source:
a) Natural polymers: The polymers, which are obtained from
natural sources such as plants and animals, are called natural
polymers. Egs. Wood, cellulose, Jute, Cotton, Wool, Silk,
Proteins, Natural rubber etc.

b) Semi synthetic: Nitro cellulose •

c) Synthetic:
(i)Organic polymers: organic polymers, which have carbon-based
chains in their backbone like: Nylon6,6, PVC, Polystyrene, Teflon,
Polyesters, Polyethylene etc
(ii) Inorganic polymers:
Inorganic polymers are a class of polymers that consist primarily of
elements other than carbon in their backbone.
Unlike organic polymers, which have carbon-based chains (like
polyethylene or polystyrene), inorganic polymers often feature elements
such as silicon, phosphorus, sulfur, nitrogen, or boron.

Examples of Inorganic Polymers:

1. Polysiloxanes (Silicones):

Silicones are the most common of the inorganic polymers. They look
like this:
 These polymers have a backbone made of alternating silicon and
oxygen atoms. Silicones are widely used for their thermal stability,
water repellency, and flexibility, found in products like sealants,
adhesives, lubricants, and medical devices.
So silicones can stand high temperatures without decomposing, but
they have very low glass transition temperatures. You've probably
seen rubber

2. Polysilazanes: Contain silicon, nitrogen, and hydrogen in the

backbone. They are used in ceramics and as precursors for advanced
materials.

3. Polyphosphazenes: These polymers consist of alternating

phosphorus and nitrogen atoms. They are notable for their flexibility,
flame resistance, and resistance to oils and chemicals, making them
useful in specialty applications such as medical devices and seals.

4. Boron-Nitrogen Polymers: These polymers contain boron and

nitrogen in the chain and have structures similar to carbon-based
aromatic compounds.

They are studied for their potential in materials science, especially for
electronic and thermal applications.
Properties of Inorganic Polymers: -

**Thermal Stability**: Many inorganic polymers, especially those

with silicon or phosphorus backbones, are highly resistant to heat.

- **Chemical Resistance**: Inorganic polymers often show better

resistance to chemicals than organic polymers.

- **Flexibility and Durability**: Polysiloxanes, in particular, are

flexible even at low temperatures and resist degradation.
Inorganic polymers are used in applications that require unique
properties like resistance to high temperatures, fire, or harsh chemical
environments. Examples include coatings, adhesives, electronics, and
specialized medical products.

• ii) The nature of monomer •

(a) Homo-polymers: Polymers formed from the same type of
monomers are called homopolymers
(b) Co-polymers Formed by combining different monomers • Eg:
styrene butadiene. For example in polystyrene butadiene. One
molecule of butadiene combines with one molecule of styrene.
The product obtained acts as a monomer to get the polymer.

Types of copolymers
- Block Copolymers
In such copolymers, block of repeating units of one type alternate with
block of another type, e.g. SBS (shoe soul) -AAAABBBBAAAABBBB

 An example of such a polymer is acrylonitrile butadiene styrene,

commonly referred to as SBS rubber.

- Statistical Copolymer (random)

Random Co-polymers: In this type of copolymers, the different
repeating units are not arranged in a systematic manner but are randomly
arranged, e.g. -ABAABABBAAABA
- Alternating Copolymers
The different repeating units alternate in each chain. If A and B
represent two different units then an alternating co-polymer will be
represented as, -ABABABAB-
  Nylon 6,6 is an example of an alternating copolymer, consisting of
alternating units of hexamethylene diamine and adipic acid.

-Graft Copolymers
In such co-polymers, blocks of one repeating units are attached or
grafted to a block of linear polymer.
type of copolymer in which one or more blocks of homopolymer are
grafted as branches onto a main chain, meaning it is a branched
copolymer with one or more side chains of a homopolymer attached to
the backbone of the main chain.

(iii) . Based on the chemical structure •

 Linear ( all thermoplastics) Monomers are joined together to form long
straight chains( no branches). The various linear polymeric chains are
stacked over one another to give a well packed structure close packed in
nature, having high densities, high melting point and high tensile
(pulling) strength.
Note: All fibers are linear polymers. eg. cellulose, silk, nylon, terylene
etc.
branched ( eg: polystyrene) :
Polymers in which the monomeric units constitute a branched chain.
Branched chain polymers have lower melting point low densities and
tensile strength as compared to linear polymers. Examples are
amylopectin, glycogen, low density polyethylene
cross-linked polymer (bakalite)
Crosslinking generally involves covalent bonds that join two polymer
chains. The term curing refers to the crosslinking of thermosetting
resins, such as unsaturated polyester and epoxy resin, and the term
vulcanization is characteristically used for rubbers.
Example is vulcanization of rubber
 Polyisoprene

IV- Based on Tacticity

Tacticity is simply the way pendant groups are arranged along the
backbone chain of a polymer. We talk about tacticity a lot when dealing
with vinyl polymers. To illustrate tacticity, we're going to start with one
of those vinyl polymers, our good friend polystyrene, which you might
now know is usually "amorphous."

In that picture you see all the phenyl groups are located on the same
side of the polymer chain. But they don't have to be this way. To
illustrate let's look at a chain of polystyrene from above in the figure
below. You can see that the pendant phenyl groups can be either on the
right or left side of the chain. If all of the phenyl groups are on the same
side of the chain, we say the polymer is isotactic. If the phenyl groups
come on alternating sides of the chain, the polymer is said to
be syndiotactic. If the phenyl groups are on both sides, right and left, but
in no particular order, in a random fashion, than we say the polymer
is atactic.
Note: Isotactic polystyrene isn't produced commercially. We're just
using it here as a hypothetical example.
In polymers, the relative stereochemistry of the polymer chain can
significantly affect its physical properties, such as crystallinity, melting
point, and mechanical strength.
There are three primary types of tacticity:
1. Isotactic:
All substituent groups (e.g., side chains) are positioned on the same side
of the polymer backbone. Isotactic polymers tend to be more crystalline
and have higher melting points.
2. Syndiotactic : The substituent groups alternate sides along the
polymer backbone. Syndiotactic polymers often exhibit intermediate
properties between isotactic and atactic polymers.
3. Atactic: The substituent groups are arranged randomly along the
polymer backbone. Atactic polymers are usually amorphous, meaning
they lack a crystalline structure, resulting in lower melting points and
different mechanical properties compared to isotactic and syndiotactic
forms.
Tacticity is particularly important in polymers like polypropylene, where
the arrangement of the methyl groups (CH₃) can greatly influence the
material's behavior.

Classification Based upon molecular force

1. Elastomers Polymers in which the intermolecular forces of attraction
between the polymer chains are the weakest (weak van der Waals forces
of attraction) these polymers consist of randomly coiled molecular
chains of irregular shape having a few cross links. Examples are natural
rubber, Buna-S, Buna-N etc.
2. Fibres :Those polymers in which the intermolecular forces of
attraction are the strongest are called fibers. These polymers held
together by H-bonding or dipole-dipole interaction. Fibres have high
tensile strenght, least elasticity having high melting point and low
solubility.
3. Thermoplastics :In thermoplastics intermolecualr forces of attraction
are in between those of elastomers and fibres. Thermoplastics become
soft and viscous on heating and rigid on cooling. Examples are
polythene, nylon-6, nylon-6,6 etc.
4. Thermosetting polymers These polymers have low molecular masses
and are semi-fluid substances. These polymers are hard and infusible.
Examples are melamine-formaldehyde, bakelite (phenol-formaldehyde)
etc.
V-According to polymerization mechanism
1.Addition (chain) polymerization: A polymerization reaction in
which monomers containing one or more double bonds are linked to
each other without the elimination of any by products, usually in the
presence of initiators is called addition polymerization.
Egs: 1. Formation of polythene.

n CH2= CH2 →[- CH2 – CH2 -]n

CHAIN POLYMERIZATION:
Chain polymerization is characterized by three distinct stages
-Initiation
-propagation
-termination.
I-Free Radical Polymerization
Free radicals are independently-existing species that have unpaired
electron. Normally they are highly reactive with short life time.
Free radical polymerizations are chain polymerization’s in which each
polymer molecules grows by addition of monomer to a terminal free-
radical reactive site known as active center.
After each addition the free radical is transferred to the chain end.
INITIATION
1. The formation of free radicals from an initiator.
2. The addition of one of these free radicals to a monomer molecule.
 Free radical can be formed by two principals
 1. Homolytic scission (homolysis) or breakage of a single bond.
 2. Single electron transferred to or from an ion or molecule
(redox reactions)
 Homolytic can be achieved by heat (thermolysis) or by light such
as U.V. (photolysis).
Example
An active center is crated when a free radical (Ro) which is
generated from an initiator attacks the -bond of the monomer
molecules.
R. + CH2 = CH R-CH2-CH or R-CH - CH2
X X X
This is more This is more
likely

PROPAGATION
The addition of monomer molecules to the active center to grow
the polymer chain.
There are two modes of chain propagation
1. Head to Tail
R-CH2-CH + CH2=CH R-CH2-CH-CH2-CH
X X X X
 2. Head to Head
R-CH2-CH + CH2=CH R-CH2-CH-CH-CH2
X X X X
Time of addition for each monomer is of the order of a
millisecond.
Thus several thousands of additions can take place in a few
seconds
TERMINATION
 The last stage of chain reaction in which the growth of the
polymer chain terminated (or stopped).
 There are two mechanisms of termination
1. Combination
Coupling together of two growing chains to form a single polymer
molecules. Polystyrene
 --CH2-CH + CH - CH2--- ---- CH2-CH- CH-CH2---
X X
2. Disproportionation
when a hydrogen atom move from one growing chain to another
 H H
 --CH2-CH + C - C--- ----CH2-CH2 + CH=CH2---
 X X H X X
2-Ionic polymerization:
a-Cationic
involves successive insertion of monomer molecules between an
ionic chain end (negative in anionic or positive in cationic
polymerization) and a counterion of opposite charge.

b-Anionic
 Ionic polymerization involves successive insertion of monomer
molecules between an ionic chain end (negative in anionic or positive
in cationic polymerization) and a counterion of opposite charge. The
macroion and the counterion exist in several forms depending on the
nature and degree of interaction between the cation and anion and the
reaction medium. Considering, for example, the organic salt A+B-,
a continuous spectrum of ionicities can be depicted (Scheme 1).11

2. Condensation (step) polymerization: It is brought by linking

together different monomers accompanied by the elimination of small
molecules like H2O, HCl, and NH3.
Egs: 1. Formation of Nylon66