Thermal Runaway in Chain-Addition Polymerizations and Copolymerizations

2
Thermal Runaway in Chain-Addition Polymerizations

and Copolymerizations
JOSEPH A. BIESENBERGER
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Department of Chemistry and Chemical Engineering, Stevens Institute of Technology,

Hoboken, NJ 07030
Publication Date: July 31, 1979 | doi: 10.1021/bk-1979-0104.ch002
The objectives of this presentation are to discuss the gener-

al behavior of nonisothermal chain-addition polymerizations and
copolymerizations and to propose dimensionless c r i t e r i a for e s t i -
mating nonisothermal reactor performance, in particular thermal
runaway and instability, and its effect upon polymer properties.
Most of the results presented are based upon work (1-8), both
theoretical and experimental, conducted in the author's labora-
tories at Stevens Institute of Technology. Analytical methods i n -
clude a Semenov-type theoretical approach (1,2,9) as well as com-
puter simulations similar to those used by Barkelew (3,4,6,7,10).
Analyses of reactor performance are limited to rate functions
and thermal energy balances
of the forms shown in equations 1 and 2. Polymer property analy-

ses are limited to chain-addition polymerizations
and copolymerizations
0-8412-0506-x/79/47-104-015$07.00/0
© 1979 American Chemical Society
Henderson and Bouton; Polymerization Reactors and Processes

ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
16 POLYMERIZATION REACTORS AND PROCESSES
with termination, whose general characteristics are shown in

equations 3,4,5 and 6. It should be noted that equations 3 and 5
are written in general form to encompass many different chain
mechanisms and therefore do not necessarily represent elementary
reactions steps. Experimental results quoted herein are limited
to polymerizations and copolymerizations of styrene (S) and acry-
lonitrile (AN) monomers via free-radical intermediates for which
the following specific reactions obtain. For homopolymerizations
we have
Termination scheme 11 applies to the geometric mean and phi factor

models and scheme 12 is required for the penultimate effect model.
All the above reaction models were used in attempts to simulate
kinetic data.
Parameters and Variables
Reaction rate functions expressing rate of polymerization R

generally depend upon the molar concentrations of monomer and
initiator, and temperature.
R - R([m], [m ],T)Q (13)

2. BIESENBERGER Thermal Runaway 17
D u r i n g p o l y m e r i z a t i o n , when i n i t i a t o r i s i n t r o d u c e d c o n t i n u o u s l y
f o l l o w i n g a p r e d e t e r m i n e d f e e d s c h e d u l e , o r when h e a t removal i s
c o m p l e t e l y c o n t r o l l a b l e so t h a t t e m p e r a t u r e c a n be programmed
w i t h a p r e d e t e r m i n e d t e m p e r a t u r e p o l i c y , we may r e g a r d f u n c t i o n s
[ r o o ( t ; ] , or T ( t ) , as r e a c t i o n parameters. A common s p e c i a l
case of T ( t ) i s t h e i s o t h e r m a l mode, T = c o n s t a n t . In t h e p r e s -
ent a n a l y s i s , h o w e v e r , we t r e a t o n l y u n c o n t r o l l e d , b a t c h p o l y -
m e r i z a t i o n s i n which [ m ( t ) ] and
0 T(t) are reaction variables,
s u b j e c t t o v a r i a t i o n i n a c c o r d a n c e w i t h t h e c o n s e r v a t i o n laws
(balances). Thus, o n l y t h e i r i n i t i a l (feed) v a l u e s , [ m ] andT , 0 0 Q
are t r u e parameters.
In a d d i t i o n t o t h e s e , we have r e a c t o r d e s i g n p a r a m e t e r s :
o v e r a l l h e a t t r a n s f e r c o e f f i c i e n t U, r a t i o o f r e a c t i o n v o l u m e t o
heat t r a n s f e r area I = V/A and h e a t e x c h a n g e r e s e r v o i r t e m p e r a -
t u r e TR . W h i l e t h e r m o d y n a m i c p r o p e r t i e s (-AH, p C ) and k i - p
netic properties (r,Ap,E ,A ,Et) a r e d e t e r m i n e d f o r t h e most

p t
p a r t by t h e monomers b e i n g p o l y m e r i z e d , i n i t i a t o r c h o i c e (Ad,Ed)
i s v i e w e d a s a p a r a m e t e r a s w e l l a s i n i t i a l monomer c o n c e n t r a t i o n
[ m ] , w h i c h c a n be a d j u s t e d t h r o u g h t h e u s e o f d i l u e n t s .
Q I twill
be shown t h a t runaway (R-A) and i g n i t i o n (IG) phenomena a r e d e t e r -
mined by t h e v a l u e s o f c e r t a i n d i m e n s i o n l e s s g r o u p i n g s , w h i c h a r e
made up o f t h e a f o r e m e n t i o n e d p a r a m e t e r s . T h u s , i f R-A i s s e n s i -
t i v e t o o n e o f t h e s e g r o u p i n g s , f o r i n s t a n c e , i t w i l l a l s o be
s e n s i t i v e t o a l l o t h e r parameters i n t h a t grouping.
Frequently function R c a n be w r i t t e n a s a s i n g l e t e r m hav-
ing t h e s i m p l e f o r m o f e q u a t i o n 1. For i n s t a n c e , w i t h the a i d
o f t h e l o n g c h a i n a p p r o x i m a t i o n (LCA) and t h e q u a s i - s t e a d y s t a t e
a p p r o x i m a t i o n (QSSA), t h e r a t e o f monomer c o n v e r s i o n , i . e . , t h e
r a t e o f p o l y m e r i z a t i o n , f o r many c h a i n - a d d i t i o n p o l y m e r i z a t i o n s
c a n be w r i t t e n a s
q
R = k a p [ / [ , / = A a p [ ]P[
m m o ] exp(-E R T)
a p g (14)
where k a p i s a lumped o r c o m p o s i t e r a t e c o n s t a n t . Free-radical

homopolymerization i s an e x a m p l e (p = 1, q = 1/2) a s seen i n
T a b l e I . F r e e - r a d i c a l c o p o l y m e r i z a t i o n , on t h e o t h e r h a n d , l e a d s
t o a sum o f t e r m s , e a c h o f w h i c h i s more c o m p l e x t h a n e q u a t i o n
\k, a s seen i n T a b l e II ( N o t e t h e p r e s e n c e o f f u n c t i o n H , g i v e n
i n T a b l e I I I f o r v a r i o u s t e r m i n a t i o n m o d e s ) . To remedy t h i s
s i t u a t i o n , approximate rate functions f o r copolymerization of the
form o f e q u a t i o n 1 a r e used i n s t e a d .
In s u c h c a s e s t h e d i m e n s i o n l e s s r a t e f u n c t i o n
R' = R/(R) (15)

o
c a n be v i e w e d a s a p r o d u c t o f s e p a r a t e f u n c t i o n s
R' = f ( t ) g ( T ' ) (16)
where

TABLE I
RATE FUNCTIONS FOR FREE-RADICAL HOMOPOLYMERIZATIONS
R. - k.[m ] = 2 f . l c . I l ] k. = f k . [ m l= 2[l]
i i o d d i d o
1 / 2
QSSA k = k (2fk,/kJ
1/2 1 / 0
ap p d' Vx
R - k [P][ra] = k [ m ] [ l ]
n
P P ap
2 k
V • k
P t [ m ] 2 k
p* s k
p / k t
LCA
R = R. + R w R
i p p
QSSA R. « R„
i t
LCA R » R.
P i
TABLE I I
RATE FUNCTIONS FOR FREE-RADICAL COPOLYMERIZATIONS
R.. = k f . [ m ] = 2 f k . f . [ l ] L
j = 1,2
IJ iJ o d J
R =
E R
ij =
k
\ [ m
o ]
= 2 f k
d [ , ]
E f
j = 1
J j
1 / 2
R = k .. [ P . ] [ m J J
= k [m.][m.][l] H k = 1,2
pjk pjk j k apjk j k
] / 1
k ., = k k . ( 2 f k . / k ..k ) 0 Q 0 I = 1,2 I * j
apjk p j k p&j d t j j til
R
pk " X) R
PJk
J
R = R » ( Y Y \ [m.][m,])[l] 1 / 2
H
p pk ^f^f a
PJ k
J k
R = R. + R « R f r o m LCA
i p p
Symmetry k a p j k = k^. R p j | < = R p ( < j from QSSA

2. BIESENBERGER Thermal Runaway
TABLE I I I
EXPRESSIONS FOR FUNCTION H

G e o m e t r i c Mean
-1
k I m ]
k p ] 2 [m ] 2
p21 l
H =
1/2 1/2
( k
tl,>
Phi Factor
k [ m ]
k
p21 [ m
l ] k
p21 p12 k [ m
l ] [ m
2 ]
pl2 2
H = + 2<|>
, / 2 ( )'/2 1/2
L (k 22)t
k k
k
K < t11>
V K
t22 tir
Penultimate effect
,1/2
r , [m
k [ m ]
p21 1 til/ z
H =
, / 2 r j Lm J + l m J 1 2
(k
V K
)
t22'
1 / 2
/k \
r [m ] +
2 2
k [ m ]
. p12 2
7 2
r [m J
2 2 + [mj]
o T T "
V K
tir k k k ; k k ; k k
where k ^ - t n l 2 > t 2r t2112 tl2 tl221 t22~ t2222

n j
(R ) = (k ) ir [ C . ] (17)
N
o ap o . J o '
(k ) = IK exp(-E; ) (18)
ap o ap ap
E ' = E /R T (19)
ap ap g o
n
f ( t ) = ir C j J (20)
and
g(T') = e x p E ' T V ( 1 + T') (21)

ap
Frequently i t i s convenient t o w r i t e
g ( 6 ) = e x p 0/(1 + e6) (22)
i n l i e u o f e q u a t i o n 21 where
e = 1/E' (23)
ap
We n o t e t h a t u n d e r f e e d c o n d i t i o n s (R') = 1 0 since f(0) = 1

g(o) = l .
C h a r a c t e r i s t i c Times
B a l a n c e e q u a t i o n s f o r b a t c h r e a c t o r s may a l l be v i e w e d a s
special cases o f the f o l l o w i n g general equation
j
where p i s a n i n t e n s i v e p r o p e r t y ( m o l a r c o n c e n t r a t i o n o r tem-
p e r a t u r e ) and p j i s t h e r a t e w i t h w h i c h p r o c e s s j c a u s e s p
t o i n c r e a s e i n v a l u e . When q u a n t i t i e s p and p j a r e made d i -
m e n s i o n l e s s t h r o u g h d i v i s i o n by t h e i r c o r r e s p o n d i n g f e e d v a l u e s
V' = p/(p) Q (25)
U 6 )
Pj ~ W o
t h e a f o r e m e n t i o n e d b a l a n c e e q u a t i o n s become p a r t l y d i m e n s i o n l e s s ,
h a v i n g d i m e n s i o n s o f r e c i p r o c a l t i m e o n l y , and t a k e on t h e f o l -
lowing g e n e r a l form
(27)
3f • E»J' »i

in which a c h a r a c t e r i s t i c time (CT) f o r e a c h p r o c e s s may be de-

f i n e d as
Xj s (P> /(Pj)
0 0 (28)
We n o t e t h a t e q u a t i o n 15 i s an e x a m p l e o f e q u a t i o n 26. I t c a n be
shown t h a t a l l d i m e n s i o n l e s s p a r a m e t e r s , a r r i v e d a t i n t h e c o n -
v e n t i o n a l manner by w r i t i n g e q u a t i o n s o f t y p e 24 i n c o m p l e t e l y
d i m e n s i o n l e s s f o r m , c a n be e x p r e s s e d a s q u o t i e n t s o f CT's.
T a b l e s IV and V c o n t a i n a p p r o p r i a t e b a l a n c e e q u a t i o n s f o r
n o n i s o t h e r m a l f r e e - r a d i c a l p o l y m e r i z a t i o n s and c o p o l y m e r i z a t i o n s ,
w h i c h a r e seen t o c o n f o r m t o e q u a t i o n 24. Following the proce-

d u r e o u t l i n e d a b o v e , we o b t a i n t h e CT's f o r h o m o p o 1 y m e r i z a t i o n s
l i s t e d i n T a b l e V I . C o r r e s p o n d i n g CT's f o r c o p o l y m e r i z a t i o n s c a n
be. o b t a i n e d i n a s i m i l a r way, and i n d e e d t h e f i r s t and f o u r t h
l i s t e d i n T a b l e V I I w e r e . The r e m a i n i n g o n e s , h o w e v e r , were d e -
r i v e d v i a an a l t e r n a t e r o u t e based upon t h e d e f i n i t i o n s i n T a b l e
VI l a b e l e d " e q u i v a l e n t " t o g e t h e r w i t h a p p r o x i m a t e f o r m s f o r p j ,
w h i c h w e r e n e c e s s i t a t e d by a p p l i c a t i o n o f t h e Semenov-type r u n -
away a n a l y s i s t o c o p o l y m e r i z a t i o n s , and w h i c h w i l l s u b s e q u e n t l y
be d e s c r i b e d . Some u s e f u l d i m e n s i o n 1 e s s p a r a m e t e r s d e f i n e d i n
terms o f t h e s e CT's a p p e a r i n T a b l e s V I I I , IX and X.
Reactor Performance
The c o n d i t i o n o f t h e r m a l runaway (R-A) i n p o l y m e r i z a t i o n and

c o p o l y m e r i z a t i o n r e a c t o r s has been c h a r a c t e r i z e d (1,7) by a
r a p i d l y r i s i n g temperature dT/dt » 0 t o g e t h e r w i t h an a c c e l e r -
2 2
a t i o n of the r i s e d T/dt > 0 . When R-A a d d i t i o n a l l y e x h i b i t s
p a r a m e t r i c s e n s i t i v i t y i t i s termed i g n i t i o n ( I G ) . Beyond i t s
r o l e as a p o t e n t i a l c a u s e o f i n s t a b i l i t y , R-A c a n a l s o a f f e c t
conversion e f f i c i e n c y . S p e c i f i c a l l y , t h e w e l l - k n o w n phenomenon
o f d e a d - e n d i n g ( D - E ) , i n w h i c h c o n v e r s i o n o f monomer t o p o l y m e r
i s a b o r t e d by p r e m a t u r e d e p l e t i o n o f i n i t i a t o r , i s e x a c e r b a t e d by
r i s i n g t e m p e r a t u r e s . T h i s i s so b e c a u s e h i g h t e m p e r a t u r e s a c -
c e l e r a t e i n i t i a t o r d e p l e t i o n r a t e s much more t h a n monomer c o n v e r -
sion rates. The phenomenon c a n o b v i o u s l y be m i t i g a t e d by i n -
c r e a s i n g i n i t i a t o r c o n c e n t r a t i o n , but t h i s has an a d v e r s e e f f e c t
on d e g r e e o f p o l y m e r i z a t i o n ( D P ) . The c r i t e r i o n f o r D-E, shown
i n T a b l e X I , was f o r m u l a t e d i n t e r m s o f d i m e n s i o n l e s s p a r a m e t e r
, shown i n T a b l e V I I I , w h i c h c o r r e c t l y r e f l e c t s t h e e f f e c t s o f
feed parameter T
Q as w e l l a s [l] Q , since k
a x has a n e g a t i v e
temperature c o e f f i c i e n t .
C r i t e r i a f o r R-A and IG, a l s o shown i n T a b l e X I , w e r e f o r m u -
l a t e d i n terms o f d i m e n s i o n l e s s p a r a m e t e r s e, a , B and b. They
a p p l y t o b o t h h o m o p o l y m e r i z a t i o n s and c o p o l y m e r i z a t i o n s f o r v a r i -
ous i n i t i a t o r s y s t e m s a t o r n e a r t h e c o n d i t i o n TR = T Q , and
w e r e d e v e l o p e d t h r o u g h m o d i f i e d Semenov-type a n a l y s e s (1,JL>Z) a n c *
numerous c o m p u t e r s i m u l a t i o n s ( 3 j 4 ^ 6 ) . Owing t o t h e f a c t t h a t
the dimensionless r a t e f u n c t i o n f o r homopolymerization c o n t a i n s

TABLE IV
BATCH MATERIAL BALANCE EQUATIONS FOR
FREE-RADICAL POLYMERIZATIONS AND COPOLYMERIZATIONS
In 1 1 I a t o r
_ d[ml . m
2 f
dt dt v
Monomer
d[m.] LCA
R + R w
-TT-- !k pk V
- = R = R. + R
dt i p ~ p
Moment
4lip-= [(2 - r)/2]R.
R
dt "
- (1 + r ) R . + (3 + 2 r ) R p + (2 + r)R p t
TABLE V
BATCH ENERGY BALANCE EQUATIONS FOR
FREE-RADICAL POLYMERIZATIONS AND COPOLYMERIZATIONS
Homo po 1 y me r i z a t i o n s
LCA
pC p Q * -AHR p - (UA/V)(T - T ) R
C o p o l y m e r i z a t i ons
L
P C p £ " (-AH j k )R p l k - (UA/VMT - T ) R
j k

TABLE VI
CHARACTERISTIC TIMES FOR HOMOPOLYMERIZATIONS
Definitions
CT Original Equ i v a l e n t Process
v-1
X. 2f[l] /(R,) o o
initiator consumption
W„/(R) monomer c o n v e r s i o n
o p o n
PC T / ( - A H ) ( R ) heat g e n e r a t i o n
p o o o
3G VI
A C T / ( A H ) ( R ) E
adiabatic induction
ad P p o - o ap
X R pC £/U heat removal

P
TABLE VI I
CHARACTERISTIC TIMES FOR COPOLYMERIZATIONS
CT Original Equivalent
X.
k
o PJ o
(-£)
X
Gjk
(G )
e o
3G \~1 -1
Gjk
ad
P I

TABLE V I I I
DIMENSIONLESS PARAMETERS FOR HOMOPOLYMERIZATIONS
Defini tion
Parameter For I n t e r p r e t a t i o n For Evaluation
B/b f I , ] / 2
a
k V i x =
" Vo J
V X / a
N " o k
e - (E' ) _ 1
ap'
E X ,/X. E /R T
ap ad G ap g o
X a d /X R (^)V(-AH)(k a p ) E; [m] [l]

o p o o
1 / 2
B
V A
ad (- A H
) ; E
P
[ m ]
o / p C
p o T
/ 2
b x,/X a d ^H)(k a x ) fE; [m] [l]
o p o o /pC T
p o
TABLE IX
DIMENSIONAL PARAMETERS FOR COPOLYMERIZATIONS
Pa r a m e t e r Def i n i t i on
ak A /X.
m
A / A
\ k m
( x } / e
<Vo l o k
1
(E')"
E A / A
' ad G
A A
ad R
B
V A
a d
b
V A
ad

w
TABLE X B
EXPRESSIONS FOR H" S
Dimensionless Termination Function S
§
H' = H/(H) Q g
2
Geometric Mean §
x r +
( l>o< lVl ^ o ^ o ^ H
JS-
+ x
CS
e x p E X P
x r
( i»o« i»o*i"i fery t*zWo fr IFFTT |
Phi Factor 5*
x X 2 r x x r x 2
» l'o''-l'o l' 0
* » ( » i > ( r i V i ( » 2 > o < 2 > o 2 + » 2>o< 2>o 2> §
=
H' £. Jl ^£1 + £l Jjl £1 J> ^
( r x r X P + r X 2m e x p
x r X 2m e x p 2 x m x 2 1
<( l>o< l'o l> l iWrj* *' l'o lVl' 2»Q' 2^ 2 lV P 2(m') 2
«* >o< 2'o 2> 2 2?TirT
P enultimate Effect
x + x
x r X
"< l>cAl>o < 2Vl + x r X
( l>o< l>o l < 2>o< 2»o 2
x _ ( x 2 ) 0 ( r 2 ) o + _
( 2>o
E' T' E'T' • E T E T

E' 2 1 T' ; E T 2 ' P2 '
x r m e x + ( x x
Dtl2 '
t iW i>o i p ( i t r i 2^iy PuTr) (x ) (r ) m exp 2 0 2 o 2 T W ) 1 Q
nx ) A m exp- Tr 2 l n
2 0 2
(x ) (r ) X m exp^Hfn o 2 2
E' T'
2 0 2 o 2 I T )

(x ) (r ) m exp ^ r + ( x ^
(x ) (r ) m ex 1 0
r + (x ) m1 0 1 P ( F T T 2 Q 2
to
POLYMERIZATION REACTORS AND PROCESSES
TABLE XI
DIMENSIONLESS CRITERIA FOR REACTOR PERFORMANCE
( p o l y m e r i z a t i o n s and C o p o l y m e r i z a t i o n s )
Phenomena Criteria
D-E a k > 1
R-A e « 1
a < 2
IG/ERA B > 20
b > 100

only one simple term

1 / 2
R' = n 1 exp E'T'/O + T-) (29)
H dp
and t h u s c o n f o r m s t o e q u a t i o n 16, i t c a n be shown by following

t h e p r o c e d u r e l e a d i n g t o e q u a t i o n 27 t h a t t h e p a r t l y dimensionless
monomer b a l a n c e e q u a t i o n
-3? " (30)

X
'JK
dt m p
c o n t a i n s o n l y a s i n g l e f u n c t i o n on t h e RHS and t h e p a r t l y dimen-

s i o n l e s s e n e r g y b a l a n c e e q u a t i o n t a k e s on a f o r m
G R
e e
w h i c h i s a m e n a b l e t o Semenov-type a n a l y s i s ( 1 ) . P e r t i n e n t d i m e n -
s i o n l e s s p a r a m e t e r s w e r e d e f i n e d i n t e r m s o f r e s u l t i n g CT's and
are l i s t e d in Table V I I I .
D u r i n g t h e d e v e l o p m e n t o f t h e s e c r i t e r i a t h e Semenov a n a l y s i s
was e x t e n d e d t o s y s t e m s w i t h h e a t - e x c h a n g e r r e s e r v o i r t e m p e r a t u r e s
d i f f e r e n t from feed temperatures (TR < T ) and w i t h d e l a y e d
Q
runaway ( l a r g e r v a l u e o f e ) , w h i c h r e s u l t e d i n s i g n i f i c a n t c o n -
c e n t r a t i o n d r i f t p r i o r t o runaway. S i n c e v a l u e s o f e for
c h a i n - a d d i t i o n p o l y m e r i z a t i o n s a r e n o t n e a r l y a s s m a l l as t h o s e
f o r t h e g a s e o u s e x p l o s i o n s i n v e s t i g a t e d by Semenov, R-A i s n o t as
s e n s i t i v e nor i s i t as e a r l y i n terrrs o f e x t e n t o f r e a c t i o n .
T h u s , t h e c r i t i c a l v a l u e o f R-A p a r a m e t e r 'a' i s n o t t h e same n o r
i s i t as c l e a r l y d e f i n e d . M o r e o v e r , i t i s p o s s i b l e t o e x p e r i e n c e
i n s e n s i t i v e ( p o t e n t i a l l y s t a b l e ) R-A. Sample e x p e r i m e n t a l r e -
s u l t s s h o w i n g s e n s i t i v e and i n s e n s i t i v e R-A have been p l o t t e d i n
F i g u r e s 1 and 2, r e s p e c t i v e l y .
In t h e c o m p u t e r s i m u l a t i o n s i t was n e c e s s a r y t o s t u d y r e -
a c t i o n s e q u e n c e s more c o m p l e x t h a n t h o s e s t u d i e d by B a r k e l e w ,
which consequently led to r a t e f u n c t i o n s having double r a t h e r
than s i n g l e c o n c e n t r a t i o n dependence. Numerous r e s u l t s f r o m b o t h
t h e o r e t i c a l and c o m p u t a t i o n a l a n a l y s e s , i n c l u d i n g t h e e f f e c t s o f
e and TR , have been d e s c r i b e d e l s e w h e r e ( s e e e s p e c i a l l y F i g u r e
8 of reference 1).
C r i t e r i a f o r s e n s i t i v i t y , B and b , are also c r i t e r i a f o r
v a l i d i t y o f t h e e a r l y R-A a p p r o x i m a t i o n (ERA), w h i c h s a y s t h a t
R-A o c c u r s v i r t u a l l y when m = 1 = I . W h i l e B f o r most f r e e -
r a d i c a l p o l y m e r i z a t i o n s l i e s w i t h i n a narrow range, which exceeds
the c r i t i c a l v a l u e , b v a r i e s w i d e l y from s u b c r i t i c a l t o c r i t i c a l
v a l u e s , d e p e n d i n g s t r o n g l y u p o n c h o i c e o f i n i t i a t o r and f e e d p a r a -
meters [ l ] and
0 T
Q . Decreasing values of b generally
depress the c r i t i c a l v a l u e of 'a' slightly. Computed R-A

ofia
o° •
•o T R \}/jt RUN o
07 975 -0035 44 0 o
0032 43 A o a •
0029 42 •
.0027 34 O o
• o °
o •
LJ o •
o •
o
O • o
u
n LJ
n
O
•
o •
A A A A A A A A A A & 6 A A ^ A A A A A A A
on A
o g ° O
A
A o o o o 0 0 o ° 8 d o o o
0 0
O D a A A 0
0
O R A O

Polymer Engineering and Science
Figure 1. Experimental data from styrene polymerization initiated with benzoyl peroxide show-
ing R-A sensitivity to parameter U/l (5)
l 0 T R [)/£ RUN
m 0 3 5 l 0 2 5 0 0 4 0 5 1
A A m m m * O
\ m .0035 52 •
A
m • .0029 53 O
• A .0028 55 A
• A 0027 56 •
0 0 2 6 5 4
• * • ft a M ^ A A a "
• & o * * *
6°

120 360 TIME SEC. 840 1080

Figure 2. Experimental data from styrene polymerization initiated with benzoyl peroxide less
R-A sensitivity to parameter 0
[I] (5)
b o u n d a r i e s f o r h o m o p o l y m e r i z a t i o n s a r e shown i n F i g u r e 3 -
1
From T a b l e s V I I I and XI we f i n d t h a t R-A may be i n d u c e d ('a
r e d u c e d b e l o w c r i t i c a l v a l u e ) by r a i s i n g T , [ l ] o r E ( v i a Ed) a s 0 0 a p
w e l l a s by l o w e r i n g U/£ . We a l s o f i n d t h a t IG may be i n d u c e d
(b i n c r e a s e d a b o v e c r i t i c a l v a l u e ) by r a i s i n g [l] , lowering T 0 0
o r l o w e r i n g kd ( v i a l o w e r Ad o r h i g h e r Ed). Consequently,
we must c o n c l u d e t h a t w h i l e a h i g h v a l u e o f T contributes to Q
t h e o n s e t o f R-A, i t s i m u l t a n e o u s l y m i t i g a t e s i t s s e n s i t i v i t y .
F u r t h e r m o r e , w h i l e i n i t i a t o r s a z o - b i s - i s o b u t y r o n i t r i l e (Ad ^ 1 0 ^ 5
s e c - 1 , Ed ^ 3 0 K c a l ) , b e n z o y l p e r o x i d e (Ad * loH sec" , 1
Ed ^ 3 0 K c a l ) and d i - t e r t - b u t y l p e r o x i d e (Ad * 1 0 ^ 5 s e c " , 1
Ed ^ 3 7 K c a l ) a r e g e n e r a l l y r e g a r d e d a s i n c r e a s i n g i n " s l o w n e s s "
i n t h e d i r e c t i o n 1 i s t e d , b e c a u s e Ad d e c r e a s e s o r Ed i n -
creases, o r both, t h e i r value o f b increases i n the order
shown, a l l o t h e r f a c t o r s r e m a i n i n g e q u a l . C o n s e q u e n t l y , we must
c o n c l u d e t h a t ' s l o w ' i n i t i a t o r s a r e more l i k e l y t o p r o d u c e u n -
s t a b l e R-A's t h a n f a s t o n e s . The a b o v e c o n c l u s i o n s i n v o l v i n g T 0
and i n i t i a t o r c h o i c e have been o b s e r v e d e x p e r i m e n t a l l y .

The r a t e f u n c t i o n f o r c o p o l y m e r i z a t i o n c o n t a i n s a summation
o f t e r m s , each o f which
R
pjk = » A ' , / 2
H- « p E ; p J k T V ( l +T-) (32)
i s more c o m p l e x t h a n e q u a t i o n 1 6 , and t h e r e s u l t i n g monomer

balance equation i s
. dm = y y x T l ( } R . (33)
dt L^tL-j j k N
k'o p j k
j k
The c o r r e s p o n d i n g e n e r g y balance
k
J G R
e e
i s c o n s e q u e n t l y n o t a m e n a b l e t o Semenov-type a n a l y s i s . The f u n c -
t i o n a l form o f f o r each o f t h e t h r e e t e r m i n a t i o n models
c i t e d i s g i v e n i n T a b l e X. In o r d e r t o remedy t h i s s i t u a t i o n ,
e q u a t i o n s 3 2 , 3 3 and 3k w e r e f o r c e d t o c o n f o r m t o 2 9 , 3 0 and 31 by
r e c o g n i z i n g a l t e r n a t i v e , e q u i v a l e n t d e f i n i t i o n s ( t h i r d column i n
T a b l e V I ) o f CT's f o r homopolymer b a l a n c e s and s u b s e q u e n t l y a p -
p l y i n g them t o c o p o l y m e r b a l a n c e s . In t h i s way, a p p r o x i m a t e c o -
polymer b a l a n c e s
|S - A" m l 1 1 / 2
e x p E ' T V O + T*) (35)
m

NON RUNAWAY B = fiO
2.1
41
32
e=o.04
6 E - * 1.467
R
e «=o.O
- RUNAWAY
s
(/^n)o 3000
r=i.o

1 1 1 1 1 1 1 1 1 1 I I I i I 1 I 1 I I I 1 I
2 3 4
10 10 10

b
Figure 3. Computed IG boundaries for homopolymerizations (4)

1/2
m I exp E ' T V O + T') - X ^ ( T - T*) (36)
G R
e e
w e r e d e v e l o p e d i n w h i c h CT's w e r e o b t a i n e d u s i n g e q u i v a l e n t d e f i -
n i t i o n s (second c o l u m n i n T a b l e VI l) and a l l i m p o r t a n t dimension-
l e s s p a r a m e t e r s f o r c o p o l y m e r s ( T a b l e I X ) , i n c l u d i n g an o v e r a l l
a c t i v a t i o n energy E', w e r e d e f i n e d i n a c c o r d a n c e w i t h t h e i r
homopolymer c o u n t e r p a r t s ( T a b l e V I I I ) . I t was f o u n d t h a t n o t
o n l y d i d p a r a m e t e r s a , B and b so d e f i n e d c h a r a c t e r i z e R-A and IG
b e h a v i o r o f c o p o l y m e r i z a t i o n s , but a p p r o x i m a t e e q u a t i o n s 3 5 and
36 c l o s e l y t r a c k the exact balance equations over wide conversion

and t e m p e r a t u r e r a n g e s , e x c e p t when one comonomer i s e x h a u s t e d o r
when t h e s y s t e m i s n e a r IG ( 7 ) . V e r i f i c a t i o n of the a p p l i c a b i l i t y
o f R-A b o u n d a r i e s t o c o p o l y m e r i z a t i o n s i s e v i d e n t i n F i g u r e 4 .
C o m p a r i s o n s between " e x a c t " c o m p u t e r m o d e l s and c o p o l y m e r a p p r o x i -

mate f o r m s (CPAF) a p p e a r i n F i g u r e 5 .
P o l y m e r and Copolymer P r o p e r t i e s
Owing t o t h e c h a i n n a t u r e o f c h a i n - a d d i t i o n p o l y m e r i z a t i o n s
and c o p o l y m e r i z a t i o n s w i t h t e r m i n a t i o n , o n l y a s m a l l f r a c t i o n o f
t h e u l t i m a t e p r o d u c t m o l e c u l e s grow a t any i n s t a n t , but t h e y grow
t o t h e i r f i n a l s i z e so r a p i d l y t h a t t h e y may be r e g a r d e d a s i n -
stantaneous product without a p p r e c i a b l e e r r o r . The f i n a l product
i s an a c c u m u l a t i o n o f a l l i n s t a n t a n e o u s p r o d u c t s formed d u r i n g
t h e c o u r s e o f p o l y m e r i z a t i o n , and i t s c u m u l a t i v e p r o p e r t i e s a r e
c o m p o s i t e s o f t h e i n s t a n t a n e o u s p r o p e r t i e s . Examples a r e d e g r e e
o f p o l y m e r i z a t i o n d i s t r i b u t i o n , DPD, c o p o l y m e r c o m p o s i t i o n d i s -
t r i b u t i o n , CCD, and t h e i r r e s p e c t i v e a v e r a g e v a l u e s , DP and CC
(see T a b l e X I I ) . D i s p e r s i o n o f t h e s e d i s t r i b u t i o n s i s c o n s e -
quently the r e s u l t of the inherent d i s p e r s i o n of the molecular
p r o c e s s e s a t e a c h i n s t a n t , termed s t a t i s t i c a l d i s p e r s i o n , t o -
g e t h e r w i t h t h e e f f e c t o f t i m e d r i f t s u p e r i m p o s e d upon i t , termed
d r i f t d i s p e r s i o n , w h i c h i s a c h a r a c t e r i s t i c o f b a t c h r e a c t o r s and
w h i c h can o n l y r e s u l t i n g r e a t e r d i s p e r s i o n i f a l l o w e d t o o c c u r .
Thus, the response o f these p o l y m e r i z a t i o n s t o changes i n a p a r a -
m e t e r , s u c h a s t e m p e r a t u r e o r c o m p o s i t i o n , may be v i e w e d a s m a n i -
f e s t i n g i t s e l f i n two w a y s , i n s t a n t a n e o u s and d e l a y e d (3).
I t i s w e l l known t h a t low v a l u e s o f T Qand [ l ] lead to
Q
h i g h DPs. T h i s i s a c c u r a t e l y r e f l e c t e d by p a r a m e t e r (v^) Q , the

i n i t i a l k i n e t i c c h a i n length (Table X I l l ) , which i s a q u o t i e n t of
feed composition r a t i o xQ and d i m e n s i o n l e s s p a r a m e t e r a ^ . T h u s ,
given x , a small v a l u e of
Q w o u l d seem t o f a v o r h i g h i n i t i a l DP.
On t h e o t h e r hand, c r i t e r i o n ak < 1 s i g n a l s a downward d r i f t o f
i n s t a n t a n e o u s DP d u r i n g i s o t h e r m a l p o l y m e r i z a t i o n (3) w h i c h has
the o p p o s i t e e f f e c t . F u r t h e r m o r e , u n d e r non i s o t h e r m a l c o n d i t i o n s ,
r i s i n g t e m p e r a t u r e s e x a c e r b a t e t h i s downward d r i f t . Consequently,
we c o n c l u d e t h a t d r i f t r e s p o n s e and i n s t a n t a n e o u s r e s p o n s e may be

BIESENBERGER Thermal Runaway
A Hoiflopolymer
4
Boundary
• • 8^41
€=0.025
• .26 S AN
• .38 AN MMA
10 2
10 3
b ™ 4 1
° 5
Figure 4. Computed IG boundaries for copolymerizations

8
Ο
Ι
ο
ο
%
V.
•a
•8
Ο
V.
I
I
ο
<j
ο
ο.
"S
8
I
S

2. BIESENBERGER Thermal Runaway
TABLE XI I
POLYMER AND COPOLYMER PROPERTIES
Instantaneous
GTJ. - 2 R / ( 2 - r ) R . = [2 - r ) ] [ l - k [m]/[l] , / 2
]
N mst i ax
k ( 2 f , / 2
ax = V kdM
= R / R = v
^ i n s t pl p l
CumulatIve
2
x w = [u ]/[v']
y = ([m,] o - [ ,])/([m] m o - tm])

TABLE X I I I
DIMENSIONLESS CRITERIA FOR POLYMER AND COPOLYMER PROPERTIES
Target Property Criterion
Isothermal Nonisothermal
Instantaneous Drift Drift
Response Response Response
High DP/LCA large ( v ) N Q large large
a > 1
N a r r o w DPD Statistical a = 1 k
Dispersion
H i g h c c (comonomer 1) l a r g e (vj) Q l a r g e 3^ ?
N a r r o w CCD Statistical ?
D i s p e r s ion

made t o o c c u r i n o p p o s i t e d i r e c t i o n s by a p p r o p r i a t e a d j u s t m e n t o f
r e a c t i o n parameters, but i t does not n e c e s s a r i l y f o l l o w t h a t an
i n i t i a l d r o p i n i n s t a n t a n e o u s DP due t o > 1 , s a y , c a n be
o f f s e t by an e x p e c t e d upward d r i f t i n i t s e f f e c t on c u m u l a t i v e DP
of t h e f i n a l product. I t may be shown ( F i g u r e 6 ) , h o w e v e r , t h a t
d r i f t c a n be r e d u c e d and t o t a l d i s p e r s i o n o f DPD t h e r e b y k e p t t o
a minimum by c o u n t e r a c t i n g downward d r i f t i n DP due t o R-A tem-
peratures with a large value of . T h e s e e f f e c t s have been
summarized i n T a b l e X I I I .
O ' D r i s c o l l , e t a l . (11) have p o i n t e d o u t t h a t t h e s i g n and
m a g n i t u d e o f t h e v e r t i c a l d i s t a n c e , vj - X] , between t h e com-
p o s i t i o n c u r v e and d i a g o n a l on t h e c c d i a g r a m a r e m e a s u r e s o f t h e
o r
d i r e c t i o n and d e g r e e o f d r i f t o f t h e i n s t a n t a n e o u s c c , ( y ) | s tn
V] . I t c a n be shown t h a t 3k i s an e q u i v a l e n t m e a s u r e o f d r i f t .
In f a c t , t h e two m e a s u r e s a r e r e l a t e d v i a
V n = ( 1 3 ) / 3 ( 3 7 )
l " l fcpo ' k k '
T h u s , when 3|< < 1 , ( y ) j t n s d r i f t s downward and when 3|< > 1 i t

d r i f t s upward. We t h e r e f o r e c o n c l u d e t h a t t o a c h i e v e a t a r g e t c c
h i g h i n comonomer 1, s a y , i n s t a n t a n e o u s r e s p o n s e c o n s i d e r a t i o n s
( T a b l e IX) s u g g e s t t h a t , g i v e n ( x j ) a l o w v a l u e f o r 3k »s r e -
0 >
q u i r e d , w h e r e a s e q u a t i o n 37 i n d i c a t e s t h a t 3^ < 1 w o u l d c a u s e t h e
c o m p o s i t i o n t o d r i f t downward, o p p o s i t e t o t h e t a r g e t d i r e c t i o n .
=
O b v i o u s l y , when 3k 1 > no d r i f t o c c u r s .
I t c a n be shown t h a t h i g h t e m p e r a t u r e l e v e l s and R-A have
v i r t u a l l y no b r o a d e n i n g e f f e c t on CCD d i s p e r s i o n b e c a u s e 3k has
a s m a l l t e m p e r a t u r e c o e f f i c i e n t , w h i c h f r e q u e n t l y e v e n t a k e s on
negative values causing d r i f t dispersion to a c t u a l l y lessen a t
high temperatures. F i g u r e s 7 and 8 show t h e s m a l l n e s s and d i r e c -
t i o n ( i m p r o v e m e n t ) o f t e m p e r a t u r e e f f e c t on d r i f t , and t h e a b i l i -
t y o f 3k t o c h a r a c t e r i z e d i r e c t i o n ( s e e c r o s s o v e r i n F i g u r e 7
and c o r r e s p o n d i n g d r i f t s i n F i g * 8) a s w e l l a s m a g n i t u d e o f d r i f t *
As a f i n a l n o t e i t s h o u l d be p o i n t e d o u t t h a t R-A p a r a m e t e r s
f o r h o m o p o l y m e r i z a t i o n and c o p o l y m e r i z a t i o n c a n be e v a l u a t e d f r o m
i n i t i a l k i n e t i c rate data using the i n t e r p r e t a t i o n s given to
c h a r a c t e r i s t i c t i m e s i n T a b l e s VI and V I I . C o u p l i n g between
c h a n g i n g r e a c t i o n v i s c o s i t y and k i n e t i c c o n s t a n t s and o t h e r t r a n s -
p o r t p r o p e r t i e s was n e g l e c t e d b e c a u s e runaway g e n e r a l l y o c c u r s
e a r l y d u r i n g r e a c t i o n , and s u c h e f f e c t s a r e c o n s e q u e n t l y o f m i n o r
importance.

POLYMERIZATION REACTORS AND PROCESSES
400
-(XN)inst
- C U M . XN
C A S E S 7,8,9
TABLE 17
300
REF. 3
/ ISOTHERMAL
200
ix
100
NON-ISOTHERMAL,
ADIABATIC
0.05 0.10 0.15 0.20 0.25

Figure 6. Computed drift curves for instantaneous and cumulative DPs (3)

BIESENBERGER Thermal Runaway

IQI
CO I QI
—-R
O
5*
9
K
6 995
y y
o
N Nst
&*.820
i Isothermal
QiQuasi-Isothermal
R Runaway
2
A Adiabatic
0 = .598 _ ____

1 ! J 1 1 ) 1 1 J
8.19 0.20 0.38 0.40 0.58 0.60 01.79
PHI 3
Figure 8. Computed drift curves for instantaneous and cumulative CCs of styrene-methyl meth-
acrylate polymers initiated with AIBN
SYMBOLS NOT DEFINED IN TEXT
A =
pre-exponential c o e f f i c i e n t i n rate constant expressions
w i t h a p p r o p r i a t e s u b s c r i p t s o r heat t r a n s f e r s u r f a c e area.
Cj = g e n e r a l r e a c t i o n component j o r d i m e n s i o n l e s s c o n c e n t r a -
t i o n o f component j .
E = a c t i v a t i o n energy i n r a t e constant e x p r e s s i o n s w i t h appro-
priate subscripts.
E^ =s d i m e n s i o n l e s s a c t i v a t i o n e n e r g y f o r c o p o l y m e r i z a t i o n d e -
f i n e d i n T a b l e IX.
E = E / R T
rk rk g o
E E E / R T
Dk - ( tjkkj " tkkkk) g o
f = initiator efficiency factor
fj = i n i t i a t o r e f f i c i e n c y f a c t o r f o r comonomer j
I = i n i t i a t o r o r dimensionless i n i t i a t o r concentration
k = rate constant with appropriate subscript

2 f k / k
kap " M d t>!£
kax - k p / ( 2 f k k ) l / 2 d t
k
a p j k = kpjk k j ( 2 f k d / k j j k )p A t M
] / Z
k
t = k + k t c t D
m = monomer o r d i m e n s i o n l e s s monomer c o n c e n t r a t i o n
mj = comonomer j o r d i m e n s i o n l e s s c o n c e n t r a t i o n o f comonomer j
m =
o generalized i n i t i a t o r o r dimensionless concentration of
generalized i n i t i a t o r
m = x-mer o r d i m e n s i o n l e s s c o n c e n t r a t i o n o f x-mer
x
P = a c t i v e i n t e r m e d i a t e s o f a l l l e n g t h s and t y p e s
P j = a c t i v e j - m e r i n t e r m e d i a t e s o f a l l l e n g t h s w i t h comonomer j
as t e r m i n a l u n i t
P = a c t i v e i n t e r m e d i a t e s o f a l l l e n g t h s and t y p e s
x
p =
x,j a c t i v e i n t e r m e d i a t e o f l e n g t h x w i t h comonomer j a s
terminal u n i t
P j = a c t i v e i n t e r m e d i a t e o f a n y l e n g t h w i t h comonomer j a s
terminal u n i t
P j P k = a c t i v e i n t e r m e d i a t e o f a n y l e n g t h w i t h comonomer j
and k a s p e n u l t i m a t e and u l t i m a t e u n i t s , r e s p e c t i v e l y
R = r a t e f u n c t i o n f o r t o t a l monomer c o n v e r s i o n ( r a t e o f p o l y -
m e r i z a t i o n ) o r any r a t e f u n c t i o n w i t h a p p r o p r i a t e s u b s c r i p t
Rp = rate function defined i nTable I
t
Rg = gas constant
r = ktc/kt or reactivity ratio with appropriate subscript
T - (T - T ) / T 0 0
U = o v e r a l l heat t r a n s f e r c o e f f i c i e n t
V = r e a c t o r volume
xj^j = number a v e r a g e DP
x w= w e i g h t a v e r a g e DP
x Q- [m]Q/[m ] 0 0
Xj = [ m j j / [ m ]
y = m o l e f r a c t i o n o f comonomer 1 i n c o p o l y m e r

A k / k
k -( tjkkj tkkkk)o
k k
+ = k / tl11 t22
t l 2
$ = 1 - m = f r a c t i o n monomer c o n v e r t e d
6 = E ' T"
a p
X.A = c h a r a c t e r i s t i c t i m e s w i t h a p p r o p r i a t e s u b s c r i p t s
y k - |<th moment o f DPD
[ ] = molar c o n c e n t r a t i o n
prime' = dimensionless q u a n t i t y
Subscripts
ap = a p p a r e n t o r lumped
d = decomposition of i n i t i a t o r
G = g e n e r a t i o n o f heat
i = i n i t i a t i o n o f polymer c h a i n s
j,k = comonomer o r r e p e a t u n i t o f t y p e j o r km w h e r e
j = 1,2 and k = 1,2

m = monomer d e p l e t i o n
o = feed c o n d i t i o n s (except i n m )
p = propagation
r = reactivity ratio
R = r e s e r v o i r ( t h e r m a l ) o r removal o f h e a t
t = termination
inst = instantaneous
LITERATURE CITED
1. B i e s e n b e r g e r , J. A., Capinpin, R. and Sebastian, D., A p p l .

Pol. Symp. (1975) 2 6 , 2 1 1 .
2. S e b a s t i a n , D. H. and B i e s e n b e r g e r , J. A., J. Appl. Pol. Sci.
(in press).
3. B i e s e n b e r g e r , J. A. and Capinpin, R., Pol. Eng. Sci. (1974)
14, 7 3 7 .
4. B i e s e n b e r g e r , J. A., Capinpin, R. and Y a n g , J. C., Pol. Eng.
Sci. (1976) 16, 101
5. S e b a s t i a n , D. H. and B i e s e n b e r g e r , J. A., Pol. Eng. Sci.
(1976) 16, 117.
6. S e b a s t i a n , D. H. and B i e s e n b e r g e r , J. A., Pol. Eng. Sci.
(in press).
7. S e b a s t i a n , D. H. and B i e s e n b e r g e r , J. A., " C h e m i c a l R e a c t i o n
E n g i n e e r i n g - H o u s t o n " , ACS Symp. Series No. 6 5 ,
W a s h i n g t o n , D.C. ( 1 9 7 8 ) .
8. S e b a s t i a n , D. H., Ph.D. Thesis i n C h e m i c a l E n g i n e e r i n g
(1977) D e p a r t m e n t o f C h e m i s t r y and C h e m i c a l E n g i n e e r i n g ,
Stevens Institute o f T e c h n o l o g y , Hoboken, New J e r s e y
9. F r a n k - K a m e n e t s k i i , D. A., "Diffusion and Heat E x c h a n g e i n
Chemical Kinetics", (1955) Princeton University Press,
Princeton.
10. B a r k e l e w , C. R., Chem. Eng. P r o g . Symp. S e r . ( 1 9 5 9 ) , No. 2 5 ,
55, 3 7 .
11. O'Driscoll, K. F. and K n o r r , R. ( 1 9 6 9 ) , M a c r o m o l e c u l e s 2,
507.
RECEIVED January 15, 1979.


Thermal Runaway in Chain-Addition Polymerizations and Copolymerizations

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2

Thermal Runaway in Chain-Addition Polymerizations

Department of Chemistry and Chemical Engineering, Stevens Institute of Technology,

The objectives of this presentation are to discuss the gener-

and thermal energy balances

of the forms shown in equations 1 and 2. Polymer property analy-

Henderson and Bouton; Polymerization Reactors and Processes

with termination, whose general characteristics are shown in

Termination scheme 11 applies to the geometric mean and phi factor

Parameters and Variables

Reaction rate functions expressing rate of polymerization R

R - R([m], [m ],T)Q (13)

Henderson and Bouton; Polymerization Reactors and Processes

netic properties (r,Ap,E ,A ,Et) a r e d e t e r m i n e d f o r t h e most

where k a p i s a lumped o r c o m p o s i t e r a t e c o n s t a n t . Free-radical

R' = R/(R) (15)

R' = f ( t ) g ( T ' ) (16)

Henderson and Bouton; Polymerization Reactors and Processes

Symmetry k a p j k = k^. R p j | < = R p ( < j from QSSA

Henderson and Bouton; Polymerization Reactors and Processes

EXPRESSIONS FOR FUNCTION H

Henderson and Bouton; Polymerization Reactors and Processes

g(T') = e x p E ' T V ( 1 + T') (21)

g ( 6 ) = e x p 0/(1 + e6) (22)

We n o t e t h a t u n d e r f e e d c o n d i t i o n s (R') = 1 0 since f(0) = 1

V' = p/(p) Q (25)

Henderson and Bouton; Polymerization Reactors and Processes

in which a c h a r a c t e r i s t i c time (CT) f o r e a c h p r o c e s s may be de-

w h i c h a r e seen t o c o n f o r m t o e q u a t i o n 24. Following the proce-

The c o n d i t i o n o f t h e r m a l runaway (R-A) i n p o l y m e r i z a t i o n and

Henderson and Bouton; Polymerization Reactors and Processes

4lip-= [(2 - r)/2]R.

Henderson and Bouton; Polymerization Reactors and Processes

X R pC £/U heat removal

CHARACTERISTIC TIMES FOR COPOLYMERIZATIONS

Henderson and Bouton; Polymerization Reactors and Processes

Parameter For I n t e r p r e t a t i o n For Evaluation

X a d /X R (^)V(-AH)(k a p ) E; [m] [l]

DIMENSIONAL PARAMETERS FOR COPOLYMERIZATIONS

Henderson and Bouton; Polymerization Reactors and Processes

Henderson and Bouton; Polymerization Reactors and Processes

ACS Symposium Series; American Chemical Society: Washington, DC, 1979.

Henderson and Bouton; Polymerization Reactors and Processes

only one simple term

and t h u s c o n f o r m s t o e q u a t i o n 16, i t c a n be shown by following

-3? " (30)

c o n t a i n s o n l y a s i n g l e f u n c t i o n on t h e RHS and t h e p a r t l y dimen-

Henderson and Bouton; Polymerization Reactors and Processes

Henderson and Bouton; Polymerization Reactors and Processes

Henderson and Bouton; Polymerization Reactors and Processes

ACS Symposium Series; American Chemical Society: Washington, DC, 1979.

Ed ^ 3 0 K c a l ) and d i - t e r t - b u t y l p e r o x i d e (Ad * 1 0 ^ 5 s e c " , 1

and i n i t i a t o r c h o i c e have been o b s e r v e d e x p e r i m e n t a l l y .

i s more c o m p l e x t h a n e q u a t i o n 1 6 , and t h e r e s u l t i n g monomer

Henderson and Bouton; Polymerization Reactors and Processes

NON RUNAWAY B = fiO

Henderson and Bouton; Polymerization Reactors and Processes

ACS Symposium Series; American Chemical Society: Washington, DC, 1979.

Polymer Engineering and Science

Figure 3. Computed IG boundaries for homopolymerizations (4)

36 c l o s e l y t r a c k the exact balance equations over wide conversion

C o m p a r i s o n s between " e x a c t " c o m p u t e r m o d e l s and c o p o l y m e r a p p r o x i -

h i g h DPs. T h i s i s a c c u r a t e l y r e f l e c t e d by p a r a m e t e r (v^) Q , the

Henderson and Bouton; Polymerization Reactors and Processes