Conversion Prediction in High Conversion Free-Radical Po Iy me rizat io ns*

S. BALKE, L. GARCIA-RUBIO, and R . PATEL

Xerox Research Centre of Canada Mississauga, Ontario L5K 2L1

The objective of this articlc. is to introduce a new general kipproach for conversion prediction i n high-coitversion freeradical polyiirerizatioiis-'"l'he hlethod of Kinetic Similarity." Using a sirigle homopolymer reference curve of methyl methacrylate (XIRIA) and one to two time-scaling parameters, the conversioit cs. tiiiie curves for AlhlA, ethyl methacrylate (EAIA), vinyl chloride (VC), ;ieq lollitrile (AN), styrene meth) 1 methacrylate (ShlhlA), and st>-rene;icrylonitrilr (SAN) could be well-descri1)etl. For hl ;\IA and VC, these parameters are shown to o b e y expectetl Arrhenius relationships over 45 to 90C and 30 to 'iO"C,respectively. The method is simple to kippl!., continrious o v e r the whole conversion range, utilizes e x istiiig knowledge at low a i i d liniiting conversions, and avoids app1ic;ition of iisiial low coltversion ;issumptions into the diffiisioir-c.oiitrolle~1 region.

INTRODUCTION
casurement of conversion of monomer to polymer during a polymerization provides accurate, precise data of great utility in process simulation and control (1-3). This usefulness originates from several aspects : Conversion is an important product property; since residual monomer levels are part o f a reactor product specification, reactor system design a n d control must take conversion as a function of time into account. Conversion is a prime determinant of transport phenomena within the reactor. It translates into a decreased free volume a n d increased viscosity during the reaction. As a result, reactions become diffusion-controlled, and mixing difficulties, as well as heat transfer problems, increase. The rate of increase in conversion is n e e d e d if rate of heat generation within the reactor is to be estimated. Conversion us. time provides a link to other polym e r properties (3). For example, molecular weight distribution, copolymer composition distribution, a n d sequence length distribution can be considered as the sum of instantaneous distributions, each weighted by a conversion increment

(4, 5 ) .
Despite its importance, a n d although recent research utilizing free volume (4,6-10) a n d polymer entanglement theories (11-15) have provided valuable insight into the mechanism of diffusion control, prediction of conversion vs. time is far from satisfactory from an engineering viewpoint.

For maximum engineering usefulncss, criteria that any conversion prediction model should satisfy include the following: General applicability to different monomers, homopolymerizaton, a n d copolymerization to complete converson. Ready incorporation of existing knowledge of a particular polymerization. Absence of the stationary state assumption beyond low conversion. Continuity a n d simplicity: one equation to describe the whole conversion rangc without segmentation and without numerical solution difficulties. No necessity for molecular weight information in the model. Minimal reliance on literaturc values of rate constants . Allowance for kinetic mechanism changes beyond low conversion. From the vast number of publications in this area, the information most relevant to these criteria are: Kinetic models for low conversions are generally available a n d satisfactory. Some very useful models to high conversion for specific homopolymers are available (e.g., 4, 7 , 10, 16-19). For copolymers, much less is known

(5, 20-23).
Final (limiting) conversion can often be predicted by assuming that the reaction ceases when the glass transition temperature (Tg) of t h e reaction mixture equals the polymerization temperature. Free volume theory has been used for the estimation (4-8, 19).
777

POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vol. 22, No. 12

S. Bulke, L. Garcia, und R. Putel

Correlations of rate parameters with free volume have so far provided the most practical microenvironment description for correlation of rate 7). The correlation shown as Fig. 19 paramters (4, in Ref. 4 of a normalized group of rate parameters us. free volume successfully superimposed data for methyl methacrylate polymerization at 70 and 90C each at two levels of free radical initiator over wide conversion ranges. Later, using the same data, the individual termination and propagation constants were separately calculated and shown to obey a similar plot, this time for 50, 70, and 90C ( F i g s . 2 and 3 in Ref. 7). Although certainly not totally satisfactory, particularly with regard to accuracy at all conversions, this enables rapid, direct estimation of these rate parameters by calculation of free volume from a specified reaction temperature and conversion. Molecular weight effects on conversion may be present via entanglement of terminating macroradicals (i.e., molecular weight information may be a necessity in any conversion model) (9, 14, 15). Very recent theoretical developments utilizing the reptation model of de Gennes for polymer diffusion (24) or combining entanglement theory with free-volume theory (25) re-enforce this likelihood. Primary radical termination and transfer to polymer represent probable mechanism additions at higher conversions (13, 26, 30). Polymerimonomer solubility effects (17, 19),and violation of the steady-state assumption (26) can also readily introduce complications. This objective of this paper is to initiate the development of a new approach that can satisfy most and, perhaps for many polymers, even all of the above criteria. Two underlying principles are involved: Formulation of the rate equation with the addition of an unknown general time function rcprcsenting nonidealities in the kinetics. This is in contrast to the usual assumption of a specific function of conversion to represent a group of rate constants. Definition of this unknown function by appeal to similarity with a single known conversion 6s. time curve. Often, this shape is implicitly considered in formulation of a mathematical model for a polymerization. However, explicit use of similarity is much less frequent. A singular example is the empirical interpolation between component homopolymerization curves of styrene and acrylonitrile in order to estimate the curves of the intermediate copolymers for purposes of experimental design (23). In other fields, examples are more readily found. In statistics, families of sigmoidal curves have been generated by scaling and shifting of axes (28). In polymer rheology, Time Temperature Superposition (29) has been a very useful related concept.
778

THEORY In the development that follows, homopolymerization is considered first, followed by copolymerization. In each case, the rate equation is first formulated, and then kinetic similarity is defined. Homopolymerization Formulation of the Rate Equation. At low conversion and using the steady state assumption:

where

and

v = V,,(1 - EX)
x t c,,
=

(lb)

k,
e

kd
Kt V V,,
E

conversion = time = initial initiator concentration = propagation rate constant = initiator efficiency = initiator decomposition rate constant = termination rate constant = volume of the reaction mixture = initial volume of the reaction mixture = shrinkage proportionality constant (often considered = (p,, - p M ) / p p where , p.,, and p,. arc densities of monomer and polymer, respectively.

When diffusion control begins, k,, becomes a function of time. Furthermore, the form of the right-hand side of E 4 1 can change if the reaction mechanism changes (e.g., primary radical termination becomes important) or if the stationary state assumption is violated. Therefore, assume that, at any conversion, such nonidealities can be accounted for by addition of a general function of time and initial initiator concentration to the right-hand side of E 4 1 after all the conversion terms are transposed to the left-hand side. Then, showing the integration to any conversion, we have:

where

f
and let

cpliLc,,)

Then, after integration, followed by expansion of the exponential in Taylor Series and retention of only the first two terms (usually a good approximation and well worthwhile, since it groups k d with other unknown parameters in a new parameter K-thus avoiding the need to independently estimate a value for kd), we obtain:
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vof. 22, No. 12

Conoersion Prediction in H i g h Conversion Free-Radical Polymerizations

A=Kt+F
where

(4)
1.80 -

-1.60 1.40

A *AL

K
and

k,c#

(44

1.20 A 1.00

0.80 0.60

For the special case of E = 0.

0.40

= -ln(l - x)

(44

Low Conversion Analysis. At low conversion,

F=O

(5)

0.0

100

200

300

400

! 1 0

The constant K in E q 4 is determined by using only the low conversion data and a single variable search. High Conversion Analysis. At high conversions, kinetic similarity with a known reference conversion us. time curve is assumed. Only this one reference curve is fit by empirical or mechanistically-based functions (third-order splines are used in this study) so that the reference conversion can be readily calculated at any time. above symbols to indicate the Therefore, using refercnce:

Fig. 1 , Churucteristic ctirlje f o r the reference honiopolyiiierizutioii.

F=;i-&

(6)

In each case, after the form is assumed, the objective of the analysis is to associate the unknown parameters with a physical meaning. The more successful this latter step, the more mechanistic can be the model. From a practical viewpoint, the more mechanistic the model, the easier and more reliable become correlation of the parameters. One Parameter Model-lncreased Kinetic Similarity. Equation 7 can b e readily rearranged to provide:

Now, for any other similar polymerization, assume:

t =
where

1 --= (A/, - &I,)

K + a7 t K

(9)

(7)
where the subscript L refers to the value calculated using limiting conversions. The meaning of Ey 7 can readily be understood by reference to Fig. 1 (which shows the reference curve dimensions), and rearrangement of this equation to give

F FL

F Fl.

( 8)

Now if, as an additional similarity requirement with the reference, we assume that a is constant, then it becomes the only unkonwn parameter in determining t , to satisfy E q 7. Since dF dF - -

dt

ax

It can be seen that, by kinetic similarity, here is meant that the ratio ofthe two indicated vertical distances F : F L are equal to those of the reference curve. In general, for E q 8 to be valid, the time values - of the reference curve must be scaled to new times, t. In the remainder octhis development, it wgl be implicitly assumed that F is always evaluated at t. Then the two essential related problems become choice of the reference curve and choice of a scaling function to relate t to t. A reference curve displaying the frequently observed sigmoidal shape, and preferably for the polymer of prime interest, is a reasonable first choice. The functional relationship needed between t and t is more difficult to anticipate. Two functional forms are considered here, involving one and two unknown parameters, respectively.
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vof. 22, No. I2

and if we consider

where is the value of t a t t = 0. Applying the Leibnitz formula to differentiate E q 12 and letting

ti

f = K&
and

- -

(13)
(14)

where K Dand KDare diffusion-controlled rate constants and possibly n = ri = 112, we obtain

K,ct

779

S. Bulke, L. Gurciu, arid R . Putel

Once a is determined by a single variable search to solve the algebraic E9s 4 , 7 , and 9 simultaneously, E q 15 implies that it will obey an Arrhenius relationship with respect to Temperature. This is, In K D = -111 ac;

e k d , exp(-k,t)

Kt

fg

+ constant,

= -E ~

RT

+, constantz ~
(15a)

where the parameters on the right-hand side of the equation have the same meaning as in homopolymerization. Since

Two-Parameter - Model. Assume that the relationship

between t and t is linear: and

t=n+bt

(16)
Then, as in the analysis of homopolymerization, assuming the Taylor Series expansion to avoid literature kd values and integrating, we obtain:

The parameter u can be used to define the-onset of the gel effect. At low conversions, for F and F to both be zero and yet have the same initial conditions:

K t=,t K
When t l j s equation becomes invalid, it is because F and/or F a r e non-zero. From that point onward, Ey 16 relates t and t. Therefore, define the intersection of E 9 s 16 and 17 as the onset of the gel effect:

where t,, = value of t at the onset of the gel effect. The parameter b is related to a relative rate of reaction during the gel effect. From E q 16.

Let

(25)
Low Conversion Analysis. At low conversion,

dt d X

-b-

dt dx

G -0
and
tc,
I -

(26)

If we assume that this rate can he expressed as first order with respect to monomer, and employing a diffusion-controlled rate constant, K D , and K!), in each case, then h would be expected to obey an Arrhenius relationship to T: In b = In k,+;
E d , ~

tcI.0

(27)

Then

+ constant,

(19a)

HT

+ constant,

Copolymerization Formulation of the Rate Equation. Assuming shrinkage during polymerization to be negligihle, the rate equation or copolymerization has been shown to be (20): In

Low conversion data can then be fit by a single variable search for the quantity 6/(1 - 0). High Conversion Analysis. At high conversions, Ey 26 and 27 are no longer valid. Furthermore, in copolymerization, composition provides a degree of freedom not present in homopolymrrization. Physically, composition affects the rate of reaction in two primary ways: The cornposition of the polymer produced interacts with molecular weight (and other microstructure, such as sequence length) to define the viscosity, or (more generally) the microenvironment for reaction. Therefore. it directly affects diffusion control. Since the propagation rate constants are usually different for the different monomers present, reaction rate can be affected by the composition drift of the residual monointrs in the reaction mixture. Two ways of applying the analysis to coploymers are used in this paper. They are as follows:
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vol. 22, No. 72

MI - /3 In M2 = MI, MZ,

(kZ1 - j3kZ2) R. d t (20)

0

where the subscripts , and refer to each respective monomer and M = concentration of monomer M,, = initial monomer concentration k = propagation rate constant R. = total concentration of free radicals
=

kii k,,

k22

Now, let R. be the sum of the low conversion value and an unknown time function g (= (p2 (t,c,,, ~ 1 . 0 ) )
780

Co nve rsio ti Prediction i n

High Con oersio t i Free-Radical Polyme rizatio ti.)

Technique. Transformations were used to permit unconstrained optimization search methods while actually constraining values of parameters to physically realizeable values (33).The objective function used for all searches utilized least squares weighted by the square of the reciprocal of the experimental value. For a two-variable search for a and b (Ey 16)to satisfy Eys 4 and 7 , for example, the objective function was:

Homopolymer Analogue. E q 24 is rearranged to provide the same form as Ey 4

(29) where

and A can be given b y E q 4 b or 4 c . Now, for kinetic similarity

$I=--$ L

qJ

dJ 1,
As for homopolymerization, the subscript l , refers to the value at limiting conditions (of both x and wI for copolymers) and above the symbol refers to the reference \?due. The equatcon is assumed to be valid only when rl, is eyaluate_d at t . If a homopolymer reference is used, then dJ and GL are replaced by F and FL, respectively. Again, the two outstanding problcms are choice of a reference_ conversion vs. time curve and of a function relating t and t. In this paper, the same homopolymer reference a s previously used- was used here. Also, the two-parameter function for t was used (Ey 16). Separation of Concersion cind Composition Contributions t o Reaction Rate. Rearranging E q 24 to obtain:

n1 and n2 were chosen to focus the search on the nonideal region while avoiding undue weighting by either very high or very low conversion data. This subjectivity was necessary to avoid drastically false optima. For the one- and two-variable searches, a wide tolerance for n1 and n2 values was experienced. Three-parameter searches were more sensitive. Once the parameters a and b, or the single parameter a, were obtained, they were used together with the low conversion value of the rate constant and the spline fit to the reference in-Eq 4 to 4escribe the whole conversion range. Since F =-0 at t = 0 when values of t < 0 were encountered, F was set equal to zero. Also, for expediency, linear regression w a s used to estimate Arrhenius plots.
RESULTS AND DISCUSSION Establishment of Reference Conversion Curve

where

and the other variables have previously been defined E y s 29 and 25. Assume

G = - G1.
GL
I

(32)

As before, G and C are evaluated at a new time, t . Therefore, to fit Ey 31 to experimental data requires a three-parameter search for P, a, and b (using E q 16). EXPERIMENTAL AND COMPUTATIONAL PROCEDURES Experimental data were obtained from the following sources: Methyl methacrylate (MMA), 45C (30) Methyl methacrylate (MMA), 50, 70, 90C (4) Ethyl methacrylate (EMA), 70, 90C (31) Vinyl Chloride (VC), 30, 50, 70C (17) Acrylonitrile (AN), 40, 60, 80C (32) Styrene Methyl Methacrylate (SMMA), 60C (22) Styrene Acrylonitrile (SAN), 60C (23)

Data for methyl methacrylate at 50C and 0.3 wt.% AIBN were chosen as reference. It is representative of the family of sigmoidal conversion curves. Also, because of wide usage of these particular data as illustrative of the gel effect, methyl methacrylate (MMA) was considered the monomer of primary interest. These data were fit by cubic splines. The coefficients defining the fit are shown in Table I , and the curve itself is that noted as 50C 0.3 wt.% AIBN in Fig. 2. It was expected that the other MMA data would be most easily interpreted, while polymers drastically different from MMA (notably, acrylonitrile (AN) and styrene acrylonitrile (SAN)) would be most difficult. Methyl Methacrylate Polymerization Results are shown in Table 2 . The fits obtained are shown in Figs. 2 through 5 . Figure 6 shows Arrhenius plots for thc low and high conversion data. (Note the different scales for the ordinates.) The equation for the low conversion line is: In

k,, =

In

K
Cd

= -

9692 lo3 T

+ 25.1664

(34)

A Data General ECLIPSE computer was used for the calculations. Cubic spline fits (32) utilized the IMSL Library (subroutine ICSVKU). Single variable searches used the Fibonacci Method. Two- and three-variable searches used the Nelder Mead version of the Simplex
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vol. 22, No. 12

Both the one-parameter and two-parameter scaling equations Eqs 9 and 16 provided good descriptions of the data. Results of the former are shown in Table 2 and Fig. 6. Limiting conversions were obtained from freevolume theory. [For polymers other than MMA, limiting conversions were considered to be the final data point, or were estimated from neighboring polymeriza78 1

S. Bulke, L. Gurciu, und R . Pate1

Table 1. Spline Fit of Reference (MMA, 5WC, 0.3% AIBN) C, ,1341674000E-02 ,2062531000E-02 .1303177000E-01 .1027992000E-01 .2884020000E-03
A
= =

C Z
- .5705650000E-05

c,
,2122728000E-07 .l 118474000E-05 - ,1570543000E-04 .5556075000E-05 - ,7030664000E-08
-

Y
.5726553000E-03 ,2617391000E-00 .5827780000E-00 .7474772000E-00 ,8360874000E-00

fK

,885867300E-05 .1920600000E-03 - ,4080944000E-03 .4243788000E-06

,2286902000E03 ,2832871000E03 .2960249000E03 .3205337000E03 .4605060000E03

I - t,-,

( ( C : A

C2)* A

+ C,)* A + Y

Fort 2 460.506
x
=

0.8629899563 + 0.0000054289' t

tions if the run was not carried to "completion." Values are listed in the respective tables.] The values of limiting conversion obtained for MMA are satisfactory except at 45"C, where the value appears high.

Table 2. Results of Model Application to MMA T ("C) 45 45 45 45 45 45 50 50 50 70 70 90 90 C C , moles/l 0.00625 0.0125 0.0250 0.0500 0.1000 0.200 0.01 71 0.0223 0.0285 0.01 71 0.0285 0.0171 0.0285

K . lo3
0.3718 0.5294 0.7863 1.0671 1.6854 2.2606 1.0643 1.2230 1.3646 6.1801 7.7685 28.5410 35.5000

X,.

Y O
85.63 85.63 85.63 85.63 85.63 85.63 87.04 87.04 87.04 91.89 91.89 96.02 96.02

ff

ffc,.0274'
1.1640 1.1585 1.1642 1.1481 1.1781 1.1556 1.1180 1.1183 1.1153 ,9536 ,9537 ,7831 ,7707

1.0128 1.0274 1.0522 1.0576 1.1 060 1.1057 1.oooo 1.0076 1.0117 0.8530 0.8651 0.7005 0.6991

From the 45C data, through

CY

was found to be related to c,,

(33) This quantity was found to be described by (ref. Table 2 and Fig. 6):
ac;0.0274= constant
t

Fig. 2. Spline fit of MMA 50", 0.3 w t . % A l B N datcr ( r a t / nrocfel applicution to other hlMA 50C tlufu iisiiig single-pnrcriiteter sculirrg equution, A -0.3 u;t.%, 0 -0.391 wt.%, -0.5 ut.% AIBN.

The Activation Energies for low and high conversion results are then 19.26and 1.99 Kcal/mole, respectively. This is in accord with expectations for the conventional

I
0 . 9 0

0.80
0.70 0.60
X

0.50
0.40

0.30 0.20 0 . 1 0

0 . 0

1 5

30

45

60
t

7 5

90

105 120 135

t

Fig. 3. Model cipplicatioiz to MMA 70C datcc iisirig s i t i g 1 e - p ~ rumster sccdiirg eyricttioii 0 -0.3 u;t.%, -0.5 w t . % 111BAi.
782

Fig. 4 . Model uppliccitiort to MhfA 90C duta irsiiig singlc-p(ircinwtcr .r.cciliiig eytccttiori 0 -0.3 u;/.%, W - 0 . 5 ict.% A1R.V.
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vol. 22, No. 12

Comversion Prediction i n High Conoersion Free-Radical Polytneri, 7 ut i o n s

0.90 I

Table 3. Results of Model Application to EMA

0.80 0.70
0.60 0.50

70 70 90 90

.0200

.0500
,00320 ,00980

7.745 1 1.82 13.762 23.530

92.10 92.10 99.23 99.00

,9323 .9347 .7366 ,7212

1.0378 1.0147 ,86221 ,81868

X 0.40
0.30 0.20 0.10

analysis as though it were time alone (c,, = 1). Results obtained are shown in Table 4 along with the fits to the data (Figs. 8 and 9). The resulting parameters showed Arrhenius relationships (Figs. 10 and 11): In K = 27.14 8.784 . 103 T ti633 . 103 T 9.219 (37)

0.0

00

10

20

30

40

50

60

70

80

90

100

t x10-1

In h = 32.51 -

(38)

Fig. 5. Model upp/iccrfioii to 45C clutn uuiiig siiigle-pcirui?ietcr s c d i r i g equutiori. A -0.2 nioles A I B N I I , - 0 . 1 nio/e.vAIBNII,0 0.05 lllOle.5 A I R S I I , 0.025 )1101f?.S AIBSII, 0.012*5 IJlOle.7 AIBSII. 3 0.0062,5 i i i o l e . ~ AIBXII.

In to = -29.78

. lo3

(39)

I .

From these equations, it appears possible that K and b have the same activation energies (17.45, 17.15 Kcalimole) within experimental error. This may be re-

l . O k 1.5

2.5

.&ko
3.0 -

0.20

0 90

-(A)

0.1
KO

060 X

0 50
040

030:

3.5
4.0

- 0

020-

/y
20

/',/
~
30

0 0 10

"

40 50 60 7 0 80

"

"

1 0

20 30 40 50 60 70 80 90

"

'

'

'

'

- -0.1
4.5

0.90

0.80 0.70

kinetics of the low conversion region and for thc diffusion control of the higher conversions. Ethyl Methacrylate Polymerizations Results of EMA are very similar to those for MMA. They are summarized in Table 3 and the agreement obtained is shown in Fig. 7. Vinyl Chloride Polymerizations Low conversion analysis was, as for the other polymers, straightforward. However, in the high conversion analysis, it was found that only the two-parameter "scaling" equations provided good descriptions of the data. The only abscissa available for the conversion curves This was used in the was the product of time and

0.60 X
0.50

A,,.

POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vol. 22, No. 12

783

S . Bulke, L. Garcia, m d R . Patel

Table 4. Results of Model Application to Vinyl Chloride T ("C) 30 50 70

K 0.1622 0.9096 4.771

XL

a 177.5 156.6 154.5

b
51.68 387.9 1415

t,, 1.762 0.335 0.0503

92.92 92.67 97.67

lated to the dominance of transfer to monomer as the termination step. Also, since polymer precipitation is known to occur in this system, the values calculated for the onset of the gel effect, t,,, likely reflect polymer solubility. Acrylonitrile Polymerizations Again, at high conversion only, the two-parameter search results were acceptable. Very good fits were obtained to a wide variety of rate curves (Figs. 12 to 1 4 ) . However, in this case, the parameters reflect many complexities in the polymerization, and the polymer itself is very remote from the MMA reference used. The

&b

0.90
0.80

0.70 0.60
X

0.50
0.40

0.30
0.20

Fig. 9. Model cippliccitiori uiri!//chloride, two-purciriieter scditig eyticitiort, 5 0 C , 0 70C.

0.10 0.0
I
i

12

24

36

48

60

72

84

96

108

parameters are listed in Table 5 . A reasonable approach for this and similar difficult systems is to choose a reference curve of the same polymer. Copolymerization Average composition data accompanying conversion for copolymerization arc inherently more uncertain than the latter because of measurement difficulties and because of the increased complexity of copolymerization us. homopolymerization (21-23).Composition data have been observed to display irregular behavior at higher conversions. Even conversion data are less reliable than for homopolymerization because of differing polymer solubilities during precipitation methods used in its experimental measuremelit.
784
POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vol. 22, No. 12

Conver.yion Predictiori

iri

High Coiicersion Free-Radical Pol!lnierizcitioris

Contributions (Eys 31 and 32). The former method readily provided good fits to the data. In the latter method, however, the irregular behavior of the composition values was reflected in the conversion us. time values calculated by the method. This was particularly severe for the styrene methyl methacrylate data. The results for the styrene aerlonitrile data were more acceptable and are shown in Fig. 15 for both approaches. It was found for these data that smoothing the composition values by using the copolymer equation removed the irregularities in the results but at the expense of a less adequate fit. In general, for the case of copolymers, it is evident that more attention must be paid to the problems of smoothing and parameter estimation before useful correlations of these values can be obtained.

0.0

12

24

36

48

60

72

84

96

108

CONCLUSIONS A definition of kinetic similarity for diffusioncontrolled polymerization reactions was introduced and shown to be useful for both homopolymerizations and compolymerizations. This was accomplished by incorporating it into a general approach that permits use of the usual kinetic modelling assumptions at low conversion but avoids them in the higher conversion region, where their validity is more questionable. The approach, which we now suggest be termed the Method of Kinetic Similarity, was applied with a single MMA, 50C kinetic curve as reference throughout. This one reference curve is the only one that required an initial empirical (or mechanistic) fit as a prelude to the use of this method. A third-order spline fit was used and is provided. This fit can be used for new polymerization systems. For MMA and EMA, a single parameter describes the nonidealities in the conversion 1;s. time curve

0.80

0.50
0.40

0.30

:/.-.-.-.-.-.1 I I I I I I I 1

0.0 0.0 60

120

180 240

300 360 4 2 0 480 540

600

Copolymer data of styrene methyl methacrylate and styrene acrylonitrile were examined using both the Homopolymer Analogue approach (Eqs 29 and 30) and the Separation of Conversion and Composition
Table 5. Results of Model Application to Acrylonitrile T (C)
40 40 40 40 60 60 60 60 80 80 80

. 108
9.826 24.6 49.13 98.26 0.491 1.228 2.457 3.685 0.246 0.491 1.228

C,,

103

X L

0.3127 0.4191 1.124 2.1113 0.2679 0.6183 1.1713 1.9610 0.9707 2.929 5.450

88.00 88.20 87.50

209.0 200.7 191.1

0.0942 0.21 17 0.4340

92.00 93.40 92.80 21 .oo 90.00 94.50

133.5 131.0 135.4 70.39 118.8 117.7

0.1 749 0.4057 0.6005 0.971 7 0.3818 2.3738

Fig. 15. M o d e l cipplicafioii to styr-eiie cicryloiiitrile, ttco-purunie t e r sculiiig eqicutiori. L L ~ = . ~ 0.5 rnolur (a), 0.7 niolcir (31, 0.9 niolur ( 0 ) ,st<yreitc honiopolyiner uriulogue, ---- .r.epnrrition of co rivers i o 11 (I 1 1 tl co nzposit io n co r i t ribu t io ns .
~

POLYMER ENGINEERING AND SCIENCE, AUGUST, 1982, Vol. 22, No. 12

785

S. Balke, L. Garcia, and R . Patel

over the whole range of conversion. When this one parameter is combined with the usual single, low-conversion-rate constant and a spline fit of the MMA, 50C reference curve, it is shown that MMA data from 45C to 90C and EMA data of70 and 90C can be well-described. Furthermore, the parameters show expected Arrhenius dependencies, which imply that the model is sufficiently mechanistic to be useful for prediction. For VC and AN, two parameters are needed to describe the nonidealities and to provide good descriptions of the data. For VC, these parameters can be interpreted in terms of Arrhenius dependencies. AN results are more complex, and an interpretation has not yet been attempted. Copolymerizations SMMA and SAN were also examined with two-parameter and three-parameter nonideality descriptions. Description of the data by the model appears to be acceptable, but irregularities in experimental composition values and the added dimension of the parameter estimation problem require more attention. O(a,b) = objective function ( E q 33) = total concentration of free radicals ( E q 20) t = time = time at onset of gel effect ( E q 18) to T = absolute temperature V = volume of the reaction mixture = initial volume of the reaction mixture v o = weight fraction of residual monomer 1 in rew1 action mixture (Ey 22) = initial value of w l (Ey 22) w,,,, X = conversion of monomer to polymer = group of rate constants ( E q 20) P E = shrinkage proportionality constant ( E q 1b) = superscript indicating value from reference curve L = subscript indicating value using limiting conversion = group of rate constants ( E y 24a) Y = integrated acceleration function ( E q 29a) 4J

R.

REFERENCES
1. W. H. Ray a i d C. E. Gall, ,Macroiiiolecule.s, 1, 425 (1969). 7 h l . Tirrell a i i t l Ii. Gromley, C h e m . K q . Sci., 36, 367 (1981). -. 3. L. H. Garcin-Ruhio, J. F. XlacGregor, and .4. E. Haniielec, .4CS Natiotial hlevting, Kew York, Aug. 1981. 4. S. T. Balke and A. E. Hamielec, J . A p p l . P o l y n i . Sci., 17,905 (1973). 5 . S. T. Balke and R. I). Patel, High Conversion Polyiierizatioii Kinetic hlodeli1ig Utilizing Ccl Perme:ttiolr Chromatography, i n .4CS S ! iirposiunr Series 138, T. Pi-ovtler. ed., American Cheniicnl Society, Washington, I X (1980). 6. K.Horie, J. hlita, a i i d H. Kaml)e, J . P o l y m . Sci.,A-1, 6,2663 (1968). 1 . R. T. Ross,Jr. and R. L. I,aiirence,AIChE S ! y t t i p . Series, No. 160, 72, 74. 8. F. L. llarteir antl A. E. Hamielec, High Coiiversioii Diffrision-Coiitrolleti Polynierizatioti, iii ACS Spposiiuiii Serirs, 104,J. N . Henderson aiid T. C. Boutoii, eds., Anierican Cheinical Societ!, Washingtoll, DC (1979). 9. J. h i . Dionisio a ~ i c K. l F. Ollriscoll, J . P o / ~ / t r iSci., . 18, 3199 (1980). 10. E;. Arai arid S. Saito, J . Chcni. Etig. ofJuputi, 9, :302 (1976). 11. J. N. Cartleirus antl K. F. ODriscoll, J . PO/!IPII. Sci., 14, 883 (1976). 12. J . N . Cardeiias and K.F. ODriscoll, J . Poly711.Sci., 15, 1883 (1977). 13. J. 11. Dionisio and K. F. OIlriscoll, J . P o / ! / t t i . Sci., 18, 241 (1980). 14. A . Ahnin and E. A. Lissi, J . Alacromol. S c i . , 4 h e r i i . , All, 287 (1977). 15. M. B. Lachinov, R. A. Siinonian, T. G . Georgieva, V. P. Ziibov, and V. A. Kahanov, J . Polym. Sci., 17, 613 (1979). 16. A. Hui aiid A. E. Hnririelec, J . Appl. Polyni. Sci., 16, 749 11972). 17. A. Alxlel Alim antl A. E. Haiiiielec, J . Appl. P o l y r n . Sci., 16, 783 (1972)). 18. T. Ishige a i i t l . 4 . E. Hmiielec, J . Appl. P o l ! / u t . Sci., 17, 1479 (1973). 19. L. H. Garciii-Rubio and A . E. Haiiiielec, J . A p p l . Pohyrri. Sci., 23, 1413, (1979). 20. K . F. ODriscoll mid R. Kiiorr, ~~\.ltrc.~-onioleculas, 2, 367, (1968). 21. hi. Johnson, T. S. Kmiio, a i i d R. R. Sniith,Eur. P o l ! y t t i . J . , 14, 409 (1978). 09 J. hl. Dionisio m t l K.F. Ollriscoll, J . Polyni. Sci., B, 17,701 (1979). 23. L. 11. Garci;i-Ruhio, Ph.D. Thesis, hlchlaster University ( 1981). 24 T. Iulig a i i t l X I . Tirrell, Xlncro?riolec~rles, 14, 1501 (1981).

RECOMMENDATIONS
Only one reference curve used for a wide variety of polymers and copolymers. Use of a reference identical to the polymer of interest might provide sufficient kinetic similarity for the need of only one parameter for nonideality description regardless of the polymer considered. Statistical evaluation of the model within the context of the experimental errors associated with conversion and composition measurements needs to be explored. This is needed to provide increased reliability in the parameter correlations. Such an evaluation is currently in progress.

NOMENCLATURE X (Eys 4 h and 4c) P (Ey 31a) = model parameter ( E q 16) = model parameter (Ey 16) = initial initiator concentration = initiator efficiency = activation energy ( E y 15a) = acceleration function ( E q 2a) = integrated acceleration function ( E q 3 ) = acceleration function ( E y 21) = acceleration function ( E y 24b) = integrated acceleration function (Ey 25) = rate parameter defined by Ey 4 a ) = initiator decomposition rate constant = copolymerization propagation rate constant (Ey 20) = group of rate constants defined by E q l a = propagation rate constant = diffusion controlled rate constant ( E y 15a) = monomer concentration of monomer i ( E q 20) = initial monomer concentration (Ey 20) = model parameter ( E y 14)
= function of E and

= function of w , and

--_

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Conoersion Prediction in High Conver.sion Free-Radical Polymerizations

25. S. K. Soh and D. C. Sundberg, J . Pol!/ni. Sci., 20, 1299 (1982); 1315 (1982), 1331 (1982), 1345 (1982). 26. H. K. Mahabadi atid K. F. ODriscoll, Makromol. Chern., 179, 1921 (1958). 27. J. A. Biesenberger and R. Capinpin, J . A p p l . Polym. Sci., 16, 695 (1972). 28. W. H. Lawton, E. A . Sylvestre, and hl. S. hiaggio, Technotnetrics, 14, 513 (1972). 29. R. B. Bird, R. C. Arnistrong, a n d 0.Hassager, Dyriamics of
Polymeric Liquids, Voluriies, Fluid hlechaiiics, John Wiley & Sons, New York (1977). K. Ito, J . Polyni. Sci., 13, 401 (1975). J. N. Cardenas and K. F. ODriscoll, J. Po/!yn~. Sci., 15,2097 (1977). L. H. Garcia-Rul)io, hl. Eng. Thesis, Xlchiastcr Uiiiversity (1975). J. Kowalik and M. R. Ohboriie, hlethods for Uiiconstriii~~ed Optimization Probleiiis, Americaii Elsevier Publishing Co., New York (1968).

30. 31. 32. 33.

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