ASSIGNMENT NO 01

COURSE TITLE AND CODE:

CHEMICAL PROCESS TECHNOLOGY-II (CHE-316)
COURSE INSTRUCTOR:
DR. SHAHID RAZA MALIK
SEMESTER:
SIXTH (6TH)
SUBMITTED BY:

MUHAMMAD ALI

DEPARTMENT OF CHEMICAL ENGINEERING

THE UNIVERSITY OF FAISALABAD, PAKISTAN

1
 POLYMERIZATION

What is Polymerization:

Polymerization is a process through which a large number of monomer molecules react

together to form polymer. The macromolecules produced from a polymerization may have a
linear or a branched structure. They can also assume the shape of a complex, three-dimensional
network. There exist several different categories of polymerization reactions, the most notable
of which being step-growth polymerization, chain-growth polymerization (both of which fall
under the category of addition polymerization), and condensation polymerization.

A polymer is a substance that is made up very large molecules that are, in turn, made up of
many repeating units called monomers. Polymerization is the process through which these
monomers come together to form the macromolecules that constitute polymers. An illustration
detailing the polymerization of the monomer styrene into the polymer known as polystyrene is
provided below.

It can be noted that polymerizations involving only one type of monomer are called photo
polymerizations whereas those involving more than one type of monomer are called
copolymerization processes. Polymerization in the simplest form can be described as a
chemical process that results in the formation of polymers. In simple words, we can basically
describe Polymerization as the process of creating polymers. When polymerization occurs, the
smaller molecules which are known as monomers via chemical reaction are combined to form
larger molecules. A collection of these large molecules forms a polymer. The term polymer in
general means “large molecules” with higher molecular mass. They are also referred to as
macromolecules.

Polymers are formed by the addition of a network of structural units or monomers as

mentioned above. The interesting part is that these are reactive molecules and are usually
linked to each other by covalent bonds. These monomers add together to form a long chain to

2
 form a product with specific properties. This whole process of formation of polymers is
polymerization. Polythene and Nylon 66 are some examples of polymers.

Mechanism of Polymerization:
Generally, polymerization consists of three steps which include initiation, propagation, and
termination. As for the reaction mechanism, the process of polymerization mainly involves two
different methods. These include the step-growth mechanism and chain-growth mechanism.

1. Step Growth Polymerization:

In step-growth polymerization, the polymers are formed by the independent reaction between
the functional groups of simple monomer units. In step-growth, each step may consist of a
combination of two polymers having a different or same length to form a longer length
molecule.

The reaction is a lengthy process and the molecular mass is increased at a very slow rate. An
example of step-growth polymerization is condensation polymerization where a water
molecule is evolved in the reaction when the chain is lengthened.

2. Condensation Polymerization:
In condensation polymerization, the formation of the polymer occurs when there is a loss of
some small molecules as byproducts through the reaction where molecules are joined together.
The byproducts formed may be water or hydrogen chloride. Polyamide and proteins are
examples of condensation polymers.

Some of the different types of condensation polymerization are given below

i. Polyamides:
They are synthetic fibers and are called as nylons. These polymers have an amide linkage
between them. Condensation polymerization of di-amines with di-carboxylic acid and also
of amino acids and their lactams will create a polyamide.

 Nylon 66: This polymer is prepared under the condition of high pressure and
temperature by the condensation polymerization of hexamethy lenediamine with
adipic acid.
 Nylon 6: Prepared by heating of caprolactam with water under high temperature. It is
used for tire cords, fabrics and ropes.

3
 ii. Polyesters:
When dicarboxylic acids and diols undergo polycondensation, polyesters are formed.
Prepared by heating a mixture of terephthalic acid and ethylene glycol at 460 k by using
zinc acetate antimony trioxide as a catalyst. Dacron or terylene are the best-known
examples for polyesters. And also, they are used for glass reinforcing materials in safety
helmets.

iii. Phenol-Formaldehyde Polymers:

These are the old synthetic polymers obtained by condensation polymerization of phenol
with formaldehyde in the presence of either an acid or base as a catalyst.

3. Chain Growth Polymerization:

In chain-growth polymerization, the molecules of the monomers are added together to form a
large chain. The monomers adding maybe the same type or different. Generally, alkenes,
alkadienyls and their derivatives are used. In this mode, lengthening of chains occurs as a
result of the formation of either free radicals or ionic species.

4
Free Radical Mechanism
 Many of the monomers like alkenes or dienes and their derivatives are polymerized in
the presence of free radicals. In the polymerization of ethene to polythene by heating or
exposing to light by using a small amount of benzoyl peroxide initiator. The phenyl free
radical formed by peroxide is added to the ethene double bond and hence formed a new
larger free radical. It is called a chain initiation step.
 This newly formed radical will react with another molecule of ethene to form another
new free radical and so on. This repeated formation of a new free radical is called chain
propagation.
 Finally, at some stage, the polymerized product will be formed and this step is called
a chain termination step. The steps are given below.
The three steps followed by a free radical mechanism.

Polymerization Chemical Reaction

5
4. Preparation of Polymers:

i. Polyethene:
We have two types of polyethylene’s and they are given below:

Low-Density Polyethene:
This type of polymers is obtained by the polymerization of ethene under the condition
of high pressure of 1000 to 2000 atmospheres at 350 to 520 k temperature in the
presence of dioxygen or peroxide initiator as a catalyst in a very small amount.
It is formed through the free radical addition and H-atom abstraction having a highly
branched structure. It is chemically inert in nature and tough but flexible. It is a poor
conductor of electricity. LDP is used for the manufacture of toys, squeeze bottles and
flexible pipes.

High-Density Polyethene:
Prepared by the polymerization addition of ethene in the presence of a catalyst like
triethyl aluminum and titanium tetrachloride. The process takes place in a hydrocarbon
solvent, in a condition of low pressure of 3 to 4 atmospheres and 343 k temperature.

ii. Polytetrafluoroethylene:
It is also known as Teflon and is manufactured by heating of tetrafluoroethylene with a free
radical at high pressure. Teflon is chemically inert and less corrosive due to the resistive
property against the corrosive agents. It is used for gaskets and not stick surface coated
utensils.

5. Classification of Polymerization:
Polymers are classified into different categories based on several factors such as source,
structures, mode of polymerization, molecular forces and growth of polymers. Let’s discuss
them in detail below.

i. Based on Source:
They are again divided into three subcategories:

6
  Natural polymers: They are found naturally in plants and animals. Resins, starch and
rubber are examples of this.
 Semi-synthetic polymers: This is a modified version of natural rubber. That means
natural rubbers are treated with chemicals to make them semi-synthetic. Cellulose
acetate and cellulose nitrate are the examples come under this subcategory.
 Synthetic polymers: Polymers which are completely man-made are called synthetic
polymers. Polythene, Nylon 66, synthetic rubber is the widely used synthetic polymers.

ii. Based on the Structure of Polymers

There are three different types.

 Linear polymers: Consists of a long and straight-chain of monomers. PVC is a

linear polymer
 Branched polymers: They are linear polymers containing some branches. Low-
density Polythene is an example.
 Network or cross-linked polymer: Polymers having cross-linked bonds with each
other is called cross-linked or network polymer. Generally, they are formed from bi-
functional or tri-functional monomers. Bakelite and melamine are examples of this
type of polymer.

iii. Based on Mode of Polymerization:

They are divided into two subcategories:

 Addition Polymers: Polymers formed by the repeated addition of monomers by

possessing the double or triple bonds. If the addition is of the same species, they are
called homopolymers and if the addition is of different monomers, they are
called copolymers. Examples are polythene and Buna-s respectively.
 Condensation polymers: These polymers are formed by repeated condensation of tri
or bifunctional monomeric units. In this reaction elimination of some small molecules
like water and hydrogen chloride will take place. Terylene and Nylon 6,6 are
examples.

7
iv. Based on Forces Between Molecules:
They are again classified into four subgroups:

 Elastomers: Polymers that are rubber-like solids and having elastic properties. Here the
polymer bonds are held together by weak intermolecular forces and that allows these
polymers to stretch. The cross-links present in the polymer between the chains helps to
retrace the original position after the removal of the applied force. Examples are Buna-s
and Buna-s
 Fibers: They are polymers having strong intermolecular forces like hydrogen bonding.
Due to this strong force molecules are kept closer, that is they are closely packed.
Because of this property, they are crystalline in nature. Polyamide and polyesters are
examples.
 Thermoplastic polymers: These are the liner or slightly changed to branched polymers
that can be softened on continues heating and hardening on cooling. Their
intermolecular force lying in between the fibers and elastomers. Polyvinyl, polystyrene
are examples of thermoplastic polymers.

Thermosetting polymers:

Polymers comes under the category of heavily branched or cross-linked, which can
mould on heating and can’t regain the original shape. So, these cannot be reused.
Bakelite is an example.