Chemistry of Polymerization
Dr. Muhammad Abdur Rashid
Associate Professor
Department of Textile Engineering
DUET, Gazipur-1707
or Step Polymerization
or Chain Polymerization
Free radical polymerization
Anionic polymerization
Addition polymerization Ionic polymerization
Cationic polymerization
Co-ordinate polymerization
Chain or Addition Polymerization
Chain polymerization is characterized by a self addition of the
monomer molecules to each other very rapidly through a chain
reaction. No byproduct is formed; the product has the same
elemental composition as that of the monomer. The
bifunctionalilty is provided by the double bonds present in the
monomer. Compounds containing reaction reactivity double
bonds can therefore, undergo a chain polymerization.
Typical example
1. Vinyl compounds 2. Allyl compounds
a. vinyl alcohol (CH2=CHOH) a. Allyl alcohol (CH2=CHCH2OH)
b. Vinyl chloride (CH2=CHCl) b. Allyl chloride (CH2=CHCH2Cl)
c. Vinyl ethyl ether (CH2=CHOC2H5)
3. Olefines
a. Ethylene(CH2=CH2)
b. Propylene (CH2=CHCH3) 6
Chain polymerization consists of three major steps:
1. Initiation
2. Propagation
3. Termination
These processes can be brought about by a free radical,
ionic or co-ordination mechanism
Free Radical Polymerization
The initiation of the polymer chain growth is brought about by
free radical is produced by the composition of compounds
called initiator. The term “chain growth” represents a process
involving a continuous and very rapidly addition of the
monomer units to form polymer chain.
Usually, many low molecular weight alkenes undergo rapid
polymerization reactions when treated with small amounts of
a radical initiator.
For example, the polymerization of ethylene
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Free Radical Polymerization
Initiators are thermally unstable compounds and decompose into
products called free radicals. If R-R is an initiator and the pair of
electrons forming the bond between the R’s can be represented
by dots, the initiators can be written as:
The decomposition of the initiator to form free radicals
can be induced by heat energy, light energy or catalyst.
A host low molecular weight compounds mainly azo
compounds, peroxides, hydro peroxides etc. are useful initiator.
See page no. 24-29
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Polymerization Stages:
Initiation:
The free radical Rᵒ attacks the double bound in the monomer molecule,
resulting in the following chemical change:
Propagation:
After initiation comes propagation. In the propagation step, the radical site at
the first monomer unit attacks the double bond of the fresh monomer
molecule. This result in the linking up of the second monomer unit to the first
and transfer of the radical site from the first monomer unit to the second by
the unpaired electron transfer process.
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Polymerization Stages:
This process involving a continuous attack on fresh monomer
molecules which in turn keep successively adding to the growing
chain one after another is term “propagation”.
The mode of addition of the incoming to the growing chain can be:
a. Head to tail
b. Tail to tail
c. Head to head
d. Tail to head
If we call the -CH2- and
-CHX- parts are head and
tail of a monomer unit
respectively, the four
modes of addition can be
represented as:
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Polymerization Stages:
Termination:
After the propagation, termination process starts, depending on the
factors like temperature, time and monomer and initiator concentrations,
exists the statistical probability of the two growing chains coming close
to and colliding with each other. Collision takes place following the
two-chain growth.
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There are four kinds of termination:
a. Termination by coupling
b. Termination by disproportion
c. Termination by chain transfer
d. Termination by inhibitors
(d)
(a)
(b)
x
(c)
Inhibitor:
The chemical compound capable of inhibiting or killing the polymer
chain growth by coupling with active free radicals is called inhibitor.
Retarder:
The compounds which slow the chain growth in polymerization is
called retarder. It also decreases the weight of polymer molecule.
Atmospheric oxygen is a good inhibitor. The inhibiting action of
oxygen is due to biradical nature.
Pᵒ + Oᵒ-Oᵒ P-O-Oᵒ
P-O-Oᵒ + Pᵒ P-O-O-P
This is why radical polymerization is generally carried out
under a nitrogen atmosphere to avoid contact with atmospheric oxygen.
Ionic Polymerization
The ionic mechanism of chain polymerization involves an attack on the
ᴨ electron of the monomer. This time, however not by the unpaired
electron of the free radical but either a negative or positive ion.
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Ionic Polymerization
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Anionic Polymerization
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Anionic Polymerization
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Anionic Polymerization
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Cationic Polymerization
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Cationic Polymerization
(ii) Propagation
Chain growth takes place through the repeated addition of a monomer
in a head-to-tail manner to the ion with retention of the ionic character
throughout
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Cationic Polymerization
(iii) Termination
Termination of cationic polymerization reactions are less well-
defined than in free-radical processes. Two possibilities exist as
follows:
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Step Polymerization
In step polymerization, the polymers are formed by the independent
reaction between the functional groups of simple monomer units. In
step-growth, each step may consist of a combination of two polymers
having a different or the same length to form a longer-length
molecule.
The reaction is a lengthy process, and the molecular mass is increased
at a very slow rate. An example of step-growth polymerization is
condensation polymerization, where a water molecule is evolved in
the reaction when the chain is lengthened.
Mechanism of Step Polymerization
Let, we consider the reaction between monohydric alcohol
(methanol) and monocarboxylic acid (acetic acid).
There is no more reactive functional group left with the product
and hence it can not react further with any reactant molecules in order to
form a different product.
Now taking ethylene glycol instead of methanol and make it
reacts with acetic acid.
The final product contain no more functional group and hence
can not react with further reactant to give any other product
Cont….
Let us replace acetic acid with adipic acid and take two
molecules each of ethylene glycol and adipic acid
……………………(i)
……………………(ii)
From (i) + (ii)
2HOCH2CH2OH + 2HOOH(CH2)4COOH HO-[CH2CH2OOC-(CH2)4-COO]2-H + 3H2O
If n molecules of adipic acid and n molecules of ethylene glycol
reacts, than we have,
nHOCH2CH2OH + nHOOC(CH2)4COOH HO-[CH2CH2OOC-(CH2)4-COO]n-H + (2n-1)H2O
Condition of step polymerization:
i. Monomer should have two reactive functional groups for
polymerization to proceed
ii. Polymerization proceeds by step wise reaction between reactive
functional groups
iii. Only one type of reaction between two functional groups is involved
in polymerization
iv. The polymer formed still contains both the reactive functional group
at its chain ends and hence is “active” and not dead as in chain
polymerization.
The most commonly used step polymerization reactions are:
1. Poly condensation
2. Poly addition
3. Ring opening
4. Amidation
5. Ester interchange
Poly Condensation
Poly condensation is brought about by monomers containing
two or more reactive functional groups such as hydroxyl, carboxylic,
amine etc. condensing with each other.
n HO-R-OH + n HOOC-R‘-COOH HO-[R-OOC-R'-COO]n-H + (2n-1)H2O
There are two types of poly condensation reaction:
i. AA-BB type:
when a pair of bifunctional monomers such as dicarboxylic
acid/dialcohol, dicarboxylic acid/diamine undergoes poly condensation,
this is usually describe AA-BB type poly condensation.
n A-A + n B-B A-(A-B)2n-1-B + By product
HOCH2CH2OH + HOOC(CH2)4COOH HO-CH2CH2OOC-(CH2)4-COOH + H2O
A A B B A AB B
Cont…..
ii. A-B type:
when a single bifunctional monomers undergoes self
condensation, it is usually describe as A-B type poly condensation. This
reaction thab can be depicted as follow:
n A-B B-(AB)n-1-A + By product
H2N-(CH2)6-COOH + H2N-(CH2)6-COOH H2N-(CH2)6-OC-NH-(CH2)6-COOH + H2O
B A B A B A B A
Poly addition
Poly addition polymerization is brought about by the migration
of atoms from one monomer molecule to another or to the intermediate
product. Vinyl monomers as well as monomer pairs with reactive
functional groups can undergo poly addition polymerization.
For example, styrene can be polymerized in the presence of perchloric
acid by this method. This process involves the following mechanism
The interesting manner in which the polymer is formed by a
simple addition at the double bond, without any free radical, carbonious
ion or carbonion being formed at all. However like the chain
polymerization polymer without elimination small molecules.
Ring opening
Monomer having a ring structure can be opened and
polymerized, if conditions are favorable. The mechanism of ring
opening polymerization can be explained by taking the example of
ethylene oxide which is a ring compound and sodium methoxide which
form an anion. This step can be conceived as the initiation of the
polymerization.
The propagation is effected by the anion attacking a fresh
ethylene oxide ring which will be opened up and in turn added on with
the simultaneous formation an anion and this process goes on.
After propagation, then the termination step and this can be
effected by adding a proton.
Amidation or Amide interchange
The reaction of one amide in a polyamide with another amide
such that the length of the polymer molecules become altered.
Ester interchange
an exchange of group that occurs when an ester is linked with
either a hydroxy compound or a carboxylic acid.
Limitation of step polymerization
• Difficult to synthesize high molecular weight polymer
• Need very high extent reaction
• Often requires very high temperature for the reaction process
• Sometimes form cyclic molecule
Q. Difference between chain polymerization and step polymerization
Q. Why the molecular weight of a polymer is to be controlled?