Polymerization

mechanisms

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Textbooks
• Basics of Polymers: Fabrication and Processing Technology. By:
Muralisrinivasan Natamai Subramanian. Published by Momentum
Press, 2015
• Introduction to Polymer Chemistry, 3rd Edition. By: Charles E.
Carraher Jr. Published by CRC Press, Tailor and Francis, 2014

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 Polymerization mechanisms

• A polymer is a substance or material consisting of very large molecules, or

macromolecules, composed of many repeating subunits.
• A polymerization mechanism is the sequence of elementary chemical reactions by
which polymerization proceeds.
• Polymerization is the process of converting monomer molecules into a polymer. Hence,
polymerization can be represented by the reaction of a few monomer units such as:

• Figure 1: The polymerisation of an ethene monomer to form a polyethene polymer. The

repeat unit is highlighted in blue.
• Polyethene is made up by the addition polymerisation reaction of ethene

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• From the figure 1, the bond lines extending at the ends in the formula of the
product indicate that the structure extends for many units in each direction.
• Note that all the atoms—two carbon atoms and four hydrogen atoms—of each
monomer molecule are incorporated into the polymer structure. Because the
structure it displays, such as the one above are usually cumbersome, the
polymerization is often abbreviated as follows:
• nCH2=CH2 → [ CH2CH2 ] n

• During the polymerization of ethene, thousands of ethene molecules join

together to make poly(ethene) - commonly called polythene. The reaction is
done at high pressures in the presence of a trace of oxygen as an initiator.

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• A polymer may be a chain of thousands of monomers, and so it is
impossible to draw the entire polymer. Rather, the structure of a polymer can
be condensed and represented as shown in Figure 2.
• The monomer is enclosed in brackets and the n represents the number
of repeating units (the saturated form of the monomer) in the polymer,
where n is any whole number.
• What this shows, is that the monomer is repeated an indefinite number of
times in a molecule of polyethene.

• Figure 2: A simplified representation of polyethene.

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 Chain reaction

• A chain reaction is a sequence of reactions where a reactive product or by-

product causes additional reactions to take place. In a chain reaction, positive
feedback leads to a self-amplifying chain of events.
• A chain reaction is a reason in which reacting species are a product of the
reaction.
• Chain reactions usually consist of many repeating elementary steps, each of
which has a chain carrier. Once started, chain reactions continue until the
reactants are exhausted.
• Fire and explosions are some of the phenomena associated with chain
reactions.
• The chain carriers are some intermediates that appear in the repeating
elementary steps. These are usually free radicals.

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• Once initiated, repeating elementary steps continue until the reactants are
exhausted.
• When repeating steps generate more chain carriers, they are called chain
branching reactions, which leads to expanded fire outbreak or explosions.
• If the repeating elementary steps do not lead to the formation of new product,
they are called chain inhibition reactions.
• Addition of other materials in the reaction mixture can lead to the inhibition
reaction to prevent the chain propagation reaction. When chain carriers react
with one another forming stable product, the elementary steps are
called chain termination reactions.

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 Mechanism of Chain Reactions

• The elementary steps used for mechanisms of chain reactions can be grouped
into the following categories:
• initiation step
• chain propagation steps
• chain branching steps
• chain inhibition steps
• chain termination steps

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 Chain initiation step

• This can be by thermolysis (heating) or photolysis (absorption of light)

leading to the breakage of a bond.
• Light (hv) can often be used to initiate chain reactions since they can
generate free radical intermediates via a photo-dissociation reaction.
Two things to note for chain reactions:
• The reaction is an equilibrium – at any given time there is only a small
concentration of the free radical present (but this will be enough)
• Note that there is a net increase of free radicals in this reaction. We’re
going from zero (in the reactants) to two (in the products).

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Example of Chain Initiation Step

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 Chain Propagation Step

• In this step, the chain carrier makes another carrier

• Elementary steps in which the number of free radicals consumed is equal to the
number of free radicals generated are called chain propagation steps. Once
initiated, the following chain propagation steps repeat indefinitely or until the
reactants are exhausted.
• Example (using CH4)
• It’s only once the free radicals are present that our substrate (CH4) gets
involved. Chlorine radicals are highly reactive, and can combine with a
hydrogen from methane to give the methyl radical, •CH3
• If you count the number of free radicals in this equation, you’ll note that there’s
one in the reactants and one in the products. So there is no net increase in the
number of free radicals. 
• This type of step is referred to as “propagation”.
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• Another example is written below

Cl. + H3CCH3 → ClH2CCH3 + H.

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• In each of these steps, a radical is consumed, and another radical is
generated. Thus, the chain reactions continue, releasing heat and light.
The heat and light cause more radicals to form. Thus, the chain
propagation steps cause chain branching reactions.

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There Are Two Propagation Steps In Free-Radical Substitution

• We can do “propagation” step this way: Take the methyl radical, and it
reacts with the Cl2 still present. This gives us CH3Cl and the chlorine
radical. Note that there has been no net change in the number of free
radicals, so this is still a “propagation”.

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• Note again that we are forming a chlorine radical! What’s so crucial about
this?
• It’s crucial because this chlorine radical can then perform Propagation
Step #1 on a new molecule of our substrate (CH4), continuing the
process.
• It’s a chain reaction – once generated, chlorine radical is catalytic. That’s
why we only need a small amount of chlorine radical for this reaction to
proceed.

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 Chain Branching Steps

• Branching reactions are elementary steps that generate more free radicals than
they consume. Branching reactions result in an explosion. For example, in the
reaction between hydrogen and oxygen, the following reaction may take place:
• Hence, In this step, one carrier makes more than one carrier.
H.+O2 → HO. + .O.
• where ⋅O⋅ is a di-radical, because the O atom has an electronic configuration 2s 2
2px2 2py1 2pz1. In this elementary step, three radicals are generated, whereas only
one is consumed.
• The di-radical may react with a H2 molecule to form two radicals.
.O.+H2 → HO. + H.
• Thus, together chain branching reactions increase the number of chain carriers.
Branching reactions contribute to the rapid explosion of hydrogen-oxygen
mixtures, especially if the mixtures have proper proportions.
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 Chain Inhibition Steps

• The steps not leading to the formation of products are called inhibition reactions or
steps. For example, the following steps are inhibition reactions.
Cl. + ClH2CCH3 → H3CCH2 + Cl2.
Cl. + HCl → H. + Cl2.
H. + ClH2CCH3 → H3CCH3 + Cl.
• Furthermore, sometimes another reactive substance ⋅A may be added to the system to
reduce the chain carriers to inhibit the chain reactions.
Cl. + .A → ClA (not reactive)
The species A⋅ is often called a radical scavenger. In food industry, radical scavengers
are added to prevent spoilage due to oxidation; these are called biological oxidants.
The mechanisms in chain reactions are often quite complicated. When intermediates are
detected, a reasonable mechanism can be proposed. Adding radical scavenger to prevent
food spoilage is an important application in food chemistry. This application came from
the application of the chain reaction model to natural phenomena.
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 Chain Termination Steps

• Is a chain reaction mechanism step in which one or more chain-carrying

species react without producing another chain-carrying molecule.
• It is most commonly encountered as a free radical reaction
mechanism step having radical reactant(s) but no radical product(s).
• (Note that not all mechanism steps which consume radicals without
producing new radicals are termination steps. Some can be propagation
steps.)

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 Example of Chain Termination Steps

•  If the concentration of Cl2 is low relative to CH4 (in other words, Cl2 is our
limiting reagent) then the rate of Propagation Step #2 will slow down as its
concentration decreases.
• Without any Cl2 to react with, our •CH3 radicals can just combine with
another free radical (such as •Cl) to give CH3Cl, for example. There is
essentially no barrier to this reaction.
• Note that here the number of free radicals decreases from 2 to zero. This is
called termination. 

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 Polymerization techniques

• The mechanism of polymerization used in the synthesis of polymers allows

for the classification of the latter into two major classes, namely, addition and
condensation polymers.
• The former kind is produced by the repeated and sequential addition of
monomers without the loss of a smaller molecule during the process.
• Therefore, no by-product is formed and the repeating unit of additional
polymers has the same formula as the alkene or functionally-substituted
alkene monomers used to make them.
• These addition reactions follow a stepwise mechanism that involves reactive
intermediates such as radicals or ions that help in the conversion of a pi bond
in the monomer into a sigma bond in the polymer. 
• The four different polymerization techniques used in the synthesis of addition
polymers are (i) radical polymerization, (ii) cationic polymerization, (iii)
anionic polymerization, and (iv) coordination catalytic-polymerization
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 Radical polymerization mechanism
• The mechanism of radical polymerization follows three steps namely, initiation,
propagation, and termination.
• In initiation reactions, continuous generation of free radicals takes place. During
initiation, a molecule called a radical initiator is broken down into free radicals
either thermally or photolytically.
• In propagation reactions, the free radicals are responsible for the growth of
polymer chains by monomer addition.
• Termination reactions end the polymer chain growth with the addition of radical
center and bimolecular reactions between two radical centers. This reaction results
in net consumption of radicals.
• Termination of chain growth finally occurs when the radical chains either combine
or participate in disproportionation reactions involving pulling hydrogen from
another radical chain.
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Assignment 1
• Give the structures of free-radical polymerization of vinyl chloride
monomer that will result in polyvinylchloride

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 Anionic Polymerization
• Anionic polymerization is a form of chain-growth polymerization that
encompasses the polymerization of vinyl monomers with strong electronegative
groups.
• This type of polymerization is often employed to produce synthetic polydiene
rubbers, solution styrene-butadiene rubbers (SBR), and thermoplastic styrenic
elastomers.
• The polymerization proceeds by formation of carbanions at polymer chain ends.
Anionic polymerizations can be divided into initiation, propagation, and
termination (chain transfer does not occur to any appreciable extent)
• The initiation step of an anionic polymerization involves a nucleophilic attack on
a monomer resulting in carbanion. Basically, all vinyl monomers with (strong)
electronegative substituents polymerize readily in the presence of these anions.

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• Typical monomers for anionic polymerization generally contain substituents
that are electron withdrawing and/or can stabilize the negative charge
through delocalization.
• These monomers include styrene, dienes, methacrylate, vinyl pyridine, and
lactones. Polar monomers, such as vinyl sulfone,
vinyl ketone, acrylonitrile (ACN), and cyanoacrylate, undergo anionic
polymerization using controlled conditions and low temperatures.
• However, at higher temperatures polar substituents often undergo side
reactions with initiators and propagating chain ends.
• Assignment 2
Give structural example of ionic polymerization

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 Cationic polymerization
• Cationic polymerization is defined as an addition polymerization reaction
mediated by a propagating carbocation. Commercially high polymers are
produced by cationic polymerization.
• The reaction is carried out in chlorinated solvents using aluminum trichloride
(AlCl3) as catalyst.
• Carbonium ions are very sensitive to polar impurities, and this often prevent
the establishment of a stationary state.

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• In cationic vinyl polymerization reactions eqs. (19)–(21), the propagating
carbocation –CH2–CH (R)+ B–.
• This carbocation is derived from vinyl monomer and an initiator [16–20].
• The growing carbocations are highly reactive but unstable and subject to a
number of side reactions such as chain transfer and termination, among which
chain transfer to monomer is most important.

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• where R3SiOK represents a potassium silanolate initiator. It can be formed
by the reaction of KOH with the cyclic monomer and D4 represents the
cyclic monomer. D represents the (CH3)2SiO group.

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 Catalytic polymerization mechanism
• Catalytic polymerization also called the Ziegler-Natta polymerization
technique, employs catalysts that are transition metal-based coordination
complexes derived from transition metal halides and organometallic reagents.

Developed in the 1950s by Karl Ziegler and Giulio Natta, this technique
allows better control over the configuration of polymers synthesized from
terminal alkenes and also facilitates the production of unbranched and high
molecular weight compounds, hence, stronger polyolefins at relatively lower
temperature and pressure than required by other addition polymerization
methods.
The polymerization of ethene using a titanium-based Ziegler-Natta catalyst is
shown in Fig. below.

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• The second class of polymers consisting of a large number of very useful
materials are those produced by the polycondensation of monomers combined
in an alternating structure. Condensation polymers are the result of the
transformation of functional groups on monomers that are bi-functional so that
each monomer can connect with two others. 
• Polymerization typically proceeds with the loss of a smaller molecule which
can be in the form of water, gas, or salt. One very well-known condensation
polymer is nylon 6,6 which is a polyamide made from adipic acid (a
dicarboxylic acid) and 1,6-hexamethylenediamine, the combination of which
leads to the loss of water molecules.
• Nylon 6,6 finds numerous applications in the production of clothing, cooking
utensils, carpets, fishing lines, and many more. 
• Polycondensation tends to be slower than polyaddition, often requiring heating
the reaction.
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• A direct consequence of the slow polymerization is generally the formation of
lower molecular weight polymers. Highly crystalline condensation polymers
with high tensile strength result from strong inter-chain interactions when
polar functional groups are present along the chains. The Fig. below shows
the formation of nylon 6,6 by the polycondensation of adipic acid with 1,6-
hexamethylenediamine.

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