Functionality Principle

Dr. Saima Shabbir, MS&E

Functionality Principle

For polymerization to take place, each

reacting molecule should be at least
bifunctional
This accounts for the average functionality
of 2 for the system
The average functionality is calculated
from the stoichiometric equivalence of
functional groups

Dr. Saima Shabbir, MS&E

Functionality Principle

To get a stoichiometric balance of COOH

and OH groups in an esterification
reaction between diacid and triol, what
should be the molar ratio of the two
reactants?
It should be 3:2 for COOH:OH
This would correspond to the average
functionality of 12/5
Or 2.4
Dr. Saima Shabbir, MS&E
 How?

Dr. Saima Shabbir, MS&E

Functionality Principle

The average functionality or functionality

factor (f) is calculated using following
expression:
f = Moles of each reactant x functionality
Total number of moles
f = 3(2) + 2(3) / 3+2
f = 6+6/5 = 12/5 = 2.4
The average functionality is greater than 2
therefore cross linking will occur
Dr. Saima Shabbir, MS&E
Functionality Principle

For bifunctional systems like AA and BB

the value of f is 2
Hence the polymer obtained is linear
And linear polymers are soluble than their
cross linked counterparts

Dr. Saima Shabbir, MS&E

Functionality Principle

For reaction between monoalcohol and

triacid in 3:1 molar ratio the average
functionality:
f = 1(3) + 3(1) / 3+1
f = 6/4
f = 1.5
The average functionality is less than 2
therefore no polymer will be formed
Dr. Saima Shabbir, MS&E
Interrelationship of f, p and Xn

No = total number of molecules initially

present giving an average functionality f
The related functional groups are present
in stoichiometric equivalence
N = total number of molecules present at
time t when extent of reaction is p
The number of molecules lost over time
period t = (No- N)

Dr. Saima Shabbir, MS&E

Functionality Principle

For each molecule lost, the number of

functional groups lost is 2
One of each kind
Hence the total number of functional
groups lost is 2(No- N)
Initial total number of functional groups =
No f
Hence p = 2(No- N) / No f
p = 2/f (1 - N/No)
Dr. Saima Shabbir, MS&E
Functionality Principle

Xn = No/N
p = 2/f (1 - N/No)
p = 2/f (1 - 1/Xn)
This is modified Carothers equation
Rearrange
Xn = 2/2 pf
p= 2/f - 2/Xn f

Dr. Saima Shabbir, MS&E

Functionality Principle

Acetic acid (CH3COOH) is used as the

end capping agent in the synthesis of
polyamides and polyesters.
If 0.01 mol of acetic acid is used with 0.99
mol each of the two difunctional reactants
then:
f = 0.99(2) + 0.99 (2) + 0.01(1) / 1.99
f = 1.99
For this case of f = 1.99 if p = 1 then Xn =
Dr. Saima Shabbir, MS&E
200
Critical Extent of Reaction at Gel
point
p= 2/f - 2/Xn f
At gel point Xn
Thus this extent of reaction is called
critical extent of reaction or critical
conversion (pc)
pc = 2 / f

Dr. Saima Shabbir, MS&E

Critical Extent of Reaction at Gel
point
The Gel point is the point at which an infinite
polymer network first appears.
The critical extent of reaction for the gel point
(pc) is given by:
pc = 2 / f
For bifunctional systems like AA and BB the
value of f is 2
pc = 2/2 = 1
Thus gelation occurs after 100% monomer
conversion

Dr. Saima Shabbir, MS&E

Critical Extent of Reaction at Gel
point
For f is 2.4
pc = 2/2.4 = 0.83
Thus gelation occurs after 83% monomer
conversion

Dr. Saima Shabbir, MS&E

Concept Check

What is the functionality factor of 0.7 mol

ehtylene glycol and 0.25 mol of a diacid?
What is critical extent of reaction for this
system?
f = 0.7(2)+0.25(2)/0.7+0.25
f = 1.9/0.95 = 2
pc = 2/f = 2/2 = 1

Dr. Saima Shabbir, MS&E