Types of Polymerization reaction

Presented by
Md. Mazharul Islam
ID: 1017032703

1
 Types of Polymerization reaction

Modern classification of polymerization according to polymerization mechanism

 Step-Growth or Condensation Polymerization

 Chain-Growth or Addition Polymerization
1. Free radical polymerization
2. Ionic polymerization
3. Coordination polymerization
 Ring opening polymerization

2
 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.

3
 Step-reaction Polymerization

Polycondensation:

4
 Step-reaction Polymerization
Polycondensation: typical example

5
 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.

 It consists of 3 steps: Initiation, propagation and termination

 Three types: 1. Free radical polymerization, 2. Ionic polymerizations,

3. Coordination polymerization

6
 Chain -reaction Polymerization

A. Chain polymerization:

7
 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-

esters are useful initiators

8
 Chain -reaction Polymerization
B. Chain polymerization: 1. Free radical polymerization

9
 Chain -reaction Polymerization
B. Chain polymerization: 1. Free radical polymerization

10
 Chain -reaction Polymerization
1. Free radical polymerization: Initiator
The rate of decomposition of initiators depends on reaction temperature and solvent

11
 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

 Free radical attack on the monomer initiating polymerization

12
 Chain -reaction Polymerization
1. Free radical polymerization: Propagation

 Chain growth stopped when free radicals site destroyed by

impurities or termination or used up all monomer 13
 Chain -reaction Polymerization
1. Free radical polymerization: Propagation
Four modes of addition considering -CH2- as head and –CHX- as tail

14
 Chain -reaction Polymerization
1. Free radical polymerization: termination
Termination by coupling, Termination by disprotonation, Chain transfer

Chain growth stops and forms a dead polymer chain 15

 Chain -reaction Polymerization
1. Free radical polymerization: termination
Termination by chain transfer:

Chain growth is transferred from one site to another and hence this
phenomenon is called chain.
transfer
16
 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

17
 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.

70
 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:

19
 Chain -reaction Polymerization

2. Ionic polymerization:
 Monomers: Isobutylene, styrene, methyl styrene and vinyly ethers

 Initiators: BF3, AlCl3, SnCl4, TiCl4

20
 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

21
 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

22
 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.

23
 Chain -reaction Polymerization

2. Ionic polymerization: Typical monomers and initiators for Anaionic polymerization

Monomers: butadiene, isoprene, styrene, acrylonitrile

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.

24
 Chain -reaction Polymerization
2. Ionic polymerization: Termination

Not a spontaneous process.

The reaction proceeds till all the monomer is consumed. The carbanion at the chain ends remains
potentially active. Polymerization can be restarted

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.

25
 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

Acts as active centre

First
step: from where propagation
starts

Mt represents transition metals : Ti, Mo, Cr, V, Ni

Heterogeneous system: metal ion solid phase and carbanion solvent phase
26
 Chain -reaction Polymerization
3. Co-ordination polymerization: monomer is inserted between metal and carbanion. also
known as insertion polymerization

The process is used to prepare

stereo-regular polymer

Zieglar-Natta catalyst

27
 Ring-opening polymerization:

C. Ring-opening polymerization:

Condensing of bifunctional low molecular weight compounds give cyclic or ring compounds having a strain
free configuration.

Conversely, a ring structure molecule with a strain configuration

can opened up and polymerized 28
 Ring-opening polymerization:
iii. Ring-opening polymerization:

Cleave the ring to form anion

Anion attacks fresh EO

Anion is caged by adding a

proton

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.

• It is catalyzed by transition metal compounds tungsten, molybdenum and rhenium.

•Mechanism: rearrangement of complex containing metal-carbene species and a
coordinated olefine forms a four membered metaloocyclic transition state

30
 Reference Books

1.Polymer Chemistry by Stevens

2. Polymer Science by V R Gowariker, N V Viswanathan, Jaydev Sreedhar

3.Text Book of Polymer Science by Fred W. Billmeyer

 Electrochemical polymerization

Electrochemical polymerization: Initiating species are produced at the electrolytic cell

containing monomer and solvents or additives.

Initiating species can be a free radical, a cation or an anion.

after the formation of initiating species, initiation and propagation steps are same

Chain growth occur at electrode surface or the bulk of the electrolytes

Category

32
Electrochemical polymerization
Example

i. Anodic free-radical initiation: Anodic free-radical initiation of

MMA using an acetate and acetic acid electrolyte

33
 Group Transfer polymerization
Group Transfer polymerization: developed in 1983 at Dupont

Organo-silicon initiator and a bifluoride catalyst is used.

 -unsaturated esters, ketones, nitriles and carboxamide can be polymerised to yield narrow
molecular weight distribution polymer.

Example

34
Salient features of polymerization reactions

Free-radical Cationic Anionic Polycondensation

Monomers have Monomers have Monomers have Monomers have

double bond and double bond and double bond and reactive functional
polymerization polymerization polymerization groups and
proceeds by an attack proceeds by an attack proceeds by an attack polymerization
of pi electron by a free of pi electron by a of pi electron by an proceeds by
radical cation or carbonium anion condensation reaction
ion of functional groups

Polymer chain growth Polymer chain growth Polymer chain growth Polymer chain growth
is rapid is rapid is rapid is slow and stepwise

No elimination of small No elimination of small No elimination of small Elimination of small

molecules molecules molecules molecules occur

As the polymerization As the polymerization As the polymerization Mostly monomers

proceeds, monomer proceeds, monomer proceeds, monomer consumed at an early
concentration steadily concentration steadily concentration steadily stage
decreases and polymer decreases and polymer decreases and polymer
concentration concentration concentration
increases increases increases

35
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

MW of the polymer MW of the polymer MW of the polymer MW of the polymer

depends on the depends on the depends on the depends on the mole
monomer and initiator monomer monomer ratio of the monomers.
concentration , concentration , concentration , Extent of conversion
temperature, and temperature, and temperature, and and reactioo time have
solvent solvent. Independent solvent a significant effect.
of initiator
concentration
Mw/Mn ranges from Mw/Mn ranges from Mw/Mn ranges from Mw/Mn ranges from 2-
1.5 to 5 1.5 to 2 less than 1.5 3
Chain branching is Chain branching is Chain branchingis Chain branching is
favored due to chain negligible negligible possible only for
transfer trifunctional monomer

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

36
 Comparison of Step-Reaction and Chain-Reaction Polymerization
Step Reaction
Growth occurs throughout matrix by
reaction between monomers, oligomers,
and polymers
DPa low to moderate
Monomer consumed rapidly while
molecular weight increases slowly
No initiator needed; same reaction
mechanism throughout
No termination step; end groups still reactive
Polymerization rate decreases steadily as
functional groups consumed
aDP, average degree of polymerization.
Chain Reaction
Growth occurs by successive addition of
monomer units to limited number of
growing chains
DP can be very high
Monomer consumed relatively slowly, but
molecular weight increases rapidly
Initiation and propagation mechanisms different
Usually chain-terminating step involved
Polymerizaion rate increases initially as
initiator units generated; remains relatively
constant until monomer depleted
37