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Basic Types
Sacramento, Isaiah Paul G.
BSChE-5
Engr. Elaine G. Mission
11/19/13
Table of Contents
ADDITION-CONDENSATION
2
ADDITION POLYMERIZATION
CONDENSATION POLYMERIZATION
2
3
CHAIN-STEP
4
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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5
6
8
8
12
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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 func
tional 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 reactiv
e
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 w
ith
the decrease in quantity of the monomer slowly with time. This type of
polymerization is generally fast, irreversible and moderately to highly exotherm
ic.
(Odian, 2004).
In other literature, addition polymerization and chain-growth polymerization
are used synonymously with each other. According to Billmeyer (1984), an additio
n
or chain-reaction polymerization involves chain reactions in which the chain car
rier
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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 shor
t
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 Polymer
ization.
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 contac
t
with each other.
Figure 9. Free Radical and Active Center.
Polymerization: Basic Types 5
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 t
he
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 f
or 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 u
sually
takes place within a fraction of a second. Thousands of monomers are added to th
e
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 depi
cts
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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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 (lactam
s),
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, th
e
polymer molecules increase continuously in molecular weight throughout the
reaction. (Billmeyer, 1984).
Figure 18. Commercially Important Polymers Prepared by Ring-Opening Polymerizati
on.
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