Division of Chemistry & Biological Chemistry

School of Physical and Mathematical Sciences

Chapter 3 Radical Polymerization

3.1 Introduction – Chain-growth polymerization

3.1 Introduction – Radical polymerization

3.2 Chemistry of radical polymerization

3.2.1 Initiation & the kinetics
3.2.2 Propagation & the kinetics
3.2.3 Termination & the kinetics
3.2.4 Chain Transfer

3.3 Kinetics of radical polymerization

3.3.1 Number-average degree of polymerization
(kinetic chain length)
Xing Yi LING, CBC, NTU 1
 2.1 Introduction
Modern polymerization classification

Polymerization

Step Chain growth

polymerization polymerization

Radical
polymerization

Ionic
polymerization
 3.1 Introduction – Chain-growth polymerization
• Monomers are bifunctional units.

• Long polymer chains are readily obtained from monomers e.g.

vinylidene compounds with general structure of CH2=CR1R2.

• The special reactivity of π-bonds in the carbon to carbon

double bonds make them susceptible to rearrangement if
activated by free-radical or ionic initiators.

• Active center created by chain growth polymerization

propagates a kinetic chain, which leads to the formation of a
single macromolecules.

• The reaction is stopped when the active center is neutralized

by termination reaction.

Xing Yi LING, CBC, NTU 3

 3.1 Introduction – Chain-growth polymerization
3 distinct stages of chain growth polymerization:
1. Initiation
– when the active center is created. It acts as a chain carrier.

2. Propagation
– involves growth of the macomolecular chain by a kinetic chain
mechanism.
– It is characterized by a long sequence of identical events,
namely repeated addition of a monomer to the growing chain

3. Termination
– The kinetic chain is brought to a halt by neutralization or
transfer of the active center.

Xing Yi LING, CBC, NTU 4

 3.1 Introduction – Chain-growth polymerization
• Polymerization in chain-growth polymerization occurs only at the
reactive end of a growing chains.

• The chain length increases rapidly from the early stage of

reaction.

• Typically, the polymer formed from chain-growth has the same

chemical composition as the monomer.

• Each unit in the chain is a complete monomer, and no residue.

Xing Yi LING, CBC, NTU 5

 3.1 Introduction – Chain-growth polymerization
Choice of initiators
• Three general categories of initiators: free radical, cationic, and
anionic initiators.
• Choice of the most appropriate initiators depends largely on the
group R1 and R2 in the monomer (CH2=CR1R2) and their effects on
the double bond.
• It depends on the ability of the alkene π-bond to react in a different
way with each initiator to produce either heterolytic (I) or homolytic
(II) fission.

Heterolytic Homolytic
(I) (II)

Xing Yi LING, CBC, NTU 6

 3.1 Introduction – Chain-growth polymerization
Choice of initiators
• In most olefinic monomers of interest group R1 is either H
or CH3. For simplicity, we can consider it to be H.

• The group R2 is classifiable as an electron-withdrawing

group,
δ+ δ-

– In general, electron withdrawing substituents, -CN, -COOR,

-CONH2, reduce the electron density at the double bond, and
favor propagation by an anionic initiator.

Xing Yi LING, CBC, NTU 7

 3.1 Introduction – Chain-growth polymerization
• Or, the group R2 is classifiable as an electron donating group:

δ- δ+

– The electron donating groups tend to increase the double bond

nucleophilicity by donating electrons, such as alkenyl, alkoxyl, and
phenyl groups.
– Electron donating groups encourage attack by cationic initiator.

• For homolytic initiator, the free radical is electrically neutral.

Therefore it is less selective and more generally used as initiator.

Xing Yi LING, CBC, NTU 8

 3.1 Introduction – Radical Polymerization
• Free radicals: independent existing species that possess an
unpaired electron
• e.g. carbon-based free radical with sp2 hybridization

≡ ≡

• Radical polymerization:
– Most widely used and versatile
– Polymerization for unsaturated monomers (with C=C bonds)
– The π bonds in the C=C makes them susceptible to
rearrangement if activated by free radicals or ionic initiators.
– Almost all unsaturated monomers can be subjected to such form
of chain polymerization

Xing Yi LING, CBC, NTU 9

 3.1 Introduction
• Radical polymerization:
– Each polymer molecule grows by sequential additions of
molecules of unsaturated monomers to a terminal free-radical
reactive site, “reactive centre”
– The growing chain radical attacks the π-bond of a molecule of
monomer, causing it to break homolytically
– The growth of the macromolecule is stopped when the active
centre is neutralized by a termination reaction.

New active
radical centre
transferred to
the new chain
end
New bond to
the methylene
(CH2)

Xing Yi LING, CBC, NTU 10

 3.2 Chemistry of radical polymerization
• 3 basic reaction stages in radical polymerization
1. Initiation – when active center is created
2. Propagation – involving growth of polymer chain,
characterized by the repeated addition of monomer to
growing chain
3. Termination – the chain growing is brought to a halt by
neutralization or transfer of the active center.

• Used widely for polymerization of the following monomers:

– CH2=CR1R2,
– CH2=CXY (1,1-disubstituted monomer),
– CHX=CHY (1,2-disubstituted monomer).

Xing Yi LING, CBC, NTU 11

 3.2 Chemistry of radical polymerization
1. Initiation

2. Propagation

3. Termination
 3.2.1Initiation
• Involves creation of free-radical active centre

– Step 1: formation of a free radicals (R•) from an initiator

– Step 2: addition of one of these free radicals to a molecule
of a monomer

Initiator → R • (Step 1)

R• + CH = CHY → RCH − CHY • (Step 2)

Xing Yi LING, CBC, NTU 13

 3.2.1 Initiation
Step 1: Formation of a free radical from an initiator
• Two principal ways to form free radicals:
(1) Homolysis scission
– Chemical dissociation of a single bond, in which the two bonding
electrons go one each other onto the two atoms associated with the
original bond

(2) Single-electron transfer process

– Transfer of a single electron to or form an ion or molecules (e.g. in
redox reactions)

Xing Yi LING, CBC, NTU 14

 3.2.1 Initiation
Step 1: Formation of a free radicals from an initiator
1. Homolysis scission
– “Thermolysis”
• Bond scission upon heat (∆),
• Many compounds contain weak bond which undergo thermolysis at useful
rate > 50 oC.

Peroxide ∆
group

∆
Azo group

R1 and R2: can be aromatic, alkyl, or H

Xing Yi LING, CBC, NTU 15

 3.2.1 Initiation
1. Homolysis scission – Thermolysis
– Peroxides (ROOR) and hydroperoxides (ROOH) are most widely used.
They are thermally unstable and decompose into radicals at a
temperature.
– Most commonly used peroxide: benzoyl peroxide
– e.g.

Further breakdown

Xing Yi LING, CBC, NTU 16

 3.2.1 Initiation
1. Homolysis scission
• “Photolysis” – homolysis by action of radiation
– Use of photochemical initiator that decompose efficiently when exposed
to ultraviolet radiation.
– Formation of free radicals begins at the instant of exposure, and
ceases as soon as the light source is removed.

hν

Benzophenone Benzoyl Phenyl

radical radical

hν

Benzoin alkyl Benzoyl Alkoxybenzyl

ether radical radical
(R = alkyl)
Xing Yi LING, CBC, NTU 17
 3.2.1Initiation
Step 1: Formation of a free radical from an initiator
2. Single-electron transfer process
• “Redox reactions”
– Used for radical polymerization at low temperature (T < 50 oC)

Cumyl Ferrous Cumyloxy Hydroxyl Ferric

hydroperoxide ion radical ion ion

– Same can be apply for all peroxide and hydroperoxide

R-O-O-R + Fe2+ R-O• + RO- (alkoxide ion) + Fe3+

– Or, Use of Co2+

R-O-O-R + Co2+ R-O• + RO- + Co3+
Xing Yi LING, CBC, NTU 18
 3.2.1Initiation
2. Single-electron transfer process
• “Redox reactions”
– Inorganic redox system
– e.g.

Persulphate Bisulphite
ion ion

Sulphate Sulphate Bisulphite

ion radical-ion radical

Xing Yi LING, CBC, NTU 19

 3.2.1 Initiation
Step 2: Addition of one of these free radicals to a molecule of a
monomer
– Active centre is created. The free radical R• attacks the π-bond of a
molecule of monomer via the same chemistry of monomer addition.

(I)

(II)

– Mode (I) predominates because the attack at the methylene (CH2)

carbon is less steric hindered, and yield a product radical that is more
stable.

Xing Yi LING, CBC, NTU 20

 3.2.1 Initiation
• Not all radicals forms from initiators are to react with
monomer. Some are lost in side reactions.
• e.g. Induced decomposition

Do not take part in the polymerization reaction!!

The efficiency of initiator may not be 100%

Xing Yi LING, CBC, NTU 21

 3.2.1 Initiation – the kinetics
d[I ]
Rate of consumption of Initiator −
dt
• For peroxides and azo compounds:

I → 2 R •
d[I ]
− =k d [ I ]
dt
Where kd = rate constant for homolytic decomposition of initiator
[I]
I = concentration of initiator

• For redox systems:

d[I ]
− = k [Ox ][ Red]
dt

• For photochemical initiation:

d[I ]
− = φ ' I abs
dt
Where φ’ = quantum yield
Iabs = the intensity of the light absorbed
Xing Yi LING, CBC, NTU 22
Example:
Calculate the half-time of benzoyl peroxide in benzene at 66 oC given that the rate
coefficient kd for dissociation of this initiator under these conditions is 8 × 10-6 s-1. What
will be the change in initiator concentration after 1 hour at 66 oC? Comment on the values
obtained.
 3.2.1 Initiation – the kinetics
• Rate Ri of formation of active centers:

kd
I 2 R

d [R• ] f = Initiator efficiency

Ri = == 2 f k d [I ] kd = Rate coefficient for
dt initiator dissociation

Concentration of reactive radicals

f =
Concentration of decomposed radicals

Radicals incorporated into polymer

=
Radicals formed by initiator
 3.2.2 Propagation
• Growth of polymer chain by rapid sequential addition of
monomer to the active centre
• Duration of each monomer addition: ~ milisecond; hence
several thousands of addition within a few seconds

Xing Yi LING, CBC, NTU 26

 3.2.2 Propagation

(I)
Head-to-tail addition

(II)

Head-to-head addition

• Mode (I) – Head-to-tail addition dominates. Why?

• If head-to-head addition occurs, it will followed immediately by a

tail-to-tail addition to generate a more stable active centre, which
will continue to propagate via head-to-tail addition.

Xing Yi LING, CBC, NTU 27

 3.2.2 Propagation

• Mode (II) only contributes significantly for the few monomers, for
which X is small (similar size to H atom).

• For general description of radical polymerization, it is reasonable to

neglect mode (II), and assume propagation proceeds exclusively by
mode (I) head-to-tail addition.

Xing Yi LING, CBC, NTU 28

 3.2.2 Propagation – the kinetics
• k
• Propagation:
p
M i + M  → M •i +1

– Assume rate of coefficient kp for propagation is independent of the length of

the growing chain:
– Given that long-chain polymer molecules are formed
– Amount of monomer consumed in the initiation stage is negligible to that
consumed by propagating chains

– Rate of consumption of monomer:

d [M]
− = k p [ M ][ M1• ] + k p [ M ][M •2 ] + ... + k p [ M ][M •i ] + ...
dt

−
d [M]
dt
( )
= k p [ M ] [ M1• ] + [M •2 ] + ... + [ M i• ] + ..

Σ [M ]
• ∞ •
If [M•] is the total concentration of all radical species, i.e. [M ] = i =1 i

d [ M]
Rp = − = k p [M ][ M • ]
dt
Xing Yi LING, CBC, NTU 29
 3.2.3 Termination
• The active centre is destroyed irreversibly and propagation
ceases.

• Chain termination can take place by:

1. Combination/ coupling
– interaction of two active chain ends
– most common route

2. Disproportionation
– interaction of an active chain end with an initiator radical

Xing Yi LING, CBC, NTU 30

 3.2.3 Termination
• Type 1: Combination
– Coupling together two growing chains to form a single polymer molecule

– Single dead polymer molecule (with degree of polymerization = x + y)

– Radical coupling reaction at “head-to-head” linkage, with initiator
fragment (the R groups) at both chain ends

Xing Yi LING, CBC, NTU 31

 3.2.3 Termination
Type 2: Disproportionation
– Abstraction of a hydrogen atom from the penultimate C atom of one
growing chain radical by another,
– And the remaining electron from the C-H bond joining the unpaired
electron on the terminal C atom to form a terminal π-bond.

– 2 dead polymers are formed, with degree of polymerization x and y

respectively.
– One with saturated end group, the other with unsaturated end group.
both with an initiator fragment at the other chain end.
Xing Yi LING, CBC, NTU 32
 3.2.3 Termination
• Depends on the monomer and polymerization conditions.

• Polystyrene, poly vinyl (CH2=CHX) chain radicals terminate

mainly by combination.

• Poly(methyl methacrylate), α-methylvinyl (CH2=C(CH3)X) chain

radical terminate dominantly by disproportionation, especially T >
60 oC.

– For poly(methyl methacrylate), X =

Xing Yi LING, CBC, NTU 33

Example:
Write down a reaction scheme for polymerization of styrene initiated by thermolysis of
azobisisobutyronitrile, including both combination and disproportionation as possible
modes of termination.
 3.2.3 Termination – the kinetics
– Termination ktc Pi + j
ktc : rate of coefficients for combination
• •
Mi + M j ktd : rate of coefficients for
disproportionation
k td P j + Pj

• Rate of consumption of radicals:

d [M • ]
−
dt
[ ][ ]
= 2k tc M • M • + 2k td M • M • [ ][ ]
Because 2 growing chains are being consumed by
each termination

d [M • ]
Rt = − = 2k t [M • ]2 Where kt = ktc + ktd
dt
• Rate of polymerization:
d [ Pi + j ] • 2 or d [ Pi + Pj ]
= k tc [ M ] = 2k tc [ M • ]2
dt dt
Xing Yi LING, CBC, NTU 36
 3.2.4 Chain transfer
• The active centre is transferred from the active chain to
another species in the polymerization

• Or:

• Chain radical abstract T (often H or halogen) from TA by

homolytic scission to yield a dead polymer molecule and
radical A•.

Xing Yi LING, CBC, NTU 37

 3.2.4 Chain transfer
• 3.2.4.1 Chain transfer with small molecules
– Chain transfer can occurs with molecules of initiator, monomer, solvent,
and deliberately added transfer agent.
– Chain transfer reaction leads to death of a propagating chain

Type 1: Chain transfer to initiator, e.g. peroxide

t-butyl peroxide

Type 2: Chain transfer to monomer, e.g. vinyl acetate

Skeletal
structure of
Xing Yi LING, CBC, NTU
the polymer? 38
 3.2.4 Chain transfer
3.2.4.1 Chain transfer with small molecules

Type 3: Chain transfer to solvent, e.g. toluene

Type 4: Chain transfer to transfer agent, e.g. carbon tetrabromide

Xing Yi LING, CBC, NTU 39

 3.2.4 Chain transfer
• Free radical is NOT destroyed in the chain transfer reaction; it is
merely transferred.
• The process terminates the chain, but at the same time generates a
new radical. If the new species is sufficiently active, another chain
will emanate from the new center.
• Chain transfer results in lower molar mass of polymer product.

3.2.3.2 Chain transfer to polymer

• Major effect on skeletal structure and properties of polymers
• Formation of branched polymer molecules

Xing Yi LING, CBC, NTU 40

 3.2.4 Chain transfer
• Type 1: Intramolecular chain transfer (back-biting reactions)
- Short chain branches; e.g. polyethylene, produced by high-pressure
free radical polymerization.
- Formed by backbiting involving 5- or 6- membered cyclic transition
states.
Lower degree of crystallinity (~ 45% onwards)
Lower melting point (105 – 115 oC, Compared to linear polyethylene (135
– 140 oC)

Xing Yi LING, CBC, NTU 41

 3.2.4 Chain transfer
3.2.4.2 Chain transfer to polymer
Type 2: Intermolecular chain transfer
e.g. polyethylene

Xing Yi LING, CBC, NTU 42

 3.2.4 Chain transfer
3.2.4.2 Chain transfer to polymer
Type 2: Intermolecular chain transfer

e.g. poly(methyl methacrylate)

• H abstraction from tertiary
C-H backbone
• Tertiary radical is more
stable

Xing Yi LING, CBC, NTU 43

 3.2.4 Chain transfer
3.2.4.2 Chain transfer to polymer
Type 2: Intermolecular chain transfer

e.g. Poly(vinyl acetate)

Product radical from H-

abstraction at a methyl group
is stabilized by electron
delocalization with carbonyl π-
bond

Xing Yi LING, CBC, NTU 44

Example:

State the differences between step and chain polymerization.

45
 3.3.1 Rate of polymerization
• At Steady state,
– Rate of radical formation ≈ Rate of [M•] loss by termination
– The net of change of [M•] = 0, the reaction is under steady state

d [R • ] d [M • ] ⇒ Ri = Rt
=−
dt dt

Ri = 2kt [M• ]2
1/ 2
 R 
[M• ] =  i 

 2kt 

– The steady-state rate of polymerization

1/ 2
d [M • ]  R 
Rp = − = k p [M ] i 

dt  2k t 

Xing Yi LING, CBC, NTU 47

 3.3.1 Degree of polymerization
• Number-average degree of polymerization xn

Moles of monomer consumed in unit time

xn =
Moles of polymer formed in unit time
− d [M] /dt
=
d [ Pi + j ] / dt + d [ Pi + Pj ] / dt
k p [ M ][ M • ]
=
k tc [ M • ]2 + 2k td [ M • ]2

Xing Yi LING, CBC, NTU 48

 3.3.1 Degree of polymerization
• Number-average degree of polymerization
1/ 2
 Ri 
Q q = k td / k t and Q [M ] = 
•


 2k t 

k p [M ] In absence of chain transfer

(xn )o =
[ M • ]k t (1 + q)

k p [M ]
=
k t (1 + q )( Ri / 2k t )1/ 2

k p [M ]
=
(1 + q )k t 1/ 2 ( Ri / 2)1/ 2
 3.3.1 Degree of polymerization
• Kinetic chain length, ν
– The average number of repeat units added to a single chain radical prior
to termination.
@ Steady rate of propagatio n Rp Rp
ν = = =
state: rate of terminatio n Rt Ri

− d [M] /dt
=
− d [M• ] / dt

k p [ M ][ M • ]
=
2k t [ M • ]2

k p [M ]
= • ( [M•] = (Ri/2 kt)1/2 )
2k t [ M ]

k p [M ] k p [M ]
= = (Ri = 2 f kd [I])
2k t 1/ 2 1/ 2
( Ri / 2) 2( f k t k d [I ])
1/ 2
Xing Yi LING, CBC, NTU 50
 3.3.1 Degree of polymerization
k p [M ]
ν =
2k t 1/ 2 ( Ri / 2)1/ 2

k p [M ]
(xn )o =
(1 + q)k t 1/ 2 ( Ri / 2)1/ 2

 2 
(xn )o =   ν
1+ q 

Q q = k td / k t = fraction of termination reactions that is proceeded by disproportionation

(xn )o = ν (xn )o = 2 ν
Termination is exclusively by Termination is exclusively by
disproportionation combination
Example:
(a) Calculate the concentration of benzoyl peroxide required to prepare polystyrene with
number-average molar mass of 750 kg mol-1 by bulk polymerization at 60 oC. Assume (i)
the initiator is 60 % efficient; (ii) the rate coefficients for initiator dissociation,
propagation, and terminations are 2×10-6 s-1, 341 dm3 mol-1 s-1, and 4 ×107 dm3mol-1s-1,
respectively; (iii) the density of styrene at the polymerization temperature is 0.88 g cm-
3; and (iv) that termination by disproportionation, and chain transfer to initiator and

monomer, are negligible.

(b) Calculate initial values of

(i) The radical concentration and
(ii) The rate of bulk polymerization expected for bulk polymerization of styrene at the
concentration of benzoyl peroxide determined in (a).
Xing Yi LING, CBC, NTU 53
Xing Yi LING, CBC, NTU 54
Xing Yi LING, CBC, NTU 55
 Chapter 3 Exercises
Q 3.1
The decomposition of azobisisobutyronitrile (AIBN) in xylene at 77
oC was studied by measuring the volume of N evolved as a
2
function of time. The volumes obtained at time t and t = ∞ are Vt and
V∞, respectively. Show that the manner of plotting used in the figure
(in next page) is consistent with the integrated first-order rate law.

Evaluate kd.

azobisisobutyronitrile

Xing Yi LING, CBC, NTU 56

3.1 (Continued)

0.2

0.0
)

-0.2
∞
Log (1- Vt / V

-0.4

-0.6

-0.8

0 50 100 150 200 250 300 350

Time (min)
 Q 3.2
Write down the mechanism for the free radical polymerization of
vinyl-acetate initiated by 2,2’-azobis(2,4-dimethylpentanenitrile)
in ethyle acetate including (a) initiation, (b) propagation, and (c)
termination by disproportionation.

Xing Yi LING, CBC, NTU 58

Q 3.3
14.45 g of methyl methacrylate were polymerized at 50 oC for 55
min using 0.2096 g of α,α’-azobisisobutyonitrile (AIBN) as initiator,
to give 1.6826 g of polymer. Radioactivity assay indicated that the
polymer sample contained 7.07 × 10-4 g of azobisnitrile.

Consider that the first-order rate constant for the decomposition of

AIBN is given by:
−7019
log k / min −1 = + 17.806
T

Calculate the initiator efficiency. The number-average molecular

weight of this polymer was found to be 390,000. Establish whether
the termination reaction takes place by combination or
disproportionation of growing chains.
 Q 3.4
Consider the free-radical polymerization of methyl methacrylate in
toluene solution at 77 oC, initiated by azobisisobutyronitrile (AIBN).
When the initial monomer concentration was 2.07 M and the initial
AIBN concentration was 2.11 x10-4 M, the initial rate of polymerization
was determined to be Rp = 2.49 x10-3 M min-1.

(a) Determine the initial rate of initiation (Ri), and kp/(kt)½ by

considering that the rate constant for the decomposition of AIBN at
77 oC is kd = 5.7x10-3 min-1, and that virtually all radicals are
capable of initiating chains.

(b) Determine the initial kinetic chain length and the expected number-
average molar mass assuming only termination mainly takes place
by combination.

Xing Yi LING, CBC, NTU 60

Q 3.5
The efficiency of AIBN in initiating polymerization at 60 oC was determined by
the following strategy. They measured Rp and ν, and calculated Ri = Rp/ν.
The constant kd was measured directly in the system, and from this
quantity and the measured ratio Rp/ν, the fraction f could be
determined. The following results were obtained from different
concentration of initiator:

[I] (g/L) ν (mol L-1s-1)

Rp/ν
0.0556 0.377 × 10-8
0.250 1.57 × 10-8
0.250 1.72 × 10-8
1.00 6.77 × 10-8
1.50 10.9 × 10-8
2.50 17.1 × 10-8