POLYMERIZATION

Basic Types

Sacramento, Isaiah Paul G.

BSChE-5
Engr. Elaine G. Mission
11/19/13

Table of Contents
ADDITION-CONDENSATION

ADDITION POLYMERIZATION
CONDENSATION POLYMERIZATION

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CHAIN-STEP

CHAIN-GROWTH POLYMERIZATION
FREE RADICAL
GENERAL MECHANISM OF A CHAIN-GROWTH POLYMERIZATION
STEP-REACTION POLYMERIZATION
GENERAL MECHANISM OF A STEP-REACTION POLYMERIZATION
RING-OPENING POLYMERIZATION
GENERAL MECHANISMS OF RING-OPENING POLYMERIZATION

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Polymerization: Basic Types 1

Polymerization
Polymerization is defined as the process
of converting a monomer or a mixture of
monomers into a polymer. (IUPAC, 1996). It is
a process where monomer molecules are
chemically reacted to form polymer chains.
(Young, 1987).

Figure 1. Monomer and Polymer.

Basic Types of Polymerization

Different systems for classification of polymerization types exist. The mostly
used are the ones established by Wallace Hume Carothers (1929) and by Paul John
Flory (1953).

Addition-Condensation
W. H. Carothers (1929) was an American chemist,
inventor, researcher and the leader of organic chemistry from
DuPont. He was credited for the invention of nylon (Hermes,
1996).
Carothers suggested the classification of
polymerization (and polymers) based on the stoichiometry of
the reaction or the difference in composition between the
monomer and the resulting polymer. These are Addition and
Condensation Polymerization. (Odian, 2004).
Figure 2. Wallace Hume
Carothers

Addition Polymerization
According to Carothers (1929), an addition polymerization is a
polymerization that results in the polymer product only. Addition Polymers are
polymers formed without losing small molecules from the monomers. The end
product has a repeating unit whose composition is the same as the monomer used.

Figure 3. Addition Polymerization of Polyethylene.

In addition polymerization, hydrocarbons with double bonds or alkenes

react with each other. The double bond is broken and new covalent bond is formed
between two monomers. (Need, 2013).
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Condensation Polymerization
Carothers (1929) defined
condensation polymerization as a
polymerization that results in the
formation of a molecule with a low
molecular weight other that the polymer
product. Condensation Polymers are
Figure 4. Condensation Polymerization of Nylon 6,6.
formed with loss of small molecules like
water from the monomer.
In order for condensation polymerization to proceed, two hydrogencontaining functional groups must be present. (Need, 2013).

Figure 5. Typical Condensation Polymers.

Polymerization: Basic Types 3

Chain-Step
P. J. Flory (1953) was an American chemist and
notable for his works in the field of polymers and he won
a Nobel Prize for Chemistry in 1974. He was with W. H.
Carothers at Du Pont (Morris, 1986).
He made a revision of Carothers work. In his great
work Principles of Polymer Chemistry, he classified
polymerization according to the mechanism of the
polymerization processes. These are Chain-Growth and
Step-Reaction Polymerization. (Odian, 2004).

Chain-Growth Polymerization
Figure 6. Paul John Flory

Chain-growth polymerization or simply chain

polymerization occurs by successive addition of monomer molecules to the reactive
end of a growing polymer chain. Usually it is the polymerization of vinyl
monomers such as ethylene, propene, and styrene.

Figure 7. Examples of Vinyl Monomers.

To begin the chain-growth reaction, an initiator or catalyst is required. Right

from the start, a product with high molecular weight is already produced along with
the decrease in quantity of the monomer slowly with time. This type of
polymerization is generally fast, irreversible and moderately to highly exothermic.
(Odian, 2004).
In other literature, addition polymerization and chain-growth polymerization
are used synonymously with each other. According to Billmeyer (1984), an addition
or chain-reaction polymerization involves chain reactions in which the chain carrier
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may be an ion or a reactive substance called a free radical (or simply radical). A free
radical is usually formed by the decomposition of a relatively unstable material
called an initiator. The free radical is capable of reacting to open the double bond of
a vinyl monomer and add to it, still leaving an unpaired electron. Within a short
amount of time of about a few seconds or less, many more monomers add
successively to the growing chain. Finally two free radicals react to annihilate each
others growth activity and form one or more polymer molecules.

Figure 8. Commercially Important Vinyl Polymers Prepared by Free Radical Polymerization.

Free Radical
A free radical is an atom, molecule, or ion that has unpaired electrons. When
an orbital has at least one unpaired electron, and/or the atom, molecule, or ion have
an odd number of electrons; then it is considered as a radical. Because of the
unpaired valence electrons, radicals are highly chemically reactive toward other
substances or even to themselves. They often polymerize when they come in contact
with each other.

Figure 9. Free Radical and Active Center.

Polymerization: Basic Types 5

General Mechanism of a Chain-Growth Polymerization

There are three major steps in the process: (1) initiation of the chain, (2)
propagation of the chain as the monomers add to the reactive site, (3) and the
termination of the reactive site to give completed macromolecules.
Initiation
Using either an initiator or a catalyst does the initiation of the chain. Initiator
functions different from catalysts though. An initiator becomes incorporated into
the polymer chain, usually at one end, and is consumed during the reaction, while a
catalyst does not get incorporated into a specific, fixed location on the chain.

Figure 10. Example of Free Radical Initiators.

This step begins when an initiator decomposes into free radicals in the
presence of monomers. The lack of stability of carbon-carbon double bonds in the
monomer makes them susceptible to reaction with the unpaired electrons in the
radical. In this reaction, the active center of the radical "grabs" one of the electrons
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from the double bond of the monomer, leaving an unpaired electron to appear as a
new active center at the end of the chain. Addition can occur at either end of the
monomer.
Different types of initiation exist, and chain-growth polymerization can be
classified depending on its type of initiation: (1) Radical Polymerization, (2)
Coordination Polymerization, and (3) Ionic Polymerization.
In Radical Polymerization, initiation starts by generating free radicals using
techniques such as thermal decomposition, high-energy radiation, or redox
reactions. Usually, free radicals are produced by thermal decomposition of
molecules containing weak bonds e. g. peroxides (OO) or azo compounds
(N=N). The formed radicals then react with the monomers.
In Coordination Polymerization, usually transition-metal catalysts are used.
The most important catalysts for coordination polymerization are the so-called
Ziegler-Natta or Ziegler catalysts, and Phillips catalysts, both are effective for alkene
polymerization. Ziegler catalysts combine transition metal compounds such as
titanium and vanadium with organometallic compounds. Phillips catalyst is a
catalyst system developed by Phillips Petroleum Co., where chromium oxide
supported on silica is the most important constituent. This catalyst is limited only to
the production of polyethylene. Ionization of the initiating species is utilized in the
ionic polymerization.
Propagation
Next step is the propagation of the chain. Rapid growth of the chain occurs as
the monomers react with the active center on the chain and then generating a new
active center. In free radical polymerization, the entire propagation reaction usually
takes place within a fraction of a second. Thousands of monomers are added to the
chain within this time. The entire process stops when the termination reaction
occurs. For example, if X were a methyl group, the monomer would be propylene
and the polymer, polypropylene.

Figure 11. Propagation Reaction of Propylene into Polypropylene.

Termination
In theory, the propagation reaction could continue until the supply of
monomers is exhausted. However, this outcome is very unlikely because most often
the propagation of the polymer chain is stopped by a termination reaction.

Polymerization: Basic Types 7

Chain termination occurs when two active centers come in close contact and react
with each other by combination or disproportionation. Both reactions yield
completed macromolecules that no longer propagate chains.
Combination occurs when the two chain-ends approach along their lines of
centers and a carbon-carbon bond is reformed between them or free electrons from
two growing chains that join and form a single chain. The following diagram depicts
combination, with the symbol (R) representing the rest of the chain.

Figure 12. Combination Reaction Mechanism.

Disproportionation occurs when the reactive center on one chain takes away
a hydrogen atom from the carbon atom neighboring the reactive center of a second
molecule. Then that neighboring chain reforms a carbon-carbon double bond at its
end in place of the missing hydrogen.

Figure 13. Disproportionation Reaction Mechanism.

Step-Reaction Polymerization
Step-reaction or step-growth polymerization
involves the reaction between the functional groups (HO,
HOOC, etc.) of any two molecules of monomers or
polymers. By repeated reaction, long chains are gradually
produced.
Mostly but not always, they are stoichiometrically
condensation polymers, meaning they lose small
molecules like water in the reaction. (Billmeyer, 1984).

Figure 14. Generic Representation of

a Step Polymerization (white dots
are monomers and black chains
represents oligomers and polymers

General Mechanism of a Step-Reaction Polymerization

According to Odian (2004), step-growth polymerization usually proceeds by
the reaction between two functional groups, for example, hydroxyl and carboxyl
groups, or isocyanate and hydroxyl groups.

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Figure 15. Examples of Stepwise Polymerizations.

In step-growth polymerization, the bi-functional or multifunctional

monomers react to form first dimers, then trimers to tetramers and they proceed to
react with themselves; longer oligomers and eventually long chain polymers are
formed. It proceeds by a relatively slow increase in molecular weight of the
polymer; molecular weight increasing with time thus, the conversion. The monomer
disappears early in the reaction far before the production of any polymer of
sufficiently high molecular weight. (Odian, 2004).

Figure 16. Monomers Used for Stepwise Reactions.

Polymerization: Basic Types 9

The easiest way to visualize the mechanism of a step-growth polymerization

is a group of people reaching out to hold their hands to form a human chain each
person has two hands (= reactive sites). There also is the possibility to have more
than two reactive sites on a monomer: In this case branched polymers are produced.
Step polymerization does not require an initiator and the end remains active
thus, no termination.

Figure 17. Typical Step-Reaction Polymers.

Comparison between Chain and Step

Reaction
Here is a summary of comparison between chain and step polymerization:
Chain
Step
1. Only species with active centers add
1. Any two potentially reactive end
monomer units.
groups can react.
2. Monomer concentration decreases
2. Monomer depletion occurs very
steadily.
rapidly.
3. High molecular weight polymer forms 3. Polymer molecular weight increases
at once.
slowly with time.
4. The concentration of reacting chains is 4. Any size species can react with
usually low compared to the nonanother and many chains are reacting at
reacting monomer and polymer.
one time.
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5. Some monomer remains even at long

reaction times.
6. Different steps operate at different
stages of mechanism (i.e. initiation,
propagation, and termination.)
7. Molar mass of backbone chain
increases rapidly at early stage and
remains approximately the same
throughout the polymerization.
8. Chains not active after termination.
9. Initiator is required.

5. Rapid loss of monomer early in the

reaction.
6. Similar steps repeated throughout
reaction process.
7. Average molecular weight increases
slowly at low conversion and high
extents of reaction are required to obtain
high chain length.
8. Ends remain active meaning no
termination.
9. No initiator necessary.

Addition-Condensation & Chain-Step

Because most of the reactions of chain-growth polymerization fall in the
addition polymerization category; and step-reaction polymerization in the
condensation polymerization category, the terminologies are often used in
synonymous with each other (addition & chain, condensation & step). But that is not
always the case. Thats why it must be clear of which is which. The two groups of
terminologies are referring to two different classification systems, which are stated
in the earlier parts of this document. Thats why one must be careful in using these
terms. Here are some of the exceptions:

Step polymerization by addition of alcohols to diisocyanates to form

polyurethanes:

Chain polymerization (ring opening of heterocycle) with loss of CO2 to form

polypeptide:

Polymerization: Basic Types

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Ring-Opening Polymerization
Ring-opening polymerization is another mode of polymerization in addition
to step and chain, consisting of a sequence of initiation, propagation, and
termination. The terminal ends acts as a reactive center and further cyclic
monomers join to form a larger polymer chain through ionic propagation. This is the
polymerization of cyclic monomers such as cyclic ethers, acetals, amides (lactams),
esters (lactones), and siloxanes. (Odian, 2004).
The polymerization of these compounds has some aspects of both chain and
step polymerization as far as kinetics and mechanism are concerned. It is
proceeding by addition of monomer to growing chain molecules like chain-growth
polymerization, though it never adds larger units. As in step polymerization, the
polymer molecules increase continuously in molecular weight throughout the
reaction. (Billmeyer, 1984).

Figure 18. Commercially Important Polymers Prepared by Ring-Opening Polymerization.

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General Mechanisms of Ring-Opening Polymerization

Ring-opening polymerization is initiated by opening of the ring to form an
initiator species, which is either an ion or a neutral molecule like water. But most of
these cyclic compounds polymerize by ionic chain mechanisms in the presence of
strong acids or bases when water and alcohols are excluded. These polymerizations
are often very rapid. (Billmeyer, 1984)

References:

Odian, G. (2004). Principles of Polymerization 4th Ed. New York: McGraw-Hill

Book Co.
Billmeyer, F. W. Jr. (1984) Textbook of Polymer Science 3rd Ed. Canada: John
Wiley & Sons, Inc.
Treloar, R. G. (1970). lntroduction to Polymer Science. New York: SpringerVerlag.
"Glossary of basic terms in polymer science (IUPAC Recommendations
1996)". Pure and Applied Chemistry. Definition 3.1, p. 2305.
Young, R. J. (1987) Introduction to Polymers. Chapman & Hall.
International Union of Pure and Applied Chemistry, et al. (2000) IUPAC Gold
Book, Polymerization.
Hermes, M. (1996). Enough for One Lifetime. Wallace Carothers, Inventor of
Nylon. Chemical Heritage Foundation.

Morris, Peter J. T. (1986). Polymer Pioneers: A Popular History of the Science

and Technology of Large Molecules p. 70-73. Philadelphia: Center for History
of Chemistry.

Polym-react. Retrieved from:

http://www.che.iitb.ac.in/faculty/sm/CL442/notes/POLYM-REACT.pdf

Polymer Synthesis. Retrieved from:

http://plc.cwru.edu/tutorial/enhanced/files/polymers/synth/synth.htm

Need (2013). Polymers. Retrieved from:

http://chemistry.need.org/curriculum/polymers

Polymerization: Basic Types

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