Chemical Engineering 160/260

Polymer Science and Engineering

Lecture 6 - Mechanism and Kinetics of
Lecture 6 - Mechanism and Kinetics of
Free Radical Chain Polymerization
Free Radical Chain Polymerization
January 29, 2001
January 29, 2001
Outline
! ! Mechanism of Radical Chain Polymerization Mechanism of Radical Chain Polymerization
" " Fundamental steps (initiation, propagation, termination) Fundamental steps (initiation, propagation, termination)
" " Kinetic chain length and molecular weight Kinetic chain length and molecular weight
! ! Chain Transfer Chain Transfer
! ! Energetic Characteristics Energetic Characteristics
" " Activation energies and frequency factors Activation energies and frequency factors
" " Rate of polymerization Rate of polymerization
" " Degree of polymerization Degree of polymerization
! ! Autoacceleration Autoacceleration
General Comments on Chain Reactions
! ! Polymerization is possible only if Polymerization is possible only if G < 0 G < 0 for the for the
transformation of monomer to polymer. This will depend transformation of monomer to polymer. This will depend
only upon the initial and final states, not the nature of the only upon the initial and final states, not the nature of the
intermediate (free radical, anion, intermediate (free radical, anion, cation cation). ).
! ! Substituents Substituents on a vinyl group will influence reactivity on a vinyl group will influence reactivity
through through inductive, resonance,and inductive, resonance,and steric steric effects effects. .
! ! Susceptibility to a particular chain mechanism depends on Susceptibility to a particular chain mechanism depends on
the degree of the degree of stabilization of the propagating center stabilization of the propagating center. .
! ! Radicals are free species Radicals are free species, but anionic and cationic end , but anionic and cationic end
groups have groups have counterions counterions that influence reactivity. that influence reactivity.
! ! High polymer is formed immediately High polymer is formed immediately in a chain in a chain
reaction. Increasing the reaction time simply increases the reaction. Increasing the reaction time simply increases the
amount of high polymer produced. amount of high polymer produced.
Effect of Substituents on Chain Mechanism
Monomer Radical Anionic Cationic Hetero.
Ethylene + - + +
Propylene - - - +
1-Butene - - - +
Isobutene - - + -
1,3-Butadiene + + - +
Isoprene + + - +
Styrene + + + +
Vinyl chloride + - - +
Acrylonitrile + + - +
Methacrylate + + - +
esters
Almost all substituents allow resonance delocalization.
Electron-withdrawing substituents lead to anionic mechanism.
Electron-donating substituents lead to cationic mechanism.
Mechanism of Radical Chain Polymerization
Initiation:
I 2R
k
d
R + CH
2
=CHY RCH
2
C
H
Y
|
|
slow
fast
Propagation:
+ CH
2
=CHY RCH
2
C
|
|
H
Y
RCH
2
CHYCH
2
C
|
|
H
Y
RCH
2
CHYCH
2
C + CH
2
=CHY R(CH
2
CHY)
2
CH
2
C
|
|
H
Y
|
|
H
Y
(thermal or photochemical bond cleavage)
(addition of hundreds or
thousands of monomers)
always the
same identity
and reactivity
for head-to-tail
reaction
Mechanism of Radical Chain Polymerization
Termination: (Reactions are similar for radical and cationic.)
Coupling (molecular weight is effectively doubled)
Disproportionation (molecular weight is unchanged)
~CH
2
C + CCH
2
~ ~CH
2
C-CCH
2
~
|
|
Y
H
|
|
Y
H
|
|
Y
H
|
|
Y
H
~CH
2
C + CCH
2
~ ~CH
2
CH + C=CH~
|
|
Y
H
|
Y
|
H
|
|
Y
H
|
|
Y
H
k
tc
k
td
Most anionic reactions have no inherent termination step.
Mechanism of Radical Chain Polymerization
Initiation:
Propagation:
Termination:
I 2R
k
d
= =
d I
dt
R k I
i d
[ ]
[ ]
M
n
+ M M
n+1

k
p
= =
d M
dt
R k M M
p p
[ ]
[ ][ ]
k
p
~ 10
2
- 10
4
liter/mole sec
M
n
+ M
m
dead polymer
k
t
k
t
~ 10
6
-10
8
liter/mole sec
k
t
= k
tc
+ k
td
R k M
t t
= 2
2
[ ]
[M ] ~ 10
-7
- 10
-9
mole/liter
Note: [M+], [M-] ~10
-2
-
10
-3
mole/liter
Azonitriles:
M
n
+ RN=NR M
n
R + N
2
+ R
Peroxides:
M
n
+ RO-OR M
n
OR + RO
Magnitudes of Reaction Parameters
G. Odian, Principles of Polymerization, 3rd Ed., 1991, p 274.
Rate of Polymerization
= =
d M
dt
R k M M
p p
[ ]
[ ][ ]
Define the rate of polymerization based upon monomer loss.
= +
d M
dt
R R
i p
[ ]
0
Assume that k
p
and k
t
are independent of size of radical.
Steady-state assumption: The net rate of production of
free radicals is zero so that the initiation and termination
rates are equal. This is usually true after about 1 minute
reaction.
R R k M
i t t
= = 2
2
[ ]
[ ]
/
M
R
k
i
t
=
[
\
|

)
j
2
1 2
R k M
R
k
p p
i
t
=
[
\
|

)
j
[ ]
/
2
1 2
~
Rate of Initiation
= =
d I
dt
R k I
d d
[ ]
[ ]
[ ] [ ]exp( ) I I k t
o d
=
ln
[ ]
[ ]
I
I
k t
o
d
=
t
k
I
I
k
d
o
o
d
1 2
1
2
0 693
/
ln
[ ]
[ ]
.
= =
Half life:
R fk I
d d
= 2 [ ]
Unimolecular decomposition:
In actual reactions, not all initiator decompositions are
effective in initiating polymerization. An efficiency
factor f is introduced to account for this.
R k M
R
k
p p
i
t
=
[
\
|

)
j
[ ]
/
2
1 2
R k M
fk I
k
p p
d
t
=
[
\
|

)
j
[ ]
[ ]
/ 1 2
R R
i d
=
Kinetic Chain Length
= average number of monomer molecules consumed for
each radical that initiates a polymer chain
= =
R
R
R
R
p
i
p
t
=

k M M
k M
k M
k M
p
t
p
t
[ ][ ]
[ ]
[ ]
[ ] 2 2
2
R k M M
p p
= [ ][ ] =
k M
k R
p
t p
2 2
2
[ ]
For initiation by thermal homolysis:
=
k M
fk k I
p
d t
[ ]
( [ ])
/
2
1 2
Typically, the initiator
efficiency f is about 0.5.
Relationship Between Kinetic Chain Length
and Molecular Weight
Coupling:
This is the most common mode for styrene, methyl
acrylate, and acrylonitrile.
Disproportionation:
Methyl methacrylate (MMA) has a combination of
coupling and disproportionation. At 70 C, MMA
termination is almost 100% by disproportionation.
X
n
= 2
(true only if there is no
chain transfer)
X
n
=
(true only if there is no
chain transfer)
Chain Transfer
Chain transfer is a chain breaking reaction leading to a
decrease in the size of the propagating polymer chain. The
active center is transferred from the growing chain to a
different species (chain transfer agent, initiator, monomer,
or polymer). The new species may initiate polymerization
or may truncate it.
M
n
+ XA M
n
-X + A
k
tr
A + M M
k
a
R k M XA
tr tr
= [ ][ ]
can initiate a
new reaction
dead
Effect of Chain Transfer on Molecular Weight
X
R
R
k M M k M S k M I
n
p
t
trM trS trI
=
[
\

)
+ + +
2
[ ][ ] [ ][ ] [ ][ ]
C
k
k
M
trM
p
C
k
k
S
trS
p

C
k
k
I
trI
p

1
2
X
R
R
C C
S
M
C
I
M
n
p
i
M S I
= + + +
[ ]
[ ]
[ ]
[ ]
1
2 2
2
2 3
X
k R
k M
C C
S
M
C
k R
k fk M
n
t p
p
M S I
t p
p d
= + + +
[ ]
[ ]
[ ] [ ]
Define chain transfer constants:
Use the kinetic chain length approach to obtain the ratio of
the polymerization rate to the sum of all termination rates:
Chain Transfer to Polymer
~CH
2
CH
2
CH
2
CH
2
|
CH
2
CH
2
CH
2
|
CH
2

4 5
6
Size of side chain
after backbiting
Short branches decrease crystallinity and are 20 - 50 times
more prevalent than long branches. A typical polyethylene
has 5 n-butyl branches and 1 - 2 each of ethyl, n-amyl, and
n-hexyl branches per 1000 carbons.
Consider a terminal free radical of polyethylene:
Long branches, formed by normal chain transfer to polymer,
affect melt flow properties.
Transfer to Chain Transfer Agent
1 1
X X
C
S
M
n n
o
S
=
[
\
|

)
j
+
[ ]
[ ]
1
2 2
2
2 3
X
k R
k M
C C
k R
k fk M
n
o
t p
p
M I
t p
p d
[
\
|

)
j
= + +
[ ] [ ]
Strong C-H bonds of aliphatics lead to small C
S
.
Acids, carbonyls, ethers, amines, and alcohols have higher
C
S
values than aliphatics due to stabilization by O, N, C=O.
Weak S-S bonds lead to large C
S
.
Carbon-halogen bonds are very weak, with excellent
radical stabilization.
Thiols have the highest C
S
due to the weak S-H bond.
Energetic Characteristics:
Activation Energies and Frequency Factors
Assume that all rate constants (k
d
, k
p
, k
t
) are Arrhenius-like.
k A
E
RT
= exp( )
A = frequency factor
E = activation energy
G. Odian, Principles of Polymerization, 3rd Ed., 1991, p 277.
Energetic Characteristics:
Activation Energies and Frequency Factors
G. Odian, Principles of Polymerization, 3rd. Ed., 1991, p 275.
Methyl methacrylate is sterically hindered, leading to low A
p
.
Energetics: Rate of Polymerization
R k M
fk I
k
p p
d
t
=
[
\
|

)
j
[ ]
[ ]
/ 1 2
ln ln
/ /
k
k
k
A
A
A
E
E E
RT
p
d
t
p
d
t
p
d t
[
\
|

)
j
|

|
|
|
|

|
|
|
=
[
\
|

)
j
|

|
|
|
|

|
|
|
=
+
|

|
|

|
1 2 1 2
2 2
E E
E E
R p
d t
+
2 2
ln ln ln ( [ ]) [ ]
/
/
R A
A
A
f I M
E
RT
p p
d
t
R
=
[
\
|

)
j
|

|
|
|
|

|
|
|
+
{ }

1 2
1 2
k
k
k
p
d
t
[
\
|

)
j
1 2 /
This is
the key.
composite activation energy,
usually ~80-90 kJ/mole
Energetics: Degree of Polymerization
=
k M
fk k I
p
d t
[ ]
( [ ])
/
2
1 2
X
n
= 2
coupling
ln
( )
ln
( )
/ /
k
k k
A
A A
E
E E
RT
p
d t
p
d t
p
d t
1 2 1 2
2 2
|

|
|

|
=
|

|
|

E E
E E
X
p
d t
n

2 2
ln ln
( )
ln
[ ]
( [ ])
/ /
X
A
A A
M
f I
E
RT
n
p
d t
X
n
=
|

|
|

|
+
|

|
|

1 2 1 2
composite or overall
activation energy
k
k k
p
d t
( )
/ 1 2
This is
the key.
Temperature Dependence of Rate of
Polymerization and Degree of Polymerization
Weight-average
molecular weight
Rate of
polymerization
1
T
Autoacceleration (Trommsdorff effect)
G. Odian, Principles of Polymerization, 3rd Ed., 1991, p 289.
R k M
fk I
k
p p
d
t
=
[
\
|

)
j
[ ]
[ ]
/ 1 2
Normally, R
p
decreases with time
because [M] and [I] drop with
extent of conversion.