‫بسم هللا الرحمن الرحيم‬

Chemical Technology 1
(10626474)
Chapter 9
Polymerization Processes
Dr. Raed Ma’ali
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 Objectives
• To understand what is meant by the
condensation and addition polymerization.
• To study some polymers that can be prepared
by condensation polymerization.
• To study the mechanisms of addition
polymerization (Free radical, Ionic, and
Coordination polymerization).
• To study what is meant by polymer blends and
their types.
• To study the industrial polymerization methods.
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 Polymerization Mechanisms
• There are two types of polymerization
mechanisms, they are:-

• Condensation Polymerization (Step Growth

Reaction).

• Addition Polymerization (Chain Growth

Reaction).
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 Condensation Polymerization
• Condensation Polymerization is a chemical
reaction in which two types of molecules of two
different functional groups or one type of
molecules with two different functional groups
can react to form the polymer chain and a small
molecule such as H2O or HX.
• ROH + R’COOH → R’COOR + H2O
• HOROH+HOOCR’COOH→ HOOCR’COOROH+ H2O
• Or 2 HORCOOH → HORCOORCOOH + H2O
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Condensation Polymerization
Examples
• Polyesters
n HOCH2CH2OH + n HOOC(C6H4)COOH →
Ethylene glycol terphthalic acid
[OCH2CH2OOC(C6H4)CO]n + nH2O
Polyethylene terphthalate (PET) + Water

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 Condensation Polymerization
Examples
Nylon (Polyamide)
• Nylon 6/6
n H2N(CH2)6NH2 + n HOOC(CH2)4COOH →
[NH(CH2)6NHCO(CH2)4CO]n + n H2O

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 Condensation Polymerization
• Nylon 6 Examples
n H2N(CH2)5COOH → [NH(CH2)5NHCO]n + nH2O
• Note: The first number indicates the number
of carbon atoms in amine and the second
number indicates the number of the carbon
atoms in carboxylic acid.
• Write the repeating unit of nylon 11 and nylon
6-10.

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 Condensation Polymerization
Examples
• Polyurethane
n HOROH + n O=C=N-R’-N=C=O →
Diol Di isocynate
[ROCONHR’NHCOO]n (PU)

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 Condensation Polymerization
Examples
• Polycarbonate

Bisphenol A Phosgene PC

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 Addition Polymerization
• It is a process in which the polymer is formed
with out the loss of small molecule.
• The most important functional group vinyl
group [C=C].
• Addition polymerization can be classified into:
 Free Radical Polymerization.
 Ionic Polymerization (Cationic and Anionic).
 Coordination Polymerization.
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 Free Radical Polymerization
• The steps of the reaction are:
• Generation of free radicals: it can be achieved by
thermal decomposition of organic compound
such as peroxide (ROOR) and azo-compounds..

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Free Radical Polymerization

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 Free Radical Polymerization
• Termination
• Combination of two radicals.

• Disproportionation

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 Free Radical Polymerization
• Transfer of free radical to dead polymer chain.

• Note: The stability of free radicals is given as 30 >

20 >10. So free radicals can be interchanged to
produce the most stable free radical.

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 Ionic Polymerization

• Ionic polymerization can be classified into:-

• Cationic Polymerization.
• Anionic Polymerization.
• Cationic Polymerization
• The initiators for cationic polymerization are:-
• H+ from acids.
• Lewis acids (BF3, AlCl3, TiCl4).
• Carbocation (R3C+).

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 Ionic Polymerization
Mechanism of Cationic Polymerization
• Initiation: H+ + H2C=CH2 → H3C-C+H2
• Propagation
It is the addition of the monomers to the main
chain.
H3C-C+H2 + n H2C=CH2 → H[CH2CH2]nCH2C+H2
• Termination
It involves the destruction of growing ion by
recombination with the counter ion or
reaction with another species. 16
 Ionic Polymerization
Anionic Polymerization
• The initiators for ionic polymerization are:-
• OH- from bases.
• Lewis bases (amines-).
• Carbanion (R3C-).
The Mechanism of Anionic Polymerization
• Initiation: X- + H2C=CH2 → XH2C-C-H2
• Propagation: it is the addition of the monomers
to the main chain.
• XH2C-C-H2+ n H2C=CH2 → X[CH2CH2]nCH2C-H2
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 Ionic Polymerization
Mechanism of Anionic Polymerization
• Termination: involves the destruction of
growing ion by recombination with the
counter ion or reaction with another species.
• Note: living polymers are polymers contain
active carbanion due to the lacking of
termination step by using suitable reagents.

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Differences between step-growth polymerization and
chain-growth polymerization
Chain-growth polymerization Step-growth polymerization
Only monomer is reactive All monomers are of equal reactivity;
monomer; dimer….hexamer…chain
Main type is addition polymerization Main type is condensation
(unsaturated monomers) polymerization (polyfunctional
monomers)
Different mechanisms operate at Same mechanism throughout
different stages of reaction (i.e.
Initiation, propagation and
termination)
High molecular weight is obtained at High molecular weight is only obtained
early stages of the polymerization near the end of the polymerization
process process
Chains not active after termination Ends remain active (no termination)
Initiator required No initiator necessary
 Coordination Polymerization
• It is carried out by Ziegler-Natta catalysts.
• Ziegler-Natta catalysts are formed from the
reactions involving compounds (halides) of
transition metals from group IV to VIII such as
Ti, V, Cr, with alkyl derivatives of metals or
hydrides from group I to III such as Al.
• These reactions are carried out in an inert
solvent and inert atmosphere.
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Mechanism of Coordination
Polymerization

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 Polymer Blends
• A polymer blend is a material in which at least
two polymers are blended together to create a
new material with different properties.
• Polymer blends can be broadly divided into
three categories:
• Immiscible Polymer Blends.
• Examples:
1- PET/PVA.
2- PS/Poly butadiene.
3- PE/PP 22
 Polymer Blends
• Compatible Polymer Blends: Immiscible
polymer blends that have sufficient strong
interactions between its components due to
the use of a suitable compatabilizer.
• Miscible Polymer Blends
• Examples:
1- PET/PBT. 2- PPO/PS.
3- PMMA/PVDF. 4- PC/ABS
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Industrial Polymerization Methods
Bulk Polymerization
• The monomer is polymerized without any
significant amounts of other materials present.
• Examples are PMMA, LDPE, PS, PC, and PET.
• Advantages
1- High purity product
2- Largest yield per reactor volume.
• The most important parameter is the controlling
of heat produced from the reaction.
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 Industrial Polymerization Methods
Solution Polymerization
• The monomer is dissolved in an inert solvent.
• Example: PS is prepared by dissolving styrene in
benzene with a suitable initiator.
• The importance of using the solvent is to absorb much
of the heat generated during polymerization.
• Disadvantages are:
1- Problems associated with handling solvents, toxicity,
flammability, and pollution
2- The solvents are expensive.
3- The yield is less than that in bulk polymerization.
4- The produced polymer contains traces of solvent. 25
 Industrial Polymerization Methods
Emulsion Polymerization
• Water is used to prepare emulsion with monomer.
• Due to the hydrophobicity of organic monomers,
emulsifiers (soap, surfactants) are used.
• The advantages are
1- Water is less expensive.
2- Good heat control.
• The products are emulsions of hydrophobic polymers
in water, so they can be used as water-based paint or
an adhesive (PVA).
• Examples are PVA, PVC, PS.
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 Industrial Polymerization Methods
Suspension Polymerization
• A suspension of monomer droplets in water is
prepared by stirring to prevent coalescence of
the monomer or polymer droplets.
• Examples are PVC, PS, PMMA, and PTFE.
• Advantages of suspension polymerization are:
1- The size of polymeric product can be controlled.
2- The polymer is easy to filter from water.
• The disadvantage is the continuous stirring of the
system. 27
 Industrial Polymerization Methods
Interfacial Polymerization
• It is a polymerization process that occurs at an interface
between an aqueous solution containing one monomer
and an organic solution containing a second monomer.
• The polymer is not soluble in any solutions.
• Advantages are:
1. Reaction proceeds very rapidly at room temperature
and atmospheric pressure.
2. Separation of polymer from interface is easier.
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