A Study of Chain-Addition Polymerizations with Temperature Variations. IV.

Copolymerizations-Experiments with Styrene-Ac rylonit riIe

D. H . SEBASTIAN arid J. A. BIESENBERGER
Department of Chemisty and Chemical Engineering Stevens Institute of Technology Hoboken, New Jersey 07030
Free-radical copolymerizations were studied under nonisothermal conditions with emphasis on their thermal runaway and ignition behavior. Computational models are presented in generalized form and compared with experiments on the system styrene-acrylonitrile.A new, useful method is proposed for the evaluation of runaway parameters from scant kinetic data.

INTRODUCTION

ecent work from these laboratories has focused on rapid, high temperature addition polymerization (1-6), with particular emphasis on the associated problems of thermal runaway (RA) and instability (2-6). Thermal instability has been characterized for chain addition homopolymerization (2-4). A blend of theory and semi-empirical analysis was used to develop dimensionless criteria which predict both the onset and character of RA (2).These were corroborated by numerical simulation (3) and further tested with experiments on free-radical styrene polymerization (4). In our most recent work, RA theory was extended to include addition copolymerization (6). It was demonstrated that copolymerization parameters can be defined which are analogous in physical i n t e r p r e t a t i o n to t h e i r homopolymer counterparts, and thus have direct application to our previously reported RA analysis. This work is an experimental investigation of RA in copolymerization and is a sequel to our experimental work on styrene, Part 111 in this series (4). The comonomer pair styrene-acrylonitrile (SAN) has been chosen as the subject ofcopolymerization analysis. The pair forms an industrially important engineering plastic, and a great deal is known about the properties and reactions ofstyrene. However, the reaction kinetics of SAN are far from ideal, and not well characterized. The reaction medium changes from homogeneous to precipitous with variation in comonomer feed composition. Even under isothermal conditions the reaction exhibits autoacceleratory behavior which is attributable to two well known phenomena. One is acceleration due to precipitation of the polymer and is characteristic of bulk AN homopolymerization. The other is the gel effect (GE) which occurs in homogeneous media. GE has been observed in styrene polymerization but to a lesser degree than was found in SAN copolymerization (7, 8).With the
190

added dimension of temperature variation, thermal runaway constitutes an additional form of autoacceleration. In spite of non-idealities, it is the claim of this work that qualitative predictions of non-isothermal behavior can be made on the basis of dimensionless criteria whose parameters have physical significance, independent of any particular kinetic mechanism. These parameters are characteristic of general processes such as reactant consumption or heat generation, and may be determined experimentally in the absence of a detailed knowledge of kinetic mechanism. In a separate but related study, reaction kinetics of free radical SAN copolymerization were reported (8). Attempts to fit the data to kinetic models based upon existing copolymerization termination mechanisms met with limited success. Although initial rates could be reproduced, subsequent reaction behavior could not. Of greater significance to this work was the determination of process time constants strictly from experimental data and their application via dimensional analysis to describe isotherma1 reaction behavior. Despite the limitations of existing kinetic models, this work will show that the parameters necessary to evaluate RAcriteria may also be evaluated directly from experimental data. Furthermore, the values of the dimensionless criteria are in quantitative accord with the expectations drawn from RA theory.

EXPERIMENTAL
Both comonomers were vacuum distilled to remove commercially added inhibitors, then stored at 273K. Initiator azo-bis-isobutyronitrile (AIBN) was twice recrystallized from chloroform with methanol, dried in vacuo, and stored at 273K. The thermal ignition point apparatus (TIPA) has been described elsewhere (4). Some modifications were made
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Vol. 19, No. 3

A Study of Chain-Addition Polymerizations with Temperature Variations

on the batch reactor, and the start-up procedure has been changed. The reactor, pictured in Fig. 1 , was constructed of stainless steel. It maintains the same outer dimensions of the original glass reactor, but the change in material along with a reduced wall thickness afforded better heat transfer. Under a new procedure, comonomer feeds (50 ml) w e r e p r e h e a t e d in a pressurized vessel separate from the reactor. The vessel was heated electrically, and controlled to a constant wall temperature. With reactor in place in the TIPA, initiator was loaded through the reactor entry pipe. When at the desired temperature, the preheater was attached to the reactor-entry pipe, and the hot monomer feeds were flushed through the initiator, dissolving it, and subsequently passing on to the reactor. Manipulation of preheater temperature assured the same initial temperature and coolant temperature. Reactions were conducted at 4 atm pressure to prevent boiling ofthe monomers at the extremes of temperature encountered during RA reactions. Reactions were stopped by a pressurized injection of 25 in1 of O.1M p-benzoquinone in toluene. This solution provided both a thermal and chemical quench as well as diluting the products to a manageable consistency. parameters could characterize the non-isothermal behavior of homopolymerizations (2-4). The parameter a predicted the onset of RA, with a value ofa < 2 identifying the transition to RA conditions for most polymerizations. The parameters b and B related to the influence of reactant consumption on RA sensitivity. Values ofb < 100 indicated loss of sensitivity due to rapid initiator decay, while B < 20 warned of monomer limited sensitivity. In conjunction with weakened sensitivity, the critical value a decreases from the value of two, and may be depressed to values near one (3). While all three of the above parameters follow directly from the dimensionless form of the balance equations, each has an independent significance when viewed as the ratio of time constants for particular reaction processes. Specifically,

THEORY Prior to any discussion of experimental results it is

necessary to establish the framework of the analysis with a brief review of our RA theory for copolymerization. In previous articles of this series it was shown that three

where Xi is a time constant for initiator consumption, A,, for monomer consumption, had for adiabatic reaction, and AR for heat removal. O u r copolymerization analysis d r e w upon the rationalization of dimensionless criteria as ratios of time constants for competitive processes, and extended the notion of characteristic times to lend physical interpretations to each of these constants (6). Thus with temperature and concentration made dimensionless, the homopolymerization balances lead us to the conclusion that the time constant for monomer decay is the reciprocal of the initial rate, i.e.,

similarly for initiator

and for heat generation

= To/($)
ialor mber
0

for To =

TR

Furthermore, AR and h a d were shown to be related to the temperature derivatives of the heat removal and generation functions in the batch thermal energy balance. Thus

Flange

Fig. I . TIPA batch reactor.

T
Reactor

and

where

dT P C P X - G,

- R,

(9)
191

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Vol. 19, No. 3

D.H . Sebastian and J. A. Biesenberger

yields wide variety of conditions, when plotted in dimensionless form, 4 vs 7 with dimensionless time defined as 7 = t/A,. Furthermore, the isothermal histories thus reduced behave in the same manner as dimensionless homopolymerization trajectories. A similar analysis can be applied to thermal histories to extract values for parameters from experimentally measurable rates. When initial and reservoir temperatures are equal, the initial value of the removal function, is zero. Thus, from E q 9 it follows that:

and The above were used as defining equations for A,,,, &, & , , time constants for copolymerization, while & and AR remain unchanged. Note that by generating physical interpretations of the parameters, the analysis transcends the kinetic forms of homopolymerization. It becomes possible to extend the application of kinetic theory intuitively to systems with kinetic schemes that defy a Semenov-type analysis. In contrast to their homopolymerization counterparts, time constants A,,,, &, and & , do not appear explicity in the dimensionless balance equations. Nevertheless, copolymerization reaction behavior conforms to the predictions by dimensionless criteria formed from the direct substitution of these time constants in place of their appropriate homopolymerization counterparts. Thus with a defined as in Eq 1 , but with &d substituted for & , the same RA criteria hold for copolymerization. Critical conditions are

which combines with E q 6 to yield:

It is possible to evaluate fb directly from the initial slope of a plot of temperature vs time. Of equal importance in the formulation of RA criteria It too can be determined solely from initial is Lad. temperature-time slopes. Recall that when T o = TR, Re is zero, thus:

The physical interpretation of these characteristic times lends new significance to the dimensionless criteria. For instance a is not a mere consequence of mathematical manipulation associated with t h e Semenov-type RA analysis. It is actually a measure of the relative rates at which competitive processes of heat generation and removal increase with temperature. This is clear from substitution ofEqs 7 and8 intoEq 1 giving:

Since the heat generation function contains the exponentially increasing reaction rate term, while the removal function is linearly dependent upon temperature, one might expect that the initial removal rate must exceed generation in order that it might keep pace as temperature rises. Indeed, our RA criterion shows that

Computing the change in initial slope with varying ini1 , , . tial temperature provides the means for evaluating 1 Induction period studies described in our kinetic analysis give a ready means for determining & for an initiator in monomer solution (8). Our experimental study of RA in styrene homopolymerization demonstrated a technique for calculating AR from cooling curve data (4). It is thus possible to evaluate all the parameters necessary to formulate criteria 1-3 without a rigorous kinetic model. These experimentally determined time constants have an added value beyond the qualitative predictions drawn from the criteria they form. In an earlier work, it was shown that complex copolymerization kinetic schemes could often be simulated by pseudohomopolymerization kinetics through substitution of appropriate copolymer forms in homopolymer balances. Thus experimental data can b e generalized for modeling purposes by using the following balances.

( %j0'2(+j
is a necessary condition to avoid RA. With knowledge of a detailed kinetic model, it is of course possible to derive analytical expressions for each of the time constants based upon defining Eqs 4 8 . More importantly, however, these parameters can still be evaluated in the absence ofa rigorous kinetic model. In a paper on isothermal copolymerization kinetics (8), it was shown that using experimental initial rate data the value of A,,, could be calculated as in Eq 4 . These values successfully united conversion histories taken under a
192

dT' - m,1I2m E'T' dt n , exp[ 1 + T'

(T' - TA) AR
(22)

All parameters can be determined from experimental data, thus even details of conversion and temperature
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Vol. 19, No. 3

A Study of Chain-Addition Polymerizations with Temperature Variations

histories may be available without resorting to complex reaction mechanisms.

r
5

90% S I N AlBN
1 2 3 4 5

Cll0=

RESULTS
Non-isothermal copolymerizations were performed for comonomer compositions of 90,80, 70, 60,40 and 20 percent SAN (note: percentage shall hereafter refer to mole percent styrene in monomer feed). RA behavior at each of these compositions was examined at 373K, and the 90, 80 and 70 percent levels at 363K as well (15). Although these temperatures exceed the normal range associated with AIBN initiated polymerization, this initiator was chosen for the specific purpose of keeping molecular weight low. Iosthermal studies showed that SAN copolymerizations exhibited a strong gel-effect (8). In order that experimental conditions most closely parallel the assumptions implicit in RA theory, it was desired to examine non-isothermal behavior devoid of late RA brought on by anomolous kinetic effects. A high rate of initiation leads to a high rate of reaction and low molecular weight of the polymer product. The former insures early runaway, i. e., RA at low conversion, and the latter tends to postpone the onset of GE to higher conversions and reduce its severity. However, both ends are achieved at the expense of a decreased RA sensitivity (3) making definition of the ignition point more difficult. All reactions were conducted at a single coolant flow rate, so the heat transfer coefficient of U = 145 J/m2 s K holds for all reactions. Initiator feed concentration was manipulated to provoke the occurrence of RA. Thus for each comonomer composition, a family of temperature profiles was generated with initiator concentration as the only variable parameter. Figures 2-6 illustrate these families for all of the AIBN initiated copolymerizations considered in this work. Additionally, a series ofbenzoyl peroxide (BP)-initiated reactions were conducted with 70 percent SAN at 373K, and these are pictured in Fig.

.03 .04 .05 .06 .07

z< t
L

n
I -

*<

OD

0 h.

I
60

180

3 00

420

540

Time sec

Fig. 3. 90 percent SANIAIBN at 373K, temperature history.

70% S I N I l B N
1 l o = .01 2 .015 3 ,0175 4 .02

100

300

Time scc

500

700

900

F i g . 4 . 70 percent SANIAIBN ut 373K, temperature history.

7.
The curves in Figs. 2-6 are computer reproductions of experimental data. They are not, however, curve fits of the data. They are point-to-point connections of data. The raw data were smooth continuous curves on the

40% S l N AlBN
1 [I],= 2 3 4
,0035 ,005 .01 .03

I
m
N 1

90% S I N I l B N
1 2 3 4

[IIo=

.07 .09 .I0 .12

85

255

425 Time sec

595

765

F i g . 5 . 40 percent SANIAIBN at 373K, tentperuture history.

80

240

400 Tine sec

560

720

Fig. 2 . 90 percent SANIAIBN ut 360K, teniperuture history.

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Yo/. 19. No. 3

chart recorder output. Selection of individual points to transform to the temperature-time domain was arbitrary, indeed, an infinite number of points could be chosen to generate these curves. Thus, actual experi193

D. H . Sebastian and J. A. Biesenberger

20% $11AlBN
1 CI&=.0025 2 ,0035 3 ,005 4 .01

.03

100

300

I
500 Tint see
700 900

Fig. 6 . 20 percent SANIAIBN ut 373K, temperature history.

100

300

500

700

900

T i m see

Fig. 7. 70 percent SANIBP

u t 373K, temperature history.

mental points are not indicated in the figures, only the resulting profiles are shown. A number of qualitative observations are immediately apparent. Comparing polymerizations at 363K to those at 37313, it is evident that a higher level of initiator is required to cause RA at lower temperatures. It is also clear that the lower temperature RA transitions are more sensitive in nature than the 37313 families. Compare, for instance, Figs. 2 and 3 . Similar incremental increases in initiator feed concentration bring greater changes in thermal behavior at 363K than at 373K. While starting at a lower feed temperature, the 363K runaway profiles rise higher above reservoir temperature than the runs at 373K3,and temperature spread between successive curves is greater. Note that change of initiator also affects sensitivity. Compare Fig. 4 , the AIBN-initiated, with Fig. 7, the BP-initiated 70 percent SAN reactions. BP is the slower decomposing initiator and its produces a more sensitive RA transition. These reactions also exhibit an induction period (the time before the onset ofRA) which is roughly twice that of the AIBN-initiated reactions. Ignition theory predicts (9) and numerical simulation has
194

confirmed (3) that the induction period should be proportional to &d. This parameter depends inversely upon reaction rate and thus should be proportional to R;'''. Since all other reaction conditions are identical, the ratio of induction periods for the AIBN and BP reactions should be inversely proportional to the square root of the rate constant for decay of these initiators. Indeed, evaluating kd for these initiators at 373K leads us to predict that BP induction periods should be 2% times the value for AIBN. Monomer feed composition variations introduce an added dimension not present in homopolymerization. Composition may affect both RA and RA sensitivity. In Fig. 8 feed composition is the variable parameter, with initiator feed concentration fixed at 0.03 m/l. Successively enriching AN content in the feeds brings about runaway in much the same way as increased initiator feed concentration. Observing Figs. 2-7, the qualitative effect of composition on RA sensitivity is apparent. As the range of90 to 20 percent styrene is traversed, the RA transitions increase in sensitivity. There is a much sharper break between RA and quasi-isothermal temperature profiles in the highest AN content reactions, Fig. 7, than in the highest styrene content reactions, Fig. 3 . In numerical simulation studies of runaway, families of temperature profiles plotted in dimensionless form vs time made dimensionless by reduction with & d , followed a common trajectory during the induction period prior to RA. A value of initial temperature is sufficient to reduce temperature (T' = [T - T,]/T,) but absence of a kinetic expression for &d prevents a priori determination of this parameter. It is known that the rate of homogeneous free-radical polymerization .is proportional to the square root of the rate of initiation, and thus is proportional to the square root of the initiator concentration. From homopolymerization analysis it can be concluded that &d is inversely proportional to the initid rate of reaction. At a given temperature and feed composition, for a specific initiator, comonomer system Ld must therefore be proportional to the inverse of the square root of the initiator feed concentration. Thus for
SAN AlBN
rll~.o3

I
60

180

300

420

540

Time sec

F i g . 8. Compositionul effects of AIBN-initiated reuctions a t

373K.

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Vol. 19, No. 3

A Study of Chain-Addition Polymerizations with Temperature Variations

any temperature profile scaling time by multiplying by [I],'@ differs from T =tl&d by only aconstant factor. This factor is the same for all curves in any RA family since all feed conditions are the same with the exception of [I],. Thus it is possible to transform the temperature histories ofFigs. 2-7 to pseudo-dimensionless plots ofT' vs t [Z],"', and these are shown in Figs. 8-12. Note that the desired effect has been achieved. For instance in F i g . 8, 90 percent SAN, it is clear that all temperature paths coincide throughout the induction period, This trend holds as styrene content is decreased to 60 percent. At the 40 percent level, Fig. 1 1 , the first sign of a breakdown appears and is amplified at the 20 percent level. This should be anticipated since the halforder dependence of rate on initiator concentration is a characteristic of homogeneous kinetics. Studies of heterogeneous bulk AN polymerization indicate a higher order dependence, with values reported as 0.7-0.8(10). Clearly a higher order would preferentially shift the high concentration curves to the right, decreasing their initial slope and increasing the induction period in

rs.

4OxSAW AlBW
1 c13,=.0035 2 ,005 3 .01
4

.03

F i g . 11. 40 percent SANIAIBN at 3731<, pseudo-dimensionless plot.

* N.

ZOfsSlN AlBW
1 Lllo=.oo25

5.

90% SAW AlBN 1 cI1, = .07 2 .09 3 .10

4
.12

2 3 4 5

.0035 ,005
.01

.03

9.
.r
4
I -

9 '

Fig. 1 2 . 20 percent SAN1AIB.V at 373K, pseudo-dimensionless

20
100
140

180

plot.

t[ 111.5

Fig. 9. 90 percent SANIAIBN at 363K, pseudo-dimensionless plot.

.03

I -

1 0

30

50

7 0

90

1[1]y

Fig. 10. 70 percent SANIAIBN at 373K, pseudo-dimensionless plot.

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Vof. 19, No. 3

pseudo-dimensionless form. This is the qualitative trend necessary to achieve the same effect with high A N contents as with high styrene contents. Beyond qualitative generalizations, it is desired to test the quantitative applicability of thermal RA theory to copolymerization. To accomplish this in a manner parallel to that for homopolymerization (4) requires that values of feed parameters and kinetic constants be inserted into the expressions for the various Characteristic times, and that the dimensionless runaway parameters subsequently be evaluated. However, earlier isothermal kinetic studies shbwed that no available kinetic model adequately reproduced SAN reaction profiles. This would pose an apparently insurmountable obstacle to any quantitative evaluation of the experimental results. The physical approach to evaluating time constants described in the previous section provides an alternative to strictly analytical solutions. Values for the time constants can be determined from experimental data, obviating the need for a kinetic model. Because the pseudo-dimensionless plots align to give a common induction period trajectory, evaluation of
195

D. H . Sebastian and J. A. Biesenberger

initial slopes is made considerably easier. Although individual slopes can be taken from each profile of the real temperature-time plots, the pseudo-dimensionless form gives and averages over some five runs with different values of [ I 1,. Recalling that the calculation of &d requires the change in initial slope with temperature, there are insufficient data to calculate this parameter for the 60, 40 and 20 percent compositions, which were reacted at only one temperature. Strictly, a wider range of data than available for the 90,80 and 70 percent levels should b e used to calculate A a d i n E q 19. F r o m t h e it is known that homopolymerization expression for
)hd T:/exp(- E ' ) For values of E ' typical of free-radical polymerization, and T oin the range of this study, the ratio on the RHS of E q 25 changes slowly with temperature. Therefore to a good approximation we should b e able to express E q 19 as

This permits the use ofdataobtained at two temperature levels separated by ten degrees, to estimate a value for
&d.

reduced by [I],"2 Table 1 lists the values of it; and for comonomer compositions of 90, 80 and 70 percent. Also included in the table are values of A, determined in the isothermal kinetic study (8).The general trend is for each parameter to decrease with increased temperature or AN content, as both serve to raise the rate ofreaction. Table 2 lists each experimental run along with the associated dimensionless RA parameters determined from the A's in Table 1 in Eqs 12, 1 3 , 1 4 , and23. From
Table 1. Experimentally Determined Time Constants System 90% SAN/AIBN 80% SAN/AIBN 70% SAN/AIBN
T,,

[\IA"

Am

[1IA'* Ac
1262 430 889 318 1042 324

[ I I ~ "A a d
17.2 13.6 12.5

363 373 363 373 363 373

481 215 489 231 387 200

Table 2. Experimentally Determined Dimensionless RA Parameters

~ ~

Oh),,
0.90

[I],
0.03 0.04 0.05 0.06 0.07 0.015 0.02 0.025 0.03 0.04 0.01 0.015 0.0175 0.02 0.03

Type' NU NU RA RA RA NU NU RA RA RA NU NR NU RA RA

a 1.65 1.43 1.28 1.17 1.08 1.78 1.54 1.38 1.26 1.09 2.08 1.70 1.57 1.47 1.20

b 5.7 6.6 7.4 8.1 8.8 5.9 6.8 7.6 8.3 9.6 5.0 6.2 6.7 7.1 8.7

E'
25.0 25.0 25.0 25.0 25.0 24.3 24.3 24.3 24.3 24.3 26.0 26.0 26.0 26.0 26.0

0.80

0.70

12.5 12.5 12.5 12.5 12.5 17.0 17.0 17.0 17.0 17.0 16.0 16.0 16.0 16.0 16.0

RA-Runaway. NR-Non-runaway.

values of b and B it is clear that all reactions were conducted in a non-sensitive regime. Parameter b is an order of magnitude smaller than the value at which initiator consumption limits sensitivity. Monomer parameter B is quite close to the suggested value for the disappearance of sensitivity. Under such conditions one must expect that the value of a associated with the transition to RA will be depressed from two. RA boundaries of a,-, vs b generated by numerical simulation of homopolymerization (3) suggest that aer should lie somewhere between 1.2 and 1.4. Indeed, our experimentally determined values of a,, fell in this region. It is important to remember that no specific kinetic model was invoked to evaluate the parameters of Table 2. With no more than the knowledge of the order of dependence of reaction rate upon each reactant, and the physical interpretation of each characteristic time, it is possible to directly interpret experimental data in terms of RA theory. The results so obtained match detailed numerical simulations of homopolymerizations as well as copolymerizations indicating a significance that transcends the details of any particular kinetic model. The technique presented in this work has potential application to reactor design and need not be restricted to polymerization reactions. Our RA parameters have analogs in explosion theory (11) and simple chemical reaction kinetics such as the first-order conversion of reactant to products (12). Although expressions for the RA parameters differ in form owing to differences in kinetics, their physical interpretation is identical to ours. It is the underlying physical significance of these parameters characterizing the competitive rates of reaction and transport processes that lends a universality to this approach. RA behavior can b e assessed without the need for kinetic and thermodynamic properties necessary to evaluate the analytical expressions for dimensionless RA parameters. Detailed simulation, of course, requires a precise model, however go-no go predictions of RA can be made based solely upon experimentation. In fact, the unified behavior of dimensionless temperature histories during the induction period makes nonrunaway profiles sufficient to calculate characteristic times and evaluate RA criteria. Plant datacan be used to predict reactor response to changes in feed parameters without actually causing RA. Certainly a series of simple bench scale experiments would be adequate to generate data for a RA analysis. Had we chosen to examine a kinetically well described system such as styrene-methyl methacrylate, our analysis might have been simplified. All parameters could have been evaluated analytically from kinetic expressions since this system can be adequately described by several kinetic schemes in the literature (13, 14). However, by treating a complex system such as SAN we were able to better elucidate the anatomy of RA theory as a collection of competing processes whose rates manifest themselves in measurable quantities. The more general meaning of each parameter is of far greater importance than the details of their kinetic derivation giving the analysis a broader range of applicability, beyond the scope of our original investigation.
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Vol. 19, No. 3

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A Study of Chain-Addition Polymerizations with Temperature Variations

ACKNOWLEDGMENT This work was supported in part by a grant from the National Science Foundation (ENG-7605053). The authors also gratefully acknowledge Dr. Joseph Domine and Dr. David Chappelear and their respective companies, Union Carbide and Monsanto, for supplying us with styrene monomer at no cost. NOMENCLATURE A,
a
= wetted area for heat transfer = )hd/)lR dimensionless ignition parameter = = = heat capacity caVg K = & / h a d dimensionless activation energy
=

A
p
T

= copolymerization time constant = density = t/& dimensionless time

Subscripts

ad cr
G
i

= adiabatic conversion
= = = = = =

b B
C, E E{

m o R

critical heat generation initiator conversion monomer conversion initial condition, evaluated at feed conditions heat removal

REFERENCES
1. J . A. Biesenberger and R. Capinpin, Polym. E n g . Sci., 14, 737 (1974). 2. J. A. Biesenberger, R. Capinpin, and D. Sebastian, Appl. Polym. Symp., 26, 211 (1975). 3. J. A . Biesenberger, R. Capinpin, and J . C. Yang,Polym. Eng. Sci., 16, 101 (1976). 4. D. H. Sebastian and J . A . Biesenberger,Polym. Eng. Sci., 16, 117 (1976). 5. L. Valsamis and J. A. Biesenberger,CEPSymposium Series, 160, 20 (1976). 6. D. H. Sebastian and J . A. Biesenberger, accepted for publication by J. A p p l . Polym. Sci. (1978). 7 . G . Mino, J. Polym. Sci., 22, 369 (1956). 8. D. H. Sebastian and J. A. Biesenberger, (1978)submitted to J. Macromul. Sci. 9. P. Gray and hl. J . Harper, Trans. Faraday Soc., 55, 581 (1959). 10. W. M. Thomas, Ado. in Polym. Sci., 2, 401 (1961). 11. J . Adler and J. W. Enig, Comb. Flame, 8, 97 (1967). 12. C . H . Barklew,Chem. E n g . Prugr. Symp. Ser., 55,37( 1959). 13. H. W. Melville, B. Noble, and W. F. Watson, J . Polym. Sci., 2, 229 (1947). 14. S. Russo and S. Munari, J. Macromol. Sci.-Chem., A-115, 2159 (1967). 15. D. H. Sebastian, PhD Thesis, Stevens Institute ofTechnology (1977).

Ed/&T, dimensionless initiator activation energy G , = thermal energy generation function = -AH R, for homopolymerization G: = dimensionless generation function = - AH R,/pC,T, for homopolymerization [ I ] = initiator concentration [m] = monomer concentration; without bracketsdimensionless = [ m ] / [ m ] , [m,] = fictitious initiator concentration = 2 [ 1 ] ;without brackets-dimensionless = [m,]/[m,], R , = thermal energy removal function = UAduR(T - TR), R: = dimensionless removal function = uAw/&pUR(T - TA) t = time T = temperature Z = dimensionless temperature = (T - T,)/T, = overall heat transfer coefficient U tiR = volume of reactor A = time constant

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1979, Vol. 19, No. 3

197