J. A. BIESENBERGER, R. CAPINPIN, and J. C.

YANG Department o f Chemistry and Chemical Engineering Stevens Znstitute o f Technology Hoboken, New Jersey
A computer study was made to determine the thermal ignition criteria and ignition boundaries for chain-addition polymerization in a well-mixed batch system using a simple kinetic model. The occurrence of thermal runaway was shown to be a function of initiator type, feed conditions, and heat transport parameters. It was found that thermal runaway does not occur early with respect to monomer and initiator conversions and that for strongly dead-ending systems, the sensitivity characteristic of ignition disappears. The role of various dimensionless Darameters in characterizing reaction behavior is also discussed.

INTRODUCTION
uring the manufacture of chain addition polymers, high reaction temperatures are often encountered. Mostly they are inadvertent and appear in the form of hot spots, which are the result of incomplete removal of reaction exotherm. Occasionally, they may be employed intentionally to facilitate rapid conversion of monomer. Almost without exception, however, high reaction temperatures are regarded as undesirable because they are expected to lead to reactor instability, low ultimate monomer conversion owing to dead-ending (D-E), and low-molecular-weight polymer with broad molecular weight distributions. As we will show later, such dire expectations may not always be justified. An extensive investigation into the phenomenon of thermal runaway in chain addition polymerizations is currently under way in our laboratories at Stevens Institute. Its objectives are threefold: first, to characterize thermal runaway in terms of pertinent reaction parameters; second, to develop criteria and boundaries which predict the onset of thermal ignition (IG) in terms of these parameters; and, third, to elucidate the effects of thermal runaway (R-A) on the properties of polymer products. Three parallel approaches are being utilized: (1)semi-theoretical analyses; (2)computer studies; and (3)experimentation. The present paper contains a computer analysis of ideal free-radical polymerizations at high temperatures for the rapid conversion of monomer to polymer with acceptable molecular weights. It thus deals with the phenomenon of thermal runaway and has as one of its primary goals the establishment of generalized ignition criteria and ignition boundaries. It is the second of a series on the subject of temperature variation during chain-addition polymerization.

In the first paper (1) we discussed thermal drift. During a recent ACS symposium on Polymerization and Polycondensation Processes (2,3) we presented a semi-theoretical, Semenov-type analysis of thermal ignition in chain-addition polymerizations. Subsequent papers will give experimental results for specific systems and will thus deal with kinetic models which exhibit non-ideal behavior such as thermal initiation, chain transfer, gel-effect, depolymerization, etc. We define thermal runaway as the state in which reaction temperature exhibits autoacceleration, i.e., rapid rise

( dt

>> 0 with upward concavity

. ( d2T > 01. We have previously defined (3) thermal

ignition (IG) as parametrically sensitive runaway. Here the transition from non-runaway to runaway is sudden and sensitive to slight variations in reaction parameters. The distinction is important. It may even prove desirable to operate a polymerizer in a runaway mode which is not unstable, i.e., not capable of igniting or extinguishing.

KINETIC MODEL
For simplicity and generality at this stage, we consider the ideal kinetic scheme shown in Table 1. Thermal initiation, reverse propagation, chain transfer and gel-effect have all been ignored for the time being to facilitate dimensional analysis under non-isothermal conditions. They will be included in subsequent studies where appropriate to a particular polymerization. For free-radical polymerizations, the concentration of initiating species [m,] is just twice the initiator concentration [ I ] , and the value of initiation rate ki is just a constant fractionf of the value of initiator decomposition
101

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

J. A. Biesenberger, R. Capinpin, a n d ] . C. Yang

Table 1. Kinetic Steps and Rate Functions for Free Radical Polymerizations
~~

Reaction
~~

Nature
{Decomposition of initiator, or initiation of kinetic chains) {Initiation of polymer chains, or propagation of kinetic chains} Propagation of polymer and kinetic chains Termination of kinetic and polymer chains by combination Termination of kinetic and polymer chains by disproportionation

Rate Function

m ,

kd

Po

P ,
P ,

+m +m
*mx

A PI
A ,P ,,

Ri = ki[m,l

p
Px + P ,

mx+r

+ mr

I
$41
T'

R, = kJm1 [PI Rt = kt[PI2

where kt = kt,

+ k,

rate kd, i.e., ki = f k,. The use off is customary and accounts for imperfect catalytic efficiency. Partly dimensionless material and energy balances for free-radical polymerization in a well-mixed batch reactor with heat removal, as they appeared in the first paper (l),appear again in Table 2, but without the gel-effect function (G = 1) and with typographical errors corrected. Corresponding characteristic times appear in Table 3. It should belnoted that characteristic time for initiator depletion, &, has been defined more appropriately in the present study

Table 2. Partly Dimensionless Balance Equations for Batch Polymerizations

Initiator balance dmodt

Al m..exp[E;(

Monomer balance dm dt
-

f m, e x ~ [ E;(
x&

z ) ] +
1

than in previous ones, hi (1, 4). In this way initiator efficiency is properly included, and the resulting modified dead-end parameter a;

h,/A; = ( ~ k / f

(2)

becomes analogous, as it should, to dimensionless group $ used in an early paper (5) which correctly characterized the dead-end phenomenon. In fact a; = 2$. Completely dimensionless balances are shown in Tubles 4 and 5. New dimensionless variables and parameters have been introduced in order to conform, where possible, to existing literature on thermal ignition in combustion processes (6-8), which has come to our attention subsequent to completion of our early studies on ignition in polymerization processes (1, 3). It must be emphasized that, while thermal ignition during polymerization does not generally result in flames or detonation, the possibility of runaway temperature with thermal instability is very real, as it is with all exothermic chemical reactions, and its formal description is identical to that of thermal explosions (9). Only the specific kinetics involved and the possible influence of runaway temperatures on polymer properties are aspects of ignition phenomena that are unique to polymerization. It should be noted that a new dimensionless temperature 8 and a new characteristic time had have been introduced. The former conforms to the literature (6-9) and automatically gives rise to the latter (see E q 5-2 in Table 5 ) , which is identical to Frank-Kamenetskii's "adiabatic induction period", and which turns out to be more useful in formulating an ignition criterion, (a < I), than A, was in our previous paper (I), (yT < I), as we shall presently show.
I02

+ (3 + 2r)
~

mmt exp[ E&(

&)]
(2-5)

Am

(2 A,aif + r ) x ~ mzexp (2E ,:

- E;) ( T 'Tl)]

Energy balance

Assumptions: constant p and QSSA Definitions of dimensionless variables

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

A Study of Chain Addition Polymerizations with Temperature Variations: I I .

Table 3. Some Kinetic and Thermal Characteristic Times Process Table 5. Some Approximate Equations
Dimensionless monomer balance

Partly dimensionless energy,balancF

Completely dimensionless,energy,balance

(5-3)
Instantaneous DP
. -

Assumptions: LCA, in addition to those made in Table 2.

Table 6. Dimensionless Parameters Table 4. Completely Dimensionless Balance Equations for Batch Polymerizations
Energy Balance

Definition

Classification
Thermal Thermal Thermal Monomer (reactant) Initiator (reactant) Initiator (reactant) Polymer (product) Polymer (product)

eR= E ,,
E

6 = B 6 - (0 - 0,)
Monomer balance-1st moment

=R , T , / E , a = URgT,2/(-AH)I Aa,E,,[ml,[mJd

( T~ TJ/R,T:

exp(- E ,I R , T d B = ( -AH)E,,[~~,/PC,R,T,~ b = (-AH)fA,,E,,[ml,[m,l~ exp[-(E,, RgToI/AipCuRgT,2 EE[ = EJEap

(vN),
-

El)/

Aap[mlo exp[-(Eap A,IAt

E~/RgT,IIAi[m~l~

Initiator b a l a n c e q t h moment

Table 7. Significance of Parameters

Second moment

+ +
(2

(3 + 2r) (1 - @) (1 - $14 aB

exp

(A)
RESULTS
In the present analysis all equations (in Table 4 ) were solved numerically on a high-speed digital computer. Two approaches were used. In the first, specific values were assigned to all reaction and reactor parameters listed in Table 8, and the balance equations were subsequently solved. Thermodynamic and transport properties were chosen with reference to a particular system, mostly styrene, initiator properties with reference to three specific initiators, azobisisobutyronitrile (AIBN), benzoyl peroxide (BP), and di-t-butylperoxide (DTBP), and heat transport parameters with reference to our own ignition-point apparatus (to be described in the third paper of this series). Feed conditions were systematically varied. The occurrence of runaway vs non-runaway
1 03

+ r) (YN),(~- @)'
aB
7

where . = d and d7 Instantaneous DP

= t/AR

Dimensional analysis has indicated that eight dimensionless parameters are necessary to describe our system. They are listed in Table 6 and their significance in terms of characteristic times is shown in Table 7.
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

1.A . Biesenberger, R . Capinpin, a n d ] . C. Yung

Table 8. Reaction and Reactor Parameters for Batch Polymerizations Monomer-polymer system Thermodynamic -AH, PC, Kinetic r, A , , E,, At, Et Initiator-type A i = f&, E i = Ed Feed conditions L~I,,, [m,],; TI) Heat transport TR, UlI where I = V/A, Thermodynamic and Kinetic Properties Monomer Styrene MMA AN

Density, glcc 0.906 0.950 C , cal/g"C 0.4 0.3 BulkConc., moleslliter 8.7 9.5 (-AH),Kcallmole 16.7 13.5 A , , liter/mol-sec 4.5 x 106 9.0 x l o 5 A,,literlmol-sec 6.0x 1 0 ' 1.1 x 1 0 ' E,, Kcallmole 6.4 4.7 E,,Kcal/mole 1.9 1.2 Initiator Kinetic Constants

0.806 0.4 15.2 18.4 3.0 x 107 3.3 x 10'2 4.1 5.4

Initiator

Benzoyl Azobis-iso- di-tert-Butyl peroxide butyronitrile peroxide (BPI (AIBN) (DTBP)

Ad, sec-'
Ei, Kcalimole
f

1.0x 1 0 1 9 1.0 x 10'5 30.5 30.0 0.6 1 .o

4.3 x 1 0 ' 5 37.0 1 .o

was thus observed as a function of initiator type, feed conditions, and heat transport parameters. The second approach was similar to that employed by Barkelew (10). Dimensionless parameters, listed in Table 6, were varied, one at a time, in order to trace the ignition boundary in dimensionless space. Upper and lower bounds were placed upon the dimensionless parameters by using the extreme values computed from all possible combinations of properties (Table 8) for the three-by-three system comprising styrene, acrylonitrile and methyl methacrylate monomers and AIBN, BP and DTBP initiators within the following range of feed conditions: 50C 5 T , 5 200C; 0.005 < [rn,], 5 0.20. Additional constraints imposed upon these computations were first that the final DP, (XN),, in all cases was not permitted to fall below 500 and second that all polymerizations were of the bulk-type. Typical values of the

dimensionless parameters for this three-by-three system are listed in Table 9. Parameter 'a' is not shown since it contains the heat transport property Ull which is peculiar to a given reactor. More than sixty-two computer runs were made using the first approach. Param-eters and variables for some of these are listed in Table 1 0-15; where case numbers are listed. Those cases omitted have been tabulated elsewhere (2, 3). From Table 11 it can be seen that initiator type (Ai, Ei), feed conditions ([m,],, [rn],, To), coolant temperature (TR) and heat transport characteristics (Ull) were varied. It is clear from Table 13 that all cases shown lie on the boundary between runaway and uon-runaway. Some results have also been plotted in Figs. 1 8 . Temperature profiles for cases 1-3 and 4-6 were previously plotted in Figs. 15 and 16, respectively, of reference 1. They show sensitivity of runaway to feed temperature (cases 1-3) and initiator concentration (cases 4-6). DP drift profiles for these cases have been plotted in Figs. 1 and 2 of this paper and the dispersion profile for cases 1-3 appears in Fig. 3 . Temperature profiles showing sensitivity to coolant temperature (TR)and heat transfer coefficient (Ull) are illustrated in Figs. 4 and 5 , respectively. It should be pointed out that in all cases cited thus far, a$ has had a value less than unit. The graphs in Figs. 6-8, however, correspond to cases 42-49 for which a$ has a value slightly in excess of unity. We note that sensitivity of runaway with respect to the parameters varied has disappeared. Furthermore, in contrast to cases 1-3 (Fig. 3 ) for which runaway contributed to broadening the product dispersion, examination of Fig. 8 reveals that high-temperature runaways produce less dispersed products than their lowtemperature counterparts. The explanation is evident from the graph. Broadening is due to a sudden thermal quench which is possible in cases 46 and 47, but which is prevented by early dead-ending in cases 48 and 49. Figures 9-22 illustrate some results using our second computational approach. These graphs are entirely in dimensionless form and thus do not correspond to a

Table 9. Some Values of Dimensionless Parameters PAN BP T,, B b

E

PAN AlBN

PAN DTBP

PMMA BP

PMMA AlBN

PMMA DTBP

PS BP

PS AlBN

PS DTBP

80C

'EE:
(YN)~,

f r

57.46 58.34 69.72 34.71 35.17 41.02 33.1 1 33.52 38.78 25000 2 1 5000 1256 1182 59.29 14010 704.3 55.77 13070 0.04277 0.04213 0.03525 0.03672 0.03625 0.03104 0.03430 0.03388 0.02929 1.829 1.832 1.859 1.571 1.576 1.637 1.467 1.473 1.545 27270 468600* 6468 66140 2667 3241 0 9252 241 3 29320 1 .o 0.6 1 .o 1 .o 0.6 1 .o 1 .o 0.6 1 .o 1 .o 1 .o 1 .o 0.0 0.0 0.0 1 .o 1 .o 1 .o 46.36 2803 0.04762 1.829 9190 1 .o 1 .o 47.06 135.8 0.04698 1.832 3655 0.6 1 .o 56.25 28.01 14500 196.0 0.03924 0.04088 1.859 1.571 391 90 1330 1 .o 1 .o 1 .o 0.0 28.37 9.476 0.04036 1.576 528.8 0.6 0.0 33.14 26.72 1379 142.1 0.03455 0.03819 1.637 1.467 401 0 2314 1 .o 1 .o 0.0 1 .o 27.04 10.85 0.03772 1.473 581.9 0.6 1 .o 31.29 1587 0.0326 1.545 441 8 1 .o 1 .o

To = 120C B b
E

'y")"
r

EE:

.Unusually large value of (v,)

104

1s due to the small value of (K,),, for DTBP

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

A Study of Chain Addition Polymerizations with Temperature Variations: 11.

particular system. Parametric sensitivity of runaway is shown in Figs. 9-11 and the absence of sensitivity in Fig.

12.
Table 10. Fixed Parameters A,, Ilmol sec Ep, At, Kcall I/mol mol sec

Figure 13 illustrates how we typically distinguished between runaway and non-runaway polymerizations by examining their temperature profiles for the onset of
upward concavity (increase in slope, _). de

Figures 14

Ei, PC,, Kcall call mol cc"C

-AH, -AS", Kcall call mot moPK

UI

1 *;"

[4.5

lo6

6.4 6 x

lo7

1.9

[~:~~ 16.7

32

+Cases 1-14. 40, 41, 46-49 ;Cases 15-39. 42-45, 50-62 Used to compute T, 'Cases 1-14 "Cases 15-62

and 15 illustrate how we typically determined whether or not a runaway was sensitive to Darameter variation. In these cases a qualitative judgment was made as to how sharply the temperature maximum 8, rises in response to a variation in a reaction Darameter, i.e.. how steeD is the 6, vs parameter curve. We observe in Figs. 14 and 15 that the disappearance of runaway sensitivity, (ignition behavior) is gradual, i.e., is not itself sensitive to

Table 11. Adjustable Parameters Case A d = Ailf, sec-I Ed = 6, Kcallmol

[mJ,
molK

[ml,,
moll1

T O , "C

TR, "C

UII x 103, callcc sec"C

1 2 3 4 5 6 7 8 9 10 11 12 13 14 2 1 22 23 24 25 26 27 28 29 30 3 1 32 33 34 35 38 39 40 4 1 42 43 44 45 46 47 48 49 50 5 1 52 53 54 55 56 57 58 59 60 6 1 62

1 0 1 5 1 0'5 1 0 ' 5 1 0 1 5 1 0 1 5 1 0 1 5 1 0 ' 5 1 0 ' 5

1015

1 0 1 5
1015 1015

1 0 1 5
1015

1015

1 0 1 5 1 0l5 1015 1 0lS 1 0 1 5 1 0 1 5 1015 1 0 ' 5 10 l 5 1 0 ' 5 1 or3 10 l 5 4.3 x 1 0 1 5 4.3 x 1 0 1 5 4.3 x 1 0 1 5 4.3 x 1 0 ' 5 1 OI5 1 0 1 5 1 0 1 5 1 0 ' 5 1 0l5 1 0 1 5 1 0 1 5 1015 1 0 ' 5
1015

1013 1 0 1 3 1 0 ' 5 1 OrJ

1013

1013

1 0 1 3
1013

1 0 1 3
1013

1 OL5
1013 1013

30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.0 30.0 30.0 30.0 37.0 37.0 37.0 37.0 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30.5 30 30 30 30 30 30 30 30 30 30 30 30 30

0.02 0.02 0.02

0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.156 0.158 0 . 160 0.032 0.034 0.02 0.02 0.0040 0.0042 0.16 0.18 0.0086 0.0088 0.040 0.044 0.0020 0.0022 0.086 0.087 0.0010 0.0012 0.0014 0.0020 0.0087 0.0087 0.0087 0.0087 0.20 0.20 0 . 10 0.10 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 6.7 6.8 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7

58 59 60 67 67 67 67 67 67 67 67 67 67 67 70 70 70 57 57 59 60 70 70 70 70 90 90 100 100 120 120 70 70 80 80 80 80 100 100 100 100 88.5 89.0 93.6 93.7 111.4 111.7 1 1 5.5 115.8 116.0 120.0 121.0 121.7 122.0

47 47 47 47 47 47 39.5 40 4 1 47 47 47 47 47 70 70 70 57 57 59 60 70 70 70 70 90 90 100 100 120 120 70 70 80 80 80 80 100 100 100 100 88.5 89.0 93.6 93.7 111.4 111.7 1 1 5.5 1 1 5.8 1 1 6.0 120.0 121 .o 121.7 122.0

0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.5998 0.5994 0.45 0.45 0.45 12 12 12 1.8 1.8 1.8 1.8 1 . 8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 6.72 6.72 1.8 1.8 1.8 1.8 16.5 14.6 12.8 11.9 8.0 8.0 8.0 8.0 8.0 8.0 10.29 10.29 10.29 14.4 14.4 14.4 14.4
105

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

I . A. Biesenberger, R . Capinpin, and J. C . Yang

Table 12. Dimensionless Parameters Case 1 2 3 4 5 6 7 8 9 10 11 12 13 14 21 22 23 24 25 26 27 20 29 30 31 32 33 34 35 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62

eyT

B = H$c

OR

4
0.1 84 0.192 0.200 0.364 0.362 0.358 0.272 0.272 0.272 0.272 0.272 0.272 0.272 0.272 0.0784 0.0779 0.0774 0.0983 0.0954 0.136 0.1 42 0.490 0.478 0.01 12 0.0105 0.104 0.1 03 0.0127 0.01 21 0.139 0.133 0.1 056 0.1050 1.47 1.34 1.24 1.04 1.06 1.06 1.06 1.06 0.0205 0.0209 0.0348 0.0350 0.202 0.204 0.231 0.233 0.234 0.266 0.274 0.280 0.283

b = B/&
168 160 152 80.0 80.5 81.5 107 107 107 107 107 82 83 107 456 459 462 393 405 280 267 73.3 75.1 3159 3350 302 306 2748 2882 226 237 271 273 23 25 27 32 22.8 22.8 22.8 22.8 1550 1520 887 833 139 138 119 118 117 101 97.6 95.2 94.1

i
1.15 1.17 1.18 1.oo 1.11 1.11 1.06 1.08 1.12 1.10 1.10 1.13 1.14 1.46 1.32 1.33 1.34 1.30 1.34 1.23 1.34 1.41 1.44 1.27 1.34 1.37 1.38 1.30 1.36 1.35 1.42 1.40 1.41 1.57 1.72 1.86 2.22 1.76 1.98 2.26 2.81 1.33 1.38 1.36 1.37 1.43 1.46 1.45 1.47 1.49 1.37 1.45 1.52 1.54

0.031 7 0.031 8 0.0319 0.0327 0.0327 0.0327 0.0327 0.0327 0.0327 0.0327 0.0327 0.0327 0.0327 0.0327 0.0329 0.0329 0.0329 0.031 6 0.031 6 0.0318 0.0319 0.0329 0.0329 0.0333 0.0333 0.0352 0.0352 0.0310 0.0310 0.0326 0.0326 0.0329 0.0329 0.0339 0.0339 0.0339 0.0339 0.0358 0.0358 0.0358 0.0358 0.0351 0.0352 0.0356 0.0356 0.0374 0.0374 0.0378 0.0378 0.0378 0.0382 0.0383 0.0384 0.0384

0.827 0.757 0.692 0.507 0.504 0.500 0.379 0.379 0.379 0.507 0.507 0.494 0.487 0.379 1.99 1.98 1.97 2.01 1.95 2.13 1.96 1.87 1.82 2.07 1.95 1.91 1.89 2.04 1.94 1.94 1.85 1.88 1.87 1.68 1.53 1.41 1.19 1.49 1.33 1.16 0.932 1.97 1.90 1.93 1.91 1.83 1.79 1.81 1.77 1.75 1.91 1.80 1.72 1.69

30.8 30.6 30.4 29.1 29.1 29.1 29.1 29.1 29.1 29.1 29.1 22.4 22.7 29.1 35.9 35.9 35.9 38.6 38.6 38.4 37.9 35.9 35.9 35.4 35.4 31.5 31.5 34.8 34.8 31.6 31.6 28.6 28.6 33.6 33.6 33.6 33.6 24.2 24.2 24.2 24.2 31.8 31.7 30.9 30.9 28.1 28.1 27.5 27.5 27.5 26.9 26.8 26.7 26.6

- 1.04 -1.13 -1.22 -1.81 -1.81 -1 3 1 -2.48 -2.42 -2.36 -1 .81 -1.81 -1 .81 -1.81 -1.81 0 0

0
0 0

0
0 0 0 0

0
0 0 0

0
0 0 0 0 0 0

0
0 0

0 0
0 0 0 0

0 0
0 0 0 0 0 0 0 0

1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.46 1.46 1.54 1.54 1.54 1.54 1.47 1.47 1.47 1.47 1.47 1.47 1.48 1.48 1.48 1.48 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47

parameter variation. Thus, we conclude that parametric sensitivity is not parametrically sensitive. However, a change in the slope at the inflection point was detected (Fig. 16)which aided us in making the necessary qualitative judgment . Thermal ignition boundaries for those runaways which were parametrically sensitive have been plotted in Figs. 17-22. They represent the product of many numerical solutions of our dimensionless system equations and they cover a wide range of values for each dimensionless parameter. They should thus apply to a wide class of free-radical chain-addition polymerizations providing, of course, that such systems exhibit ideallike behavior up to the point of onset of thermal runa106

way. We note that the ignition boundaries are limited to values of B and b in excess of 20 (Fig. 17) and 100 (Fig. 18), respectively, below which runaway was adjudged to be insensitive to these parameters by the procedure described above. In Fig. 18 it is noted that when b 2 2000, the curves become relatively independent of 6 . Figure 2 0 shows the effect ofparameter EE;. It should be pointed out that for a given monomer-initiator system, the value of &I is constant. In Fig. 22, a comparison between computer ignition boundaries and the theoretical ignition boundary, Z(e,a,O,) = 1, is shown. It is seen that for very large values of B and b, the computer boundaries approach
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

A Study of Chain Addition Polymerizations with Temperature Variations: 11.

Table 13. ignition Variables Case
1 2 3 4 5 6 7 8 9 10 11 12 13 14 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62

Table 14. Polymerization Variables

% 'G

T,,"C
58 59 60 67 67 67 67 67 67 67 67 67 67 67 70 70 70 57 57 59 60 70 70 70 70 90 90 100 100 120 120 70 70 80 80 80 80 100 100 100 100 88.5 89.0 93.6 93.7 111.7 111.4 115.4 115.8 116.0 120.0 121.o 121.7 122.0

T,,"C
62 142 171 74 150 160 68.8 171 177 81 152 74 151 183 93 211 221 76 200 70.6 187 95.6 152 85 302 118.5 223 118 299 140.7 246 97 167.5 100 124 139 159 130 150 164 168 100.0 307.8 122.4 267.2 143.3 216.0 147.4 198.6 229.5 139.2 148.9 213.1 231.7
=

Tf,"C
47 142 171 47 150 160 39.5 171 177 47 152 47 151 183 70 211 221 57 200 59 187 70 151 70 302 90 233 100 299 120 246 70 163 80 80 131 159 100 100 155 165 89.2 307.8 93.9 267.2 111.6 210.5 115.7 116.0 225.3 120.2 121.2 213.1 231.7
~

IG

$1~

T;G

Case
1 2 3 4 5 6 7 8 9 10 11 12 13 14 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62

T,,"C
62 142 171 74 150 160 68.8 171 177 81 152 74 151 183 93 211 221 76 200 70.6 187 95.6 152 85 302 118.5 233 118 299 140.7 246 97 167.5 100 124 139 159 130 150 164 168 110.0 307.8 122.4 267.2 143.3 216.0 147.4 198.6 229.5 139.2 148.9 213.1 231.7

Tf,"C
47 142 171 47 150 160 39.5 171 177 47 152 47 151 183 70 211 221 57 200 59 187 70 151 70 302 90 233 100 299 120 246 70 163 80 80 131 159 100 100 155 165 89.2 307.8 93.9 411.3 111.6 210.5 115.7 116.0 225.3 120.2 121.2 213.1 231.7

7;

clrf
0.395 0.999 0.999 0.564 0.999 0.999 0.306 0.999 0.999 0.551 0.999 0.465 0.999 0.999 0.278 0.999 0.999 0.331 0.999 0.405 0.999 0.999 0.999 0.038 0.999 0.378 0.999 0.047 0.999 0.450 0.999 0.444 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.0797 0.999 0.139 0.999 0.645 0.999 0.702 0.988 0.999 0.705 0.761 0.991 0.999

Of
0.970 0.795 0.595 0.970 0.654 0.576 0.970 0.593 0.520 0.970 0.732 0.970 0.699 0.445 0.950 0.789 0.734 0.950 0.624 0.950 0.622 0.936 0.510 0.950 0.883 0.950 0.744 0.950 0.772 0.950 0.633 0.970 0.859 0.629 0.460 0.329 0.301 0.704 0.489 0.385 0.369 0.950 0.876 0.950 0.911 0.950 0.752 0.950 0.800 0.705 0.590 0.532 0.467 0.408

D-E No Yes Yes No Yes Yes No Yes Yes No Yes No Yes Yes No Yes Yes No Yes No Yes Yes Yes No Yes No Yes No Yes No Yes No Yes Yes Yes Yes Yes Yes Yes Yes Yes No Yes No Yes No Yes No Yes Yes No No Yes Yes

No Yes Yes No Yes Yes No Yes Yes No Yes No Yes Yes No Yes Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes

0.188

0.47

6.5

0.253

0.40

4.0

0.132

0.30

2.4

0.231

0.45

3.5

0.180

0.37

2.7

0.047

0.28

7.5

0.042 0.065 0.181 0.005

0.22

6.5

0.23 0.20 0.25

6.6

5.2 6.5 6.3

0.058

0.27

0.006

0.22

6.1

0.075

0.24

5.4

0.066

0.29

6.1

No
Yes No Yes No Yes No No Yes No No Yes Yes
~~

0.022

0.29 0.26

5.9 6.5

0.0111 0.25

0.110

5.2

0.117

0.25

0.138 0.133
IS

4.8

0.25 0.23

4.6 4.2

2.55 7.44 3.74 374 4.36 3.25 564 2.54 1.68 344 5.09 257 3.05 0.903 175 10.1 8.83 203 7.69 234 8.21 438 6.94 176 7.87 153 8.37 168 7.25 173 6.92 167 8.99 205 119 3.85 2.37 169 65.4 2.85 2.03 945.3 7.44 131.1 9.14 157.3 7.67 162.2 50.11 6.78 176.5 170.5 6.87 5.95

. . . . . . . . . . . . . . . . . . . . . . . .

* These values correspond to 8

2 at which temperature

arbitrarily defined as

having ignited

the theoretical boundary. From numerous computer solutions, the results show that when B 2 500 and b 2 2000, the computer ignition boundary approaches the theoretical boundary to within 6 percent. However, for free-radical polymerizations, the value of B rarely exceeds 100 and therefore, the computer boundary will deviate from the theoretical one. Thus the ignition criterionZ(E,a,O,J > 1.35 (for 0, = 0) was recommended (3)rather than Z(e,a, 0,) > 1. It was found that when 0, decreases below 0 (for fixed values of the other parameters), the value of I ( ~ , a , 0at ~) ignition decreases and approaches 1. This result is confirmed by the correPOLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

sponding values of I , which was close to 1, for cases 1-14 of Table 12. Ultimate dispersion (DN)f for a number of computer runs as a function of parameter 'a' has been plotted in Fig. 23. In essence this graph demonstrates how temperature variations affect polymer dispersion.

CONCLUSIONS
The following conclusions are evident from the results in the tables and figures. Chain-addition polymerizations are susceptible to thermal runaway and, under appropriate conditions, thermal ignition. In the thermal ignition region the
107

J. A. Biesenberger, R . Capinpin, and J. C. Yang

Table 15. Polymer Properties

1 2 3 4 5 6 7 8 9 10 11 12 13 14 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62

62 142 171 74 150 160 68.8 171 177 81 152 74 151 183 93 21 1 221 76 200 70.6 187 95.6 152 85 302+ 118.5 233 118 299+ 140.7 246 97 167.5 100 124 139 159 130 150 164 168 110.0 307.8 122.4 267.2 143.3 216.0 147.4 198.6 229.5 139.2 148.9 213.1 231.7

321 268 293 316 287 296 326 293 300 301 278 303 273 305 310 270 278 315 290 320 290 309 301 320 250 309 272 315 272 315 289 302 259 320 314 314 314 314 310 311 311 314.5 250.0 308.5 281.5 308.5 281.5 308.5 281.5 281.5 320.0 314.5 281.8 286.0

47 142 171 47 150 160 39.5 171 177 47 152 47 151 183 70 21 1 221 57 200 59 187 70 151 70 302++ 90 233 100 299++ 120 246 70 163 80 80 131 159 100 100 155 165 89.2 307.8 93.9 267.2 111.6 210.5 115.7 116.0 225.3 120.2 121.2 213.1 231.7

208 268 293 208 287 296 208 293 300 208 278 201 273 305 222 270 278 222 290 222 290 230 300 222 250 222 272 222 272 222 289 208 255 289 304 313 315 281 302 309 310 235.6 250.0 235.6 243.0 235.6 275.0 235.6 267.0 281.5 235.6 235.6 281.8 286.0

9462 9047 8652 8485 8448 8375 6379 6379 6379 6379 6379 4913 4986 6379 1424 1415 1406 5534 5369 6398 6118 8883 8669 9732 9176 19390 19170 34190 32600 62410 59500 1917 1906 11820 10790 9991 8359 1896 1896 1896 1896 4250 41 73 4996 4978 8607 8524 7544 7472 7425 6547 6347 6212 6154

4270 1390 1036 5279 1996 1730 5519 1033 905 3065 1274 2799 951 775 382 87 80 1559 320 2041 541 4076 2115 2700 86 5089 1531 8888 306 18350 5011 442 172 10960 6677 4092 2621 1409 979 771 738 1123 76.26 1189 159 2564 1309 2353 1412 1228 2345 2172 1230 1148

2.07 3.64 4.43 1.89 2.81 3.08 2.1 5 3.79 3.84 1.84 3.18 1.86 3.1 4 3.59 1.92 6.1 5 6.62 1.92 6.42 1.99 4.64 1.64 2.1 5 2.08 31.3 1.91 4.85 2.0 30.2 1.87 4.51 2.04 4.21 2.42 4.99 1.83 1.93 2.55 4.69 1.84 1.83 2.01 17.1 1.99 10.7 1.82 2.80 1.79 2.66 2.68 1.82 1.76 2.33 2.48

,LCA used for ( d < , b u tnot for (ih),, (T,),,, refers to the ceiling temperature corresponding to the monomer conversion at T , +Tm> (TJ, "Ti > (Td,

system is sensitive to parameters such as To, T B , [mO],, [m], and U/Z. The latter conclusion is apparent from the results in the tables and graphs corresponding to cases 1-41 and 50-62. Sensitivity (IG) does not always accompany runaway, and runaway does not generally occur early with respect to monomer and initiator conversion, i.e., at low conversion. We conclude that in such cases the early runaway assumption (ERA) employed by Semenov (3, 9) is not always valid for polymerizations.
108

Thermal runaway transforms an otherwise conventional polymerization (isoth CONV) into a dead-end polymerization (thermal D-E), even under conditions such that a; < 1. Cases 1-41 and 50-62 are examples of this. Runaway always reduces polymerization time, Tf, and ultimate DP, FN)f, often dramatically; but, interestingly, it does not always increase ultimate dispersion, (DN)f, of the degree-of-polymerization distribution, DPD. In support of this observation are cases 42-45,

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

A Study of Chain Addition Polymerizations with Temperature Variations: 11.

46-49 (compare (DN),values in Table 13), compare (DN), values in Table 17 of reference 1.
Initiators are susceptible to runaway in the following increasing order: DTBP, BP, AIBN; that is, lower values

of T , are required to produce runaway. Compare cases 15-17 with 18-20 and 32-33 with 36-37. It appears possible to meet design objectives of high conversion in short time rf with an acceytable target degree of polymerization (xN), by utilizing high values of T o with concomitantly large temperature increases due to incomplete removal of reaction exotherm, as often occurs in industry. In fact, rising temperature profiles lie in the direction of the optimum with respect to minimum polymerization time (11) and, under appropriate D-E conditions, also with respect to minimum drift dispersion in DPD (1, 12).

CASES 1-3

/-

T0=6O0C

1 0 1 2 1 4 I

Fig. 1 . DP drift profiles f o r cases 1-3 i n Tables 11 -1 5.

c
0

0.2

/-\
CASES 4 and 5 -CUM.

0 . 4 (P

0.6

0.8

1 . 0

Y n

--- INST. TN

I I I I

\\

Fig. 3. Cumulative dispersion index drqt profilesf o r cases 1-3 in Tables 11-1 5.

\ \

\
\
\

0.3

0.2
T'
0.1

-0.1

-0.2'
0 0
0.1

0.2

0.3 + 0.4

0.5

0.6

0.7

4)
Fig. 4. Temperature drift profiles f o r cases 7-9 in Tables 11-15.
109

Fig. 2 . DP drift projiles f o r cases 4 und 5 i n Tables 11-15.

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

J. A, Biesenberger, R . Capinpin, and J. C . Yang

A good parameter for predicting isothermal CONV/D-E polymerization is a; = B/b, as previously concluded (1, 4, 5). Large values of b indicate early runaway with respect to initiator decay. We note that cases 31 and 35, for example, which have the smallest values of a; and the largest values of b, are extremely
conventional by nature and exhibit early runaway with respect to $. Furthermore, their ultimate DPDs are broad as expected because the tendency of their DPs to

----I

0.5
CASES 1 0 and II

0.4

0.3

0.2
T'

0.1

401
o L I

ai

'

'

0.4 1

05 I

'

I0 . 6I

' 07

0.3

(9

Fig. 7 . LIP drift profiles f o r cases 46-49 in Tables 11-15,

- 0.1
-0.2
0
I

U/I = 5.998 x

cal/cc-sec-oc
I I I

0.2
0.4

0.6

0.8

1 . 0

Fig. 5 . Temperature drift profiles f o r cases 10 and 1 1 i n Tables 11-15.

16.5 X I O - '

'

0 0.25

0.20 -

i'
/
I

[m.].=o.0020

r\ 0.0014

/ / / 2

0.0010

1
" 0

1
0 . 1

1
+

0 . 2

03

OA

0.5

0 . 6

07

Fig. 6 . Temperature drift profiles f o r cases 42-45 in Tables 11-15.

110

Fig. 8 . Temperature and cumulative dispersion index drift profiles f o r cases 46-49 in Tables 1 1 -1 5.
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

A Study of Chain Addition Polymerizations with Temperature Variations: I I .

drift downward, owing to the conventional nature (under isothermal conditions) of these polymerizations, is reinforced by runaway temperatures. Even such polymerizations dead-end under runaway conditions, however. We note that in cases 31 and 35,T , > (TJ,.. This indicates that the results obtained for these cases using the irreversible model are subject to doubt and to obtain more accurate theoretical predictions a kinetic model with depolymerization should be used. By contrast, cases 42-45 and 46-49 are strongly D-E and borderline D-E, respectively, by nature (under; isothermal conditions) according to their values of ak and b < 100. In fact, the former possess the largest values of a;. It is interesting to note that they no longer exhibit parametric sensitivity. We might even term their runaway as stable. Furthermore, their ultimate values of (DN), indicate that dispersion has actually been reduced by runaway. The same phenomenon was observed in cases 7-9 (Table 17) of reference 1, and the reason for it is believed to be the compensating effect (12) of rising temperatures, which tend to decrease

a = 1.89
6.32

1 0

b*256
I 1

*0.04

8 932 b.256 =0.04

I I

EE;=I.467 IL/&=3000
?q=O.O

8Q

F i g . 9. Dimensionless temperature drift profiles showing parametric sensitivity with respect to parameter a.

8 z

12

1 6

20

F i g . 1 1 . Dimensionless temperature drift profiles showing parametric sensitivity with respect to 0,.

o -2.00 b=256
E =0.04

E ; = 1.467 A,.

0.0 3000

r =1.0

1
8
0

8.17

b=256

=o.w

E E : = 1.467

Wn&= 3000

8 =o.o r = 1.0

I
6

I 8

I
1 2

1 0

I 1 4

1 0

Fig. 10. Dimensionless temperature drift profiles showing parametric sensitivity with respect to B .
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

Fig. 12. Dimensionless temperature drift profiles showing nonsensitivity with respect to parameter a for small value of B .
111

J. A. Biesenberger, R . Capinpin, a n d ] . C. Yang

I4

( x ~ ) on ~ the ~ ~natural ~ , tendency of (;;N)inst to drift upward

under isothermal conditions (1). In general, runaway is accompanied by small values of a E , and large values of B , b, OR. Of course, a necessary condition for runaway is a small value of E to insure the requisite sharp upward curvature of the heat generation curve (3),f(T)g(O). It should be pointed out that the small value of E is due mainly to the large value of E ifor free-radical initiators, since E , and E tfor most chain addition monomers are small. Parametric sensitivity (IG) occurs for large values ofB and b, and disappears when B < 20 and b < 100. This is evident in Figs. 13-15.
2.0-

1 2

b * 256 6.004 eE * 1467

3000

e,=oo r -10
10-

em
6-

4-

i
B =50
b.256 E =004
6E , = 1.467

0
12

I
I5

I
1 6

I
I7

I
I8

1.6-

13

I4

I 19

I
20

Fig. 15. Om us a for various values of B .

1.2 du -

(~,b=3000 c), = o 0

r.1.o

dr

0 . 8-

0 . 0

Fig. 13. d8ld.r us r for two values of parameter a

B = 32
148 80.04 4:=1.467

(u,).,I 3000

eR =o.o
r = 1.0

12

F i g . 16. Plot of the maximum slope of the curves shown in Fig. 14 us h.

1 0

em

I
195-

, #+
RUNAWAY

G E =1467
o=

3000

e,=oo
r.10

I
20

30

40

50

I 60

I
70

I 80

90

Fig. 14. 8 , us a for various values of b.

112

Fig. 17. Computer ignition boundaries plotted as a vs B curves with b as parameter.

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

A Study of Chain Addition Polymerizations with Temperature Variations: I I .

Its disappearance is coincident with the negation of the ERA. We have also noted that while D-E is exacerbated by large values of a; = B / b , due to either large T o or small [m,], or both, susceptibility to runaway is actually mitigated. In fact, large values of a; sometimes will cause sensitivity (IG) to disappear altogether. This may be observed, e.g., in graphs of a vs B(Figure 17) as b increases (& decreases) at fixed values of B. The explanation is that D-E causesf(.) to drop sufficientlyto offset the rise in g ( 8 ) due to climbing temperatures. Criteria for the ERA are (3): and They insure that monomer and initiator do not drift ap reciably from their initial values, i.e., [m ] = [ m ] , respectively, prior to onset of runaan [m,]i=[mO],, way. These inequalities can also be derived by stating that the characteristic times for monomer and initiator depletions, h, and At, respectively, are much greater , , during the period prior to the onset of ignition. than A

=no4
SL

= ,467

RMAWbY

t
17

I , I I

Ha.O 0 1MY)OO

r=Io

, ,

1
b = 256 E.004
E , = 1.467

102

,03

1 0

Fig. 18. Computer ignition boundaries plotted as a vs b curves with B as parameter.

RUNAWAY

(YL=MOO r =1.0
I
I 1

1 . 3

---Theoretical -Computer

IG Bound. Runs

1.61

20

I 30

I 40

I 50

I 60

I 70

en

90

100

Fig. 19. Computer ignition boundaries plotted as a vs B curves with E as parameter.

I. 5

--------------1

05
I65

O J
20 30
I

I 40

I 50
11

1 60

TO

80

90

0 . 0 2

0.06

a 1 0

014

1 0.18

022

0.26

Fig. 20. Computer ignition boundaries plotted as a vs B curves with &, as parameter.
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

Fig. 22. Comparison between theoretical ignition boundary and computer ignition boundaries.
113

J. A. Biesenberger, R . Capinpin, a n d ] . C . Yang

I

t II

/ I

which was proposed elsewhere (3) for chain addition polymerizations in the special case On = 0, and which we thus recommend as the criterion to use even with moderate deviations from the ERA. We note that when E = 0.04, for example, criterion alG4 2 corresponds to yT 5 1 as we suggested in an earlier paper (1).Cases 11, 22, 25,27,31,33,35,37,39,51 and 53 correspond to 0, = 0 and B > 20, b >> 100 (i.e., ERA valid). For all these cases IIG = 1.35 as expected. We have found that in general the upper limit ofalGin range (5) corresponds to large values of the pair B , b and that the lower limit corresponds to small values. In fact, when aIGtakes on values at or below the lower limit, B and b are such that IG sensitivity is gone.

SOME GENERALIZATIONS
A summary of general conclusions concerning the role

I4

v
0
a4

MWEAK D-E
I
R.A

,1-

l 2
QI

1 0

Fig. 23. Ultimate cumulative dispersion index vs a f o r conventional, weak D-E and strong D-E polymerizations.

The use of the characteristic time approach is reasonably since the temperature rise during the induction period is relatively small. For chain addition polymerizations B virtually always exceeds 20, but not by much. Therefore, runaway is not expected to be early with respect tom. This is confirmed by our observation that runaway was generally found to occur at values of @ between 0.25 and 0.35. As suggested in our previous paper (I), yT is an acceptable IG parameter, but the IG criterion is not as simple as expected yT < 1. We have since found that parameter a = cyT is more convenient, but the IG criterion for the special case OR = O is not as simple for polymerizations either as expected ( a Ie) from Semenovs theoretical analysis. Even our modified theoretical criterion (2, 3), I(a,c,OR)> I, is not entirely adequate for the more general case where On is not necessarily zero and E is not neglected with respect to unity. A primary reason for the latter is that the ERA, which is inherent to the theory, is not generally valid for polymerizations. It should be pointed out that the modified theoretical criterion for OR = 0 approaches Semenovs criterion (to within 99.9 percent) when E < 0.0006. However, E for most chain addition polymerization is greater than 0.025. Consequently, our modified theoretical boundary departs from Semenovs boundary. We have found in the present study on the basis of numerous computations that the value of a for chainaddition polymerizations with OR = 0 at the IG point lies within the range

of various dimensionless parameters in characterizing reaction behavior is presented in Table 16. The significance of a in determining thermal runaway and the significance of B and b in characterizing its parametric sensitivity, as well as the validity of the ERA, have been established. However, the effect of temperature profile on polymer properties is a more complex matter and requires further elaboration. Its elucidation will establish the quotient of reaction parameters Blb = a k as an important property parameter of the polymer product. Figure 23 illustrates how ultimate dispersion varies with parameter a for three classes of kinetic behavior: conventional, borderline (weak) D-E and strong D-E. All classifications are based upon parameter a; and thus refer to how the polymerizations would behave under isothermal conditions. It is instructive to observe the wide variety of polymer dispersion characteristics possible when thermal parameter a is varied from adiabatic conditions ( a = 0) through the ignition region (1 5 a 5 2) towards the quasi-isothermal regime ( a >> 1). It is also interesting to note that runaway temperatures generally appear to inflect the most damage upon conventional-type polymerizations. In summary: our findings show that conventional polymerizations produce narrower polymers under quasi-isothermal (Q-I) conditions than under runaway (R-A) conditions but there is a peculiar minimum at the ignition boundary; borderline D-E polymerizations also produce narrower polymers under Q-1 conditions than under runaway conditions, which are also narrower than their corresponding conventional counterparts, but there is now a maximum at the ignition point; and, strong D-E polymerizations actually produce narrower
Table 16. Summary of Effects of Dimensionless Parameters Under Non-Runaway Conditions ObjectivelParameter Avoid R-A Avoid IG Avoid D-E Short T~ Large (xd,
only when tE: > 1

EE!, -

OR
s -

(Y~),,

1 5aIG52 where the upper limit confirms the criterion, l(a,E , 6,) > 1.35
114

(5)
(6)

- s I - - - s s s l l s
s

I -

- - I s s -

? = small, I = large value of parameters

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

A Study of Chain Addition Polymerizations with Temperature Variations: 11.

polymers under runaway conditions than under Q-I conditions with a similar maximum dispersion at the ignition boundary. These interesting results can be explained on the basis of a coupling effect between concentration (monomer and initiator) drift and temperature drift in terms of E 9 4 5 in Table 4 . As we have previously shown, (1, 5), ultimate DP and DPD are direct products of the drift characteristics of (;;N)inst. It is thus convenient when attempting to explain the above results to consider the thermal effect to be superimposed upon a natural isothermal behavior (12). This is the reason we have chosen to classify reactions according to the isothermal behavior of (;;N)inst. Three classes of isothermal behavior as determined by ai are illustrated in Fig. 24 and three classes of thermal behavior as determined by a (or I) in Fig. 25. Thus, nine combinations of drift behavior are possible, which account for the wide variety of results observed when temperature variation acts upon ultimate polymer dispersion. The fact that thermal runaway exacerbates dispersion in conventional polymerizations (curve I in Fig. 23) is easily explained by the fact that drift dispersion due to both CONV (Fig. 24) and quasi-adiabatic (Q-A) (Fig. 25) behavior tend to drive &,Jinst in the same direction, viz., downward, and thus they reinforce one another. The - before the thermally-induced polymerization dead-ends ) effect ~ ~ drift ~ ~ recovery. (D-E) upward sweep of ( x ~can The minimum at the R-A boundary is due to just such recovery which is additionally reinforced by the
I

a=2
0

0.5

F i g . 2.5. Dimensionless temperature drift profiles f o r three types of thermal behavior: quasi-isothermal, runaway and quasiadiabatic.

thermal-quench (declining) portion of the R-A curve in

/STRONG D-E

Fig. 25.
Drift dispersion under runaway conditions is greater than under Q-I conditions for weak D-E polymerizations (curve 2 in Fig. 23) simply because runaway transforms weak D-E into strong D-E, thereby producing a The maximum at the R-A sharp upward drift boundary is due to continual reinforcement in the drift downward, followed by upward, and then of again downward, caused by the alignment of the R-A curve ofFig. 25 with the weak-D-E curve ofFig. 24. It is apparent that cases 46-49 (Fig. 8 ) lie to the left of this maximum. Finally, in perhaps the most unexpected result, viz., that of strong D-E (curve 3 in Fig. 23), we find that runaway drift produces the least dispersion. This is due - the cancellation of the sharp upward D-E drift of to (x,Jinst (Fig. 24) by the steep rise in temperature which acts to force (xN)inst in the opposite direction. Both effects are present in E9 2 4 (Table2 ) ;one is a drop inm, due to D-E and the other is a rise in T convoluted by a negative temperature coefficient ( E l p - E l < 0). The maximum in (DJf is due to the thermal quench in the R-A profile, which reinforces rather than cancels the upward drift in -

FN)inst.

FN)inst,

05

(XN)inst.

(P
Fig. 24. Instantaneous DP drift profiles f o r conventional, weak D-E and Strong D-E systems.
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2

ACKNOWLEDGMENT
This work was sponsored in part by a grant from the National Science Foundation (GK-34079).
115

I . A. Bicscnbcrgcr, R. Capinpin, a n d J . C. Yang

NOMENCLATURE
A A,
= rate constant pre-exponential
= wetted surface area = heat capacity = dispersion index

CP
DN

initial kinetic chain length defined in Table 6 density dimensionless time monomer conversion initiator conversion

E
El

= activation energy
= dimensionless activation energy defined as

Subscripts
apparent (lumped) decomposition final generation initiation monomer consumption or maximum value (as in 0,) initial value propagation heat removal or reservoir (as in T R ) termination termination by combination termination by disproportionation x,y-mer

E/R,T,

f(~)

= defined

as (1 - @) (1 - +)*/a

defined as exp (

1+E0 ) heat effect number defined in reference 1. heat of polymerization ignition function or (with brackets) initiator concentration rate constant characteristic length defined as VIA, fictitious initiator concentration monomer concentration free-radical intermediate concentration rate of reaction initial rate of reaction defined as (k& [ m ] ,
initial rate of initiation defined as ki[m,], universal gas constant ceiling temperature maximum temperature temperature dimensionless temperature defined as (T - To)/To time overall heat transfer coefficient volume degree of polymerization instantaneous degree of polymerization

[mold

REFERENCES
1. J. A. Biesenberger, and R. Capinpin, Polym. Eng. Sci., 14, 737 (1974). 2. J. A. Biesenberger, R. Capinpin, and D. Sebastian, Am. Chem. Soc., Diu. ofPolym. Prep., 16, 365 (1975). 3. J. A. Biesenberger, R. Capinpin, and D. Sehastian, to be Dublished in A.C.S. Adu. in Chem. series. 4. J. A. Biesenberger and R. Capinpin,J. Appl. Polym. Sci., 16, 695 (1972). 5. Z. Tadmor and J. A. Biesenberger,]. Polym. Sci., B3, 753 ( 1965). 6. P. H. Thomas, Proc. Roy. Soc., A262, 192 (1961). 7. W. Squire, Combustion Flame, 7, 1 (1963). 8. J. Adler and J. W. Enig, Combustion Flame, 8, 97 (1967). 9. D. A. Frank-Kamenetskii, Diffusion and Heat Exchange in Chemical Kinetics, Princeton University Prcss (1955). 10. C. R. Barkelew, Chem. Eng. Prog. Symp. Ser. No. 25,55,37 (1959). 11. M . E. Sacks, S-I. Lee, and J. A. Biesenberger, Chem. Eng. Sci., 27, 2281 (1972). 12. M . E. Sacks, S-I. Lee, and J. A . Biesenberger, Chem. Eng. Sci., 28, 241 (1973).

Greek Symbols
dimensionless temperature characteristic time kth moment of the degree of polymerization distribution

116

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1976, Vol. 16, No. 2