POLYMERIZATION KINETICS

THERMODYNAMICS Tells us where the system would like to go eventually !! ie.defines relationships between macroscopic variables at equilibrium EXAMPLES SUGAR + OXYGEN PRODUCTS + ENERGY KINETICS Tells us how fast the system takes various reaction paths

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 = CONSTANT x CONCENTRATION REACTION

] TERMS
n

RATE OF DISAPPEARANCE d _ M _ = OF MONOMER 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
O O

POLYESTER

This group reacts as readily as This group

HO - C ~~~~~~~~~~~~~~~~~~~~~~ C - OH O O HO~~~~~~OH

HO - C ~~~~~~ C - OH

HO~~~~~~~~~~~~~~~OH

WAS FLORY RIGHT?

25
-1 -1 4

s ec
A

20

( g equ iv / l) k x 10

15

10

0 0 5 10 Chain Length: N 15 20

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] = k 2[A][B] dt

Reaction Rate = -

N.B. [A] AND [B] ARE THE CONCENTRATIONS OF FUNCTIONAL GROUPS However, esterifications are acid catalyzed and in the absence of added strong acid
2 d[A] = k 3 [A] [B] dt

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

If

[A] = [B] c = [A] = [B]

Hence

dc = k3 c 3 dt

dc = k3 3 c co

t =0

dt

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 1 2 2 c0 k t = _____ - 1 3 2 (1-p)

300

1 2 ( 1 - p)
200

0 0 100

100

Redrawn from the data of Flory,P.J., J.A.C.S.,61, 3334 (1939)

0 0 1000 2000

Time (mins)

ACID CATALYZED REACTION

d [COOH ] - _______ = dt

k' [COOH ] [OH ]

100

2 dc - __ = k'c dt

80

c 0 k't =

1 ___ + constant (1-p)

1 (1 - p)

60

40

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

_ N0 x n = __ N
c0 = __ c c0 = __ c0
200

(1-p)

1 (1 - p) 100

ie

_ xn =

1 ___ (1-p)

__ Mn =

_ M0 x n =

M 0 __ (1-p)

0 0.0

0.2

0.4

0.6

0.8

1.0

Conversion, p

KINETICS OF FREE RADICAL POLYMERIZATION

We need to consider the following steps

INITIATION PROPAGATION (CHAIN TRANSFER) TERMINATION

INITIATION

O C O O

O C O 2 C O

Benzoyl peroxide

Decomposition

I2

kd

2R

H R + CH 2 C X R CH 2

H C X

ki . . R + M M1 Addition

INITIATION
I R. + M kd ki 2R . M1 .

ASSUME DECOMPOSITION IS THE RATE LIMITING STEP i.e. k i >> k d

THEN WE SHOULD ONLY HAVE TO CONSIDER k d . d[ M d[ I ] 1 ___ 1] __ ___ i.e. = = kd [ I ] dt 2 dt BUT; ONLY A FRACTION f OF RADICALS INITIATE CHAIN GROWTH
O C O O + C O O C O + CO2

d[ M. 1] ___ ri = dt

= 2 f kd [ I ]

PROPAGATION

M 1. + M M 2. + M In general; M x. + M

kp kp

M 2. M 3. rp = d[ M] - __ dt = k p[ M ][ M . ]

kp

. M x+1

Assumption; reactivity is independent of chain length

TERMINATION
COMBINATION
H CH 2 C X ktc CH 2 + H C CH 2 X H C X H C X CH 2

. M. x + My

k tc

M x+y

DISPROPORTIONATION
H CH 2 C X ktd CH + H C CH 2 X H X H X C + H C CH 2

. M. x + My

k td

Mx + My

RATE OF TERMINATION
d[ M. ] ___ rt = dt Where

= 2 kt [ M.][ M. ] k
td

k t = k tc +

OBTAINED FROM :

. .

Both reactions are second order Rate of removal of chain radicals = sum of the rates of the two termination reactions

SUMMARY
ri = d[ M. 1] ___ = 2 f k dt [I]

rp =

d[ M] - ___ = k p [ M ][ M . ] dt

d[ M. ] ___ 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 [ M. ] =

fk d [ I ] ______ kt

1/2

RATE OF PROPAGATION
RATE OF PROPAGATION = RATE OF POLYMERIZATION rp = substituting; rp = R
p

kp

fk d[ I ] ______ kt

1/2

[ M ]

BUT [ I ] IS NOT CONSTANT . d[ I ] from - __ = kd [ I ] obtain dt HENCE Rp = [ I ] = [ I 0] e -k d t

[ [
kp

f kd ____ kt

1/2

[ M ] [ I0 ] 1/2

] [ e -k

t/2

WHAT DOES THIS TELL US ?

1. IF WE WANT TO INCREASE Rp INCREASE [ M ] OR [ I ] But; changing [ I] also changes mol. wt. - more on this later ! For ethylene at 130 0C and 1 bar pressure 2. R
p

~ k p / k 1/2 t

k p / k 1/2 ~ 0.05 t

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

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

3. TROMSDORFF EFFECT

40

20

0 0 500 1000 1500 2000

Time (mins)

CONVERSION
[ M0 ] - [ M ] ___________ [ M0 ] Amount of monomer used up _______________ Amount of monomer at start

DEFINITION ;

in initial stages of reaction we can assume [ I ] = [ I ] = constant

0

Conversion
1.0

d[ M ]= ___ dt

- kp

Integrating Ln

fk d [ I ] ______ kt

1/2

[ M ]

[___ M ] fk d [ I 0 ] = - k p ______ [ M0 ] kt

1/2

MAXIMUM CONVERSION
USUALLY THERE IS A FIRST ORDER DECAY IN INITIATOR CONCENTRATION

i.e.

d[ I ] __ = - k d[ I ] dt 2 kp ___ kd

[ I ] = [ I ] e
0

-k t
d

and

M ] Ln [___ = [ M0 ]

hence

fk [ I 0] d ______ k
t

] [ 1 - e -k t ]
d

1/2

Conversion t/2

CONVERSION = 1 - exp -

2 kp

f [ I0] 1/2 ______ k t kd

] [ 1 - e-k
)
=

]}

1.0

MAX CONVERSION ( t 1 - exp -

2 kp

f [ I 0] ______ kt kd

1/2

AVERAGE CHAIN LENGTH

DEFINE KINETIC CHAIN LENGTH RATE OF MONOMER ADDITION 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 polymerization of these chains is

1,000,000 _________ = 10,000 100

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 __ = ri

kp [ M ] _______________ 2 (f kd k t ) 1/2 [ I ] 1/2

i.e.

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

THE DEGREE OF POLYMERIZATION THEN DEPENDS UPON THE MECHANISM OF TERMINATION _ xn = - disproportionation _ xn = 2 - 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 ____________________________ rate of termination [2 k td+ k tc ][ M .] 2 ___________________ 2 . [ k + k tc ][ M ]
td

[2 k td + k tc ] = ___________ kt

HENCE k p [ M. ][ M ] ____________
[ 2 ktd + k
tc

_ xn

] [ M .]

_ xn =

kp [ M ] _______________ 1/2 [ I ] 1/2 [f k d k t ]

CHAIN TRANSFER
Chain transfer can occur to solvent,added agents,etc. d[ M . ] _____ r = = - k [R':H ][ M.] R' : H + M . M H + R' . tr tr dt
x x

d[ M. ] ___ dt

= 2k

2 . ] + k [ M2 . ] + k [ T ][. M ] [ M td tc tr

CAN THEN OBTAIN _ xn kp [ M ] _____________________________ =

1/2 1/2

200

Ethylbenzene
160

[f k d k

[ I ]

+ ktr [ T ]

Toluene 10 xn
5

120

OR 1 1 C [ T ] ___ ____ _ = ___ + where C = k tr / k p _ xn [ M ] (x )

n0

80

Benzene
40

0 0 10 20 30

[ S ] /[M]

Redrawn from the data of R.A.Gregg + F.R.Mayo, Faraday Soc. Discussions,2,328(1947)