Free Radical Polymerizations Associated With

the Trommsdorff Effect Under Semibatch

Reactor Conditions. I: Modeling
ASIT B. RAY, D. N. SARAF, and SANTOSH K. GUFTA*

Department of Chemical Engineering

Indian Institute of Technology
Kanpur-208 016 , India

Several important polymerizations [e.g., poly(methy1 methacrylate) (PMMA),

polystyrene] exhibit gel and glass effects during polymerization. These are associ-
ated with the decrease of the diffusivities of the macroradicals and monomer
molecules with increasing viscosities of the reaction mass. A new model has been
developed to account for the gel and glass effects, both under batch and semibatch
reactor operations. The free volume theory of Vrentas and Duda has been used to
account for the changes in the diffusion coefficients. The model parameters are
tuned using experimental data on the isothermal bulk and solution polymeriza-
tions of MMA in batch reactors. Conversion histories and molecular weights have
been obtained for cases where solvent, initiator or monomer are added to (or
removed from) the reaction mass after some reaction has taken place. In addition,
studies involving step changes in temperature have been carried out. It is found
that the conversion us. time behavior after such step changes depend upon a
complex interplay of three factors: polymer concentration, molecular weight, and
the temperature at the point these changes are effected.

INTRODUCTION temperature, T , and the reaction mixture becomes

glassy in nature. Then the propagation rate constant,
n recent years, polymer reaction engineers have
I started focusing their attention on the mathemati-
cal modeling of various physical phenomena in in-
k,, also becomes diffusion controlled. As a conse-
quence, the reaction stops short of complete monomer
conversion. This effect is referred to as the glass
dustrial polymerization reactors. One such phe-
effect. In addition to these, the initiator efficiency, f,
nomenon, diffusion-controlled reactions under semi-
decreases with time at high monomer conversions.
batch reactor conditions, plays a n important role in
This is referred to as the cage effect. We have as-
free radical chain growth polymerizations and is the
sumed f to be constant, following several workers
focus of the present study.
( 1-51. to keep the model simple.
The three most important reaction rate constants,
Several workers have attempted to model the gel
k,, k,, and k , (= k,,+ k t d ) (see Table I), in free
and glass effects using semi-empirical, time varying
radical polymerization are associated with diffusional
rate constants for the termination and propagation
limitations (1-7). The gel or Trommsdorff effect repre-
reactions. These have been reviewed by O’Driscoll
sents the effect of decreasing diffusivity of macroradi-
(10) and Hamielec (1 1). Most of these models involve
cals, P, (due to increasing viscosity of the reaction
discontinuities in either the monomer conversion or
mass) on the termination rate constants, k,, and ktd
the chain length, or both, at which the diffusional
and was first observed by Norrish and Smith (6), and
restrictions become operative. This artificiality causes
Tromsdorff et aL (7). It is exhibited (8, 9) a s a sudden
problems in the use of these models for control and
increase in the rate of polymerization and the weight
optimization work.
average chain length, pw. In the later stages of reac-
Chiu et aL (21, in a major departure from the past,
tion, the glass transition temperature, Tg.of the reac-
considered diffusional limitation as a n integral part of
tion mass becomes higher than the polymerization
the termination and propagation reactions from the
very beginning of polymerization. They used the free
‘To whom correspondence should be addressed, volume theory of Fujita and Doolittle [as discussed by

1290 POLYMER ENGlNEERlNG AND SCIENCE, AUGUST 1995, Vol. 35, No. 16
 Free Radical PolymerizationsAssociated with the Trornmsdorff Efect. I
Table 1. Kinetic Scheme for Polymerizationof MMA.
Initiation
Propagation
kfC
Termination by combination Pn + Pm Dn + rn
+
Termination by Pn+Pm --f Dn+Dm
disproportionation
kf
Chain transfer to monomer Pn+M + P, +On
Chain transfer to monomer
ks
Pn+S-+S‘+D,
via solvent S .+ M ‘ZtS+ PI
or
ks
P,+M + D,+P,
Bueche (1211 for the diffusivity. Recently, Achilias and
Kiparissides (13, 14). developed the model of Chiu
et aL further. In their theory, there was only one
curve-fit parameter, the remaining being obtained
using independent measurements on nonreacting
systems. Their theory used the diffusion theory of
Vrentas and Duda (15-17), and the theory of excess
chain-end mobility (18). This class of theories has
been used in several studies having a n engineering
bias.
Even though Louie and Soong (19, 20) used the
model of Chiu et aL (2) for the simulation and opti-
mization of semibatch reactors, such an extension to
semibatch operation is questionable. This arises from
the use of the initial initiator concentration, [I],, in
the model to account for the molecular weight depen-
dence of the diffusivity of polymer radicals. I t is un-
clear as to what should be used in place of [ I], in the
model after the addition of initiator, monomer or
solvent to the reaction mass. This is a n important
question, since such additions are made routinely in
industrial reactor for optimal performance. A similar
controversy arises in the application of the theory of
Achilias and Kiparissides (13, 14) to semibatch reac-
tors. Here, an empirical curve-fit parameter, j C , , , is
correlated to the initial number average chain length,
p n , o . This study attempts to resolve this important
question using a new model. The model parameters
are then obtained (“tuned’)using curve-fit of experi-
mental data on MMA polymerization in isothermal
batch reactors (in the absence of monomer, solvent
or initiator additions). The model is then used to
predict how the monomer conversion and molecular
weights would change after intermediate addition of
pure components to the reaction mass. The behavior
of the system under step changes in temperature is
also predicted. These predictions need to be con-
firmed experimentally. However, even without this,
one can use this model for model-based optimal con-
trol with adaptation, provided we “tune” the parame
ters periodically on-line. Adaptive optimal control
(using intuitively meaningful models) is being prac-
ticed in the chemical and petrochemical industry,
POLYMER ENGINEERING AND SCIENCE, AUGUST 1995, Vol. 35, No. 16
and can be used in the polymerization industxy as
well.
FORMULATION
The kinetic scheme of free radical polymerization of
methyl methacrylate is summarized in Table I (see
Nomenclature for definitions). This mechanism de-
scribes several other free radical chain polymeriza-
tion systems as well. The mass balance equations for
a well-mixed semibatch reactor in which components
can be added or vaporization can take place, can
easily be written. These can be summed up to give
the equations for the moments of the radical
(A,, A,, A, 1 and dead ( p,, p p2 macromolecular
species. The complete set of equations [ordinary dif-
ferential equations (ODES)] for a fairly general set of
reactor operating conditions are presented in Table 2.
The equations are written in terms of total moles of
the various components, since it is easier to work
with these for semibatch reactors. The volume occu-
pied by the initiator, I, is neglected. The volume, V,,
of the liquid reaction mixture is expressed as a sum
of the volumes of the three pure components:
monomer, polymer, and solvent. It is assumed that
there is no polymer at the beginning. The equations
in Table 2 account for the addition of (liquid) initia-
tor, monomer, and solvent, as well as for the vapor-
ization of monomer and solvent through the terms
Rli(t),RLm( t ) ,R J t), and Rum(t), Rus(t ) respectively.
The pressure in the vapor space (of volume V’) above
the liquid reaction mass can change with time due to
vaporization, as well as due to release of vapor at
some desired rate, V,Ct). This necessitates the intro-
duction of equations for three additional variables,
M U , S u , and NU.
The monomer conversion, x,in such reactors can
be written in terms of the total monomer ( JmI) added
till time t as
(1)
The most important part of the model are the equa-
tions for the gel and glass effects. The model of Achil-
ias and Kiparissides (13) was modified so as to apply
for semibatch reactors. The rate constant, k, ( = k,,,
since k,, = 0 for PMMA) has been written (13) using
the free volume theory of Vrentas and Duda ( 15- 17)
as
where i,b is given in Table 3 ( E q c). The same notation
has been used as in Ref. 13. We now use the proce-
dure of Chiu et aL (2) to simplify Eq 2. We define a
reference (subscript: ref) state a s Cp, = 4, = 0, = 1.
1291
 Asit B. Ray, D. N . Saraf. and Santosh K. Gupta
Table 3. Gel and Glass Effect Equations.

Table 2. Model Equations for MMA Polymerizationin

Semibatch Reactors.

dM AoM RM A0
2. -= - ( k , + k,) __ - k -- k,S -
dt VI ' VI Vl

dS
4. -= Rl,(t) - R,,(t)
dt

dA, RM A A04
6. -=k,-+k M---k-
dt Vl V, V,

7.

Equation 2 can be rewritten in terms of this as

~ ~ = The parameter, Bt. defined in Eq

where, I J J ~y/VJp.
3 is somewhat similar to 8,,c,s [ = r,$'3Dref] used by
Chiu, Carratt, and Soong (CCS) (2). The term, r:, in
Eq 3 is expected to be insensitive (2) to the monomer
conversion, x , temperature, T , and the number aver-
age chain length, pn, of the polymer present. The
dS " SV term, Dref, is a function of T and p n ,r e f , and, accord-
15. - = R
dt "'- V J ( M v + S v + N Y ) ing to the free volume theory of Vrentas and Duda
dN N" ( 15- 17). is inversely proportional to p:. r e f . Thus, the
16. -= -VJ
dt (Mv+S"+NY) term D,eJp?,reJ, is expected to be a function of T
X only. 8, in Eq 3 is, therefore, expected to be a func-
17. T = T r e f + ___
FiCFmrx tion of T alone, a s indicated in Eq 3. It may be empha-
18. F l = S(MWs)+.$,(MW,) sized that in the earlier theory of Chiu et al, the term
S(MW) M(MWm) Ot,ccs was a function of T and was proportional to
19. v,=L+---- + (Cm-M)(MWm) [ I]; while in the present model 8, is a function of T
Ps Pm PD
dP M v + S Y + N Y dT RT alone-the earlier dependence on[ I]; having been
20. -= R- + - ( R v m + R,, - V,) replaced by the term pz, the square of the current
dt vg dt Vg
value of the number average chain length. Use of p,,
in the expression for 8, enables modeling of semi-
batch reactor operation.
In a similar manner (13). we can write an expres
sion for k,. This is given a s Eq b in Table 3, with
OP(T)= f 2 / 3 D $ . fmand DreJare associated with the
diffusion-cum-reaction of macroradicals with
monomer. The complete set of equations for the gel
Pm Ps PP and glass effects is given in Table 3.
24. 6,= 1 - 6, - 6s I t may be added that a similar expression could
also be written for the diffusional effects on the initia-
tor efficiency, f. This would introduce some addi-

1292 POLYMER ENGINEERING AND SCIENCE, AUGUST 1995, Vol. 35, No. 16
 Free Radical PolymerizationsAssociated with the TFornmsdorff Effect. I

tional tuning parameter in our model, which, we Table 4. Parameters Used for Polymerizationof
believe, are not necessary at this stage. What could MMA (4, 14,21-29).
possibly be achieved by incorporating such an equa- prn = 966.5 - 1.1(T - 273.1) kg/m3 (Ref. 23)
tion accounting for the decrease in f at high conver- pp = 1200 kg/rn3 (Ref. 2)
sions, can be alternatively accomplished by the equa- pQ= 844.18 - 1.07165(T- 323.1) kg/rn3 (Ref. 22)
(Benzene)
tions for k , and k , alone with slightly different values C ,=CP,,=1676J/kg-K (Ref. 23)
of the parameters Q t and 0,. 8’ =2017.17 (benzene at 65°C) J/kg-K (Ref. 24)
Table 4 compiles (4, 14, 21-29) the values of the %i = 1.69 x 1014 s- ’; for BPO (Ref. 25)
various parameters and the several correlations used. ~ ’
k: = 1.053 x 1015s ; for AlBN (Ref. 21)
kg0,014.917x 10’ m3/mol-s (Ref. 21)
Numerical integration of the equations in Tables 2 k,,,,-9.8 x l o 4 m3/mol-s (Ref. 21)
and 3 is done using the double-precision version of ktc= 0.0
Gear’s algorithm (NAG library routine D02EJF). A k, = 0.0
tolerance of is used. Decrease of tolerance did ki = kp
not affect the results much. k, = 0.0
E d = 125.40 kJ/rnol; for BPO (Ref. 25)
The initial conditions used are given by Ed = 128.45 kJ/rnol; for AlBN (Ref. 21)
( ,y, M ”, S’, N U not used): E, = 18.22 kJ/rnol (Ref. 21)
at t = O : E,, =2.937 kJ/mol (Ref. 21)
(MW,) =0.10013 kg/rnol
(MW,) =0.07811 kg/mol
Constitutive Parametersfor the Gel and Glass Effects
qz =8.22 x m3/kg (Ref. 26)
:v =7.70 x m3/kg (Ref. 27)
:v =9.01 x m3/kg (Benzene) (Ref. 28)
M,p=0.18781 kg/rnol (Ref. 28)
y= 1 (Ref. 14)
,V, = 0.149 + 2.9 X 10 - 4[T(K) - 273.1 1 (Ref. 29)
V,,=O.O194+1.3x 10-4[T(K) -273.1 - 1051; (Ref. 29)
for T < (105+273.1) K
V,,=0.025+1.0 x 10-3[T(K) - 171.11 (Benzene) (Ref. 4)
Best-Fit Correlations (BFCs) From This Study:
f = 0.52997; for AlBN (bulk polymerization)
R,,(t) and R,,(t) were taken to be zero in the pre- +
f = - 0.178974ff 0.5414; for BPO-Benzene
sent simulations. Also, the energy equation was not log,,[O,(T), S] = 1.2365506976057 X 10’
used. The continuity conditions accounting for sud- - 1.0277928295174 X 1O 5 (1 / T )
+2.2665992726301 X l o 6 (1/ T ’ )
den additions of (liquid) monomer, solvent, and initia-
log,,[O,(T), s] =1.58323 x 10’- 1.24953 x l o 5 (1/T)
tor (at the temperature of operation) in a semibatch +2.5596 X l o 7 (1/ T ‘ )
reactor can easily be written and are of the form
y(tkf)= y(t;) + y,, where y, moles of pure y are
added at time t,. +
The initiator efficiency, gel, and glass effect parame Ps Prn
ters, f, Q , , and 0,. can be obtained by curve-fitting
(tuning) available experimental data (8, 9) on MMA
polymerization under isothermal conditions in a optimal values of the three parameters for one of the
batch reactor. The Box complex technique (30) is experimental runs, in 30 iterations.
used. We minimize the normalized sum of square
errors RESULTS AND DISCUSSION
The values of Q t . 0,. and f , which minimize E are
computed for each of the different experimental runs
of Balke and Hamielec (8) and of Schulz and Har-
borth (91, to give what we term as “individually opti-
where “exp” and “th” indicate experimental and theo- mized’ parameters (IOP). These are listed in Table 5
retical values, respectively, and N, and NMnare the along with values of the error, E,,,, and the values of
number of data points available for x and M,. Alter- N, and NMn used for curve fitting. The conversion
natively, we could have used conversion and the histories computed using these parameters (solid
weight average molecular weight, M,, in our error curves) are compared with the experimental results
function, E, to obtain good fits with M, data while in Fig. 1 for one set of experimental conditions (8).
overpredicting M,. In fact, no simultaneous good fit The model results for the number and weight average
for x, M,,, and M , histories can be obtained using a molecular weights for bulk polymerization of MMA
single k,. The computer code incorporating the Box with AIBN using the IOP values of Table 5, are shown
complex procedure took a CPU time of 74 s on a in Fig. 2 for the same set of conditions. The theoreti-
supermini HP 9000/850S computer to converge to cal results compare favorably with experimental re-

POLYMER ENGlNEERlNG AND SCIENCE, AUGUST 1995, Vol. 35, No. 76 1293
 Asit B.Ray, D. N . SaraJ and Santosh K. Gupta
Table 5. Optimal Values of the Parameters for the Individual ExperimentalRuns (8,9) for MMA Polymerization.

T Ill, IOP BFC

t%) (mol m - 3 ) ff N, NMn 0, ts) 0, ts) f ElOP 0, (s) 0, ts) f EBFC

50* 25.8 0.0 36 0 5.45941 X 6.89852X 10l6 0.4207 0.639 4.50790X 5.79066X 10l6 0.52997 1.681
20.18 0.0 16 0 4.98751x 4.69629x 10l6 0.4386 0.389 0.229
15.48 0.0 17 0 4.69177X lo2' 6.65225X 10l6 0.3928 0.795 0.559
70* 25.8 0.0 19 19 5.38182X 10l6 5.66049X 10" 0.6335 0.849 4.23997X 10l6 3.63103X 10" 0.52997 1.457
15.48 0.0 12 12 4.48209X 10l6 2.54906X lo1' 0.6493 0.447 1.188
90* 25.8 0.0 18 18 3.74311 x 10" 1.70677x 10' 0.5700 0,909 3.19535x 10l2 2.14411x 10' 0.52997 1.259
15.48 0.0 11 11 3.24727X 10l2 2.74496X 10' 0.6049 0.266 0.479
50@ 41.3 0.0 13 0 4.30814X 4.93027X 10l6 0.5026 0.092 4.50790X 5.79066X 10l6 0.54150 0.542
0.2 14 0 5.53051X 10" 4.31431 X 10l6 0.3646 0.185 0.50570 0.646
0.4 20 0 7.35777X 0.71221X 10l6 0.3865 0.323 0.46991 0.219
0.6 18 0 4.00000X lo2' 1 .OOOOO X 1017 0.5101 0.029 0.43412 0.027
0.8 18 0 9.14076X 1 .OOOOO X lot5 0.4426 0.031 0.39832 0.035
0.9 18 0 8.34569X 3.28803X loi5 0.3902 0.055 0.38042 0.048
70@ 41.3 0.0 12 0 3.95185X 10l6 2.63082X 10" 0.6542 0.079 4.23997X 10l6 3.63103X 10" 0.54150 0.261
0.2 16 0 7.35327X lot6 2.13873X 10" 0.5451 0.417 0.50570 0.975
0.4 18 0 1.32050X 1017 5.07391 X 10'' 0.5116 0.134 0.46991 0.297
0.6 18 0 4.19775 X 1017 3.72875X 10" 0.4229 0.038 0.43412 0.071
0.8 18 0 3.77101 X 1017 1.00000X 10'' 0.4141 0.030 0.39832 0.031
0.9 18 0 3.79900X 1 Oi7 4.78629X 10" 0.3150 0.043 0.38042 0.168
'AIBN (8).
@ BPO-Benzene (9).

'Y 1 --
t AlBN 50°C n
-- AIBN 90°C D

f," = o

I
mol/m3
o a,b : 25.8
a c , d : 15.48
10'

3
=.
f
e
"-- 10)
0 80 160 240 320 LOO
Time,min
Fig. 1 . Conversion histories for AIBN polymerized MMA at
90°C for two initiator loadings.f : = 0. Data points of Balke
and Hamielec (8) shown. Solid curves represent model r e
sulk using individually optimized parameters (fop)given i
Table 5. Dotted curves correspond to model results using the
n
10'; I I
0.2
I I
0.4
I
0.6
I "
0.0
' 1.0
bestJt correlations ( B E ) in Table 4. Conversion
Fig. 2. M,, and M , for AIBN polymerized MMA at 90°C for
sults (8)on d t ) a s well as M,,(t). Results on M, fz
three initiator loadings. = 0. Notation as i
n Q. 1 . ExperC
mental data of Ealke and Hamielec (8)also shown.
show larger discrepancies, specially in the gel-effect
region. This is similar to what was observed by Chiu
et aL (2) and Achilias and Kiparissides (13,14). Simi-
lar agreement between theory and experiment is also parameters, or of the variance, but minimization of
observed at other conditions (8, 9) but plots are not ElOpis preferred since the error terms are normal-
provided for the sake of brevity (they can be supplied ized. This model of estimating errors is particularly
on request). Better agreement of x, M,,as well a s M, suited to our case where the values of M,,are far
cannot be achieved using a single k,. It must be larger than those of x, and normalization avoids the
mentioned that the curve-fit achieved with our model errors in M,, to dominate EIop.The same final values
is as good as observed with earlier theories for for the parameters are obtained when we start with
isothermal batch reactors. Our model, however, has different initial guesses for them, confirming that the
the advantage that Ot is independent of the initial final values correspond to a global minima of EIop.
conditions and so can be used for describing Table 5 shows the values of Elop to be fairly low for
the operation of semibatch reactors as well as batch most cases.
reactors. It is necessary to develop correlations for O t . ep,and
It may be added that the value of EIop/(Nw+ NM,) f in terms of appropriate variables (like temperature,
gives a n idea of the 95% confidence limit for the solvent fraction, etc.) so that we can generate results

1294 POLYMER ENGINEERING AND SCIENCE, AUGUST 1995, Vol. 35, No. 76
 Free Radical PolymerizationsAssociated with the TrornmsdorffEffect. I

for polymerizations under conditions for which exper-
imental data are not available, even if this worsens
the curve-fit. It has already been mentioned that Ot
and OP are expected to be functions of temperature
alone for a given polymer. Similarly, we would expect
f for any initiator to be a function off:, solvent used
and possibly, of temperature, since these influence
the viscosity of the medium which, in turn, decides
the strength of the cage effect. It has been reported
(2, 13, 21, 22) that f is not too sensitive a function of
temperature for T between 50 and 90°C, and so we
have Jf,"for ) a given initiator and solvent. We at-
tempted to develop some correlations along these
lines for MMA polymerization for $,(T), OJT), and
Jinitiator, solvent, f:). A regression analysis gives the
equation for f for this system as given in Table 4. I t is
stantaneously) added, after which an updated value
of f," is used. An alternative would be to model f
using an adaptation of the newer theory of Achilias
and Kiparissides (14). and relate it to current values
of appropriate variables as has been done in this
paper for k , and k,.
We now present model results for semibatch reac-
tor operation, using the parameters tuned on batch
reactor data. Only a single instantaneous intermedi-
ate addition (IA)or removal (IR) of a pure component
(at the same temperature a s the reaction mass) is
considered. The effect of adding (or removing by flash-
ing) pure monomer to the reaction mass at different
times is shown in Figs. 3 and 4. These reflect the
interesting interplay of the effects of polymer concen-
tration and molecular weight ( M u )on the viscosity,

""1
to be mentioned that use of the two correlations for f
gives fairly good agreement with experimental data in
the pre gel-effect region. Since f accounts for several
physical steps (e.g., diffusion of radicals away from AIBN-MMA 7OoC
each other, further reactions of radicals, etc.), it is 0.80
not surprising that f differs for the two initiators,
and is a function off,". Table 4 also gives the best-fit c I 1 1 1 1 : I

correlations (BFCs) obtained from plots of the individ-

ually optimized values of 8( and OP us. 1/T. I t is
observed (see Table 5) that for values off," > 0.4, the
individually optimized values of 8, and OP differ s u b
stantially from the values predicted by the BFCs. In
fact, these points were given much less weightage
while obtaining the BFCs since negligible amounts of
gel and glass-effects are exhibited for these condi-
tions. The values of the error, E,,,, associated with Tirne,min
the use of the correlations are given in Table 5. Fig Fig. 3. Effect of intermediate addition (IA)and removal (IR)
ures 1 and 2 (dotted curves) show the model results of pure monomer on the conversion histories for AIBN initt
using these correlations. For this as well as the other ated bulk polymerization of MMA. Solid curves denote non
cases studied (8.9). the agreement with experimental M / I R results a t three values of [I]o, Dotted curves give
results with lA and IR of monomer as described in the text.
results is still fairly good. It is found that the curve-fit
(or value of E ) is somewhat sensitive to the value of
O t . This is also true of the theories of Chiu et aL (2)
and Achilias and Kiparissides (13). and is a common
undesirable feature of this set of models.
There is one problem that remains before one can
simulate semibatch reactors, viz, the value of f,"to
be used after the addition of pure components to the
reaction mass. One plausible model is described here.
In a semibatch reactor, SMWJ kg of solvent,
M(MW,) kg of monomer, and (5, - M ) ( M W , ) kg of
polymer are present at any time, t (these values get
3
updated with the addition of pure components). The I:
mass of initiator is neglected. We can envisage an C
equivalent initial mixture corresponding to this I
"state" as one comprising of S(MW,) kg of solvent
(since solvent is not consumed by reaction) and
[M(MW,) + (cM - M)(MW,)I = 5,(MW,) kg of
monomer. Thus, we could use an equivalent value,
fZequivalent given by Eq a in Table 4 to estimate f for
semibatch reactor operation. This equation predicts
f,"to be the actual initial value (since = ,[ M,) for a I" 0 0.2 0.4 0.6 0.8 1.o
batch reactor. Similarly, for a semibatch reactor in Conversion
which R,,, R,,, R,,, and R,, are zero, f,"remains at Fg. 4. Effect of lA and IR of pure monomer for the case of
its initial value till some pure components are (in- Fg. 3 on M,, and M , .

POLYMER ENGINEERING AND SCIENCE, AUGUST 1995, Vol. 35, No. 16 1295
 Asit B.Ray, D. N. Saraf; and Santosh K. Gupta
and so on the gel effect. 1 m3 of a n initial mixture is
polymerized at 70°C with [ I ] , = 20.18 mol/m3. At t =
25 min (conversion = 16.43%.point a) 2.6972 mol of
pure monomer (at 70°C) are added instantaneously
to this mixture. This amount is chosen so if it had
been added at t = 0, the initial value of [I], would
have been 15.48mol/m3. The instantaneous addition
of monomer leads to a sudden drop in the value of
the monomer conversion ( Eq 1) to point d ,since the
conversion is based on the total amount of liquid
monomer added till time t. The gel effect is found to
get delayed with respect to polymerization with [I], =
15.48 mol/m3 and without any LA. This is because
the polymer concentration as well as M , (see Fig. 4 )
are lower at point a“ than at point a‘.The viscosity of
the reaction mass at point a“ is, thus, lower than at
point a’, leading to lower diffusional resistances. If,
on the other hand, we add the same amount of
monomer later on during the gel effect (at point b:
t = 68.5 min, monomer conversion = 58.03%).we find
that the gel effect occurs earlier than in the case with
[I], = 15.48 mol/m3 but without IA.This is because
the polymer concentration a s well as M , are higher
at point b than at point b’. The viscosity corre-
sponding to point b is higher than at point b‘,
leading to diffusional limitations being higher at b . A
similar explanation can be given for the effect of
monomer flashing. We, thus, observe that instanta-
neous addition of monomer influences the gel effect
through the viscosity and we must look at both the
polymer concentration as well as the value of M , to
predict the future course of polymerization.
Figures 5 and 6 show the effect of adding 10.32mol
of AIBN at t = 25 min (point a in the pre-gel effect
region where the monomer conversion is 14.63%)to
the reaction mass which starts with 15.48 mol of
AIBN in 1 m3 of AIBN-Mh4A mixture. It is observed
that the gel effect occurs even earlier than when the
initial mixture has 25.8 mol m-3 of AIBN. This is
because the viscosity of the reaction mass and so the
0 20 LO 60 80 100
Timepin
Fig. 5. A l B N initiated M M A polymerization with f,”= 0 at
70°C. Solid curves represent cases with [I], = 15.48 and 25.8
mol/rn3 with no intermediate addition (IA) of pure cornpo
nents. Dotted curue shows results when 10.32 mol ofinitiator
is added at t = 25 min (point a) to a system which started
with 15.48 mol AIBN in 1 m3 A I B N - M M A mixture at t = 0.
1296
diffusional resistance corresponding to point a is
higher than at point a’ ( Fg. 6)because of the higher
value of M , (the effect of the slightly higher polymer
concentration at point a’ is dominated over by the
much higher value of M J It may be noted that the
final value of M , for the IA case is different. Thus,
intermediate addition of AIBN may have important
influences on the product properties. If 10.32 mol of
AIBN are added later [e.g., at t = 74.25 min (point b
where the conversion is 58.14%)],negligible changes
in the conversion or M,, histories are observed. How-
ever, M,, is again found to change slightly. Negligible
changes in the conversion, M , a s well as M , histo-
ries are observed when 10.32 mol of AIBN are added
still later at t = 85 min (point c: conversion = 90.56%).
This is because point c lies in the glassy region, and
addition of initiator at this stage does not serve much
purpose since diffusional limitations are very high.
The effect of adding or removing pure solvent to a
partially reacted BPO-Benzene-Mh4Asystem is shown
in Figs. 7 and 8. A 1 m3 starting mixture having
I, = 41.3 mol, with f,” = 0.1 is used. Isothermal poly-
merization at 50°C is carried out till time t = 120 min
(point a). At this time, 1.351 mol of pure solvent (at
50°C)is added instantaneously (this choice effectively
makes f,”= 0.2 after the addition), or 1.081 mol of
pure solvent is removed (to make f,”= 0 after the
removal). It is to be noted that the gel effect corre-
sponding to -f: = 0 or 0.2 with no IA or intermediate
removal (IR) is not duplicated since the conditions of
viscosity at t = 120 min for the various cases differ. In
fact, similar explanations can be made for the course
of polymerization following IR or IA as in the earlier
cases. Figures 7 and 8 also show the sensitivity of
the M , history when IA or IR is done at a later time
(e.g., at point b: t = 325 min, conversion = 56.01%.or
at point c: t = 400 min, conversion = 94.53%).It is to
1o7
AIBN 7OoC
0 0.2 0.4 0.6 0.8 1.0
Conversion
Fig. 6. M, and M , us. conversion for the case of Fg. 5.
Curvesfor IA of 10.32 rnol of A l B N at point b ( t = 74.25 mid
also shown.
POLYMER ENGINEERING AND SCIENCE, AUGUST 1995, Vol. 35, No. 16
 Free Radical PolymerizationsAssociated with the TrommsdorflEffect.1
1.0- 1.0 a. C'

0.8- f I--

3 1 1 1 1 ~: x - a m o ~ / r n ' 1
- Isothermal I
s
.-
0.60-
I
I b" I
I
C 0.6- /
.- I
U
0,
,/
E 0.4 - BPO-BZ-MMA S O T
u
____ with 1A

I I
0 120 240 360 480 600 0 70 140 210 2 80 350
Time,min Time.min
Fg. 7. BPO initiated MMA polymerizationin benzene at 50"C, m. 9. Effect of step increase (SI) and decrease (SO) of tern
with I(t = 0) = 41.3 mol, V,(t = 0) = 1 m3. Solid curves repre peraturefrom 70 to 90°C or 50°C at different locations, on the
sent cases without IA of solvent, with f: = 0, 0.1 and 0.2. conversion. Solid curves indicate isothermal results. SI and
Dotted curves show results when 1.351 mol pure solvent is S D results shown by dotted curves.
added instantaneously (IA,Jor 1.081 mol is removed (I@ at
points a, b, or c.

3
f
r
H

c b
Mn I
I

105'
0 0.2
' 0.C
I
0.6
I I
0.8
Conversion
Fg. 8. Variation of M, and M, for the system described in
Fig. 7.
be observed that addition of pure solvent even at a
late stage (point c) leads to higher (= 100%) final
monomer conversions, as well as different values M,
and M,. An important inference from these results is
that the continuous vaporization of solvent inevitably
present in any industrial semibatch reactor may have
important consequences on M,, and on product
properties, and needs to be accounted for properly in
any model for such reactors (through the term R,, in
Table 2). using appropriate correlations for mass
transfer coefficients.
The effect of step changes in temperature at some
point during polymerization is shown in Figs. 9 and
10 (results on M, are not being presented). Isother-
mal polymerization of a n AIBN-MMA mixture with
[ I ] , = 25.8 mol/m3 is carried out at 70°C.The tem-
perature is suddenly increased (SI, step increase) to
90°C at point a ( t= 25 min, conversion = 18.29%).It
is found that the gel effect occurs earlier compared to
the isothermal 70°C case because of the higher rates
associated with higher temperatures. It is also found
I
I
1.0
105~
0 0.2 0.4 0.6 0.8 1.0
Conversion
Fg. 10. Effect of step increase (SI) and decrease (SO) of
temperaturefrom 70 to 90°C or 50°C at different locations on
M, . Notation same as in Fig. 9.
that the gel effect occurs later than for the 90°C
isothermal case since M, and polymer concentration
are both lower at point a than at a". When the
temperature of the reaction mass is decreased sud-
denly (SD, step decrease) from 70 to 50°C at point a,
the reaction slows down (Fig. 9) because of lower
temperatures. However, for this SD case, the gel ef-
fect occurs later than for the 50°C isothermal case.
This is because the effect of lower M, at point a
(compared to point a') dominates over the effect of
higher polymer concentration at that point. The vis-
cosity is, thus, lower at point a. This leads to the gel
effect occurring later than for the isothermal 50°C
case. Step increases in temperature at point b lead to
similar results. However, a step decrease in tempera-
ture from 70 to 50°C at point b ( t = 63.5 min, conver-
sion = 60.4%)leads to the gel effect occurring earlier

POLYMER ENGINEERING AND SCIENCE, AUGUST 1995, Vol. 35, No. 16 1297
 Asit B. Ray, D. N . Saraf, and Santosh K. Gupta

than for the 50°C isothermal case. This is because the =Specific heats of pure (vapor)
value of M, at point b is only slightly lower than at monomer or solvent, J kg- K - ' '.
point b ' , but the polymer concentration is much Dn =Dead polymer molecule having n
higher. The latter effect predominates and, therefore, repeating units.
the viscosity at point b is higher. Decreasing the =Activation energies for the
temperature near the glassy region (point c, t = 75 reactions in Table 1 , kJ mol-'.
min, conversion = 90.68%) leads to an almost instan- =Mass of liquid in reactor at time t,
taneous attainment of the glassy region correspond-
kg.
ing to 50°C. while a step increase in temperature at
point c from 70 to 90°C leads to a lowering of the
f =Initiator efficiency.
f," =Initial volume fraction of solvent
viscosity of the reaction mass primarily due to higher in reaction mixture.
temperatures (at point c, M , is higher and polymer
AHr, p r o p =Enthalpy change of propagation
concentration is very slightly lower than at point c',
reaction, J mol-'.
so the increase in conversion for the SI case from
1 =Moles of initiator at any time t ,
point c in Fig. 9 can only be because of the lowering
mol.
of viscosity due to higher temperatures thereafter).
Thus, we observe that the polymer concentration, =Initial molar concentration of
temperature, and the M, at the point of step change initiator, mol m-3.
are important in deciding the further course of reac- =Rate constants for the reactions
tion. in Table 1 at any time t, s-' or m3
We would like to add that some recent (31) experi- mo1-ls-l.
mental results taken in our laboratory on a well- =Intrinsic (in absence of gel and
stirred, PC-interfaced, 1-liter SS Parr reactor do in- glass effects) rate constants, m3
deed confirm the theoretically predicted SD curve mol-'s-'.
from point a inFig. 9. More detailed experimental kt. kt. 0 =ktc + ktd: 'tc, o + 0.

tests are in progress and will form the subject of k s , kp, kjl o , etc. =frequency factors for intrinsic rate
discussion of part I1 of this series. constants, s-' or m3 mo1-l s-l.
M =Moles of monomer in liquid phase,
CONCLUSIONS mol.
A new model is described in this work which can be MU =Moles of monomer in vapor phase,
used to simulate the operation of batch as well as mol.
semibatch reactors. The model-parameters have been Mn =Number average molecular weight
tuned using isothermal experimental data on batch = (MWm)(hl + p l ) / ( h o + po),kg

reactors. The variation of conversion and molecular mol-'.

weights are then predicted for simple operations in =Weight average molecular weight
the semibatch mode, e.g., instantaneous addition and = ( M W m ) ( A 2 + p2)/(A1+ pl).kg
flashing of solvent, monomer, and initiator, step in- mol-'.
crease and decrease in temperature, etc. It is found =Molecular weights of pure
that conversion histories depend upon an interesting monomer and solvent, kg mol- I .
and complex interplay of three factors: polymer con- NU =Total moles of inert in vapor phase,
centration, molecular weight, and temperature at the mol.
time these changes are effected. Detailed explana- P =Total pressure, atm.
tions are offered to explain model results in terms of pn =Growing polymer radical having n
the viscosity of the reaction mass. The model, after repeat units.
experimental confirmation, is well suited for use for R =Primary radical.
on-line adaptive control and optimization. R =Universal gas constant, atm-m3
mol--' K-'.
ACKNOWLEDGMENT
=Rate of continuous addition of
This work was supported through financial support (liquid) initiator, monomer, or
received from the Council of Scientific and Industrial solvent to reactor, mol s - ' .
Research, New Delhi, India through research scheme =Rate of evaporation of monomer or
NO. 22(0232)/93/EMR-I1. solvent, rnol s - ' .
=Moles of solvent in liquid phase,
NOMENCLATURE mol.
A =Jacket area, m2. S" =Moles of solvent in vapor phase,
CFm, C i , q p , C;,gs =Specific heats of pure (liquid) mol.
monomer, polymer or solvent, J S' =Solvent radical.
kg-' K-'. t =Time, s.
liq
Cp. mix =Specific heat of liquid reaction T =Temperature, K.
mixture at any time t, J kg-' K-'. Tref =Reference temperature, K.

1298 POLYMER ENGINEERING AND SCIENCE, AUGUST 1995, Vol. 35, No. 16
 Free Radical Polymerizations Associated with the Trommsdor-Effect. 1

=Temperature of continuous liquid 2. W. Y . Chiu, G. M. Carratt, a n d D. S. Soong, Macre

T/ molecules. 16,348 (1983).
feed, K.
3. T. J. Tulig and M. V. Tirrell, Macromolecules, 14, 1501
TJ =Jacket fluid temperature, K. (1981).
U =Overall heat transfer coefficient,J 4. F. L. Marten and A. E. Hamielec, A m Chem SOC., Symp.
m-2 s - l K-1 Ser., 104,43 (1979).
Vl =Volume of liquid at time t, m3. 5. S. K. Soh and D. C. Sundberg, J. Polym Sci., Polym
=Volume of vapor space a t time t, Chem Ed., 20, 1331 (1982).
vg 6. R. G. W. Norrish a n d R R. Smith, Nature, 150, 336
m3. (1942).
v7- =Rate of vapor release from reactor, 7. V. E. Trommsdorff, H. Kohle, a n d P. Lagally, MaJcromoL
mol s-'. Chem, 1, 169(1947).
X =Monomer conversion (molar). 8. S.T. Balke a n d A. E. Hamielec, J . Appl Polym Sci., 17,
905 (1973).
9. G. V. Schulz a n d G. Harborth, Makromol Chem, 1. 106
Greek Letters (1947).
10. K. F. ODriscoll, PureAppl Chem. 53,617(1981).
e p . ot =Adjustable parameters in the 11. A. E. Hamielec, Chem Eng. Commun, 24, 1 (1983).
model, s. 12. F. Bueche, Physical Properties of Polymers, Interscience,
= kth ( k = 0.1.2,. . .) moment of live New York, (1962).
(P,) polymer radicals = 13. D. Achilias a n d C . Kiparissides, J . Appl Polym Sci,35,
1303 (1988).
Ez= nkpn,mol. 14. D. S.Achilias a n d C. Kiparbsides. Macromolecules, 25.
AZf, AFf =Latent heat of vaporization for 3739 (1992).
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mol-'. Ed. 15,403 (1977).
16. J. S. Vrentas a n d J. L. Duda, J. Polym Sci., Polym
Pk = kth ( k = 0, 1.2,...) moment of Phys., Ed., 15. 417 (1977).
dead ( 0,) polymer chains = 17. J . S. Vrentas and J. L. Duda, AIChEJ, 25, 1 (1979).
E=
: ,nkDn, mol. 18. S. K. Soh and D. C . Sundberg, J . Polym Sci.. Polym
Chem Ed, 20, 1315 (1982).
Pn =Number average chain length at
19. B. M. Louie and D. S. Soong, J. Appl Polym Sci., 30.
time t= (A, + p l ) / ( A o + k0). 3707 (1985).
Prnq P p . Ps =Density of pure (liquid) monomer, 20. B. M. Louie a n d D. S. Soong, J. Appl Sci., 30. 3825
polymer or solvent at temperature (1985).
T (at time t ) , kg m-3. 21. V. R. Kumar and S. K. Gupta, Polymer. 32,3233 (1991).
=Volume fractions of monomer, 22. B. Agarwal a n d S. K. Gupta, J. PoLym Eng.. 12,257
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24. R. C. Weast, ed., Handbook of Chemistry a n d Physics,
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