Basic Types
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
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).
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.
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).
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
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.
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.
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.
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.
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.
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.
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).
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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).
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References:
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