Polymerization

Dr. Md. Nurnobi Rashed

PhD in ICAT (HU, Japan), Postdoc. (AIST, Japan)

Lecturer
Department of Chemistry, BUET.

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 Polymerization & functionality

Polymerization is a process or chemical reactions where the monomer units

are covalently connected to form a polymer.
✓ Polymerization may occur only if the monomers involved in the reaction
have the proper functionalities.

Functionality is a very useful concept in polymer science. The functionality

of a molecule is the number of sites it has for bonding to other molecules
under the given conditions of the polymerization reaction. Thus, a bifunctional
monomer, i.e., a monomer with functionality 2, can link to two other
molecules under suitable conditions.
Styrene, C6H5CH=CH2, for example, has functionality 2 because of the
presence of a carbon-carbon double bond.

The minimum functionality required for polymerization is 2

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 A polyfunctional monomer is one that can react with more than two
molecules under the conditions of the polymerization reaction.

Thus, divinyl benzene (I) is tetrafunctional in reactions involving

additions reaction across the carbon-carbon double bonds, while glycerol
(II) is trifunctional in polyesterification reactions.

4
(II)

In general, the functionality is the number of

(I) bonds that a given monomer can form.

Functionality in polymerization is, however, defined only for a given reaction

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 What is the functionality of the following monomers in reactions with (i)
styrene, C6H5CH=CH2 and (ii) adipic acid, HOOC(CH2)4COOH?

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 Repeat unit and chain structures for-
(a) polytetrafluoroethylene,
(b) poly(vinyl chloride), and
(c) polypropylene.

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 Monomers such as phenol–
formaldehyde are trifunctional;
they have three active bonds,
from which a three-dimensional
molecular network structure
results.

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 Synthesis of polymer

Polymer molecules may be synthesized by four different methods:

(a) Addition polymerization (Chain reaction polymerization)

(b) Condensation polymerization (Step reaction polymerization)

(c) Ring opening polymerization

(d) Oxidative polymerization

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 (a) Addition polymerization
Addition polymerization may be defined as the process in which monomer units
are added together to form a polymer molecule without losing any small
molecules. For example, conversion of ethylene to polyethylene.

n(CH2=CH2) → (--CH2-CH2--)n

Depending on the mechanism addition polymerization may be classified into

three classes. These are-

i. Free radical addition polymerization

ii. Cationic addition polymerization
iii. Anionic addition polymerization

Whatever may be the method, the addition polymerization consists of three steps:
i. Initiation synonym-Start
ii. Propagation andExtention
iii. TerminationEnding
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 i) Free radical polymerization

The polymerization reaction is initiated by the decomposition of some organic

and inorganic peroxides such benzoyl peroxide, hydrogen peroxide, diazo
compounds etc. The decomposition is carried out by the application of heat.

Peroxides → Radical

These radicals serve as the active centres and cause chain propagation by
combining with monomer.

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 (iii)

Here. hydrogen transfer

results in the formation
of two molecules with
one saturated and one
unsaturated end group

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ii, iii) Ionic addition polymerization Polystyrene
Polyisobutene,
Polypropylene
Polyvinyl ethers

Polyvinyl cyanide, Methyl acrylate, PVC etc. are formed by anionic

polymerization process

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 Inhibition/Retardation of Polymerization
badha deua
• Some substances, when present in the monomer or in the polymerization
system, suppress chain formation and/or by reacting with primary
radicals or propagating chain radicals (before they could grow to
polymeric size) to yield either nonradical products or radicals that are too
low in reactivity to undergo propagation. Such substances are called
inhibitors or retarders depending on their effectiveness.

• An inhibitor prevents polymerization completely as long as it is present in

the system, whereas a retarder reduces the rate of polymerization but does
not stop it completely.
vebechinte shomponno kora
• Inhibitors are deliberately added to monomers to prevent polymerization
during storage or shipment. So, before carrying out any polymerization, the
inhibitors should be removed or, alternatively, additional amounts of
initiators should be added to compensate for the inhibitors.

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 Figure 1: Compares these effects, schematically, on the rate of free-radical
polymerization.

Figure 1: Comparison of conversion-time plots for normal, inhibited, and retarded free-
radical polymerization.
✓ Curve 1: normal polymerization in the absence of inhibitor/retarder.
✓ Curve 2: inhibition; polymerization is completely stopped by inhibitor during the initial
induction period but at the end of this period with the inhibitor having been completely
consumed, polymerization proceeds at the same rate as in normal polymerization
(curve 1).
✓ Curve 3: retardation; a retarder reduces the polymerization rate without showing an
induction period.
✓ Curve 4: inhibition followed by retardation.
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 The difference between inhibitors and retarders is simply one of degree and not
kind. Both are either chain transfer agents (TA) or substances (Z) that add to
propagating polymer radicals and thus provide an alternative reaction path :

If the rate of reaction in Eq. (b or c) is very much greater than that of the reaction
in Eq. (a) and the new radicals T. and MnZ. do not reinitiate by adding to monomer,
then high-molecular-weight polymer will not be formed and the rate of polymerization
will be practically zero during the period TA or Z is present in the system. This is a case
of inhibition and the duration is known as the induction or inhibition period.

On the other hand, if the rate of reaction in Eq. (b or c) is comparable to that of the
normal propagation reaction in Eq. (a) and the new radicals T. and MnZ. do not
reinitiate or reinitiate only slowly, then the rate of polymerization will be slowed down
but not reduced to zero. This is a case of retardation.

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 ❑ A large number of other substances are also active inhibitors. These
include oxygen, NO (one of the most effective inhibitors, so much so that
some highly reactive monomers can be distilled only under an atmosphere
of NO), aromatic nitro compounds, numerous nitroso compounds, sulfur
compounds, amines, phenols, aldehydes, and carbamates

❑ An interesting inhibitor is molecular oxygen. Being a diradical, oxygen

reacts with chain radicals to form the relatively unreactive peroxy radical
:

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 Thermodynamics of addition polymerization
The ease of polymerization of monomer mainly depends on the polarization of the double
bond.

Why polymerization of styrene molecule is much easier than ethylene?

Styrene is more unsymmetrical than ethylene;
hence, it has much polarization than ethylene
In the equation, T * delS is the product of temperature
and the change in entropy. This term represents the
amount of energy that can potentially be "lost" due to
the increase in disorder (entropy) of the system at a
certain temperature. If T * delS is positive and larger
than delH, it can lead to a negative delG, making the
process spontaneous. If T * delS is negative or
smaller than delH, the process might be
non-spontaneous

ΔG = ΔH -TΔS ΔG = -ve how possible?

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• Regardless of the chain initiation mechanism—free radical, cationic, or
anionic—once a reactive center is produced it adds many more molecules in a
chain reaction and grows quite large extremely rapidly, usually within a few
seconds or less.

• However, the relative slowness of the initiation stage causes the overall rate of
reaction to be slow and the conversion of all monomers to polymers in most
polymerizations requires at least 30 minutes, sometimes hours.

Evidently, at any time during a chain polymerization process the reaction

mixture will consist only of unreacted monomers, high polymers and
unreacted initiator species, but no intermediate sized molecules. The chain
polymerization will thus show the presence of high-molecular-weight
polymer molecules at all extents of conversion.

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(b) Condensation polymerization (Step growth polymerization)
Condensation polymerization is the process in which many monomer
molecules unite together to form a big macromolecule with the loss of some
simple molecules, usually water, carbon dioxide etc. The most common
example of condensation polymerization is the formation of nylon 6,6 from
adipic acid and hexamethylene diamine.

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 (b) Condensation polymerization, continued

➢ The terms “step polymerization” and “condensation polymerization” are often used
synonymously.
➢ Step polymerization occurs by stepwise reaction between functional groups of
reactants.
➢ The reaction leads successively from monomer to dimer, trimer, tetramer,
pentamer, and so on, until finally a polymer molecule with large DP is formed.
➢ However, that reactions occur at random between the intermediates (e.g.,
dimers, trimers, etc.) and the monomer as well as among the intermediates
themselves.
➢ In other words, reactions of both types, namely, occur equally.

➢ Thus, at any stage the product consists of molecules of varying sizes, giving a
range of molecular weights.

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 (b) Condensation polymerization, continued

➢ The average molecular weight builds up slowly in the step

polymerization process, and a high-molecular-weight product is formed
only after a sufficiently long reaction time when the conversion is more
than 98%.

➢ Consider, for example, the synthesis of a polyamide, i.e., a polymer with

amide (–CONH–) as the characteristic linkage. If we start with, say,
hexamethylenediamine and adipic acid as reactants, the first step in the
formation of the polymer (nylon) is the following reaction producing a
monoamide.

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 (b) Condensation polymerization, continued

The reaction continues step-by-step to give the polyamide nylon-6,6. The overall
reaction may thus be represented as

Condensation
polimarisation

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(c) Ring opening polymerization:

• Ring opening reaction always provides a species, which has two sites for
reacting with other substances.
• That is this reaction produces a bifunctional species, which is a
fundamental requirement of polymerization.

The examples of such reactions are given below-

(i)

Ethylene Bifunctional
oxide species

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 (ii)

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 (iv) Oxidative Polymerization
The oxidative polymerization is carried out by the polymerization of monomeric
materials. There are two different oxidative polymerizations:
a) Electrochemical oxidation and
b) Chemical oxidation

(a) Polymerization by Electrochemical Oxidation

✓ In this polymerization an electrolytic solution of monomeric substance is
prepared normally in acetonitrile-sulphuric acid mixture.

✓ Electricity is passed through the solution either at constant current density or at a

constant voltage using platinum sheets as the electrodes.

✓ The polymerization reaction takes place at anode. Normally the polymeric

materials are deposited in solid form, which may be scratched out from the anode
surface.

✓ The properties of polymeric materials to some extent depend upon the bath
composition, temperature and current density of polymerization.
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 (b) Polymerization by Chemical Oxidation

▪ In chemical oxidation of the polymerization process, some well-known

oxidizing agents such as ammonium persulphate (NH4)2S2O8,
hydrogen peroxide H2O2 are used.

▪ The monomeric materials are usually taken in water acetonitrile

mixture using as solvent. Required amount of oxidizing agent is added
and then stirred for several hours (10-14 hours).

▪ The polymeric materials are formed and settled down at bottom of the
flask which is then filtered off.

▪ The common examples of polymers, those are prepared by oxidative

polymerization are: polyacetylene, polyaniline, polypyrole, poly
thiophene etc. and their derivatives also. The mechanism of oxidative
polymerization is shown below:

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 ✓ Here, a new type of polymeric materials (conductive polymers) are
formed.
✓ The science of conducting polmer is developing rapidly because of
micro-electronic industry.
✓ The main use is in manufacturing of rechargeable battery, electronic
sensors, diodes etc.

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 So, this is used in electricity carrying wires, squeeze bottles, toys, flexible
pipes etc.
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 Triethyl aluminium and
titanium tetrachloride
(Ziglar-Nata) catalyst

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 Chemically inert and non-corrosive

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