POLYMERIZATION KINETICS

THERMODYNAMICS KINETICS

Tells us where the system Tells us how fast the

would like to go eventually !! system takes various
ie.defines relationships reaction paths
between macroscopic
variables at equilibrium

EXAMPLES

SUGAR + OXYGEN PRODUCTS + ENERGY

CRYSTALLIZATION IS ALSO A PROCESS CONTROLLED

BY KINETICS, AS WE WILL SEE LATER
 POLYMERIZATION KINETICS

STEP GROWTH - SLOW

Can use statistical methods

as well as kinetics to describe
mol. wt. distributions - more
on this later

CHAIN Polymerization - FAST

Can apply statistical methods

to an analysis of the
microstructure of the products,
but not the polymerization
process and things like mol .wt.
 KINETICS OF STEP GROWTH
POLYMERIZATION

WHY BOTHER ?

•How long does it take to

make polymer ?

•Can we speed up the reaction ?

•What is the relationship between

kinetics and the Mol. Wt. Of the
product ?
 REVISION

RATE OF
REACTION
[
= CONSTANT x CONCENTRATION ] TERMS
n

RATE OF DISAPPEARANCE
OF MONOMER = - d_M_
dt

= k x [CONCENTRATION ]n TERMS
 KINETICS OF POLYCONDENSATION

KEY ASSUMPTION - FLORY

The reactivity of a functional group

is independent of the length of the
chain to which it is attached

EXAMPLE:
DIBASIC ACID + GLYCOL POLYESTER

O O
This group HO - C ~~~~~~~~~~~~~~~~~~~~~~ C - OH
reacts as
readily as O O HO~~~~~~OH
This group
HO - C ~~~~~~ C - OH

HO~~~~~~~~~~~~~~~OH
 WAS FLORY RIGHT?

25

-1
s ec 20
-1
( g equ iv / l)

15

10
4
k x 10

5
A

0
0 5 10 15 20
Chain Length: N

Redrawn from the data of Flory,P.J.,

Principles of Polymer Chemistry,Cornell
University Press, 1953, p71
KINETICS OF POLYCONDENSATION

A - A + B - B A- AB - B

Kinetic equation for this type of

reaction is usually of the form:

d[A]
Reaction Rate = - = k 2[A][B]
dt

N.B. [A] AND [B] ARE THE CONCENTRATIONS

OF FUNCTIONAL GROUPS

However, esterifications are acid catalyzed

and in the absence of added strong acid

d[A] 2
- = k 3 [A] [B]
dt
 MORE KINETICS
d[A] 2
- = k 3 [A] [B]
dt
If [A] = [B]

c = [A] = [B]

Hence
dc
− = k3 c 3
dt
c t
dc
∫c c 3 = k3 ∫ dt
t =0
o

1 1
2 k3 t = 2 − 2
c co
 EXTENT OF REACTION
Define
p = EXTENT OF REACTION

In this example

# OF COOH GROUPS REACTED

LET p = ____________________________________
# OF COOH GROUPS ORIGINALLY PRESENT

Then
c = c 0 (1-p) 400
20

And 300
1
1
2 c0 k t = _____ - 1
2 ( 1 - p)
2 0
0 100
3 2
(1-p)
200

100

Redrawn from the data of Flory,P.J., 0

J.A.C.S.,61, 3334 (1939) 0 1000 2000
Time (mins)
 ACID CATALYZED REACTION

d [COOH ]
- _______ =
100
k' [COOH ] [OH ]
dt
80
dc 2
- __ = k'c
dt 60
1
(1 - p)
1
___
c 0 k't = + constant 40
(1-p)
20

Note; the concentration of the acid

catalyst (a constant) is included in k' 0
0 200 400 600 800
Time (mins)

Redrawn from the data of Flory,P.J.,

J.A.C.S.,61,3334(1939)
 NUMBER AVERAGE DEGREE
OF POLYMERIZATION

_ N
x n = __0
200

= __
c0
= __
c0
c (1-p)
1
c0 (1 - p)

100
_ 1
___
ie xn =
(1-p)

__ M
_
__0
0
Mn = M0 x n = 0.0 0.2 0.4 0.6 0.8 1.0
(1-p) Conversion, p
 KINETICS OF FREE RADICAL
POLYMERIZATION
We need to consider the following steps

•INITIATION

•PROPAGATION

•(CHAIN TRANSFER)

•TERMINATION
 INITIATION

O O
C O O C
kd .
I2 2R
Benzoyl peroxide O
2 C O
Decomposition

ki .
H H
.
R + M M1
R + CH 2 C R CH 2 C
X X Addition
 INITIATION
kd ASSUME DECOMPOSITION IS THE
I 2R . RATE LIMITING STEP
ki i.e. k i >> k d
R. + M M1 .

THEN WE SHOULD ONLY HAVE TO CONSIDER k d

.
d[ I ]
___ 1 ___1]
__ d[ M
i.e. - = = kd [ I ]
dt 2 dt
BUT; ONLY A FRACTION f OF RADICALS INITIATE CHAIN GROWTH
O
C O + CO2

O
+ C O
d[M .1]
___
ri = = 2 f kd [ I ]
O
dt
C O

2
 PROPAGATION

kp
M 1. + M M 2.
kp
M 2. + M M 3. d[ M]
rp = - __ = k p[ M ][ M . ]
dt
In general;
kp
M x. + M .
M x+1

Assumption; reactivity is
independent of chain length
 TERMINATION

COMBINATION

H H
CH 2 C + C CH 2
k tc
M .x + M .y
X X
H H M x+y
ktc
CH 2 C C CH 2
X X

DISPROPORTIONATION
H H
CH 2 C + C CH 2
k td
M .x + M .y
X X
H H Mx + My
ktd
CH C + H C CH 2
X X
RATE OF TERMINATION

M. ]
d[___
rt = - = 2 kt [ M.][ M. ]
dt

Where k t = k tc + k td

OBTAINED FROM :

.
.
Both reactions are second order

Rate of removal of chain radicals

= sum of the rates of the two
termination reactions
 SUMMARY

M .1 ]
d[___
ri = = 2 f k d [I]
dt
d[ M]
rp = - ___ = k p [ M ][ M . ]
dt

M. ]
d[___
rt = - = 2 k t [ M. ][ M . ]
dt

PROBLEM :
We don't know [ M . ]

SOLUTION :

Assume a steady state

concentration of
transient species
STEADY STATE ASSUMPTION

[ M.] = CONSTANT

This means that radicals

are consumed at the same
rate as they are generated

ri = rt

2f kd [ I ] = 2 k t [ M. ] 2
1/2
[ M. ] = [ fk d [ I ]
______
kt
]
 RATE OF PROPAGATION
RATE OF PROPAGATION = RATE OF POLYMERIZATION

rp = R p

[ fk d[ I ]
]1/2
substituting; rp = kp ______ [ M ]
kt

BUT [ I ] IS NOT CONSTANT

.

d[ I ] -k d t
from - __ = kd [ I ] obtain [ I ] = [ I 0] e
dt

HENCE

Rp = [ [
kp ____
kt]
f kd 1/2
[ M ] [ I0 ] 1/2 ] [ e -k d
t/2 ]
 WHAT DOES THIS TELL US ?

1. IF WE WANT TO INCREASE Rp But; changing [ I] also changes

INCREASE [ M ] OR [ I ] mol. wt. - more on this later !

For ethylene at 130 0C and

1 bar pressure
k p / k 1/2
t ~ 0.05
2. R ~ k p / k 1/2 0
p t For ethylene at 200 C and
2500 bar pressure
k p / k 1/2
t ~ 3.0

100

100% 40%
20%
80
60% 10%
80%

60

3. TROMSDORFF EFFECT
40

20

0
0 500 1000 1500 2000

Time (mins)
 CONVERSION

[ M0 ] - [ M ]
___________ Amount of monomer used up
DEFINITION ; = _______________
[ M0 ] Amount of monomer at start

in initial stages of reaction we Conversion

can assume [ I ] = [ I ] = constant
0 1.0

1/2
[ ]
d[___
M ]= - kp fk d [ I ]
______ [ M ]
dt
kt
Integrating

[ ]
[___
M ] fk d [ I 0 ] 1/2
Ln = - k p ______ t
[ M0 ] kt t
 MAXIMUM CONVERSION
USUALLY THERE IS A FIRST ORDER DECAY IN INITIATOR CONCENTRATION

d[__
I ] -k t
i.e. = - k d[ I ] [ I ] = [ I ] e d
0
dt
and
1/2
2 kp fk [ I0 ]
Ln [___
M ]
[ M0 ]
= - ___
kd
[
______
k
d
] [ 1 - e -k t ]
d

hence Conversion
CONVERSION = 1.0

1 - exp - {2 kp [ f [ I0] 1/2

______
k t kd ] [ 1 - e-k d ]}
t/2

MAX CONVERSION ( t ∞) =

{ [ ] }
1/2
1 - exp - 2 kp f [ I 0]
______
kt kd t
AVERAGE CHAIN LENGTH

DEFINE KINETIC CHAIN LENGTH

RATE OF MONOMER ADDITION

ν =
TO GROWING CHAINS
_____________________________
RATE AT WHICH CHAINS
ARE STARTED

This is the average number of

monomers polymerized per
chain radical at a particular
instant of time during the
polymerization
 KINETIC CHAIN LENGTH

CONSIDER A TIME PERIOD t

let us say that

1. 100 chains are started

2. 1,000,000 monomers are reacted
in this time period

Then the average degree of 1,000,000

polymerization of these chains _________ = 10,000
is 100
 KINETIC CHAIN LENGTH
THERE WILL BE SOME OBVIOUS ERRORS (e.g. What about
chains that were initiated, but did not terminate just before
the start of the chosen period ?), BUT THESE DECREASE AS
t SMALL

IN THE LIMIT OF A TIME PERIOD dt

rp kp [ M ]
= __ = _______________
ν ri
2 (f kd k t ) 1/2 [ I ] 1/2

[____
M ] 1/2
i.e. ν ~ c.f. rp ~ [ M ] [ I ]
1/2
[ I ]

THE DEGREE OF POLYMERIZATION THEN DEPENDS UPON

THE MECHANISM OF TERMINATION
_
xn = ν - disproportionation
_
xn = 2 ν - combination
INSTANTANEOUS NUMBER AVERAGE CHAIN LENGTH

What if termination occurs by both mechanisms ? define an

average number of dead chains per termination reaction

rate of dead chain formation

____________________________
ξ =
rate of termination

[2 k td+ k tc ][ M .] 2
___________________
[2 k td + k tc ]
= = ___________
2
[ k + k tc ][ M ] . kt
td

HENCE

_ k p [ M. ][ M ]
____________
xn = 2
[ 2 ktd + k tc ] [ M .]

_ kp [ M ]
_______________
xn = 1/2 [ I ] 1/2
ξ [f k d k t ]
 CHAIN TRANSFER
Chain transfer can occur to solvent,added agents,etc.
d[ M . ]
_____
R' : H + M . M H + R' . r = = - k [R':H ][ M.]
x tr x dt tr

M .]
d[___ 2
- = 2k [ M . ] + k [ M 2. ] + k [ T ][. M ]
dt td tc tr

CAN THEN OBTAIN 200

_ kp [ M ] Ethylbenzene

_____________________________
160

xn =
1/2 1/2 Toluene
ξ [f k d k t ] [ I ] + ktr [ T ] 10
5
120

xn
OR 80

1 1 C [ T ]
Benzene
___
_ = ___
_ + ____ where C = k tr / k p
40

xn (x ) [ M ]
n0 0
0 30
10 20
[ S ] /[M]

Redrawn from the data of R.A.Gregg + F.R.Mayo,

Faraday Soc. Discussions,2,328(1947)