Addition Polymerization

Requirement: Unsaturated
Monomer
https://www.youtube.com/watch?v=HpPHN7fcLHI
 Polymerization Steps

Initiation
I R*(Reactive Species)

Propagation H H H
CH2 CHY

CHY R CH2 C* R CH2 C CH2 C*

R* + CH2
Y Y Y
Termination
H H H H

R CH2 C CH2 C* + S R CH2 C CH2 C S

(Counter species)
Y Y Y Y

https://www.youtube.com/watch?v=TvaZkGZ7zW0
 Initiator(I)
Free Radical
I Cationic
Ionic
Anionic

.C C
. C C +C C-

Depends on the inductive and resonance characteristics of the

substituent(s) present
- +
CH2 CH Y Y: alkoxy(OR), alkyl(R ), phenyl, alkenyl(R=R’)
Cationic initiation

+CH - Y: cyano(CN), aldehyde(OCH), ketone(COC),

CH Y
2
acid(COOH), ester(RCOOR’)
Anionic initiation
 Free Radical Initiators
Thermal Initiators

Peroxides and Hydroperoxides: dissociation due to the

cleavage of weak peroxide linkage
Most common :Benzoyl peroxides

O O O
/h .
Ph C O O C Ph Ph C O

Ph C O
. Ph
. + CO
2

Ph
. Ph Ph cage effect: solvent cage
O O traps the radicals for
some period before they
Ph C O
.+ Ph
. Ph C O Ph diffuse apart
 O O
O Ph O
Ph C O O C Ph .
+ Ph
Ph C O O C Ph
.
induced decomposition
O O
.
Ph C O Ph + Ph C O

Induced decomposition and cage effect are the waste reactions

Other e.g. of peroxide initiator: diacetyl peroxide, di-t-butyl

peroxide(initiates reaction above 100ºC)
 Hydroperoxide:

Ph C O OH (Cumyl peroxide)

Promoter: Induces decomposition of peroxides at lower temperature,

e.g. rapid decomposition of benzoyl peroxide at room temperature in
the presence of N,N-dimethylaniline
O O CH3 O
CH3
+
Ph C O O C Ph + Ph N Ph N O C Ph + Ph CO2
(unstable)
CH3 CH3

O CH3 O
CH3
+ .
Ph N O C Ph Ph N +. + Ph C O

CH3 CH3
 Azo compounds: driving force behind decomposition of the stable
nitrogen molecule

CN CN CN

(CH3)2C N N C (CH3)2 2 (CH3)2C . + N2

2,2’-Azobisisobutyronitrile
(AIBN)

CN CN

CN (CH3)2C C (CH3)2
. CN
2 (CH3)2C
(CH3)2C C N C (CH3)2
Persulfates: they are generally used in aqueous solution e.g.
potassium persulfate

-O SO-OSO - 2SO4-.
3 3

SO4-. + H2O HSO4- +.OH

2.OH H2O + 1/2O2
 Redox initiators

Aqueous redox initiators

Oxidation-reduction reaction initiate polymerization. Initiates reaction
at moderate temperatures of 0-50°C and even lower temperature.
Extremely useful in industries for low temperature emulsion
polymerization.

H2O2 + Fe2+ OH- + OH. + Fe3+

Fe2+
ROOH OR. + OH- + Fe3+
Fe2+
-O .
-O
3SO-OSO3
- 3SO-O + SO42- + Fe3+

Other metal ions used are Ti3+, Ag2+, Cu2+, Ce4+

 Nonaqueous redox initiators: organic peroxides react in non aqueous
solution by redox process in the presence of amines, hydrazine,
formic acid

CH3 O O

C6H5 N + Ph C O O C Ph

CH3

CH3 O O CH3
+ +.
[C6H5 N O O C Ph Ph CO O-] C6H5 N C6H5COO. +
+ C6H5COO-
CH3 CH3
 Photoinitiators

Photolytically dissociation of peroxides and azo compounds.

Independent of temperature, reactions can be conducted even
at a very low temperature.
Narrow wavelength light used, better control of polymerization.
Reaction can be stopped simply by removing the light source.

O OH O OH
Ph C CH Ph Ph C
. + CH Ph
.

O O O
.
Ph C C Ph 2 Ph C
 Propagation

head-to-tail
H H
H
.
R CH2 C. + CH2 CH R CH
2
C CH
2
C

Y
Y Y Y

head-to-head
H H H
.
R CH2 C. + CH2 CH R CH2 C C CH2

Y Y Y
Y (not favorable due to steric repulsion)
 Termination
H H

CH2 C C CH2
H H Y Y
. .C Coupling
CH2 C + CH2

Y Y

CH CH + CH2CH2
Y Y

Disproportionation

H H
when relatively high
. CH2 initiator or viscosity level
CH2 C + .R CR

Y
Y
 Chain Transfer
Transfer of reactivity from the growing polymer chain to
another species. Results in broad molecular weight
distribution.Transfer takes place to monomer, initiator or
solvent.
ROOR
CH2 CHOR + RO
.
H
. Y
CH2 C
CH2 CHY .
Y CH2 CY + CH2 CH2

Y
Telomers: Small sized polymers formed(DP = 1-5) when rate of transfer is
much higher than rate of propagation

Chain transfer to polymer: branched polymer

H Mx
. . M
Mx + CH2 C Mx-H + CH2 C
CH2 C
Y Y
Y
Living Polymerization: No chain transfer or termination takes place.
Radical chain ends remain active when all the monomers is used up.
Addition of more monomer results in a further increase in molecular
weight. All the chains grow to approximately the same length and the
polydispersity is approximately 1.
Initiation
ki
I
kd
2R. R. + M M1.

-d[I]
= kd[I] [I]= [I]0e-kdt log([I]/[I]0)=kdt
dt

-d[R.]
= 2kd[I]
dt

d[M.]
= 2fkd[I] = Ri
dt

f = Radicals that initiate a polymer chain

Radicals formed from initiator
Propagation

kp
M1. + M M2.

kp
M2. + M M3.

kp
Mx. + M Mx+1.

-d[M] .]
Rp = = kp[M][Mx
dt
Termination
ktc Mx+y

Mx. + My.
ktd
Mx + My

Rt -d[M.] . 2
= = 2kt[Mx ] (assuming two radicals are consumed)
dt
Kt= ktc + ktc
Under the steady state condition:

2fkd[I] = 2kt[M.]2

[M.] = (
fkd[I]
)1/2
kt
(kinetic chain length) kp[M] Rp
 = =
2kt[M.] Rt

DP =  (termination by disproportionation)
DP = 2 (termination by coupling)
 Inhibition and retardation

Polymerization Suppressors

(a) (c)

(b)

Time

(a) reaction without additives; (b) reaction in the presence of a

retarder; (c ) reaction in the presence of an inhibitor
Same substance can act as an inhibitor or retarder, depending on the
concentration of the substance
Inhibitor prevents premature polymerization e.g. alkylated phenol is
added to vinyl monomer during shipment

oOH.
OH
R R
. + R R
R’H +
R’

R
R

R’
.

Monomer must be distilled before use to remove OR’

OH

the initiator. Inhibition is common with purified R R

monomer because of the presence of oxygen

R
Gel effect/Trommsdorff effect/Norris-Smith
effect/Autoaccelaration: Reaction rate increases with conversion. In
the viscous medium,chain mobility is reduced hence the probability of
termination decreases but the small molecules diffuse in for
polymerization and there is a marked increase in polymerization rate.

Potential hazard-exlosion-efficient stirring

recomemded
autoaccelaration

time
 Thermodynamics of Radical Polymerization

ΔG = ΔH - TΔS

ΔH is negative, formation of σ bond from  bond is exothermic

ΔS is negative
However ΔH > ΔS, ΔG is negative and polymerization is
thermodynmically feasible
With increase in temperature ΔG becomes more negative and
depolymerization takes place
Temperature at which ΔG =0 : ceiling temperature

Ceiling temperature:
kp
Mx. + M Mx+1.
Kdp : dispropagation constant
kdp
Mx. + M Mx+1.

-d[M]
= kp[M][Mx.] - Kdp[Mx.]
dt

Reaction will cease if d[M]/dt is zero

Kdp = kp[M] Temperature Tc at which these
two terms are equal is called
ceiling temperature
 Polymerization of dienes:
Isolated diene: act as cross-linker

= =

Conjugated dienes: undergo polymerization, give cis or trans

product
CH2=CH-CH=CH2

H CH2----
C=C
-----CH2 H

trans