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Chemistry of Material
Chemistry of Material
Presented by
Md. Mazharul Islam
ID: 1017032703
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Types of Polymerization reaction
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Step-reaction Polymerization
A. Step polymerization:
The reaction takes place in a stepwise manner through a reaction between functional groups of the
monomer. The process is slow. example: condensation, addition, ring-opening, amidation and ester-
interchange reactions.
Polycondensation:
Monomer containing two or more reactive functional groups condensing with each other.
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Step-reaction Polymerization
Polycondensation:
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Step-reaction Polymerization
Polycondensation: typical example
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Chain -reaction Polymerization
B. Chain polymerization:
Chain polymerization is characterized by self addition of the monomer molecules, very rapidly
through a chain reaction.
No by product is formed.
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Chain -reaction Polymerization
A. Chain polymerization:
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Chain -reaction Polymerization
B. Chain polymerization: 1. Free radical polymerization
Free radical is formed by the decomposition of initiators in presence of heat energy, light
energy and catalyst.
More monomer units are added, the length of polymer chain increases.
Initiators: Initiators are Azo compounds, peroxides, hydroperoxides, per acids, and per-
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Chain -reaction Polymerization
B. Chain polymerization: 1. Free radical polymerization
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Chain -reaction Polymerization
B. Chain polymerization: 1. Free radical polymerization
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Chain -reaction Polymerization
1. Free radical polymerization: Initiator
The rate of decomposition of initiators depends on reaction temperature and solvent
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Chain -reaction Polymerization
1. Free radical polymerization: Initiation
The pi electrons are not very close to the nucleus, therefore, they are susceptible to
attack by other reactive species
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Chain -reaction Polymerization
1. Free radical polymerization: termination
Termination by coupling, Termination by disprotonation, Chain transfer
Chain growth is transferred from one site to another and hence this
phenomenon is called chain.
transfer
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Chain -reaction Polymerization
1. Free radical polymerization: Inhibitors
Inhibitors are chemical substances capable of inhibiting or killing the chain growth by combining
with the active free radicals and forming either stable products or inactive free radicals.
Example: Hydroquinone, nitrobenzene, dinitrobenzene, and benzothiazine
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Chain -reaction Polymerization
1. Free radical polymerization: Inhibitors
Why oxygen is a good inhibitor?
Significance of inhibitor:
preservation of monomers during production and storage
It can be removed via distillation or by washing the monomer with an aqueous
solution of sodium and potassium hydroxide.
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Chain -reaction Polymerization
2. Ionic polymerization:
Involves an attack of pi electrons of the monomer and forming either a positive and negative ion.
Cationic polymerization:
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Chain -reaction Polymerization
2. Ionic polymerization:
Monomers: Isobutylene, styrene, methyl styrene and vinyly ethers
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Chain -reaction Polymerization
2. Ionic polymerization:
Lewis acid BF3 acts as a catalyst in the ionic polymerization in presence of small amount of
water and methanol
initiation
Propagation
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Chain -reaction Polymerization
2.Ionic polymerization: termination
Termination occurs when a collision between the growing C+ ion and anion takes place.
i. Donation of a proton to the counter ion, resulting in the formation of double bond at the end
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Chain -reaction Polymerization
2. Ionic polymerization: Anionic polymerization
Involves the attack on the pi electron pair of the monomer by an anion. Carbanion is formed
The strongly negatively charged anion pushes the pi electrons pair of the monomer double bond
down to sigma electron level.
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Chain -reaction Polymerization
Initiators: Alkyl or aryl derivatives of alkali metals: butyl lithium, triphenyl methyl potassium,, ethyl
sodium. Alkali metal alcoxide, hydroxide and amide also be used for the anionic polymerization
process.
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Chain -reaction Polymerization
2. Ionic polymerization: Termination
The polymer formed in this process is called living polymer. They are alive and keep on growing as
long as we supply a fresh quantity of monomer just as many of the living organisms grow as long as
food is available.
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Chain -reaction Polymerization
3. Co-ordination polymerization:
Polymerization reactions specially for olefines and dienes catalyzed by organo- metallic compound fall
in this category.
A co-ordination bond is formed between C atom of monomer and metal of the catalyst
Heterogeneous system: metal ion solid phase and carbanion solvent phase
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Chain -reaction Polymerization
3. Co-ordination polymerization: monomer is inserted between metal and carbanion. also
known as insertion polymerization
Zieglar-Natta catalyst
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Ring-opening polymerization:
C. Ring-opening polymerization:
Condensing of bifunctional low molecular weight compounds give cyclic or ring compounds having a strain
free configuration.
Attack of anion is on the activated rings rather than the pi electron pairs of C=C in anionic chain
polymerization 29
Metathetical polymerization
• Metathetical polymerization:
• Olefine metathesis is an exchange reaction wherein the alkyldiene moieties of the
reactant molecules are redistributed through the cleavage and reforming of olefinic double
bonds to form new product molecules.
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Reference Books
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Electrochemical polymerization
Example
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Group Transfer polymerization
Group Transfer polymerization: developed in 1983 at Dupont
Example
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Salient features of polymerization reactions
Polymer chain growth Polymer chain growth Polymer chain growth Polymer chain growth
is rapid is rapid is rapid is slow and stepwise
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Salient features of polymerization reactions
Free-radical Cationic Anionic Polycondensation
The process is The process is The process is The process is
exothermic exothermic exothermic endothermic
Suitable for bulk, Suitable for solution Suitable for solution Suitable for bulk,
solution, suspension technique and due to technique and due to solution, emulsion and
and emulsion moisture sensitivity moisture sensitivity melt techniques
techniques unsuitable for unsuitable for
suspension and suspension and
emulsion technique emulsion techniques
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Comparison of Step-Reaction and Chain-Reaction Polymerization