Hanyang Univ.

Spring 2008
Chap 9. Chain-growth Polymerization
Chain-Growth Polymerization (Addition) Processes
1. Free radical Initiation Processes
2. Cationically Initiated Processes
3. Anionically Initiated Processes

4. Group Transfer Polymerization
5. Coordination Polymerization

Hanyang Univ.
Spring 2008
Chain-Growth Polymerization
Step-Growth Polymerization
1. Molecular weight increases steadily.

2. High molecular weight polymers are found at the end.

3. Long reaction time needs to synthesize high conversion and high molecular weight.
1. Only growth reaction adds repeating units one at a time to the chain

2. Monomer concentration decreases steadily throughout the reaction

3. High Molecular weight polymer is formed at once; polymer molecular
weight changes little throughout the reaction.

4. Long reaction times give high yields but affect molecular weight little.

5. Reaction mixture contains only monomer, high polymer, and about 10
-8

part of growing chains.

Hanyang Univ.
Spring 2008
(1) I nitiation
k
d
: Initiator decomposition rate constant
: 10
-4
~ 10
-6
L/mole sec

Unstable radical
Chain Growth Polymerization
Heat (60C)
UV k
d

Primary radical
AIBN
Bond Energy = 46 kcal/mole
| || | = I M k R
i i

Hanyang Univ.
Spring 2008
(2) Propagation
k
p
: 10
2
~ 10
4
L/mole sec (much faster than step-growth polymerization)
(Repetition of similar reaction)

Chain Growth Polymerization
| || | = M M k R
p p

Hanyang Univ.
Spring 2008
(3) Termination
(a) Coupling or combination
Chain Growth Polymerization

Hanyang Univ.
Spring 2008
(b) Disproportionation
k
t
=k
tc
+k
td
10
6
~ 10
8
L/mole sec
(3) Termination
Chain Growth Polymerization
| || | | |
2
= = M R M M k R
t k t
td
k
td
k

Hanyang Univ.
Spring 2008
(4) Chain Transfer
Kinetic chain length
Monomer, Polymer, Solvent or Chain transfer agent
Physical chain length
Chain Growth Polymerization

Hanyang Univ.
Spring 2008
Chain Growth Polymerization
Kinetic Chain Length :
kinetic chain length of a radical chain polymerization is defined as the
average number of monomer molecules consumed (polymerized) per
each radical, which initiates a polymer chain.

ex) Monomer # 4000 Disproportionation

=4,000/4 =1,000
Determined by steps 1, 2, 3. (Initiation, propagation, and termination)
(No chain transfer)

Physical Chain Length :
This condition contains Step 1, 2, 3, 4.
Radical
1,2,3,4

Hanyang Univ.
Spring 2008

Non-Polymerization Reaction

Peroxide induced Bromination of Toluene

1) Initiation
Two types of reaction
- R-O-O-R 2RO (1)
- R-O + Br
2
ROBr + Br (2)
- R-O + CH
3
ROH + CH
2

(3)

Two radicals and two kinetic chains are formed by decomposition of
each ROOR molecules
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
2) Propagation
- Br + CH
3
HBr + CH
2
(4)
- CH
2
+ Br
2
CH
2
Br + Br (5)


Two special features
The number of active species is fixed.
Same reactions are repeated during the kinetic chain reaction.
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
3) Termination
- 2 Br Br
2

- 2CH
2
CH
2
CH
2

- CH
2
+ Br CH
2
Br + Br



Net Effect of Kinetic Chain Reaction:
One ROOR molecule can cause formation of Br2, |CH2CH2|, |CH2Br,HBr, .

Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
Time
R
e
a
c
t
i
o
n

R
a
t
e

Induction period
Steady state
Chain reaction R
i
= R
t
In proportion to the O
2
concentration
Comparison between Chain Polymerization & Chain Reaction
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
In the case of Chain reaction, there are induction periods, due to the
existence of inhibitor.
When an active center is formed, the reaction rate would be faster and
then go to steady state.
The whole reaction rate is reaching a plateau region.
After that, reaction rate decreases due to a loss of monomers or initiators.


Linear Chain-Growth:
Polymer of high DP
n
found easily in early reaction

Linear Step-Growth:
high extent of reaction value required to obtain high DP
n
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
Comparison Free Radical Reaction & Ionic Reaction

- Ionic Initiation multiple bond addition, ring opening polymerization
- Radical Initiation Ring-opening polymerization is not initiated.
CH
3
CH
3
CH
2
R

CH
3
C H
3
CH
2
H
CH
2

C H
3
CH
2
C H
2
C H
3
CH
2

+
+
For the cationic initiation, it will not be free radical.
Ex)
Because of resonance stability
Kinetic Chain Reaction
isobutylene

Hanyang Univ.
Spring 2008
Ionic Free Radical
Anionic Cationic
Ring opening + - -
End-groups Generally, combine with counter-ion or gegenion
E.g. R
+
AlCl4

Degree of association depends on below
Solvent-system polarity
Stability of end group
Type & size of scounter-ion
Temp.

Degree of association influences:
Reaction rates
Termination rate
Stereospecificity



Truly Free Radical
(no association)
Termination Depend on monomer
consumption, Living polymer or
Block copolymer
unimolecular Combination or
disproportionation reaction
Bimolecular
combination or
disproportionation

Comparison between Free Radical Reaction & Ionic Reaction

Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
A) Free Radical Termination
CH
2
CH
X
CHCH
2
X
CH
2
CH CH CH
2
X X
CH CH
X
CH
CH
2
X
CH CH
X
CHCH
2
X
H
H
unsaturated group.
.
.
.
.
..
k
tc
(coupling
or combination)
k
td
(disproportionation)
+
Comparison between Free Radical Reaction & Termination Step of Ionic Reaction
Two molecules involved
= bimolecular reaction
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
B) Cationic Termination
Anionic capture is similar to combination of free radical reaction.

But, this reaction cant include increasing of MW because of unimolecular reaction
CH
2
CH
R
CH
2
CH
R
X
AlCl
4
AlCl
3
[XY]
+
Y
EX)

X= Cl Y=
+
-
-
-
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
C) Anionic Termination
Termination is rare but can occur by loss of a hydride ion





Unimolecular type termination occurs
CH
2
CH
R
M
-
-H
-
+
CH CH
R
+ HM
CH
R
H
R
[XY]
+
-
proton release
+
..
+
HY
+
Y
The proton release is similar to disproportination of free radical..
But, one chain joins in the reaction unimolecular reaction
C) Anionic Termination
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
Anionic Cationic
Termination Termination
Free Radical
Termination
Reaction rate Unimolecular
High concentration of growing
chains 10
-2
~10
-3
molar Rates 10
4
~10
5

times higher than free radical
Bimolecular
Relativity low
concentration 10
-8
~10
-9
molar occurs at high
Rates
AE
Activation Energies Similar
Chain Transfer Negligible + +
Disadvantage Rigorous Purity or precautions
Polymer System Solution or Bulk Wide variety of
polymer systems,
Gas, Solid, Solution,
Bulk, Precipitation,
Suspension, Emulsion

Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
Free Radical Initiated Polymerization of Unsaturated monomers

Kinetic Scheme

Initiation
Two step sequence-Both enter into overall rate
1. Initiator decomposition

I
2
2I-

2. Addition of Initiator fragment to the monomer, Initiation of Chain growth.

I-+M IM-


The efficiency of Initiator - Determined by competition of desired reaction and side reaction


Primary radical species
Generally, 0.5 << f << 1
k
d

k
i

Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
A.Cage Effect primary recombination
Initiator fragments surrounded by restricting cage of solvent


Ex)











(acetyl peroxide)






CH
3
C O O C CH
3
O
O
Kinetic Chain Reaction
O
O

C H
3
CH
3
O
O


Hanyang Univ.
Spring 2008
I) Recombination possible I
2
2I-

II) If elimination reaction occurs while the free radical in-cage,







Formation of stable molecules due to Radical combination.
And formation of Inactive Species.


Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
B. Induced Decomposition Secondary combination

I) Through Radical attack on peroxide molecules

-R + R'-O-O-R' RH + -R'OOR' R'=O + R'O-

Finally, R- + R'OOR' ROR'+ R'O-

Total number of radical does not change, but among them half molecules were wasted.

II) Chain Transfer to Solvent

(In this case, since just one radical was obtained half molecules were wasted.)
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
III) Reaction with Chain Radical







Since not all Molecules participate in the initiation Efficiency factor

f: Initiator Efficiency
= mole fraction of initiator fragments that actually initiate polymer chains.
0.5 < f < 1.0
Kinetic Chain Reaction
I + M
.
I M n
.
I M n
. + I
2
I M n I
+
I
.

Hanyang Univ.
Spring 2008
C. Reaction Rate






If [M-] is representative for the concentration of chain radical,

That is , M- = IM-
or = I [M-]

f ~ 1 R
i
is unrelated with [M]
f=|[M]
f < 1 R
i
is related with [M]

[M] , f
[I
2
] , f due to induced decomposition
by convention, two radical formation.
] [ 2
] ][ [
] [
2
I fk
M I k
dt
M d
R
d
i
i
=
=

=
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
D. Initiator

- containing compounds.









O O S S N N
O O
O
C
CH
3
O
CH
3
C
O O
O
C
O
C
O O C
CH
3
CH
3
C
CH
3
CH
3
Kinetic Chain Reaction
Acetyl peroxide 80~100C
Benzoyl peroxide 80~100C
Cumyl peroxide 120~140C

Hanyang Univ.
Spring 2008














N N C
CH
3
CN
C
CN
CH
3
CH
3
CH
3
C
CH
3
CN
CH
3

.
+ N
2
2
50~70C
AIBN 2,2' azobisisobutyronitrile

Kinetic Chain Reaction
C H
3
O O CH
3
CH
3
CH
3
CH
3
CH
3
C H
3
O OH
CH
3
CH
3
Hydroperoxides, cumyl or t-butyl
80~100C
t-butyl peroxide

Hanyang Univ.
Spring 2008
Propagation







Termination


+
= =
n
k
k
p p
IM
IM M I
M M k
dt
M d
R
p
p
2
] ][ [
] [
By convention
Since 2 radical elimination
2
] )[ ( 2
] [
- + =
-
= M k k
dt
M d
R
td tc t
M
.
M
.
k tc
k td
Kinetic Chain Reaction

Hanyang Univ.
Spring 2008

Overall Rate of Polymerzation









Radical concentration

Difficulty of measurement, low concentration. (~10
-8
molar)

Thus, it is impractical using this therm.

[M-] elimination is desirable.


] ][ [ ~
] ][ [ ] ][ [
- =
- + - =
M M k R R
M M k M I k R
p p o
p i o
(# of propagation step >>> # of initiation step)

Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
[M-] elimination methods

Steady-State Assumption

Radical concentration increases at the start, comes to steady state simultaneously
and then reaction rate change becomes 0. (active centers created and destroyed at the same time)
R
i
= R
t













2
1
2
1
2
2
1
2
2
]
2
[
] [ ) ( ] [
] )[ ( 2 ] [ 2
t
i
td tc
d
td tc d
R
R
or
I
k k
fk
M
M k k I fk
=
+
= -
- + =
2
1
2
1
2
) ( ] ][ [
] ][ [
] [
td tc
d
k k
fk
I M k
M M k
dt
M d
R
+
=
= =

Kinetic Chain Reaction

Hanyang Univ.
Spring 2008
Mostly in case of f<1 system [I
2
]
1/2
(Square Root Dependence of [I
2
])

Odian Fig. 3-4

MMA using BPO
Vinyl Acetate
using AIBN

R
p
[I
2
]
1/2

O O
O
C
O
C
O
C O
N N C
CH
3
CN
C
CN
CH
3
CH
3 CH
3
C
CH
3
CN
CH
3
.
2
BPO
-CO
2

2
30
0
C
+ N
2

Azobisisobutyronitrile
Kinetic Chain Reaction
H
.

Hanyang Univ.
Spring 2008
+ BPO +
system
In case f < 1, but SRD is not applicable,
] [ ] [
2
1
2
M I R
p

2
3
2
1
2
] [ ] [ M I R
p

Because f is dependent on [M]

Why?

Due to induced decomposition of toluene + [I
2
]

Kinetic Chain Reaction
+ BPO + C H
3

Hanyang Univ.
Spring 2008
At S-S assumption
(1) Disproportionation
Knowing that


Kinetic Chain Length (KCL)
) (
chain) polymer a initiates ( radical each
ed) (polymeriz consumed molecules monomer of number average the
i t
p
R R
R
KCL
=
=
=
dt
M d
R R R
tc td t
] [ -
= + =
(2) Coupling or combination
term
tc
tc
dt
M d
R
k
] [
chains) polymer 2 from product polymer 1 (
2
1
const. rate the
-
=
=

Hanyang Univ.
Spring 2008
(3) Both (1)+(2)


Kinetic Chain Length (KCL)
) 1 (
2 2
2
1
t
td
t
p
td tc td
p
tc td
p
t
p
R
R
R
R
R R R
R
R R
R
R
R
KCL
+
=
+ +
=
+
= =
) 1 (
2
case, in this
:
y R
R
KCL
ionation disproport by caused n terminatio of f raction
R
R
y def ine
t
p
t
td
+
=
=

Hanyang Univ.
Spring 2008
The more concentration of monomer,
The less concentration of initiator,

(1) Dispropotionation
(2) Coupling
Degree of Polymerization
Kinetic Chain Length (KCL)
v =
n
DP
v = 2
n
DP
dt Polymer d
dt M d
DP
n
/ ] [
/ ] [


= =
Monomer consumption rate
polymer formation rate
n
DP
n
DP

Hanyang Univ.
Spring 2008
) 3 ( ] [ 2
) 2 ( ] [ ] [
1
2
) 1 (
) 1 (
2
2
1
2
1
2
2
1
2

I fk R R
M I f
k
k
k R that knowing
y
DP
R
R
y where
y R
R
R R
R
DP
R
R R Polymer
d i t
t
d
p p
n
t
td
t
p
tc td
p
n
p
tc td
= =
)
`

=
+
v
=
=
+
=
+
=
=
+ =

(3) Dispropotionation & Coupling

Polymer formation rate
Monomer consumption rate
Kinetic Chain Length (KCL)

Hanyang Univ.
Spring 2008
From (1),(2),(3)
In case of no Chain transfer, and valid S-S assumption

) 4 (
] [ ) 1 (
] [
2
1
2

)
`

+
=
I f
k
k
k y
M k
DP
t
d
t
p
n
) 5 (
) 1 (
] [
2 2

p t
p
n
R k y
M k
DP or
+
=
Kinetic Chain Length (KCL)

Hanyang Univ.
Spring 2008
M- + XY MX + Y-

Chain transfer agent

If Chain transfer occurs R
p
is unchangable but has an effect on DP
n

( Since [Y-] instead of R
p
=k
p
[M][M-] )

ex)
(1) Chain transfer occurs by solvents or additives
In this case, High chain transfer coefficient.

(2) Transfer occurs by monomer or polymer

Chain Transfer

C C
H
X
H
H
R
.
+ C C l
4
C C
H
X
H
H
R
C l
+ C C l
3
.

Hanyang Univ.
Spring 2008
Inhibitor
When Y take part in chain opening reaction, polymer moves from one site to another.
In this case, hydroquinone etc. are used as inhibitor.

Retarder
When the reactivity of Y is low, controlling the MW of the monomer including
these two materials, Mercaptan etc. are used as Retarder.
Chain Transfer
Inhibitor and Retarder
2
1
2
2
]} [ { ] [
] [ ) 1 ]( [
] [
] ][ [ 2 ) 1 ( ] [ 2
] ][ [ 2
2 ) 1 (
2
] [
2
1 ] [
I
k
f k
M that Knowing
XY k y M k
M k
XY M k y M k
M M k
R y R
R
dt
Polymer d
R
DP
R R R
dt
Polymer d
t
d
tr t
p
tr t
p
tr t
p p
n
tr tc td
= -
+ + -
=
- + + -
-
=
+ +
= =
+ + =

Like this, when chain transfer condition arises

Hanyang Univ.
Spring 2008


+ + + =
+ + + =
+
)
`

+
=
+
)
`

+
=

] [
] [
] [
] [ 1 1
] [
] [
] [
] [
1 1
] [
] [
] [
] [
) 1 ( 1
] [ ] [ ) 1 (
] [
0 ,
, ,
0 ,
2
1
2
2
1
2
M
T
C
M
S
C
DP DP
M k
T k
M k
S k
DP DP
M k
XY k
I f
k
k
M k
y k
DP
XY k I f
k
k
y k
M k
DP
T S
n n
p
t tr
p
s tr
n n
p
tr
t
d
p
t
n
tr
t
d
t
p
n
From the slope of a graph
Chain transfer coefficient Cs
See Odian
P.235
1
[5]/[M]
DP
n

Chain Transfer

Hanyang Univ.
Spring 2008
Assume : no chain transfer
Temperature Dependence of R
p
and DP
n
mole kcal E e k k
mole kcal E e k k
mole kcal E e k k
(1) I f
k
k
k M R
M I f
k
k
k R
t
RT E
t
t
d
RT E
d
d
p
RT E
p
p
t
d
p p
t
d
p p
t
d
/ 5 ~ 2
/ 30
/ 8 ~ 5
]] [ ln[ ln ] ln[ ln
] [ ] [
/
/
/
2
1
2
2
1
2
1
2

=
=
=
+
(
(
(

|
|
.
|

\
|
+ =

|
|
.
|

\
|
=

Hanyang Univ.
Spring 2008
slope of lnR
p
/T is ( + )

as T | lnR
p
|

but Rate of Increase + as d lnR
p
/dT +


Temperature Dependence of R
p
and DP
n
0
15 2 7
2 2
] ln[
ln
. , ] [ ], [ ), 1 (
2 2
2
1
2
>
+
=
+
=
|
|
.
|

\
|
=
=
RT RT
E E
E
dT
k
k
k d
dT
R d
T of t independen f const M I assume and Eq From
d t
p
t
d
p
p

Hanyang Univ.
Spring 2008


Temperature Dependence of R
p
and DP
n
+ + v |
+ | |
+ + v |
<

=

=
v
= = v
+
=
n
n p
n
d t
p
i
p
t
p
t
p
n
DP T
DP but R I
DP T as
RT RT
E E
E
dT
d
R
R
R
R
y R
R
DP
] [
ln ,
0
15 2 7
2 2
ln
,
) 1 (
2
2 2

Hanyang Univ.
Spring 2008
Ceiling Temperature
Polymerization and Depolymerization are in equilibrium
G
p
= H
p
TS
p
H
p
: Heat of polymerization
S
p
: Molecular arrangement changes between monomer and polymer
At eq. State G
p
=0
Monomers can no longer be persuaded to form polymers by chain
polymerization above a certain temperature. ceiling Temperature(T
c
)


Ceiling Temperature Polymer-Depolymerization Equilibria


Hanyang Univ.
Spring 2008
Rate Eq. of Polymerization Reactions
at Depolymerization prominent Temperature
If,
M T
c

Hanyang Univ.
Spring 2008
k
sec
-1
k
dp
k
p
[M]
k
p
[M]- k
dp

300 400 500 Tc
T
c
: No reaction above T
c
Stable blow T
c

Ceiling Temperature Polymer-Depolymerization Equilibria


Hanyang Univ.
Spring 2008
Monomer -AH

kcal/g mole T
c
C (bulk)
St 16 235
MMA 13 164
Ethylene 26 407
Propylene 21 300
o-methyl St. 7 6

Odian Fig 3-18
Entropy changes for all polymers are not so different.

AS
p
= S
p
- S
m
() value of S
p
is higher
AH
p
= H
p
- H
m
if () , exothermic.


Ceiling Temperature Polymer-Depolymerization Equilibria


Hanyang Univ.
Spring 2008
Trommsdorff Effect or Gel Effect

restricted mobility of polymer radical
k
p
( relative to [M] )
( k
p
const. in reaction progress, k
t
drop off in reaction progress )
Autoaccerelation effect
The increasing viscosity limits the rate of termination because of
diffusional limitations

Hanyang Univ.
Spring 2008

t
80%
60%
40%
10%
autoacceleratioan
as [M
0
] drastic in .


Trommsdorff Effect or Gel Effect

kt
e

= 1 one would expect + as t | But | as [[M

0
] |