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Subject Code Chem 3 Chemistry 3 (Reactions and Interactions of Organic and Inorganic Compounds)
Module Code 5.0
Lesson Code 5.8 Free Radical Polymerization
Time Limit 30 minutes

TA ATA
Components Tasks
(min)a (min)b

Target By the end of this module, the students are expected to be able to:

1. Explain the mechanisms involved in free radical polymerization 0.5

2. Recognize examples of polymers synthesized via free radical min
polymerization

Hook It was previously thought by many chemists of the early 1900s that molecules 3 mins
with molecular weights of more than a few thousands are non-existent. However,
a German chemist and Nobel laureate Hermann Staudinger refuted this claim
based on his experience in studying natural compounds like rubber and cellulose.
Staudinger proposed that these natural compounds called polymers (from the
Greek poly (many) and meros (parts)) were composed of macromolecules of
about 10,000 or more atoms. He further proposed that these macromolecules are
formed like chains by repetitive bonding of many smaller molecules called
monomers. (Reusch, W. and Clark, J, 2020).

Figure 1. (a) Natural rubber latex (left) made of (b) polyisoprene molecules (top right).
The compound’s monomer is (c) isoprene (bottom right). (Images from
www.britannica.com and Creative Commons)

Rubber, shown in figure 1, is one of the many naturally occurring polymeric

compounds. In the body, several biomolecules are also polymeric. Examples of
these are the polypeptides comprising the proteins, and the polysaccharides that
are important in the body’s energy production.

Chem 3 LG 5.8 Free Radical Polymerization | Page 1 of 7

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In this lesson, we will discuss one of the mechanisms involved in the formation
of polymers – the free radical polymerization also known as addition
polymerization or chain-growth polymerization.
Check your knowledge!

Before we proceed to the discussion, let us check your prior knowledge by trying
to answer the following questions:

1. Polymers formed via addition polymerization are often used as plastics.

The atoms/groups which make up the monomers determine the
properties of the plastic. An example of this is polystyrene. Which
monomers join together to form polystyrene?
2. Whilst the plastics formed by addition polymerization reactions are
useful for many things, numerous problems arise when they are
disposed of. One method of reducing these problems is by chemical
recycling. Which word is used to describe the breaking down of long
chained polymers into shorter chained ones, as it happens in chemical
recycling?

Ignite A. Addition Polymers 18.5

mins
Polymers that are formed by chain addition reactions of alkene or
functionally substituted alkene monomers are also referred to as
addition polymers. Recall that the most thermodynamically favored
chemical reactions of alkenes are addition reactions, which are known
to proceed in a stepwise mechanism by way of reactive intermediates
(Kennepohl et al., 2020). Depending on the type of initiator species and
the propagating site of reactivity, addition polymerization may be
classified as (Kennepohl et al., 2020).:

a. Radical polymerization, with a free radical as the initiator and a

carbon radical as the reactive intermediate
b. Cationic polymerization, with an electrophile as an initiator and a
carbocation as the reactive intermediate
c. Anionic polymerization, with a nucleophile as an initiator and a
carbanion as the reactive intermediate
d. Coordination catalytic polymerization, with a transition metal
complex as an initiator and a thermal catalytic complex as the
reactive intermediate

B. Alkenes as Monomers in Free Radical Polymerization

Recall that the double bond of an alkene molecule contains one pi and
one sigma bond, with the pi bond being relatively weaker than the sigma
bond. As an example, figure 2 below shows the sigma and pi bonds in
an ethene or ethylene molecule. It is the weaker pi bond that is
susceptible to the addition of the radical initiator thereby converting the
pi bond into a sigma bond with an accompanying release of energy and
resulting in the generation of a carbon radical in a mechanism that will
be discussed in detail in the succeeding section. Most of the simplest

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polymers are synthesized by treating an alkene monomer with a small
amount of a radical catalyst (McMurry, 2008).

Figure 2. Illustration of the sigma (a) and pi (b) bonds in an ethene molecule. As
shown in (c), in between the two sp2-hybridized carbons is one sigma and one pi
bond. (Image from https://brilliant.org/wiki/sigma-and-pi-bonds/)

C. Mechanism of Free Radical Polymerization

Let us consider, for example, the radical polymerization of ethylene to

form polyethylene, commonly used in plastic containers:

(Klein, 2015)
As previously mentioned, the reaction is initiated by a free radical. This
makes this type of polymerization essentially a radical reaction, and it
follows the typical mechanism, which includes initiation, propagation
and termination.

Initiation
Typically, the radical catalyst being used as an initiator is a peroxide,
such as benzoyl peroxide (McMurry, 2008). With the aid of heat,
pressure, or UV light, the weak O-O bond of the peroxide undergoes
homolytic cleavage forming two alkoxy radicals (Klein, 2015).

(Klein, 2015)

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One of these radicals then adds to the pi bond of the alkene. In this
process, the pi bond is converted into a sigma bond with one electron
pairing up with the odd electron on the alkoxy radical. The other electron
in the pi bond remains on the other carbon thereby generating a carbon
radical (McMurry, 2008).

(Klein, 2015)

Propagation

The next step is when the actual polymerization starts. The carbon
radical formed in the initiation step adds to the pi bond of another alkene
molecule or monomer resulting in the formation of a new carbon radical.
Repetition of this process hundreds or thousands of times allows the
elongation of the polymer chain (McMurry, 2008).

(Klein, 2015)

Termination

Whenever two radicals come in contact with each other, the chain
elongation is eventually ended. One possible chain-terminating reaction
is the coupling of two growing radical chains (McMurry, 2008).

(Klein, 2015)

Chem 3 LG 5.8 Free Radical Polymerization | Page 4 of 7

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The reaction may be made to favor propagation instead of termination if
the conditions are carefully controlled, allowing the generation of very
large molecules of the polymer with over 10,000 repeating monomer
units (Klein, 2015).

Substituted ethylenes, also called as vinyl monomers, can also undergo

radical polymerization to form polymers with substituent groups on
alternating carbon atoms along the polymer chain (McMurry, 2008).
Examples include polyvinyl chloride, polypropylene and polystyrene.

In the case of substituted ethylene, the highly substituted radical is

always the one that adds to the less substituted end of the monomer, and
this process is called head-to-tail polymerization (Smith, 2017).

(Smith, 2017)

D. Common Polymers Formed from Ethylene and Substituted

Ethylene

Below is a table showing the common synthetic polymers formed

through the radical polymerization of ethylene and substituted ethylene
monomers and their common applications (Klein, 2015). These
synthetic polymers are commonly found in many household materials.

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Navigate GRADED FORMATIVE ASSESSMENT 9 mins

Instructions: (9 points each) Draw the steps of the free radical polymerization
mechanism that converts the given monomers into their respective polymers
using radical (R* or RO*) as the initiator species:

1. 2. Vinyl chloride

3. Propylene

Answer:

(Let -R be -C6H5 for styrene, -Cl for vinyl chloride, and -CH3 for propylene)

3 points

3 points

3 points

Knot In this lesson, we have learned one of the most common mechanisms in the 1 min
synthesis of polymers from alkene monomers – the Free Radical
Polymerization.

Just like any other radical reactions, this mechanism involves three major steps:
initiation, propagation, and termination. In the initiation step, the catalyst is
cleaved homolytically with the aid of heat, pressure, or UV light to form free
radicals. The radical then adds to the pi bond of the alkene monomer thereby
converting the pi bond into a sigma bond, and a carbon radical, which is the
Chem 3 LG 5.8 Free Radical Polymerization | Page 6 of 7
 PROPERTY OF THE
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reactive intermediate. In the propagation step, the carbon radical adds to the pi
bond of another monomer resulting in a longer chain and a new carbon radical.
Repetition of this process over a hundred or thousand times will result in further
elongation of the chain. The process ends when a radical combines with another
radical in the termination stage.

This mechanism is very useful in the synthesis of many polymers that have
industrial uses.

a
suggested time allocation set by the teacher
b
actual time spent by the student (for information purposes only)

References:

Bewick, S. et al. (2021). Polymerization – Addition Polymers. Chemistry LibreTexts.

https://chem.libretexts.org/Bookshelves/Introductory_Chemistry/Book%3A_Introductory_Chemistry_(CK-
12)/25%3A_Organic_Chemistry/25.19%3A_Polymerization_-_Addition_Polymers

Kennepohl, D. et al. (2020). Radical Additions to Alkenes – Chain-Growth Polymers. Chemistry LibreTexts.
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map%3A_Organic_Chemistry_(McMurry)/08%3
A_Alkenes-_Reactions_and_Synthesis/8.10%3A_Radical_Additions_to_Alkenes_-__Chain-
Growth_Polymers#title

Klein, D. (2015). Organic Chemistry 2nd Edition. John Wiley and Sons.

McMurry, J. (2008). Organic Chemistry 7th Edition. Thomson Brooks/Cole.

Smith, J.G. (2017). Organic Chemistry 5th Edition. Mc Graw Hill.

Prepared by: Paul Randy P. Gumanao Reviewed by: Melba C. Patacsil

Position: SST-III Position: SST-V
Campus: PSHS-SRC Campus: PSHS-CARC

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