Mechanism of Polymerization

As for the reaction mechanism, the process of polymerization mainly

involves two different methods. These are the step-growth mechanism and
chain-growth mechanism.

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.

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
Polyamides
They are synthetic fibres 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
hexamethylenediamine with adipic acid.
  Nylon 6: Prepared by heating of caprolactam with water under high
temperature. It is used for tyre cords, fabrics and ropes.

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.
Phenol-Formaldehyde Polymer
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.
Novolac on heating with formaldehyde undergoes crosslinking and forms
an infusible sold mass named as Bakelite. They are used for combs,
electric switches and phonograph records.
Melamine – Formaldehyde Polymer
It is formed by the condensation polymerization of melamine and
formaldehyde in certain conditions. They are used for the manufacture of
unbreakable crockery.

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, alkadienes and their derivatives are
used.

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.
Chemical Bonding
It is called a chain initiation step. This newly formed radical will reacts
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
 Bulk polymerization

Bulk polymerization or mass polymerization is carried out by adding a

soluble initiator to a pure monomer in liquid state. The initiator should
dissolve in the monomer. The reaction is initiated by heating or exposure to
radiation. As the reaction proceeds the mixture becomes more viscous.
The reaction is exothermic and a wide range of molecular masses are
produced.
 Bulk polymerization is carried out in the absence of any solvent or
dispersant and is thus the simplest in terms of formulation. It is used for
most step-growth polymers and many types of chain-growth polymers. In
the case of chain-growth reactions, which are generally exothermic, the
heat evolved may cause the reaction to become too vigorous and difficult to
control unless efficient cooling.

Bulk polymerization has several advantages over other methods, these

advantages are
 The system is simple and requires thermal insulation.
 The polymer obtained is pure.
 Large castings may be prepared directly.
 Molecular weight distribution can be easily changed with the use of a chain
transfer agent.
 The product obtained has high optical clarity

Disadvantages
 Heat transfer and mixing become difficult as the viscosity of reaction mass
increases.
 The problem of heat transfer is compounded by the highly exothermic
nature of free radical addition polymerization.
 The polymerization is obtained with a broad molecular weight distribution
due to the high viscosity and lack of good heat transfer.
 Very low molecular weights are obtained.
 Gel effect should be there

Emulsion polymerization

Emulsion polymerization is a type of radical polymerization that usually

starts with an emulsion incorporating water, monomer, and surfactant. The
most common type of emulsion polymerization is an oil-in-water emulsion,
in which droplets of monomer (the oil) are emulsified (with surfactants) in a
continuous phase of water. Water-soluble polymers, such as certain
polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as
emulsifiers/stabilizers.
 Advantages of emulsion polymerization include:
 High molecular weight polymers can be made at fast polymerization rates.
By contrast, in bulk and solution free radical polymerization, there is a
tradeoff between molecular weight and polymerization rate.
 The continuous water phase is an excellent conductor of heat, enabling fast
polymerization rates without loss of temperature control.
 Since polymer molecules are contained within the particles, the viscosity of
the reaction medium remains close to that of water and is not dependent on
molecular weight.
 The final product can be used as is and does not generally need to be
altered or processed.

Disadvantages of emulsion polymerization include:

 Surfactants and other polymerization adjuvants remain in the polymer or
are difficult to remove
 For dry (isolated) polymers, water removal is an energy-intensive process
 Emulsion polymerizations are usually designed to operate at high
conversion of monomer to polymer. This can result in significant chain
transfer to polymer.
 It cannot be used for condensation, ionic or Ziegler-Natta polymerization,
although some exceptions are known.
 Solution Polymerization

Solution polymerization is a method of industrial polymerization. In this

procedure, a monomer is dissolved in a non-reactive solvent that contains
a catalyst. Notable polymers produced using this method are
polyacrylonitrile (PAN), polyacrylic acid (PAA) and sodium polyacrylate.

. During this process, the solvent liquid absorbs the heat generated by the
chemical reaction which controls the reaction rate. The liquid solvent used
in the solution polymerization procedure usually remains a solvent for the
resulting polymer or copolymer.
Synthetic elastomers can also be produced using the solution
polymerization process. This method produces a more precise polymer
than emulsion polymerization methods.

The advantages include precise control of the chemical reaction, control of

the resulting heat and viscosity, and control over the auto acceleration of
the process.
The disadvantage of the process is the difficulty involved in the removal of
excess solvent from the finished polymer.
 Suspension Polymerization

Suspension polymerization is used only in free radical type processes.

The monomer is mechanically dispersed in a media, usually water. There
are cases where an organic media is used in which neither the polymer nor
the monomer is soluble in the organic media.
 styrene- a liquid
 vinyl chloride- a gas at room temperature
For suspension polymerization, there are two phases, water and organic,
and the starting point may be 10 parts of the former, and 1 part of the latter.
The initiator used can be water soluble or organic soluble [benzoyl
peroxide, AIBN (Azobis-isobutyronitrile), or (NH4)2(SxO4)y.] Usually the
initiator is organic soluble. AIBN

A suspension agent is a material that gives a surface activation that

keeps droplets from become larger (droplets coming together to form larger
droplets is called coalescence.)

Coalescence is also used for when the polymer molecules in a solution

come together as the solvent evaporates, an example of which is the film
formation that occurs for a paint system.
Suspension polymerization is similar to bulk polyerization, and it could be
considered “bulk polymerization within a droplet.

POLYCONDENSATION TECHNIQUES
In polycondensation, the reaction proceeds between monomers containing two
or more reactive functional groups (e.g., hydroxyl, carboxyl and amino)
condensing with each other.
The main features regarding polycondensation are: (i) To proceed the
polymerisation, monomers should have two reactive functional groups.
(ii) The polymerisation takes place by step-wise reaction between reactive
functional groups.
(iii) Only one type of reaction (e.g., condensation reaction in this case) between
two functional groups is brought about in polymer formation.
(iv) The polymer formed still consists of both the reactive functional groups at its
chain end.
Some examples are:
I) CH3OH + HOOC-CH3 ⇒ CH3COOCH3 + H2O
II) CH2OH-CH2OH + HOOC-CH3 ⇒ HOCH2CH2OOCCH3 + H2O
HOCH2CH2OOCCH3 + CH3COOH ⇒ CH3COOCH2CH2COOCH3 + H2O
 Solution Polycondensation
In the solution polycondensation technique, all the reactants are dissolved in an
inert solvent as a solution; therefore, the whole system is in a homogeneous phase.
In this method, the reaction can be carried out at low temperature during which
mass and heat transfer processes are comparatively easier. The solvent can also
help as an entrapping agent for the byproduct formed; hence the removal of the
byproduct from the final product and solution becomes easy. This technique is
useful in the preparation of liquid polyester resin from the glycols and unsaturated
dicarboxylic acid using high boiling aromatic hydrocarbon as solvent.

Melt Polycondensation
The production of polyethylene terephthalate from dimethyl terephthalate and
ethylene glycol, and nylon 66 are prepared by using melt polycondensation
technique. In this method, one of the monomers used is solid, which cannot
decompose around its melting point. The reaction has to be carried out in an inert
atmosphere of N2 or CO2 to avoid side reactions such as oxidation,
decarboxylation, etc. Sometimes the reaction is carried out under reduced pressure
to initiate the removal of the byproduct.
The major disadvantage of this technique is removal of the byproduct becomes
extremely difficult because there is much increase in the viscosity of the medium.
The polymer formed is in molten state at the reaction temperature and it is
important to isolate it from the reactor during hot condition, otherwise it will
solidify inside the reactor and removal becomes very hard

PET, poly-( ethylene terephthalate ) manufacturing

PET resins are produced commercially from ethylene glycol (EG) and either
dimethyl terephthalate (DMT) or terephthalic acid (TPA). Firstly produce the
intermediate bis-(2-hydroxyethyl)-terephthalate (BHET) monomer and either
methanol (DMT process) or water (TPA process).
PET is sometimes referred to as polyester and is made from mono-ethylene glycol
(MEG) and purified terephthalic acid (PTA), which is derived from crude oil and
natural gas. These two crude oil derivatives are reacted under a controlled set of
conditions to form a polymer.

CH3OOC COOCH3 + HOCH2CH2OH⇒HO - (OC COOCH2CH2O)nH +

2nCH3OH
DMT EG PET

HOOC COOH + HOCH2CH2OH ⇒HO - (OC COOCH2CH20)nH + 2nH2O

Poly(ethylene terephthalate), or PET, is a thermoplastic polyester resin. Such
resins may be classified as low-viscosity or high-viscosity resins. Low-viscosity PET
typically has an intrinsic viscosity of less than 0.75, while high-viscosity PET
typically has an intrinsic viscosity of 0.9 or higher.
PET is used extensively in the manufacture of synthetic fibers (i. e., polyester
fibers), which compose the largest segment of the synthetic fiber industry. Since it
is a pure and regulated material meeting FDA food contact requirements, PET is
also widely used in food packaging, such as beverage bottles and frozen food
trays that can be heated in a microwave or conventional oven. PET bottles are
used for a variety of foods and beverages, including alcohol, salad dressing,
mouthwash, syrups, peanut butter, and pickled food. Containers made of PET are
being used for toiletries, cosmetics, and household and pharmaceutical products
(e. g., toothpaste pumps). Other applications of PET include molding resins, X-ray
and other photographic films, magnetic tape, electrical insulation, printing sheets,
and food packaging film.
Polypropylene manufacturing
Polypropylene is made from the polymerization of propylene gas in the presence
of a catalyst system, usually Ziegler-Natta or metallocene catalyst. Polymerization
conditions (temperature, pressure and reactant concentrations) are set by the
polymer grade to be produced.
Polypropylene is produced by the chain-growth polymerization of propene:

Various production processes exist with some general similarities. They are taking
place either in a gas-phase (fluidized bed or stirred reactor) or a liquid-phase
process (slurry or solution). An example of flow diagram corresponding to each of
the two types of processes is illustrated in figure 1 bellow. The gas-phase
polymerization is economical and flexible and can accommodate a large variety of
catalysts. It is the most common technology in modern polypropylene production
plants. Relevant technologies are Novolen®, Unipol® (gas-phase processes),
Borstar® and Spheripol® (liquid-phase processes).
The obtained powder is finally conveyed to powder silos and then converted into
pellets that incorporate a full range of well-dispersed additives.