Chapter - 3 Polymer Synthesis and Technology

CHAPTER 3
POLYMER SYNTHESIS
AND TECHNOLOGY
Learning objectives
Distinguish between addition and condensation
polymerization
Describe essential features of addition and
condensation polymerization
Identify polymerization process used on basis of
polymer composition
Distinguish several types of polymerization
technology and each features
2
Two main kinetic schemes

synthetic approaches
THERMODYNAMICS
Tells us where the system would like to go eventually i.e
defines relationships between macroscopic variables at
equilibrium
KINETICS
Tells us how fast the system takes various reaction paths.
WHY KINETICS OF POLYMERIZATION
BOTHER?
How long does it take to make polymer?
Can we speed up the reaction?

What is the relationship between kinetics and the Mol.
Wt. of the product?
3

1. chain growth (Addition) polymerization
molecules of the same or different monomers
add together
2. stepwise (Condensation) polymerization
Combination by exclusion of a small molecule
(usually water) extensively used by nature
4

1. Chain growth (Addition) polymerization
unsaturated compounds
e.g., alkenes and their derivatives can participate
most important of the chain polymerization methods
a) Free radical
Cationic
b)Ionic
Anionic
polymerization.
5
chain growth (Addition) polymerization

a) Free radical
alkenes and their derivatives are polymerized in the
presence of initiator
benzoyl peroxide, acetyl peroxide, tert-butyl peroxide,
etc
Measure of the efficiency of the chain propagation

reaction
kcl
vp
vi
# of monomer units consumed

# of active centres produced
Where : kcl The kinetic chain length
chain growth (Addition) polymerization

Initiation
an initiator molecule is decomposed or allowed to undergo
a chemical reaction to generate an active species
This "active species," which can be a free radical or a cation or an
anion
Initiation consists of 2 steps:
a. Dissociation step: the initiator forms two radical species. The
labile bond can be broken by heat of irradiation (uv, gamma).
b. Association step: addition of a single monomer molecule to the
initiating radical.
7
Free radical polymerization

then initiates the polymerization by adding to the
monomer's carbon-carbon double bond.
or R
assume decomposition is the rate limiting step i.e. ka >> kd
Then we should only have to consider kd.
ka is the monomer association rate constant

8

Example: benzoyl peroxide
benzoylperoxide
Benzoylperoxide
Free radicals
addition of the first monomer molecule:

.
The initiator efficiency, f, is seldom 100 %, since the

recombination and other side reactions of the free radicals
can occur during the initiation reaction
10
Propagation
A process of monomer units addition to the initiated
monomer species.
The newly generated "active species" adds to another
monomer in the same manner as in the initiation step.
Additional monomers are added sequentially during
subsequent propagation steps. Propagation continues until
termination process occurs
11
On the addition of each monomer, the free radical moves

to the end of the chain.
In general;
Assumption; reactivity is independent of chain length12

Termination: two propagating radical chains meet their
free-radical end.
There are 3 mechanisms of termination:
1.Combination
2. Disproportionation
3.Chain transfer
13

1. Combination Termination : To give a single terminated chain through the formation of a covalent
bond between the 2 combining radical chains.
2. Termination by disproportionation: One terminated chain will have an unsaturated carbon group
while the other terminated end is fully saturated.
3. Chain transfer To give hydrogen abstraction from an initiator, monomer, polymer, or solvent
molecule.
(where a hydrogen is transferred from one chain to the other)
where R represents a long-chain portion

14

COMBINATION
Example :
DISPROPORTIONATION
15

Example:
Chain transfer
I Mx-1M+ SH
+ SH
I MX-1MH + S
Ktr
+ S
16

RATE OF TERMINATION
17
Free-radical polymerization kinetics

Assuming that : the propagation step has equal reactivity with other steps
I Mx+ M kp
IMxM
Ra=Rp= kp[I Mx] [M]
Where: Ra= the overall rate of polymerization in a free-radical polymer
Rp = the rate of chain propagation
the radical concentration is not known [ M . ]
Assume: the total radical population obtains a steady-state concentration

over the most of the polymer process.
the radicals are formed in the initiation step = the radicals are consumed in
the termination step
18
STEADY STATE ASSUMPTION

This means that radicals are consumed at the same
rate as they are generated
ri = r t
19
STEADY STATE ASSUMPTION

RATE of propagation = RATE of polymerization
rp = R p
20
What does it tells us?

If we want to increase Rp, increase [ M ] OR [ I ]
CONVERSION
In initial stages of reaction we can assume [ I ] = [ I0 ] =

constant
Integrating
21
Initiator concentration is usually first order decay
22
Maximum conversion
23

Chain initiating step RO-OR
a radical initiator
2RO
radicals
Chain propagation step
24

Chain termination step
Combination
Disproportion
Reaction with impurity
25
Cationic Polymerization initiation step
1) Priming
2) Initiation Step
26
3) Propagation
4) Termination by combination
27

Initiation step
28
Cationic Polymerization termination step

Chain termination
29
Monomers that are best able to undergo cationic

polymerization are those with electron-donating
substituent
30
Anionic Polymerization
the growing chain end bears a negative
Initiation
31
Termination
32
The growing chain end bears a negative
Non terminated chains are called living polymer the chains

remain active until they are killed
33
Summery of addition
polymerization
Once initiation occurs, the polymer chain forms very

quickly
The concentration of active species is very low.
Hence, the polymerization mixture consists of
primarily of newly-formed polymer and un-reacted
monomer
Since the carbon-carbon double bonds in the
monomers are, in effect, converted to two single
carbon-carbon bonds in the polymer, so energy is
released making the polymerization exothermic with
cooling often required
34
Stepwise (Condensation) polymerization

involves a repetitive condensation reaction (two
molecules join together, resulting loss of small
molecules as water, alcohol, etc.,
formation of high molecular mass polymers between
two bi-functional monomers
product of each step is again a bi-functional species
and the sequence of condensation goes on.
Since, each step produces a distinct functionalised
species and is independent of each other; this process
is also called as step growth polymerization
35

The type of end polymer product is dependent on the
number of functional end groups of the monomer.
Monomers with two reactive end groups creates
linear polymers
with more than two end groups give three
dimensional polymers which are cross linked.
36

Example 1 : Polyester Condensation Reaction
Formation of esters starts with an organic acid and an
alcohol
Since have only one functional group each cannot form a

polyester
When the two reactants each have bi-functionality, a
linear polymer is formed:
37
Polyethylene terephthalate commercially called

fiber Dacron
38

Example 2
polyamides, known widely as the nylons polymerization
Nylon 4 The number 4 indicates the number of

carbon atoms in the mer
39
Summery of condensation polymerization

The polymer chain forms slowly, sometimes requiring
several hours to several days
Since most of the chemical reactions employed have
relatively high energies of activation, the polymerization
mixture is usually heated to high temperatures
Step-reaction polymerizations normally afford polymers
with moderate molecular weights, i.e., <100,000
Branching or cross linking does not occur unless a
monomer with three or more functional groups is used
40
Summery
41
Technology of polymerization
Monomers may be polymerized by the following methods
(1) polymerization in homogeneous systems
(2) polymerization in heterogeneous systems
polymerization in homogeneous systems
The homogeneous polymerization techniques involve
pure monomer or homogeneous solutions of monomer
and polymer in a solvent.
42
can be divided into two methods:
(a)the bulk
(b) the solution polymerizations
(a)the bulk
simplest technique and produces the highestpurity polymers
Ingredients :
monomer,
monomer-soluble initiator,
43
monomer, monomer-soluble initiator
used for the preparation of polyethene,

polystyrene, etc.
Advantage
Disadvantage
Final product form
Difficult of removing the lost

traces of monomer
High yield per reactor volume
Dissipating heat produced

during the polimerization
Easy polymer recovery
increase temperature(hot spot)
minimum
contamination of product
viscosity is very high(at the

end)
Minimum viscosity (at the

beginning)
uneven polymerization
44
(b) the solution polymerizations
requires the correct selection of the solvents.
Both the initiator and monomer be soluble in
each other.
solvent are suitable for boiling points, for the
solvent-removal steps
Ingredients : monomer
initiator
solvent
45
monomer + initiato+ solvent
used for the preparation of polyvinyl acetate,
poly (acrylic acid), and polyacrylamide
Advantage
Disadvantage
Solvent has low viscosity

& acts as a dilute
Reduce monomer
concentration
Thermal control is easier than Solvent may terminate the

growing polymer chain, leading to
in the bulk
Solvents have suitable
low molecular weight polymers
Solvent aids in removal of heat
Difficult to remove solvent

from final form and not
suitable for dry polymer
Temperature control is easy
Small production per

reactor volume
46
melting or boiling points

for the conditions of
polymerization
Polymerization in heterogeneous systems
Suspension (Bead or Pearl) polymerization

A polymerization consists of an aqueous system with
monomer as a dispersed phase and results in polymer as a
dispersed solid phase
at the end the particles harder and they can be removed
by filtration, then washing
Ingredients : water-insoluble monomer & initiator,
suspention medium (water-usually)
47
monomer & initiator
water
Wate
r
Advantage
Monomer
Disadvantage
Solvent cost and recovery Polymer purity is low

operation are cheap
Polymerization to high
conversion
Reactor cost may higher

Initiator
than the solution cost

Low viscosity due to the accept contaminated
product
suspension
Easy heat removal due to
the high heat capacity of
water
Excellent heat transfer
because of the presence
of the solvent
48
Emulsion polymerization
Polymerization is initiated when the water-soluble radical
enters a monomer-containing micelles.
Ingredients : water-insoluble monomer,
water-soluble initiator,
dispersing medium (water), fatty acid,
surfactant such as sodium salt of a long chain
49

50

Surfactant
Initiator
Micelles formation
Monomer
Polymerization
51

Advantage
Overcomes many environmental problems: solvent
is water
If final desired product is polymer washed with water
to remove the soap phase by coagulation
52

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CHAPTER 3

Two main kinetic schemes

Can we speed up the reaction?

Two main kinetic schemes

Two main kinetic schemes

chain growth (Addition) polymerization

Measure of the efficiency of the chain propagation

# of monomer units consumed

Where : kcl The kinetic chain length

chain growth (Addition) polymerization

Free radical polymerization

ka is the monomer association rate constant

Free radical polymerization

addition of the first monomer molecule:

Free radical polymerization

The initiator efficiency, f, is seldom 100 %, since the

Free radical polymerization

Free radical polymerization

On the addition of each monomer, the free radical moves

Assumption; reactivity is independent of chain length12

Free radical polymerization

Free radical polymerization

where R represents a long-chain portion

Free radical polymerization

Free radical polymerization

Free radical polymerization

Free-radical polymerization kinetics

Assume: the total radical population obtains a steady-state concentration

STEADY STATE ASSUMPTION

STEADY STATE ASSUMPTION

What does it tells us?

In initial stages of reaction we can assume [ I ] = [ I0 ] =

Initiator concentration is usually first order decay

Free radical polymerization

Chain propagation step

Free radical polymerization

Reaction with impurity

Cationic Polymerization initiation step

Cationic Polymerization initiation step

Cationic Polymerization initiation step

Chain propagation step

Cationic Polymerization termination step

Monomers that are best able to undergo cationic

Non terminated chains are called living polymer the chains

Once initiation occurs, the polymer chain forms very

Stepwise (Condensation) polymerization

Stepwise (Condensation) polymerization

Stepwise (Condensation) polymerization

Since have only one functional group each cannot form a

Stepwise (Condensation) polymerization

Polyethylene terephthalate commercially called

Stepwise (Condensation) polymerization

Nylon 4 The number 4 indicates the number of

Summery of condensation polymerization

used for the preparation of polyethene,

Final product form

Difficult of removing the lost

High yield per reactor volume