Chapter 6.

Free Radical Polymerization

6.1. Introduction
Table 6. 1 Commercially Important Vinyl Polymers

6. 2 Free Radical Initiators

Four types

Peroxides and hydroperoxides

Azo compounds

Redox initiators
Photoinitiators
6.2.1. Peroxides and Hydroperoxides
( ROOR ) ( ROOH )
Thermal homolysis
O O O
Ph C O O C Ph 2 Ph C O
∆
Decomposition
O

Ph C O Ph + CO2

Radical combination Wastage reaction ∵ Cage effect

2 Ph Ph Ph
(confining effect of solvent molecules)
O O
Ph C O + Ph Ph C O Ph

Induced decomposition Wastage reaction

O O O Ph O
Ph C O O C Ph + Ph Ph C O O C Ph
O O

Ph C O Ph + O C Ph
Radical stability
CH3 CH3 O O

Ph C O > CH3 C O > Ph C O > CH3 C O

CH3 CH3 Unstable radical

Stable radical
More wastage reaction
Less wastage reaction

Half-lifes
BPO (Benzoyl peroxide)
CH3 CH3
O O
CH3 C O O C CH3
Ph C O O C Ph
CH3 CH3

1.38 h at 145oC 1.4 h at 85oC

CH3
O O
Ph C O O H
CH3 C O O C CH3
CH3

1.7 h at 130oC 1.1 h at 85oC

 Promoters
O O CH3
Ph C O O C Ph + Ph N
CH3

CH3 O O
+ -
Ph N O C Ph + Ph C O
CH3

CH3 O
+ O C Ph
Ph N +
CH3

No initiation of polymerization Initiation of polymerization

∵ No N in polymers
6.2.2. Azo Compounds

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

AIBN (Azobisiso(butyronitrile))

Radical combination
CN CN
CN (CH3)2C C(CH3)2
2 (CH3)2C
CN
(CH3)2C C N C(CH3)2

C N C N
(CH3)2C (CH3)2C
6.2.3. Redox Initiators

Production of free radicals by one–electron transfer reactions.

Useful in low–temp polymerization and emulsion polymerization

OOH O
-
Ph C(CH3)2 + Fe2+ Ph C(CH3)2 + OH + Fe3+

- 3+
HOOH + Fe2+ HO + OH + Fe

- O SOOSO - - -
3 3 + S2O32- SO4 + SO42- + S2O3

Radicals in aqueous phase

6.2.4. Photoinitiators

hν
RSSR 2 RS

O OH O OH
hν
Ph C CH Ph Ph C + CH Ph
O O O
hν
Ph C C Ph 2 Ph C

The major advantages of photoinitiation:

The reaction is essentially independent of temp
Polymerization may be conducted even at very low temperatures
Better control of the polymerization reaction
The reaction can be stopped simply by removing
the light source
6.2.5. Thermal Polymerization

CH2 CH

CH2 CH CH3 CH
2
∆ +

H
Ph Ph

Diels-Alder dimer

Transfer of H atom to monomer

Molecule-induced homolysis

Rapid formation of radicals by reaction of nonradical species

6.2.6. Electrochemical Polymerization

_
RCH CH2 + e- RCH CH2

+
RCH CH2 + e-
RCH CH2

Radical ions : initiate free radical or ionic polymerization or both

Particularly useful for coating metal surfaces with polymer films

6. 3 Techniques of Free Radical Polymerization Techniques

Method Advantages Disadvantages

Bulk Simple Rxn exotherm difficult to control

No contaminants added High viscosity

Suspension Heat readily dispersed Washing and drying required

Low viscosity Agglomeration may occur
Obtained in granular form Contamination by stabilizer

Solution Heat readily dispersed Added cost of solvent

Low viscosity Solvent difficult to remove
Used directly as solution Possible chain transfer with solvent
Possible environmental pollution

Emulsion Heat readily dispersed Contamination by emulsifier

Low viscosity Chain transfer agents often needed
High MW obtainable Washing and drying necessary
Used directly as emulsion.
Works on tacky polymers
6. 4 Kinetics and Mechanism of Polymerization
Initiation Formation of the initiator radical
Addition of the initiator radical to monomer
Initiator R
R + CH2 CH R CH2 CH

Y Y
Propagation
CH2 CH + CH2 CH CH2 CH CH2 CH

Y Y Y Y

Coupling or combination
Termination
CH2 CH HC H2C
CH2 CH + HC H 2C
Y Y
Y Y

Disproportionation
CH CH + H2C H 2C

Y Y
Coupling almost exclusively at low temp Polystyrene
CH2 CH + HC H 2C CH2 CH HC H 2C

Disproportionation
PMMA
CH3 CH3 CH3 CH3
CH2 C + C H 2C CH C + HC H2C

C O O C C O O C

OCH3 OCH3 OCH3 OCH3

∵ Steric repulsion
Electrostatic repulsion
Availability of α H for H transfer PMMA 5; PSt 2
 kd
Initiation Initiator R
ki
R + M M1
Propagation
kp
M1 + M M2
kp
M2 + M M3

kp
Mx + M M(x+1)

Termination
ktc
Mx + My M(x+y) Coupling

ktd
Mx + My Mx + My Disproportionation
Initiation rate (Ri)
d[M •]
Ri = = 2fk d [I]
dt
where
[M•] = total conc of chain radicals
[I] = molar conc of initiator
f = initiator efficiency = 0.3 ~ 0.8
Termination rate (Rt)
d[M •]
Rt = − = 2k t [M •]
2

dt

Steady-state assumption Ri = Rt
fk d [I]
2 fk d [I] = 2k t [M •] [M •] =
2
kt
Propagation rate (Rp)
d[M] fk d [I]
Rp = − = k p [M •][M] = k p [M] Rp ∝ [I], [M]
dt kt
Average kinetic chain length (ν )

= Average # of monomer units polymerized per chain initiated

Rp Rp k p [M •][M] k p [M] k p [M]

ν= = = = =
Ri Rt 2k t [M •]
2
2k t [M •] 2(fk t k d [I])
1
2

DP = ν Disproportionation

2ν Coupling
• Gel effect, Trommsdorff effect, Norris-Smith effect

Occurs in bulk or concentrated solution polymerizations

η↑ Chain mobility↓ Rt ↓ [M•] ↑

Rp ↑ Release of more heat Ri ↑ Rp ↑

Autoacceleration Explosion
Polymerization of MMA in benzene 50°C benzoylperoxide

Gel effect
• Chain transfer reactions
Transfer of reactivity from the growing polymer chain
to another species

1) C.T. to Polymer
Chain-end radical abstract a H atom from a chain
Chain branching
2) Backbiting : intramolecular chain transfer

3) C.T. to Initiator or Monomer

Important with monomers containing allylic hydrogen,

such as propylene
Resonance-stabilized radical

Reactive radical

∴ High-mol-wt polypropylene cannot be prepared

by free radical polymerization
 CH3 CH3
CH2 C + CH2 C allylic hydrogen

COOCH3 COOCH3
Propagation C.T. to monomer
CH3 CH3
CH3 CH2
CH2 C CH2 C
CH2 CH + CH2 C
C OCH3
COOCH3
COOCH3 COOCH3
O

CH3 CH3 CH2

CH2 C CH2 C CH2 C
C OCH3
COOCH3 COOCH3
O
Resonance-stabilized radical Resonance-stabilized radical

∴ High-mol-wt PMMA can be prepared by free radical polymerization

4) C.T. to Solvent or Chain transfer agents

CCl4

Thiol (RSH)
Transfer reaction rate
R tr = k tr [M •][T ]
where T = transfer agent
Kinetic chain length
k p [M] w/o transfer agent
ν=
2k t [M •]
Rp k p [M •][M] k p [M]
ν tr = = =
R t + R tr 2k t [M •]2 + ∑ k tr [M •][T ] 2k t [M •] + ∑ k tr [T ]
with transfer agent
1 2k t [M •] + ∑ k tr [T ] 1 ∑ k tr [T ] 1 ∑ C [T ]
= = + = + T

ν tr k p [M] ν k p [M] ν [M]

k tr
= CT Chain transfer constant
kp
1 1
= +
∑ C [T ]
T

ν tr ν [M]
Table 6.5 CT for St and MMA

Benzene Strong C-H bond Low CT

Toluene Benzylic H Higher CT
CHCl3
Resonance stabilization
CCl4 CCl3• C T↑
CBr4 CBr3•
RSH Weak S-H bond Large CT

When [T] is high, ktr >> kp ⇒ Very-low-mol-wt polymer

Telomerization Telomer

CH3 CH2 CH2 CH2 CH2

-H

Cl C Cl Cl C Cl Cl C Cl Cl C Cl

Cl Cl Cl Cl
ο Inhibitors
Added to monomers to prevent polymerization
during shipment or storage
Must be removed by distillation of monomer or extraction

Alkylated Phenol
OH . O
O O
R R R R R R R R
R' . + R'H + .

.
R R R R

OR' O O
R' .
R R R R R R
+ 'R +

R R'
R R
 Inhibitor

No inhibitor

% Polymerization

More inhibitor

0 Time
Induction period

Induction periods are common even with purified monomer

because of the presence of oxygen, which is, itself, an inhibitor.
ο Living free radical Polymerization
No chain termination or chain transfer
o Atom Transfer Radical Polymerization (ATRP)
Polymerization of styrene
Transfer of Halogen atom
CH3CHCl + Cu(I)(bpy) CH3CH . + Cu(II)(bpy)Cl

Ph Ph

Preventing radical termination H2C CH propagation

reactions from occurring Ph

CH3CHCH2CH .
CH3CHCH2CHCl + Cu(I)(bpy) + Cu(II)(bpy)Cl
Ph Ph
Ph Ph

bpy = bipyridyl =

N N
o Addition of a Stable Free Radical

CH3 CH3
H3C H3C
. + .
CH2CH O N CH2CH O N
Ph Ph
H3C H3C
CH3 CH3

TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy)
Too stale to initiate polymerization
Promotes decomposition of BPO to
benzoyloxy radicals
Propagation Prevent termination

DP =
[M]o
[I]o
All the chains are initiated at about the same time.
No chain termination or transfer reactions.
The chains all grow to approximately the same length.
Polydispersity is low.
ο Emulsion Polymerization

Smith-Ewart kinetics ⎛ N⎞
R p = k p [M]⎜ ⎟
⎝2⎠
where [M] = concentration of monomer in the polymer particle
N = # of polymer particles
Rate of radical entry into the particle
Ri
ρ=
N
Average kinetic chain length
k p [M] k p [M] k p [M]N
ν= = =
ρ R i 2fk d [I]
N
DP = ν
0 .4
⎛R ⎞
N = k⎜ i ⎟ (a s [E])0.6
⎝µ⎠
where k = constant (0.37~0.53)
µ = rate of increase in the volume of a polymer particle
[E] = concentration of micellar emulsifier
as = interfacial area occupied by an emulsifier molecule
in the micelles

N ∝ [I] , [E] R p ∝ [I] , [E] DP = ν ∝ [I] , [E]

0. 4 0 .6 0.4 0 .6 − 0 .6 0. 6
6.5. Stereochemistry of Polymerization

Steric and electrostatic interactions are responsible for stereochemistry

of free radical polymerization
1) Interaction between Terminal unit & Monomer
Mirror approach
Y X. Y
C C Y X Y X . Y
CH2 CH2
X C C C
Y CH2 CH2 CH2 X etc
H C C
H X Isotactic polymer

Nonmirror approach
Y X. X
C C Y X X Y . Y
CH2 CH2
Y C C C
Y CH2 CH2 CH2 X etc
H C C
H X
Syndiotactic polymer
 2) Interaction between Terminal unit & Penultimate unit

CH3
CH3
CH2 C CO2CH3
CH2 C CO2CH3

CH3 CH3
C C
H CO2CH3 H CO2CH3
C C
H H
C C
CO2CH3 CO2CH3
P CH3 P CH3

P: bulkiest group
Syndiotactic
If terminal carbon has sp2 planar structure,
Interaction between terminal unit & monomer is dominant factor

If terminal carbon has sp3 hybridization,

Interaction between penultimate unit & terminal unit is dominant factor

Stereoregularity ↑ as T↓

Free radical polymerization of MMA at T < 0 oC

Crystalline polymer
Syndiotactic

(Expect) As size of substituent groups ↑, stereoregularity ↑

CH3
CH2 C
C O
O CH2

(Experiment) bulkier substituent

Less syndiotactic than PMMA under the same conditions

6.6 Polymerization of Dienes
6.6.1. Isolated Dienes

Cooperative addition of one double bond to the other of the monomer

Cyclic polymer

5- or 6-membered ring

Cyclopolymerization:
Formation of a cyclic structural unit in a propagation step

Independent reaction Crosslinked polymer

Cyclopolymerization of divinylformal

Head-to-tail
head-to-tailmode
mode Six-membered ring
six-membered ring

R R R
. .
R. +
O O O O O O O O

Head-to-head
head-to-tailmode
mode Five-membered
five-membered ring
ring
R .
R

O O O
O
 Diallyl monomer Highly crosslinked polymers

O
C Used for manufacturing
O electrical or electronics items
(circuit boards, insulators,
O television components, etc)
C
O preimpregnating glass cloth or fiber for
fiber-reinforced plastics
Diallyl phthalate

O O Used for applications requiring

O
good optical clarity
O 2 (eyeware lenses, camera filters,
panel covers, and the like)

Diethylene glycol bis(allyl carbonate)

6.6.2. Conjugated Dienes
. H H .
H R.
H2C CH C CH 2 RH 2C CH 2 C CH 2 RH 2C C CH CH 2
1,3-butadiene

1,2-addition 1,4-addition
cis trans
CH 2CH CH 2 CH 2 CH 2 H
CH C C C C
H H H CH 2
CH 2

Pendant vinyl groups unsaturation in the chain

20% 80%
Isoprene (2-methyl-1,3-butadiene)
CH2 C CH CH2
CH3

CH3 CH3 cis trans

CH2CH CH2CH CH2 CH2 CH2 H
CH3 C C C C C
CH
H H H CH2
CH2 CH2
3,4-addition cis-1,4-addition trans-1,4-addition
1,2-addition
Natural rubber
(Hevea) Predominant
10%
As T↑ , cis-1,4 ↑
 s-trans trans-1,4

s-cis cis-1,4 As T↑ , cis-1,4 ↑

CH2
CH
s-cis cis-1,4
C
CH2 Sn(n-C4H10)3 ~ 100% at 60oC
 Table 6.6 Structures of Free Radical-Initiated Diene Polymers

percent

Polymerization
cis-1,4 trans-1,4 1,2 3,4
Monomer Temperature(℃)
Butadiene -20 6 77 17 -
20 22 58 20 -
100 28 51 21 -
233 43 39 18 -
Isoprene -20 1 90 5 4
-5 7 82 5 5
50 18 72 5 5
100 23 66 5 6
257 12 77 2 9
Chloroprene -46 5 94 1 0.3
46 10 81-86 2 1
100 13 71 2.4 2.4
 6.7 Monomer Reactivity
kp: -C6H5 < -CN < -COOCH3 < -Cl < -OCOCH3

o Three factors in monomer reactivity

1) Resonance stabilization of free radicals: kp↓

-C6H5 > -CN > -COOCH3 > -Cl > -OCOCH3

Reactive monomer Stable monomer
Stable radical Reactive radical

Inverse relationship between monomer reactivity and kp

Radical reactivity is the major factor.
R R
R R

R +

Reactive monomer Stable radical

2) Polarization of double bond by substituents: kp↓

Extreme polarization prevents free radical polymerization

e.g.
CN CH2 CH
CH2 C No radical polymerization
OCH3
CN
Anionic Cationic polymerization

C C C C C C

Heterolytic fission Homolytic fission

3) Steric hindrance: kp↓

X CH CH CH CH
CH2 CH > CH2 C > >
Y X Y
X
kp: MMA < MA

H H
H
C
CH2 C
CH2 C H
COOCH3
COOCH3
MA
MMA

∵ Resonance stabilization of the radical by hyperconjugation and

steric hindrance

Overlap of p-orbital with σ bonds

 o Free energy of polymerization
∆Gp = ∆Hp - T∆Sp
∆H < 0 : exothermic, π-bond in monomer → σ-bond in polymer
favorable
∆S < 0 : monomer → covalently bonded chain structure
unfavorable ∴ Degree of freedom (randomness) ↓

(1) The higher the resonance stabilization of monomer, l∆Hl ↓

(2) Steric strain in polymer, l∆Hl ↓
(3) Decrease in H-bonding or dipole interaction on polymerization, l∆Hl ↓

energy Monomer Polymer

π-bond σ-bond
Resonance
Stabilization
of monomer ∆H Steric strain
Decrease in H-
bonding or dipole
interaction
Table 6.7 ∆H and ∆S of Polymerization

-△H -△S
Monomer (kJ/mol) (J/mol)
Acylonitrile 77 109
1,3-Butadiene 78 89
Ethylene 109 155
Isoprene 75 101
Methyl methacrylate 65 117
Propylene 84 116
Styrene 70 104
Tetrafluoroethylene 163 -
Vinyl acetate 90 -
Vinyl chloride 71 -
o Polymerization-depolymerization Equilibrium
kp where
Mx + M M(x+1) kdp = depropagation rate constant
kdp

kdp

kp [M]

kp [M] - kdp

Rp = Rdp

Tc T
Ceiling temperature
At Tc
k p [M •][M] = k dp [M •]

Equilibrium constant

K=
[M •] =
1
=
kp
[M •][M]e [M]e k dp
where [M]e = equilibrium monomer concentration

∆G = ∆Go + RT ln K
where ∆Go = ∆G in standard state
(pure monomer or 1-M solution monomer,
pure polymer or 1-M repeating units of polymer)
At equilibrium
∆G = 0
∆Go = ∆Ho - Tc∆So = - RTc ln K = RTc ln [M]e
∆H o ∆H o ∆S o
Tc = ln[M]e = −
∆S o + R ln[M]e or RTc R
 ∆S o
− ∆H o ∆S o
R ln[M]e = −
RTc R

ln[M]e ∆Ho
R
1

1
Tc
Table 6.8 Tc of Pure Liquid Monomers

Monomer Tc(℃)
1,3-Butadiene 585
Ethylene 610
∆H o
Isobutylene 175 Tc =
∆S o + R ln[M]e
Isoprene 466
Methyl methacrylate 198
α-Methylstyrene 66
Styrene 395
Tetrafluoroethylene 1100
CH3 CH3
CH2 C CH2 C
-△H = 35 kJ/mol

Tc = 66 oC

Resonance stabilization Steric strain in polymer

6.8 Copolymerization

Reaction Rate
k11
M1• + M1 M1• k11 [M1•] [M1]
k12
M1• + M2 M2• k12 [M1•] [M2]

k21
M2• + M1 M1• k21 [M2•] [M1]

k22
M2• + M2 M2• k22 [M2•] [M2]

where k11 and k22 : self-propagation rate constant

k12 and k21 : cross-propagation rate constant

o Steady-state assumption for [M1•] and [M2•]
k12 [M1•] [M2] = k21 [M2•] [M1]
o Rate of consumption of M1 and M2
d[M1 ] k 21 [M1 ][M2 •]
− = k 11 [M1 •][M1 ] + k 21 [M2 •][M1 ] [M1 •] =
dt k 12 [M2 ]
d[M2 ]
− = k 12 [M1 •][M2 ] + k 22 [M2 •][M2 ]
dt
o Instant composition of copolymer
d[M1 ] [M1 ] ⎛ k 11 [M1 •] + k 21 [M2 •] ⎞
= ⎜⎜ ⎟⎟
d[M2 ] [M2 ] ⎝ k 12 [M1 •] + k 22 [M2 •] ⎠
o Monomer reactivity ratio
k 11 k 22
= r1 = r2
k 12 k 21

o Copolymer (composition) equation

d[M1 ] [M1 ] ⎛ r1 [M1 ] + [M2 ] ⎞
= ⎜⎜ ⎟⎟
[
d M2 ] [ ] [ ] [
M2 ⎝ M1 + r2 M2 ⎠ ]
o Instantaneous composition of feed and polymer
f1 = mole fraction of M1 in the feed f1 = 1 − f2 =
[M1 ]
[M1 ] + [M2 ]
f2 = mole fraction of M2 in the feed
F1 = mole fraction of M1 in the copolymer d[M1 ]
F1 = 1 − F2 =
d[M1 ] + d[M2 ]
F2 = mole fraction of M2 in the copolymer

d[M1 ] [M1 ] ⎛ r1 [M1 ] + [M2 ] ⎞ d[M1 ] F1 [M1 ] = f1

=
= ⎜⎜ ⎟⎟
d[M2 ] [M2 ] ⎝ [M1 ] + r2 [M2 ] ⎠ d[M2 ] 1 − F1 [M2 ] f2

F1 f1 ⎛ r1f1 + f2 ⎞ 1 − F1 1 f ⎛f +r f ⎞
= ⎜⎜ ⎟⎟ = − 1 = 2 ⎜⎜ 1 2 2 ⎟⎟
1 − F1 f2 ⎝ f1 + r2 f2 ⎠ F1 F1 f1 ⎝ r1f1 + f2 ⎠

1 f2 ⎛ f1 + r2 f2 ⎞ r1f1 + 2f1f2 + r2 f2
2 2

= ⎜⎜ ⎟⎟ + 1 =
F1 f1 ⎝ r1f1 + f2 ⎠ r1f1 + f1f2
2

r1f1 + f1f2
2

F1 =
r1f1 + 2f1f2 + r2 f2
2 2
 F1 d[M1 ] f1 [M1 ]
F= = f= =
F2 d[M2 ] f2 [M2 ]

d[M1 ] [M1 ] ⎛ r1 [M1 ] + [M2 ] ⎞ ⎛ r1f + 1 ⎞ r1f 2 + f

= ⎜⎜ ⎟⎟ F = f ⎜⎜ ⎟⎟ =
d[M2 ] [M2 ] ⎝ [M1 ] + r2 [M2 ] ⎠
⎝ f + r2 ⎠ f + r2

fF + r F = r1f + f 2 f (1 − F) ⎛ f2 ⎞
2 = r2 − ⎜⎜ ⎟⎟r1
F ⎝F⎠
Finemann and Rose Equation
r2

f (1 − F)
F - r1

0 f2
F
 r1f1 + f1f2
2

F1 =
r1f1 + 2f1f2 + r2 f2
2 2

1) r1 = r2 = 1
No preference for homopolymerization or copolymerization
Random copolymer
F1 = f1
e.g. M1 = ethylene M2 = vinyl acetate
r1 = 0.97 r2 = 1.02

2) r1 = r2 = 0
Alternating copolymer

F1 = 0.5

e.g. M1 = styrene M2 = maleic anhydride

r1 = 0.041 r2 = 0.01
3) 0 < r1, r2 < 1

More common
e.g. M1 = styrene M2 = methyl methacrylate
r1 = 0.52 r2 = 0.46

Azeotropic copolymerization
d[M1 ] [M1 ] d[M1 ] [M1 ] ⎛ r1 [M1 ] + [M2 ] ⎞
= ⎜⎜ ⎟⎟
=
d[M 2 ] [M 2 ] d[M2 ] [M2 ] ⎝ [M1 ] + r2 [M2 ] ⎠

r1 [M1 ] + [M2 ] [M1 ] = 1 − r2 1 − r2

=1 f1 =
[M1 ] + r2 [M2 ] [M2 ] 1 − r1 2 − r1 − r2
4) 1 << r1 and r2 << 1
Essentially homopolymer
e.g. M1 = styrene M2 = vinyl acetate
r1 = 55 r2 = 0.01
M1 = styrene M2 = vinyl chloride
r1 = 17 r2 = 0.02
5) r1• r2 = 1 Ideal copolymerization k 11 k 21
=
cf. r1= r2 = 1 Real random copolymerization k 12 k 22
The more r1 and r2 diverge, the less random r1f1 + f1f2
2

F1 =
r1f1 + 2f1f2 + r2 f2
2 2
e.g. M1 = MMA M2 = vinyl chloride
r1 = 10 r2 = 0.1
r1f1 + f1f2 r1 f1 + r1f1f2 r1f1 (r1f1 + f2 )
2 2 2
r1f1
F1 = = = =
f
2
r1 f1 + 2r1f1f2 + f2
2 2 2
(r1f1 + f2 )2 r1f1 + f2
r1f1 + 2f1f2 + 2
2

r1 o
P1
o
X1 o
P1 X 1P1 P2
cf. Ideal solution = =
P1 + P2 X 1P1 + X 2P2
o o
P1
o

X1 o
+ X2
P2
 Table 6.9 Reactivity Ratios
M1 M2 r1 r2 Temperature(℃)
Styrene Methyl methacrylate 0.52 0.46 60
Styrene Acrylonitrile 0.40 0.04 60
Styrene Vinyl acetate 55 0.01 60
Styrene Maleic anhydride 0.041 0.01 60
Styrene Vinyl chloride 17 0.02 60
Styrene 1,3-Butadiene 0.58 1.35 50
Styrene Isoprene 0.54 1.92 80
Methyl methacylate Vinyl chloride 10 0.1 68
Methyl methacylate Vinyl acetate 20 0.015 60
Methyl methacylate Acrylonitrile 1.20 0.15 60

Methyl methacylate 1,3-Butadiene 0.25 0.75 90

Ethylene Tetrafluoroethylene 0.38 0.1 25
Ethylene Acrylonitrile 0 7 20
Ethylene Vinyl acetate 0.97 1.02 130
1 << r1 and r2 << 1

r1• r2 = 1
r1 =10, r2 = 0.1

r1 = r2 = 0

0 < r1, r2 < 1

r1 = r2 = 1 1 − r2
f1 =
2 − r1 − r2
Azeotropic composition
Q-e Scheme (Alfrey-Price Treatment)
k12 = P1Q2 exp (- e1e2)

where P1 = reactivity of radical M1•

Q2 = reactivity of monomer M2
e1 = polarity of monomer M1
e2 = polarity of monomer M2

k 11 P1Q 1 exp(− e 1e 1 ) ⎛ Q 1 ⎞
r1 = = =⎜ ⎟ exp[− e 1 (e 1 − e 2 )]
k 12 P1Q 2 exp(− e 1e 2 ) ⎜⎝ Q 2 ⎟⎠

⎛Q ⎞
r2 = ⎜⎜ 2 ⎟⎟ exp[− e 2 (e 2 − e 1 )]
⎝ Q1 ⎠
Styrene: standard
Q = 1.00 e = - 0.80
Resonance factor Polarity factor
( + steric factor)
+ : electron-withdrawing group
- : electron-donating group
Table 6.10 Reactivity (Q) and Polarity (e) of Monomer

Monomer Q e
1-vinylnaphthalene 1.94 -1.12
p-Nitrostyrene 1.63 0.39
p-Methoxystyrene 1.36 -1.11
Styrene 1.00 -0.80
Methyl methacrylate 0.74 0.40
Acrylonitrile 0.60 1.20
Methyl acrylate 0.42 0.60
Vinyl chloride 0.044 0.20
Vinyl acetate 0.026 -0.22
 CH2 CH CH2 CH CH2 CH
+

O C CH3 O C CH3

O O
Little tendency

Resonance-stabilization No resonance-stabilization
M1 = Styrene M2 = Vinyl acetate r1 = 55 r2 = 0.01
Styrene Q = 1.00 e = - 0.80 Vinyl acetate Q = 0.026 e = - 0.22
CH3 CH3
CH2 CH
+ CH2 C CH2 C

C OCH3 C OCH3

O O
M1 = Styrene M2 = MMA r1 = 0.52 r2 = 0.46
Styrene Q = 1.00 e = - 0.80 MMA Q = 0.74 e = 0.40

Each radical has about twice as much tendency to react with

its opposite monomer
∵Polar effect
Copolymerization of styrene and maleic anhydride
Strong tendency toward alternation (r1 and r2 = ~ 0)

1) Polar effects in the transition state

Electron transfer

Nonbonded resonance form

 Electron transfer

Nonbonded resonance form

2) Formation of Charge-transfer complexes between comonomers

Homopolymerization of charge-transfer complex

~ (DA)n D+..A- + D+..A- ~ (DA)n+1 D+..A-

charge-transfer complex

<Evidence>
(1) Rp maximum when monomer composition ratio = 1:1
maximum conc. of donor-acceptor complex
(2) Alternation is independent of monomer feed ratios,
and other reactive monomers included with the feed fail to react
while alternating copolymer is forming
(3) Rp is enhanced by addition of Lewis acids,
which increase the acceptor properties of one of the monomers

(4) Chain transfer agents have little effect on the mol. wt.
of the copolymer
Other compounds that undergo free radical-initiated copolymerization
with vinyl monomers are CO and SO2

R R O
CH2 CH CO CH2 CH C

polyketones
R
R
CH2 CH SO2
CH2 CH SO2

polysulfones

alternation