TYPES OF

POLYMERIZATION
By Dr. Deepali N. KANEKAR
 Chain Growth Polymerization (addition)

 Chain-growth polymerization is a reaction in which the high-

molecular-weight polymer is produced early in the
polymerization process and the polymer yield (the
percentage conversion of the monomer into the polymer)
gradually increases with time.

 In this polymerization, unsaturated monomer molecules add

onto the active site on a growing polymer chain one at a
time. In chain-growth polymerization, a polymer is
synthesized from monomers in four steps.
1. Chain initiation step is the reaction to generate a chain carrier (intermediates such as radicals and
ions in the chain propagation) in chain polymerizations.

2. Chain propagation step is a step in which an active centre on the developing polymer molecules
adds one monomer compound forming a new polymer molecule that is one repeat unit longer with
a new.

3. Chain transfer step is a key step in which the active center of polymer A receives an atom from B
compound and gets terminated. Then the B molecule forms an active center. In this step the active
point only shifts to another molecule and does not disappear. This step may occur in coordination,
ionic, and free radical polymerizations.

4. Chain termination means that the active center disappears in chain polymerization, causing the
termination of chain propagation.
Free radical Polymerization:

 Chain-growth polymerization reactions require the presence of an initiator, a compound

that reacts with the monomer to form another reactive compound, which begins the
linking process.
 The most widely used initiators are compounds such as peroxides that break down to an
unstable species called a radical (or free radical).
 A radical is a reactive compound that contains an unpaired electron; in chemical
formulas it is commonly given the generic designation R ·
initiation

The first step in polymerization involves addition of the initiator radical (R · ) to the monomer to form a new radical
having the unpaired electron on a carbon atom, as can be seen in the polymerization of ethylene (CH2=CH2):

propagation

The new radical then adds to a second ethylene molecule:

termination

Ethylene molecules are added successively to the chain until very little ethylene is left. At this point the chain is
terminated, either by a combination of two chains
or by a disproportionation reaction involving the transfer of a hydrogen atom from one of the growing
chains to the other:

The structure enclosed in brackets, ―[CH2―CH2―]n, is the repeating unit of the polymer chain. The
number of repeating units, n, varies according to the length of the polymer chain or, in other words,
the molecular weight. Because polymer chains do not all terminate at the same length, reference is
normally made to a polymer’s average molecular weight.
Because growing polyethylene chains are very flexible, the radical at the chain end may curl around and

abstract a hydrogen atom from a CH2 group at some point in the middle of the chain, thus forming a new
radical site from which chain growth continues.

Figure: The formation of a branched polyethylene structure through the process of

backbiting, or chain transfer.

This reaction, shown in Figure, is referred to as backbiting or, more technically, chain transfer. The result
is a polymer chain with the branched structure of low-density polyethylene (LDPE).
Example 2:

If an atom larger than a hydrogen atom—for example, chlorine (Cl)—is attached to one of the carbon atoms, the
initiator radical adds preferentially to the other carbon:

This selectivity results from the increased crowding afforded by the chlorine atom as well as from a stabilizing
effect of the chlorine atom on the radical. Subsequent radical additions to the monomer, vinyl chloride, proceed the
same way, with the result that polyvinyl chloride contains chlorine atoms predominately on alternate carbon atoms:

This type of reaction, termed head-to-tail polymerization, is characteristic of most vinyl monomers, regardless of
the type of initiator employed.
 Ionic initiation
Ionic initiators may be cationic (positively charged) or anionic (negatively charged).
 Cationic Polymerisation:
Cationic initiators are most commonly compounds or combinations of compounds that can transfer a
hydrogen ion, H+, to the monomers, thereby converting the monomer into a cation. Polymerization of styrene
(CH2=CHC6H5) with sulfuric acid (H2SO4) typifies this process:

Polymerization then proceeds by successive additions of the cationic chain end to monomer molecules. Note
that, in ionic polymerization, an oppositely charged ion (in this case, bisulfate ion [HSO 4−]) is associated with
the chain end to preserve electrical neutrality.
 Anionic Polymerisation:

 Anionic polymerization is defined as a chain reaction polymerization in which the active centers for
propagation are anions, which can be in the form of free ions, paired ions, or aggregated species.

 The term “anion” will be considered as an atom or group of atoms with a negative charge and an unshared pair
of electrons. Anions can be considered to be the conjugate bases of the corresponding Bronsted acids, as shown
in Equation

 Two broad types of monomers can be polymerized anionically: vinyl diene, and carbonyl-type monomers with
difunctionality provided by one or more double bonds; and cyclic (e.g., heterocyclic) monomers with
difunctionality provided by a ring that can open by reaction with nucleophiles.
 Anionic Polymerization:
reaction to generate a chain carrier
 For vinyl monomers, it is generally considered that there must be substituents on the double bond that
can stabilize the negative charge that develops in the transition state for monomer addition as shown in
Equation.

 These substituents must also be stable to the anionic chain ends; thus, relatively acidic, proton donating
groups (e.g., amino, hydroxyl, carboxyl, acetylene functional groups) or strongly electrophilic functional
groups (e.g., cyano, carbonyl, nitro, sulfonyl) that can react with bases and nucleophiles must not be
present or must be protected by conversion to a suitable derivative.
Zeigler-Natta Polymerisation
 Zeigler-Natta Polymerization:

1. Cossee and Arlman proposed that the first step in an insertion

polymerization is transmetallation between TiCl4 and AlEt3 to
generate a titanium-alkyl species (Figure 2(i)).

2. This is followed by coordination of ethylene to form a π-complex.

3. The π-complex (Figure 2(ii)) is stabilized through the donation of π-

electrons of ethylene to the vacant titanium dx2-y2 orbital and back-
donation from the filled titanium d (dyz) orbital to the empty π ∗
orbital of ethylene.

4. Next, the titanium-alkyl bond is polarized, and the methylene carbon

attacks one of the ethylene carbons to yield a four-membered
transition state as in (Figure 2(iii)).

5. In the last event, ethylene inserts into the metal-methylene-carbon

bond and one ethylene molecule is added to the starting species (i).

6. The insertion of ethylene leads to the creation of a vacant site, but at a

different place than the original vacant site. This closes the catalytic
cycle, and two carbon atoms are delivered to the initial species.

7. Repeated insertion of ethylene as depicted in Figure 2 results in the

formation of a long polyethylene chain.
Condensation Polymerization or
Step Growth Polymerization
1) What is meant by
Condensation ?
Physically, condensation is a process in which a gas phase change to a liquid phase under certain conditions (i.e.
temperature and pressure) and this phenomenon can be seen in nature many times.

In terms of chemical reaction, on the other hand, condensation is process in which two monomers react to form a larger
molecule and eliminate a smaller molecule (usually water, ammonia, methanol or hydrogen chloride).

•As an example, the reaction of two monofunctional compounds, n-hexylamine and hexanoic acid gives one amide of
molecular weight of 199

NOTE: the same reaction can produce polymer if the reactants have two functional group ( NH2-CH2-NH2 &
HOOC-CH-CH2-COOH). Examples of polymers prepared by condensation reaction are Kevlar, nylon and Terylene.
2) Condensation (step-growth)
polymerization
In this type of polymerization method, monomers with di or multi-function groups are necessary at least to
form a polymer. A difunctional monomer or equal molar amounts of two different difunctional monomers
can form a linear high molecular weight polymer.
In a step-growth polymerization, the molecular weight of the polymer chain builds up slowly and there is only
one reaction mechanism for the formation of polymer. The distinct initiation, propagation, and termination
steps of chain-growth polymerization are meaningless in step-growth polymerization. The polymerization
reaction proceeds by individual reactions of the functional groups on the monomers. Thus, two monomers
react to form a dimer.
Monomer + Monomer …………. Dimer + H2O
The dimer may now react with another dimer to produce a tetramer, or the dimer may react with more
monomer to form a trimer.
Monomer + Dimer………………….Trimer + H2O
Dimer + Dimer………………………..Tetramer + H2O
This process continues, each reaction of the functional groups proceeding essentially at the same reaction rate
until over a relatively long period of time, a high molecular weight polymer is obtained.
 Monofunctional condensation reaction Vs. Difunctional condensation
polymerization
Monofunctional condensation reaction: you can recall that making an ester requires a Carboxylic Acid, an Alcohol
and an Acid catalyst.

Difunctional condensation polymerization: If we started with a diol (a molecule with two alcohol groups HO-R-
OH instead of a normal alcohol ROH), and reacted it with a dicarboxylic acid (HOOC-R-COOH) then the
esterification could happen at either end of the molecule forming a long molecule containing multiple ester
linkages.

Structural Unit
The formation of polyesters, polyamides and polyurethane represent a typical
condensation polymerization. These reactions can be written in a general from as:

Two Structural Unit

One Structural Unit

 Polyurethane:
Polyaddition

The second class of step-growth polymers is polyaddition polymers. Polyaddition polymers do not form small-
molecule by-products, and polymer examples of this class includes PUs and epoxy resins.
 Some of the similarities and differences in the step-growth and chain-growth polymerization are listed in
the Table below*

*J. K. Stille, Step-growth polymerization, Colorado State University, Fort Collins, CO 80523, 1981.
Free radical polymerization. Animation (IQOG-CSIC) - YouTube