Untitled

Viscosity Rise during Free Radical Crosslinking Polymerization with
Inhibition
Victor M. GonzálezRomero and Christopher W. Macosko
Citation: J. Rheol. 29, 259 (1985); doi: 10.1122/1.549790

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Viscosity Rise during Free Radical Crosslinking
Polymerization with Inhibition
VICTOR M. GONZALEZ-ROMERO* and

CHRISTOPHER W. MACOSKO, University of Minnesota,
Department of Chemical Engineering and Materials Science,
Minneapolis, Minnesota 55455
Synopsis
A study of the viscosity rise during free radical crosslinking polymerization is
presented. Techniques were developed for monitoring isothermal viscosity rise
during fast polymerization reactions. The chemical system used was composed of a
dimethacrylate resin in styrene monomer, t-butyl perbenzoate initiator, and hy-
droquinone as the inhibitor. When reduced viscosity is plotted versus conversion,
data at all temperatures collapsed into a single curve. A theoretical equation is
suggested for the time required to reach the gel point in free radical crosslinking
polymerization with inhibition. This equation showed good agreement with ex-
perimental observations.
INTRODUCTION
Viscosity is the most important material property in polymer
processing operations that involve flow. In reactive polymer pro-
cessing, as soon as the reaction begins, heat evolves, affecting
conversion and viscosity. In general, the viscosity rises first
slowly, then more rapidly and finally goes to infinity, indicating
gelation. Modeling of flow stages in reactive processes requires an
expression that relates viscosity to process conditions and the
state of polymerization. In general, viscosity is a function of tem-
perature (T), reactive group conversion (X), and shear rate (1'):
T\ = T\(T,X,-Y). (1)
Temperature influences viscosity in two opposing ways. Rais-

ing the temperature will cause viscosity to drop at a given conver-
• Permanent address: Facultad de Ciencias QUimicas, Universidad de Guadala-

jara, Jalisco, Mexico.
© 1985 by The Society of Rheology, Inc, Published by John Wiley & Sons, Inc.
Journal of Rheology, 29(3), 259-272 (1985) CCC 0148-6055/85/030259-14$04.00
260 GONzALEZ·ROMERO AND MACOSKO
sion (X), but at the same time will increase the reaction rate
causing an increase in X and thus viscosity. Because of this, it is
necessary to relate viscosity explicitly to X.
Viscosity rises for several polyurethane systems have been re-
ported in the Iiterature.i " 4 It has been found that the viscosity of
these systems is independent of the shear rate up to the gel point.
Furthermore, Castro and Macosko--" reported that data at differ-
ent temperatures collapsed into a single curve when the reduced
viscosity, Tj/Tjm, is plotted against conversion. Thus
Tj/Tlm = (X), (2)
where TIm is the initial (monomer) viscosity, TIm = TI(T,X =0).

Sibal, Camargo, and Macosko" measured the isothermal viscos-
ity rise during the anionic polymerization of nylon 6. They found
an exponential dependency of viscosity on conversion. Valles and
Macosko.v" using silicone networks, related viscosity to struc-
tural parameters using a probabalistic recursive method.
Radical chain growth systems are widely used in reinforced
plastics. Nevertheless, little work has been done on monitoring
viscosity during free radical bulk polymerization.P-" Adam et al. lO
studied the viscosity rise for the solution copolymerization of sty-
rene and divinyl benzene. They measured viscosity in situ in the
reaction bath during the copolymerization using a magnetic
sphere rheometer. Since the reaction was in solution, reaction
rates were considerably slower than those found in reactive pro-
cesses like reaction injection molding (RIM); thus, it is not advis-
able to use their results for modeling purposes.
Recently, Landin and Macoskoll,12 have reported some prelimi-
nary results for viscosity rise during free radical bulk copolymeri-
zation of methyl methacrylate (MMA) and ethylene-glycol-
dimethacrylate (EGDMA). Following Valles and Macosko.S? they
related viscosity to structure parameters using branching theory.
In this work, we present a study of the viscosity rise during the
free radical copolymerization of a styrene-dimethacrylate (SDM)
system with inhibition. Using a kinetic model previously devel-
oped." we postulate an equation for the time required to reach
the gel point and a correlation for viscosity as a function of con-
version and temperature.
VISCOSITY RISE DURING POLYMERIZATION 261
EXPERIMENTAL
Materials
The polymerization resin used in this study contains equal
parts by weight of a dimethacrylate monomer and styrene. They
were used as received from the Union Carbide Corporation. The
resin also contains 1% by weight of t-butyl perbenzoate peroxide
used as a free radical initiator, and an undetermined amount of
hydroquinone which is the inhibitor in the commercial styrene.
This mixture is stable at room temperature for over 2 weeks. Our
samples were held at about 5°C. Hereafter, we will refer to the
chemical system as styrene-dimethacrylate (SDM).
Apparatus
Viscosity rise during polymerization of the SDM system was
monitored at. isothermal conditions using a cone and plate con-
stant-stress rheometer (Deer; Rheometer Marketing Limited,
Leeds, England). In this rheometer, the moving cone exerts con-
stant torque on the sample shearing it against a stationary plate.
This is accomplished by controlling the power supplied to a drag
cup motor. Viscosity may be obtained by measuring the angular
velocity of the cone. The cone angle was 0.013 rad and the diame-
ter was 50 mm. Some studies were done using a constant shear
rate Rheometries Mechanical Spectrometer with 50-mm-diam
parallel plates.l"
Isothermal viscosity measurements were made possible by the
use of an environmental chamber. A system for fluid injection
was devised (Fig. 1). When this system is attached to the rheome-
ter, viscosity measurements can be made without opening the
environmental chamber. This results in better thermal equilib-
rium within the chamber and easier gap setting. The injection
system allows very rapid loading and temperature equilibration
ofthe sample which are desired features for monitoring viscosity
of fast polymerizing systems.
The system designed essentially consists of a cap for the lower
plate. The bottom of this cap rests on the lower fixture, while the
top of the cap replaces its surface. On the bottom surface of the
262 GONzALEZ-ROMERO AND MACOSKO
r - - - - - - - - - - --,
I Tempera lure :
I Control I
I I
I I
I I
I I
Injecf_ I
I
I I
L I
Fig. 1. Sketch of the injection system used for viscosity monitoring of fast
polymerization reactions. This system allows rapid sample loading and tempera-
ture equilibrium.
cap, a channel was cut which extends from one end to a hole
drilled in the center. Aluminum tubing is run from the hole,
through the slot, and outside the environmental chamber. This
allows the material to be injected between the fixtures after the
gap is set. This injection device was also used by Sibal, Camargo,
and Macosko" to monitor viscosity during nylon 6 polymerization.
Procedure
Disposable injection tubes were cut from 2-mm-diam alumi-
num tubing. After positioning of the cap with its injection tube on
the lower fixture, the desired test temperature is selected. After
temperature equilibration, the gap between the two fixtures is
set. The resin may now be injected by a syringe to monitor its
viscosity as a function of time. The chemical system used has
negligible reaction at room temperature, but it is highly reactive
at the fixture temperature. Thus, mixing may be done at room
temperature in a separate operation. Injection time was less than
3 s. Heat transfer calculations indicate that the sample reached
the test temperature within 2°C in that period.
RESULTS
Figure 2 shows a viscosity rise at two different shear rates
using parallel-plate geometry. The differences between the two
sets of data are within the experimental errors. Figure 3 shows
viscosity versus shear rate for several samples quenched before
~'"
'"'""
"'"
'"'" ISOTHERMAL
VISCOSITY
RISE
'~" a SCM Sys1em
79'C
7] fls")
(Pe-s) A 0-1000
A '" - 2000
a
a
'0-3~1------:'=-----:-:
10 100
Time (min)
Fig. 2. Isothermal viscosity rise for the SDM copolymer system at 79'C. The
data was obtained in the Rheometries Mechanical Spectrometer using parallel-
plate geometry. The arrow marks the point of sample failure at the plate perime-
ter . .y (s -1): (0) 1000, ~ (2000).
0.10 '"
".
21 min
0-0-00-0-o-o
'!'
e 0.01 0--0--0-0--0--o
19min
l:'"
17min
~
.".1 ,,,I
0.001
101 10 2 10~ 104
'(( 5·1)
Fig. 3. Viscosity versus shear rate for samples at three different extents of
reaction. The specimens were isothermally cured at 77'C. The reaction was
stopped by cooling and the addition of inhibitor (FeCl z). The gel point at this
temperature occurred at 27 min.
5,----,---..,.----,----,----,
a INITIAL VISCOSITY
SDM System
4
3 7)m=2.8 x10-~ e 1494/r

71mx 10
(Pa- s)
3
1
20 40 60 80 100 120
Temperature (Oe)
Fig. 4. Initial viscosity of the SDM copolymer system as a function of temper-

ature. Symbols are experimental values and the solid line is the best fit according
to Eq. (3),
the gel point. This graph indicates that, at least for the moderate
shear rates (100 s - 1) or shear stresses (50 Pal used here, we
should not observe shear thinning. Thus all the viscosity results
below will be considered as Newtonian. Initial monomer viscosity
of the SDM system was measured as a function of temperature.
To prevent any reaction from taking place, no initiator was added
to the resin. Good correlation for the initial viscosity as a function
of temperature was found by an Arrhenius expression
TJm = A"'lexp(E.,/T). (3)
The best fit using least squares was obtained when E = (1494 K)
and A"'l = 2.8 X 10- 5 (Pa s), Agreement of this equation with
experimental results may be seen in Figure 4.
We used this monomer viscosity to remove the temperature
effect from the viscosity expression [Eq. (2)]. Reduced viscosity
(TJ/TJm) versus time for different temperatures are shown in Figure
5. It may be observed that the viscosity remains almost constant
at the beginning of the reaction; then, after a certain time, it rises
sharply indicating gelation. Temperature has a strong effect on
the viscosity profiles. Changing temperature from 82 to 92°C will
change the gel time from 1000 to about 100 s.
VISCOSITY RISE DURING POLYMERIZAT10N 265
SDM System
103 I' :
92°C I' ,
~ I:
es-c " :
"--l ~ : 87°C
102 1"1 V
TJ
li l
I"
84'C:
~
TJ m , ." : '
10 1 I I :
Ii':
. I
I.I,' .....
~ ~.~~
10° ! rl't&"-
.. ,
o --
"uO 800 1200
Time (s)
Fig. 5. Isothermal viscosity rises for the SDM system. Data were obtained
using a constant stress (Deer) rheometer.
DISCUSSION
Kinetics
Gel times for free radical crosslinking are known to occur at
very low conversions. 12,14,15 Up to the gel point, most of the reac-
tion will take place between the inhibitor and the radicals. We
have proposed a simplified kinetic mechanism which has shown
reasonable agreement with experimental results.!" Due to the
severe diffusional limitations for the radicals in this highly cross-
linked system, free radical termination with another radical was
neglected. Thus, the simplified mechanism may be represented by
the reactions:
Initiation: I i; 2R'
-- 1,
k
Propagation: R it + M~Rit+1> (4)
I nhibitio n: R it + Z~Pm
where I and Z are the initiator and inhibitor concentrations, M
the total concentration offunctional groups, R" the concentration
of radicals of length n, and Pn is the concentration of unreactive
chains of length n.
If it is assumed that the concentration of the initiator remains

constant, the species balances under isothermal conditions are:
Initiator: I = 10 (5)
Monomer: dM/dt = kpMR T, (6)
Total radical population: dRTldt = 2fkdIo - kzZR T, (7)
Inhibitor: dZ/dt = - kzZR T, (8)
where R T = !;'~lRri is the total radical concentration, 10 is the
initial initiator concentration, and fis the initiator efficiency.
Inhibition reactions are faster than propagation reactions (kzl k p
~ 1). Thus, if the concentration of inhibitor is greater than the
radical concentration (Z > R T ) , no significant polymerization will
occur. As the inhibitor is depleted, the monomer will react with
the radicals and polymerization will occur. The simplest case to
consider will be that in which the inhibitor has been depleted (Z
= 0). For this, Eqs. (6) and (7) may be written as
dX/dt = k p(l - X)R T, (9)
dRTldt = 2fkd1o, (10)
with X = (Mo - M)/Mo being the fractional conversion of reactive

groups. Integrating Eq. (10) between t and t1> we obtain:
RT(t) - RT(t 1 ) = 2fkd Io(t - t 1 ) · (11)
Now define the inhibition time tz as the time at which the

concentration of radicals would be zero under the present condi-
tions (R T -'" 0 -'" Z -'" 0; t 1 = tz ) . Thus, Eq, (11) becomes
R T = 2fkdIo(t - tz)· (12)
Substituting in Eq. (9) we obtain
dX/dt = 2fkdIokp(1 - X)(t - tz)' (13)
Notice that tz is the time at which polymerization would start if

the inhibitor is ideal (kz/k p -'" co), In such a case, tz will be the time
required to consume the inhibitor by the radicals produced.
If no propagation takes place, the radicals will be consumed at
the same rate at which they are produced (quasi-steady-state ap-
proximation), i.e., dRT/dt == 0. Under these conditions from Eq.

(7), we obtain
RT = 2fkd10 1k z Z . (14)
Using Eq. (8) gives

dZldt = - 2fkd1o. (15)
This equation shows that the rate of consumption of inhibitor is
independent of its concentration (zero-order reaction) which has
been observed experimentally by a number of workers.l'v'" By
integrating Eq. (15)
Z = Zo - 2fkd1ot. (16)
Letting Z ~ Oat tz , one obtains
tz = Z o/(2fk d1o)· (17)
Substituting Eqs. (12), (16), and (17) in Eq. (9) gives
dXldt = (k p/kz)(1 - X). (18)

tz - t
Integrating using the conditions X = 0 at t = 0, one obtains
X = 1 - (1 - t/tJkp/k,. (19)
The quasi-steady-state approximation for the radical popula-
tion may be tested by comparing predictions of Eq. (19) with the
solution ofthe complete set of balance Eqs. (5) to (8),13 As may be
seen in Figure 6, up to 10% conversion (X = 0.1) eq. (19) gives
about the same results as the numerical solution of the complete
set of balance equations.
Gel Time
Conversions at the gel point (Xg ) may be evaluated by sub-
stituting the experimental values for gel times into Eq. (19). Ex-
perimental gel times were obtained by extrapolating to zero the
last points of a plot of(T]/T]m)-l (Fig. 7). This was found to be more
convenient than having to estimate the value at which T]/T]m goes
to infinity. Using these results in Eq. (19), it was found that, at
the experimental conditions, the gel conversion was independent
1.0
I
I
I
I
0.8 1
1
I
1
0.6 X= I Runge-
X 1-(1-l/l z)'p/k, : Kulla
(OSSA) ~
I
0.4 I
I
1
I
0.2 I
I
200 400 600 800

Time (s)
Fig. 6. Theoretical conversion profiles for the SDM copolymer system at
100°C. The solid line was obtained by numerical integration of the kinetic equa-
tions. The dotted line was obtained using quasi-steady-state approximation for
the radical population (i.e., dRyidt = 0), Eq. 19.
1.0 0
TCOC)
~c 00 o 82
Itc 0 c 84
o.a -0"
oJ>.0
0 0
0 '" 89
<J,j> C 0 o 92
'" c 0
~'" c 0
0.6 0", c
, c
c
0.4
0.2
o
o
TIME (5)
Fig. 7. Inverse viscosity ratio versus time. Isothermal gel times were obtained
by extrapolating the last points of each curve to zero using linear regression (_._).
rrci (0) 82, (D) 84, (.0.) 89, (0) 92.
1500 -,.,....,....--~-
1"", . . . . . . .- - . . . , . . . . - - - - . . . . . . . . ,
iSOTHERMAL GEL TIMES
1200
.0
t g :I z {1-11-Xg)kz/ko}
900
tq(S)
600
300
01 1 ",~
80 90
Tem perature (Oe)
Fig. 8. Isothermal gel times for the SDM copolymer system. Symbols are ex-
perimental results and the solid line is the prediction of Eq, (20).
of temperature. The value obtained was X g = 0.0069 ± 0.0004.

Thus, from Eq. (19) we find the expression for the gel time
tg = tAl - (1 - Xg)kzlk p ] . (20)
Figure 8 shows a comparison of experimental gel times with those

predicted by Eq. (20). The parameters used were tz = 1.8945 x
10 -18 exp(17,600fT) and kzfk p = 25. These parameters were mea-
sured independently by differential scanning calorimetry. Details
of the parameter estimation have been given by Gonzalez.l" The
agreement with experimental observations is good, particularly
considering the complexity of the system.
Gel times at higher temperatures may be measured using a hot
plate and a spatula. A small amount of resin (less than 1 crrr') was
quickly placed on top of the hot plate using a syringe. The resin
was sheared against the hot plate with a spatula. The gel time
was determined as the time when the material feels stiff. The
temperature of the hot plate was measured using a J-type (30
gauge) thermocouple connected to a digital readout. The ther-
mocouple junction was wrapped with teflon tape to avoid contact
with the metal surface. Temperature was measured when the
thermocouple was pushed with the spatula against the hot plate.
Experimental gel times obtained by this method are shown in
35, i" ," i
30
25 kz/kp
tg:: tz [1-( 1-xg) J
20
-.,
~ 15
- Gi
CD 10
~oo 110
T(OC)
Fig. 9. Isothermal gel times obtained using a hot plate and a spatula. The
solid line was predicted using Eq. (20) and the same parameters as in Fig. 8.
Figure 9. Again, agreement with Eq. (20) is quite reasonable

using the parameters given above.
Through the use of Eqs. (3) and (19), an expression for the
reduced viscosity of the kind suggested by Eq. (2) may be ob-
tained. This is accomplished by evaluating conversions, using Eq.
(19), for each of the experimental viscosity rises. Equation (2)
may be fitted to an empirical expression
TJ/TJm = (1 - g) -Mg>, (21)
where g = XIXg and ("fj(g) > 0 for all g. Equation (21) satisfies the
boundary conditions of TJ = TJm at X = 0 and TJ = 00 at X = X g .
Once the form of the function ("fj(g) is chosen, its parameters may
be found by regression analysis using experimental data.
The simplest form of ("fj(g) is a linear function of g. Thus
TJ/TJm = (1 - g)- a"g - b". (22)
Linear regression was used to fit Eq. (22) to the experimental

results. The best-fitting parameters obtained were a"fj = 0.863
and b.; = 0.0687. A comparison ofEq. (22) to experimental results
is shown in Figure 10. A similar equation was obtained by Cas-
tro" for polyurethane systems. As can be seen, Eq. (22) provides a
good correlation for the viscosity as function of temperature and
conversion. Equations (20) and (21) may be used in process simu-
lations to predict pressure drop and gel times under practical
conditions.
TEMP. (Oe)
o 82
'" 84
c 87
o 89
<) 92
2 6 8
Conversion X 10'
Fig lO. Isothermal viscosity rise versus monomer conversion. Symbols are
experimental results from Fig. 5 and the solid line is the best fit to Eq. 22. T("C):
(0) 82 (6) 84, (0) 87, (0) 89, (0) 92.
CONCLUSIONS
A study of the viscosity rise during free radical polymerization
of a styrene-dimethacrylate copolymer system was carried out.
An injection device for a cone and plate rheometer was developed.
This apparatus allowed us to measure viscosity during fast poly-
merization reactions. Viscosity measurements during polymeri-
zation would be impossible without the use of such a device. Neg-
ligible shear rate dependency was found up to the gel point. The
quasi-steady-state approximation for the radical population
seems to be valid up to the gel point. This approximation allows a
simple analytical expression for the reactive group conversion as
a function of time.
Gel times were obtained by extrapolating the reciprocal of re-
duced viscosity to zero. An expression for the gel time was sug-
gested. This expression requires kinetic data, as well as knowl-
edge of conversion, at the gel point. Good agreement of this
expression with experimental results was observed. Kinetic con-
stants were obtained independently by DSC.
When reduced viscosity was plotted versus conversion, the data
at all temperatures collapsed within experimental error to a sin-

gle curve. An empirical equation for the viscosity as a function of
conversion and temperature was obtained using experimental
viscosity data along with a kinetic model.
Even though good agreement between the experimental values
and theoretical correlations was shown in this work, we need to
keep in mind that experiments were performed within a narrow
temperature range and only one composition of the chemical sys-
tem was used. Further work is needed to see if the same correla-
tions hold for different copolymer compositions and initiator and
inhibitor levels.
This work was supported by the Union Carbide Corporation. A fellowship to
V. M, Gonzalez from the Mexican National Council on Science and Technology
(CONACYT) is gratefully acknowledged. Susan Bailey collected and reduced
much of the data.
References
1. S. D. Lipshitz and C. W. Macosko, Polym. Eng. Sci., 12,803 (1976).
2. E. B. Richter and C. W. Macosko, Polym. Eng. Sci., 18, 1012 (1978).
3. J. M. Castro and C. W. Macosko, Soc. Plast. Eng. Tech. Pap., 28, 434 (1980).
4. J. M. Castro, S. J. Perry, C. W, Macosko, J. Rheal. to appear.
5. P. W. Sibal, R. E. Camargo, and C. W. Macosko, ProcessPolym. Tech. Eng" 1,
147 (1938-84).
6. E. M, Valles and C. W. Macosko, Macromolecules, 12,521 (1979).
7. D. R. Miller, E. M. Valles, and C. W. Macosko, Polym. Eng. Sci., 19, 272
(1979),
8. M. Gordon and R. J, Roe, J. Polym. SCl., 21, 75 (1956).
9. R, S. Whitney and W. Burchard, Makromol. Chem., 181, 869 (1980).
10. M. Adam, M, Delsanti, R. Okasha. and G. Hild, J. Phys. Lett., 40, L-539
(1979l.
11. D. T. Landin and C. W. Macosko, Org. Coat. Appl. Polym. Sci. Proc., 48, 422
(1983).
12. D. T. Landin and C. W. Macosko, Am. Chem. Soc. Symp. Ser. S. S. Labana
and R. A. Dickie, Eds. 243, 33 (1984),
13. V. M. Gonzalez, Ph.D. thesis, University of Minnesota, Minneapolis, 1983.
14. C, Walling, J. Am. Chem. Soc., 67, 441 (1945).
15. H. Galina, K. Dusek, Z. Tuzar, M. Bohdanecky, and J. Stokr, Eur. Polym. J.,
16, 1043 (1980).
16, P. J. Flory, Principles of Polymer Chemistry, Cornell University Press,
Ithaca, NY, 1953.
17. D, Proffitt, Proc. 37th Ann. Can! Rein! Plastics/Composites Inst. S.P.I.,
Session 22·D, 1 (1982).
Received May 4, 1984

Accepted August 31, 1984

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Viscosity Rise during Free Radical Crosslinking Polymerization with

Citation: J. Rheol. 29, 259 (1985); doi: 10.1122/1.549790

Additional information on J. Rheol.

VICTOR M. GONZALEZ-ROMERO* and

Temperature influences viscosity in two opposing ways. Rais-

• Permanent address: Facultad de Ciencias QUimicas, Universidad de Guadala-

Tj/Tlm = (X), (2)

where TIm is the initial (monomer) viscosity, TIm = TI(T,X =0).

3 7)m=2.8 x10-~ e 1494/r

Fig. 4. Initial viscosity of the SDM copolymer system as a function of temper-

If it is assumed that the concentration of the initiator remains

dX/dt = k p(l - X)R T, (9)

dRTldt = 2fkd1o, (10)

with X = (Mo - M)/Mo being the fractional conversion of reactive

RT(t) - RT(t 1 ) = 2fkd Io(t - t 1 ) · (11)

Now define the inhibition time tz as the time at which the

R T = 2fkdIo(t - tz)· (12)

Substituting in Eq. (9) we obtain

dX/dt = 2fkdIokp(1 - X)(t - tz)' (13)

Notice that tz is the time at which polymerization would start if

proximation), i.e., dRT/dt == 0. Under these conditions from Eq.

Using Eq. (8) gives

dXldt = (k p/kz)(1 - X). (18)

200 400 600 800

iSOTHERMAL GEL TIMES

of temperature. The value obtained was X g = 0.0069 ± 0.0004.

Figure 8 shows a comparison of experimental gel times with those

35, i" ," i

Figure 9. Again, agreement with Eq. (20) is quite reasonable

Linear regression was used to fit Eq. (22) to the experimental

at all temperatures collapsed within experimental error to a sin-

Received May 4, 1984

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