FUNDAMENTALS OF POLYMER ENGINEERING

POLYMERIZATION REACTIONS

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 POLYMERIZATION REACTIONS
 For polymerization it is required that the monomer molecule is
capable of being linked to two (or more) other molecules of
monomer by chemical reaction (functionality). 

 Functionality of two or higher is needed.

 Polymerization is the formation of polymers from small units.
 Polymers can occur naturally (proteins, carbohydrates) and can be
synthesized (nylon, Teflon, polyethylene).

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 CHAIN GROWTH POLYMERIZATION
 This type of polymerization is a three step process involving two chemical
entities. It initially exists as simple units. In nearly all cases, the monomers
have at least one carbon-carbon double bond. Ethylene is one example of a
monomer used to make a common polymer.
 

 The other chemical reactant is a catalyst. In chain-reaction polymerization,

the catalyst can be a free-radical peroxide added in relatively low
concentrations. The formation of a free radical from an organic peroxide is
shown below: 
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 CHAIN GROWTH POLYMERIZATION
 Initiation
The first step in the chain-reaction polymerization process, initiation,
occurs when the free-radical, catalyst reacts with a double bonded carbon
monomer, beginning the polymer chain. The double carbon bond breaks
apart, the monomer bonds to the free radical, and the free electron is
transferred to the outside carbon atom in this reaction.

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 CHAIN GROWTH POLYMERIZATION
 Propagation
The next step in the process, propagation, is a repetitive operation in which the physical chain of
the polymer is formed. The double bond of successive monomers is opened up when the
monomer is reacted to the reactive polymer chain. The free electron is successively passed
down the line of the chain to the outside carbon atom. 

This reaction is able to occur continuously because the energy in the chemical system is
lowered as the chain grows. Thermodynamically speaking, the sum of the energies of the
polymer is less than the sum of the energies of the individual monomers. Simply put, the
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single bonds in the polymeric chain are more stable than the double bonds of the
monomer.
 CHAIN GROWTH POLYMERIZATION
 Termination
Termination occurs when another free radical (R-O.), left over from the original splitting of the
organic peroxide, meets the end of the growing chain. This free-radical terminates the chain by
linking with the last CH2. component of the polymer chain. Termination can also occur when two
unfinished chains bond together. Both termination types are diagrammed below. Other types of
termination are also possible. 

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Example of addition polymers

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 IONIC POLYMERIZATION

 Anionic Polymerization
 Cationic Polymerization

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 ANIONIC POLYMERIZATION
 The mechanism of anionic polymerization is a kind of repetitive conjugate addition
reaction. Electron withdrawing groups (ester, cyano) or groups with double bonds
(phenyl, vinyl) are needed as the R groups because these can stabilize the propagating
species by resonance. Examples:
Initiation
KNH2 ⇔ K+ + NH2-

NH2- + M → NH2M-

Propagation
NH2Mn- + M → NH2Mn+1-
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Termination
 Anionic addition polymerization is a form of chain-growth
polymerization or addition polymerization that involves the polymerization of vinyl
monomers with strong electronegative groups. This polymerization is carried out
through a carbanion active species. Like all chain-growth polymerizations, it takes
place in three steps: chain initiation, chain propagation, and chain
termination. Living polymerizations, which lack a formal termination pathway, occur
in many anionic addition polymerizations. The advantage of living anionic addition
polymerizations is that they allow for the control of structure and composition
 Anionic polymerizations are used in the production of polydiene synthetic rubbers,
solution styrene/butadiene rubbers (SBR), and styrenic thermoplastic elastomers.
 Initiation by electron transfer
 Initiation by strong anions

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 Living anionic polymerization
Living polymerization was demonstrated by Szwarc and co workers in 1956. Their initial
work was based on the polymerization of styrene and dienes. One of the remarkable features
of living anionic polymerization is that the mechanism involves no formal termination step.
In the absence of impurities, the carbanion would still be active and capable of adding
another monomer. The chains will remain active indefinitely unless there is inadvertent or
deliberate termination or chain transfer.

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 CATIONIC POLYMERIZATION
 Cationic polymerization is a type of chain growth polymerization in which
a cationic initiator transfers charge to a monomer which then becomes reactive. This reactive
monomer goes on to react similarly with other monomers to form a polymer.  The types of
monomers necessary for cationic polymerization are limited to olefins with electron-donating
substituents and heterocycles.
  Examples of effective catalysts are AlCl3, AlBr3, BF3, TiCl4, SnCl4, and in some cases strong
acids such as H2SO4. 
 They usually require a co-catalyst, namely a Lewis base such as Water, acetic acid or alcohol:
BF3 + H2O ⇔ H+BF3OH-
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10/26/2020
 CATIONIC POLYMERIZATION
Monomers that polymerize in the presence of these catalysts include
isobutylene, styrene, alpha-methyl styrene, butadiene, vinyl alkyl ethers
and many other monomers having electron-donating substituents that
enhance the electron-sharing ability of the double bond of the vinyl
monomers.

H+BF3OH- + CH2=CHR → H3C-C+HR + (BF3OH)-

They all can be readily polymerized to high-molecular weight polymers.

H3C-C+HR + n CH2=CHR → H(-CH2-CHR-)nCH2-C+HR

However, some other monomers, such as propylene and other olefins,

reach only low to medium molecular weights when polymerized with 14
strong Lewis acids. 10/26/2020
• Free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the
successive addition of free-radical building blocks.
• Free radicals can be formed by a number of different mechanisms, usually involving separate initiator
molecules.
Types of initiation and the initiators
• Thermal decomposition
• Photolysis
• Redox reactions
• Persulfates
Propagation
• During polymerization, a polymer spends most of its time in increasing its chain length, or propagating.
• After the radical initiator is formed, it attacks a monomer. 
• In an ethene monomer, one electron pair is held securely between the two carbons in a sigma bond. The
other is more loosely held in a pi bond.
• Once a chain has been initiated, the chain propagates until there are no more monomers (living
polymerization) or until termination occurs.
Termination
• Combination
• Radical disproportionation
• Combination of an active chain end with an initiator radical
• Interaction with impurities or inhibitors 15
 CATALYTIC/ COORDINATION
POLYMERIZATION

 In 1963 Karl Ziegler and Giulio Natta received the Nobel prize in chemistry for their discovery of
coordination compound catalysts for addition polymerization reactions. These Ziegler-Natta catalysts
provide the opportunity to control both the linearity and tacticity of the polymer.
 A typical Ziegler-Natta catalyst can be produced by mixing solutions of titanium(IV) chloride (TiCl 4) and
triethyl aluminum [Al(CH2CH3)3] dissolved in a hydrocarbon solvent from which both oxygen and water
have been rigorously excluded. The product of this reaction is an insoluble olive-colored complex in which
the titanium has been reduced to the Ti(III) oxidation state.

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 Assignment 1

Total Marks 10
 Write down the following details for any 20 polymers.
 1. Monomers
 2. Polymerization reaction
 3. Polymerization Technique
 4. Properties
 5. Application
Submission Date: December 04, 2019.
Note: Late submission will carry -5 marks.
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