Kinetics of Polymerization

Kinetics of Polymerization
Course: 303
Physical chemistry III
What is polymer??
• A macromolecule build up with series of repeating
units.
• Repeating unit is called monomer.
Poly means many; mer or meros is for
Hermann Staudinger
monomer or part, i.e. molecule
Nobel Prize in 1953
containing many monomer or parts.
High molecular weight, highly viscous. Applications
•Automotive
Iron Chain •Aerospace
Containing 1000 to
500,000 repeating units. •Medical
•Building
•Consumer Goods
Polystyrene •Packaging
Modern age as polymer age
Polydimethyl siloxan or silicone
Usage
Stone age → Bronze age → Iron age → Polymer age

Mode of Polymerisation
(i) Condensation or step growth polymerisation:
• These polymers are obtain from condensation
reactions of bi-functional or tri-functional
monomers, i.e. elimination of small molecules
like water, alcohol, HCl etc.
→
Dacron or polyethylene terephthalate
(ii) Addition or Chain polymerisation:
• Obtain from chain reaction initiated by active chain
carrier.
• Repeated or continuous addition of monomer
molecules to the growing chain.
• Monomers are unsaturated compounds.
• 80% polymer are produced by this method.
n CH2=CH2 → -(CH2-CH2)n-
Polystyrene
kinetics
• Step growth polymerization
Consider the polymerization
 Reaction is catalyzed
by trace amount of acid
Rp = rate of polymerisation
Stoichiometric ratio, r = a/b=1 [a]=[b]

Integrating from [a]0 to [a]
D.P. Increases linearly with time, i.e. M.W. of polymer increases with time
Degree of polymerization: No. of monomer units present in a polymer chain.

Extent of reaction (p): The fraction of reactants or their functional groups
that have reacted at time t.
• Refers to percentage of reaction conversion
P=
[For Bifunctional molecules]
or (Carother’s Equation)
When p=1 (100% conversion) D.P. becomes ꚙ, i.e polymer has infinitely high
M.W
Phenomenon is called gelation, where polymer forms insoluble gel (less useful
product). Also known as incipient gelation.
General Carother’s equation:
fav = average functionality
•At gelation D.P. becomes ∞
Extent of reaction or % conversion necessary to reach infinite M.W

Chain or Addition polymer
• Chain reaction is initiated by initiator.
R1 R2 R1 R2
I + C C I C C
I = Initiator
• Based on the type of initiator
(i) radical (ii)anionic (iii) cationic
R1 R2 R1 R2 R1 R2
C C C C C C
Heterolytic Homolytic
• Substituent present in the monomer determine the

mechanism.
(i) Electron Donating Group (EDG): such as alkenyl,
alkoxy, acetates etc.
H EDG H EDG
C C Or I C C
H
Prefers positive species Positive charge on the active
(Cation) centre is stabilized by EDG
•Cationic mechanism is followed for monomer with ED-substituents.

(ii) Electron Withdrawing Group (EWG): such as -CN,
-CONH2 -COOR etc. reduces the electron density at the double
bond.
H EWG Stabilizes the active
withdrawing electron density
I C C
•Anionic mechanism is preferred
• Free radical: In radical electron density or electrical neutrality
is less both EDG and EDG can stabilize radical.
• Substituents with resonance stabilization.
• Free Radical polymerization is less selective towards
substituent present.
• Initiator: heat and/ or photo labile compounds decomposes to
produce free radicals
• example - benzoyl peroxide, cumyl peroxide, azo-bis
isobutyronitrile (AIBN)
H H H
C O O C 2 C O =2R
H H H
benzoyl peroxide
CH3 CH3 CH3

H3C C N N C CH3 H3C C + N2 AIBN
CN CN CN
• Chain polymerization has three distinct stages
(1) Initiation (2) Propagation and (3) Termination
• Initiation: Free radical are generated from decomposition

of Initiator which deliberately added to reaction medium
kd
I 2R (primary radical)
Heat
•Primary radical react with the monomer molecule to give

secondary radical
ki
R + M RM or M1 (secondary radical)
Ri = 2kd [I] Rate of Initiation
Decomposition of Initiator is slower (activated process)

• Initiator Efficiency (f): all radical generated are not
available for initiation.
(a)Recombine due to solvent cage (cage effect)
R + R I Initiator
(b) May react to growing chain
R + Mn RMn or P Dead polymer

Growing chain
(c) React with impurities present in the reaction medium
R + O2 R-O-O
• Fraction of primary radical is lost.
f is always less than unity
Ri = 2fkd [I] Rate of initiation
• Propagation: secondary radical or monomer radical

(M∙1) grow to long chain radical species very fast by
continuous addition of monomer molecules.
kp
M1 + M M2 Mn
1650 monomer units added in 1.24 s
Rp = kp [M ][M] Rate of Propagation

• Termination: growing chain lose their activity and
stop to grow further.
• Two ways
(1) Coupling or combination of two growing
chains.
ktc
Mn + Mm Pn+m (single dead polymer)
(2) Disproportinationkbetween two growing chains

td Pn + P m
Mn + Mm (two dead polymers)
H
ktd
R C C + C C R R C C H + C CH R
H H
• Rate expression
Rt = 2kt [M ]2 Two radicals are consumed
kt = ktc + ktd
Applying steady state approximation: Concentration of

reactive species (i.e. radical) is constant through out
the reaction.
Ri = radicals generated Rt = radicals consumed
Ri = Rt
2fkd [I] = 2kt [M ]2
Monomer radical conc.

• Rate of polymerization: most of the monomer is consumed in
propagation step.
Rate of polymerization = Rate of propagation
Rp = kp [M ][M] Rate of thermal polymerization
Rp is directly proportional to [I]1/2 and [M]
• Ri = Rt
Rt = 2 f kd [I]
 Rate of termination will increase with initiator concentration.

• Degree of polymerization: refers to chain length of
the polymer.
where
 Chain length or M.W. of polymer linearly increases with monomer

conc. whereas decreases with square root initiator conc.
To get high M.W. polymer initiator conc. should be low.
Initiator conc. increases the Rp whereas decreases the chain length of
the polymer.
• Average kinetic chain length ( ῡ ): average no. of
monomer molecules reacting with a radical from its
initiation to termination.
• Monomer attached with each primary radical.
(For Disproportination)
( Termination by Coupling )
 Two radical centre are present in a chain for termination by

coupling whereas one in case termination by disproportination.
Photochemical chain polymerization
• Photo sensitizer (initiator) absorbs the light
and undergo decomposition to free radicals.
hv
Cs 2R
light
Io I
b
Photon absorbed per seconds = a (Io - I)
a =cross sectional area
From, Beer-Lambart law of the reaction cell
ε = Molar extinction coefficient

Substituting the value of I
Since When x is very small
V= a.b = volume of the cell

• Quantum yield (φ)
( Rate of initiation )
• Rate of propagation (Rp)
Rp = kp [M ][M]
• Rate of termination (Rt)

Rt = 2kt [M ]2
• S.S.A Ri = Rt
Rate of Photochemical chain

polymerization

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Kinetics of Polymerization

Stone age → Bronze age → Iron age → Polymer age

Stoichiometric ratio, r = a/b=1 [a]=[b]

Degree of polymerization: No. of monomer units present in a polymer chain.

[For Bifunctional molecules]

fav = average functionality

•At gelation D.P. becomes ∞

Extent of reaction or % conversion necessary to reach infinite M.W

• Substituent present in the monomer determine the

•Cationic mechanism is followed for monomer with ED-substituents.

CH3 CH3 CH3

• Initiation: Free radical are generated from decomposition

•Primary radical react with the monomer molecule to give

Ri = 2kd [I] Rate of Initiation

Decomposition of Initiator is slower (activated process)

(b) May react to growing chain

R + Mn RMn or P Dead polymer

(c) React with impurities present in the reaction medium

• Propagation: secondary radical or monomer radical

Rp = kp [M ][M] Rate of Propagation

(2) Disproportinationkbetween two growing chains

Applying steady state approximation: Concentration of

Monomer radical conc.

Rp = kp [M ][M] Rate of thermal polymerization

Rp is directly proportional to [I]1/2 and [M]

 Rate of termination will increase with initiator concentration.

 Chain length or M.W. of polymer linearly increases with monomer

 Two radical centre are present in a chain for termination by

ε = Molar extinction coefficient

Since When x is very small

V= a.b = volume of the cell

• Rate of termination (Rt)

Rate of Photochemical chain

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