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CONTROLLED DEGRADATION OF
POLYPROPYLENE A COMPREHENSIVE
EXPERIMENTAL AND THEORETICAL
INVESTIGATION
c. TZOGANAKIS,* Y. TANG, J. VLACHOPOULOS,
and A. E. HAMIELEC
Department of Chemical Engineering
McMaster University
Hamilton, Ontario, L8S 4L7 Canada
Abstract
Experimental and modeling studies of the free-radical-induced degradation of polypropylene (PP) in the melt phase have been carried out.
Experiments have been performed in a single-screw plasticating extruder
using a peroxide as the free-radical source. Concentration of the peroxide was in the range 0.01-0.6 wt%. Results in the form of melt flow
index (MFI) values, viscosity curves, and molecular weight distribution
(MWD) of the produced resins are presented here. Based on these
results, a constitutive equation describing the shear viscosity of the melt
as a function of shear rate, temperature, and molecular weight has been
derived. The extensional viscosity of these resins has been determined as
a function of strain rate using Cogswells analysis of converging flows.
A previously developed kinetic model (plug flow) has been used to
simulate the changes of the average molecular weights of the MWD, and
a sensitivity analysis of this model has been carried out.
*Resent address: DuPont Canada Inc., Research Center, Kingston, Ontario,
K7L 5A5 Canada.
319
Copyright 0 1989 by Marcel Dekker. Inc
TZOGANAKIS ET AL.
320
1.
INTRODUCTION
i
i
FF
Powder
peroxide
peroxide
Crosslinked
&
Narrow MWD
propylene.
kd
Initiation
I
kl
Chain Scission
P
2Ro
+ Ro4
Pr
+ P:-+ + R
k2
Transfer
Pn
+ PP,;r
+ PY+ Pn.s
Thermal Degradation
k4
Termination
P;
+ P+
Pn +Pr
(a)
Radical Attack
CH CH-CH2-CH-CH2
2- I
I
CH3
CH3
Hydrogen Abstraction
+ R ' -..CH2-C-CH2-CH-CH2
-+"A
CH3
Peroxide Radical
-I
CH3
(b)
Polymer Radical
CH3
Polymer Radical
Degradation (&Scission)
-CH~-~H
CHZ=f-CHz
CH3
Polyclefin
RH
TZOGANAKIS ET AL.
322
TABLE 1
Industrial Peroxides Used for PP Degradation
2,5-Dimethyl-2,5-di-r-butylperoxy
hexane (DHRP)
2,5-Dimethyl-3-hexin-2,5-di-t-butylperoxide
(DYBP)
Di-t-butylperoxide (DTBP)
Dicumylperoxide (DCUP)
net result is a significant narrowing of the MWD due to the random nature of
the radical attack on the polymer chains. The resulting polymer has a much
higher melt flow index (MFI), and reduced viscosity and elasticity. In the fiber
production field this leads to easier melt draw, finer and more uniform filaments, and faster line speeds [S]. At relatively moderate peroxide concentration levels, degradation is favored against crosslinking (Fig. l), and a general
reaction scheme is presented in Fig. 2. Crosslinking is prevented due to the
steric hindrance of the methyl group in the PP chains. Peroxides used in this
type of degradation reaction are subject to certain limitations. The half-life
time at 130C must be higher than 1 h and smaller than 10 h [4]. Furthermore,
the peroxide must not evaporate easily at the temperature of the extruded
polymer melt and must produce no odor or color change in the polymer.
Examples of peroxides industrially accepted for this degradation reaction are
given in Table 1 .
dl
dt
- = -kdI
CONTROLLED DEGRADATION OF PP
dQ2
-- dt
-Q313
+ Q1/3
2Qo
Q I - QO
where
f = 0.6
The value off was obtained by fitting the model to experimental data from
ampule experiments [ 111.
In order to solve the system of Eqs. (1)-(4) the closure method of Hulburt
and Katz [ 12) was employed, according to which
111.
EXPERIMENTAL
TZOGANAKIS ET AL.
324
AP,,,
2nB7,
(9)
where nB is the Bagley correction [13] as calculated from plots of the total
pressure drop versus L/D of the die (Bagley plots). The apparent extensional
viscosity was then calculated according to the equation [ 141
YA
4Q
3
7TR
Q being the volumetric flow rate and R the capillary radius. The extensional
strain rate (&) was calculated using the following
CONTROLLED DEGRADATION OF
PP
325
In the past, Schroff et al. [15] have used the same approach and they have
found quantitative agreement between experimental results and values predicted by means of the forementioned procedure. Recently, Laun and Schuch
[ 161 showed that calculations of the extensional viscosity of polymer melts
using Cogswells simple method are in surprisingly good agreement with data
from more accurate methods for the determination of polymer extensional
viscosities.
0.4
ai
0.0
6.0
8.0
10.0
12.0
14.0
16.0
In IM)
TZOGANAKIS ET AL.
326
lower molecular weights and the high molecular weight tail is removed in a
controlled fashion as we progressively step up to higher peroxide levels. An
explanation of the elimination of the high molecular weight tail can be given if
one considers the random nature of the degradation reaction. Since the peroxide
radicals abstract preferentially the tertiary hydrogen atoms from the polymer
chains, longer chains react with a faster rate because they contain a larger
number of active sites (i.e., tertiary hydrogen atoms). As a result the polymer
elasticity, which mainly is due to the long chains, drops significantly as it
has been demonstrated by extrudate swell measurements of these controlledrheology resins [ l l ] . In Figs. 4-6 the experimentally measured M,,A?,,, and
A?? are compared with the model predictions. It can be seen that there is good
agreement. The modifications of the MWD, caused by the degradation process,
have a pronounced effect on the rheological properties of the polymer. The
free-radical-induced degradation affects to a great extent both the viscous and
the elastic behavior of the polymer as opposed to shear degradation, which
mainly affects the elastic one [ 171. The effect of the peroxide concentration on
the MFI is shown in Fig. 7. The MFI was measured at 230C using 2.16 kg and
0.0
0.2
0.4
0.6
0.0
4.0
Model
3.0
M e a s u r e d by
SEC
LD
z
*
2.0
15
1 .o
..---
- -- -0-
-0 - - -0- I
0.0
0.00
--.
0.20
0.40
0.60
1.5
Model
by SEC
Measured
1.0 I
+,
0'
.'\
Is
0.5 - a@\,
0\
0'
*-c\ 0- \
0.0
-a-I
-0- - - -0- - I
0.80
TZOGANAKIS ET AL.
328
800.
.' 6 0 0 .
z
.
E
2.30 C
2.16 K g
5.00 K g
0)
X
7
-5
400.
U
w
-
200.
0.
0.0
0.2
0.4
0.6
0.8
4.0
-.-E
3.0
-.->x
;2.0
1.o
0.5
1.5
1.0
2.0
2.5
3.0
FIG. 8. Flow curves of PP resins produced by using different peroxide concentrations. (Viscosity measured at 190C.)
TABLE 2
Correlation for Shear Viscosity of Controlled-Rheology Polypropylene Resins
ln(q) = A, + A , In(?)
+ A,
(ln(+)),
where
A,
A,
A,
A,
A,
A,
A,
A,
A,
A,
A,,
= -0.1052E
= -0.2613E
+ 02
+ 00
= -0.9517E - 02
= -0.24248 -t- 00
0.3471E - 03
= 0.1351E - 01
= 0.4731E
01
= -0.1319E
00
= -0.3852E - 01
= 0.5952E - 02
= -0.98098 - 03
and
T[=]"C
?[=Is-'
In(+)
+ A,,T
+ A,
In(M,)
In(+) In(A?,)
3.5
TZOGANAKIS ET AL.
330
3.5
3.0
m
A
2.5
1 4 7 8 s-
443
148
44
15
4
2.0
1.5
1 .o
0.5 I
0.0
0.2
0.4
0.6
0.8
FIG. 9. Variation of shear viscosity with peroxide concentration at four shear rate
levels (viscosity measured at 190C).
Fig. 10 where the intrinsic viscosity is plotted versus A?,,,. A summary of all the
data presented so far is given in Table 3. From this table it is worth noting that
the polydispersity ratio goes asymptotically to a value of 2 . This verifies the
random nature of the degradation scheme and shows that branching does not
occur under the present reaction conditions.
A power-law model was fitted to the experimental data from the shear
viscosity measurements and the variation of the power-law index and the
consistency index with peroxide concentration and
of the polymer is
illustrated in Figs. 11-14. Generally, it is known that as the width of the MWD
broadens, the non-Newtonian behavior of the melt is enhanced. It can be seen
from Figs. 11-12 that as the molecular weight decreases and the MWD
becomes narrower, the power-law index increases. That is an indication of the
increased Newtonian nature of the melt. As mentioned earlier, three different
dies were used in the viscosity measurements and Bagley plots were con-
CONTROLLED DEGRADATION OF PP
331
4.0
-. 3.0
Ol
.-E
t;
.0
>
.-u
.-cC
2.0
YI
1.0
"."
1.
3.
FIG. 10. Intrinsic viscosity of the produced resins as a function of their molecular
weight.
structed for all the polymers. Such typical plots are given in Figs. 15 and 16 for
the starting PP resin and the resin produced using 0.1 % peroxide. The variation
of the Bagley end correction with shear rate is shown in Fig. 17 for four of the
PP resins produced in this study. The effect of the peroxide concentration on
the Bagley correction is presented in Fig. 18, and it is seen that the Bagley
correction decreases with increasing peroxide concentration. This is a consequence of the changes effected on the MWD of the polymer. Finally, the
variation of the Bagley correction with the A?, of the polymer is presented in
Fig. 19 for three different shear rate levels.
As it was explained in a previous section, the entrance or Bagley end
correction was used in the calculation of the extensional viscosity of all the PP
resins in this work. This was done by using Eqs. (9)-(12), and the results are
presented in Fig. 20 where the extensional viscosity is plotted versus the
extensional strain rate. It can be noted that the extensional viscosity changes
264
269
262
92
110
99
3.25
3.32
3.39
2.40
2.14
2.23
110
108
95
50
59
47
0.150
0.200
0.300
0.400
0.500
0.600
11
12
13
14
10
323
3.69
136
0.100
118
40 1
3.96
152
0.075
89.2
26.0
141
136
513
467
4.43
0.050
4.85
197
177
0.040
69.5
18.6
158
583
4.85
210
0.030
45
50
53
82
239.0
240.0
229.0
170.0
153.8
126.0
92
513.0
505.0
500.0
441.0
335.8
233.6
210.5
174.7
59.0
91.9
120.4
33.9
102
85
27.8
45.6
7.8
23 1
0.020
17.0
MFI,
12.8
850
665
5.53
267
0.010
3.1
,b
309
MFI,
171
1117
8.00
6.17
348
O.OO0
M,, X
195
Mz X lo-
M,,,/Mn
M, x 10-3
(wt %)
Peroxide
concentration
Run
number
TABLE 3
Summary of Experimental Results
Iu
0.7
0.6
0.4
0.3
0.00
0.05
0.10
0.15
0.20
0.25
%I
FIG. 11. Variation of power-law index with peroxide concentration at three temperature levels.
0.7
0.6
0.5
0.4
0.3
2.0 0
4.00
6.00
8.00
10.00
t m w * to6
FIG. 12. Variation of power-law index with weight average molecular weight at
three temperature levels.
4.5
3.5
2.5
1.5
0.0
0.2
0.6
0.4
0.8
FIG. 13. Variation of consistency index with peroxide concentration at three temperature levels.
15.
A
\
12.
9.
6.
3.
0.
2.00
4.00
6.00
lllvlw
8.00
10.00
lo6
30.
25.
20.
15.
Downloaded by [Technical University of Crete] at 08:34 14 September 2015
10.
5.
0.
-8.
0.
8.
24.
16.
40.
32.
48.
L/D
12
10
8.
4.
2.
0.
-8.0
0.0
8.0
16.0
24.0
32.0
40.0
48.0
L/ D
190C).
10.
8.
6.
4.
2.
0.
0.
800.
400.
1200.
1600.
FIG. 17. Variation of Bagley correction with shear rate for four PP resins.
8.
6.
4.
2.
0.
0.00
0.02
0.04
0.06
0.08
0.10
0.12
FIG. 18. Effect of peroxide concentrationon the Bagley correction of the produced
resins.
8.
6.
4.
2.
0.
0.1
0.2
0.3
mw
0.4
lo+
FIG. 19. Correlation between the Bagley correction and the weight-average molecular weight of the CR resins.
1 4
,.-.-b
12
2. l o
Y
.-f
>
z
T = 190 C
v)
.r
rn
PP
0.01 w t . %
0.02
0.03
0.04
0.05
0.1
2
0
0.
50.
100.
150.
200.
250.
300.
FIG. 20. Extensional viscosity of the resins produced as a function of the strain
rate. (Calculations using Cogswells method [ 141.)
TZOGANAKIS ET AL.
338
dramatically even at low peroxide levels. Here, it must be pointed out that by
means of the present method, CR polypropylene resins which exhibit an
elongational viscosity almost independent of strain rate can be produced. This
is advantageous in fiber spinning, where development of weak spots can
introduce large variations in the extensional strain that the melt experiences.
This means that such resins will not tend to neck when subjected to simple
extensions [ 191. As indicated by our preliminary laboratory experiments, when
these resins are used in fiber spinning, draw resonance occurs at draw ratios
considerably higher than those observed in the spinning of the starting PP.
VI.
SENSITIVITY ANALYSIS
Although the predictions of the kinetic model were in good agreement with the
experimental data, it is necessary to determine how perturbations or uncertainties of the model parameters affect the predictions. This is important because
our knowledge of the parameter values may not be precise. The results of such
a sensitivity analysis can be very useful in directing further research toward
either more accurate estimation of the model parameters or better process
control.
Generally, sensitivity analysis is concerned with fluctuations of the model
predictions caused by deviations of system parameters from their nominal
values. The purpose of the present analysis was to determine the effects of
uncertainties in kd, f, T , and I , on the model predictions. The model equations
(1)-(4) can be written in the following dimensionless vector form
and
CONTROLLED DEGRADATION OF PP
339
with Qi,o being the value of the "i moment at time zero. The dimensionless
variables were introduced to ease the numerical integration of the sensitivity
equations. The sensitivity coefficient for the parameter pi and the model output
Yi is defined as the first partial derivative of Y j with respect to pi
a Yi
+..
= -,
'I
i,j=l, ...,4
aPj
6,
if pi is an initial condition
rl
The full sensitivity equations are given in Appendix I along with the dimensionless form of the model equations. These equations are integrated along
with the model equations to give the complete time history of the sensitivity
matrix during the degradation reaction. The results are presented in the following normalized form
p.. =
lJ
$3
'I
yi
for the purpose of demonstrating the relative influence of the parameters on the
model outputs (predictions). Finally, the sensitivity of the average molecular
weights on the parameter variations was calculated by means of the equations
given in Appendix 11.
TZOGANAKIS ET AL.
340
Some of the sensitivity analysis results are presented in Figs. 21-24. In Fig.
21 the effect of the peroxide decomposition efficiency on the model outputs is
shown. It can be seen that all the normalized sensitivity coefficients are
positive. This means that positive deviations from the nominal value of the
efficiency will increase the model outputs. If the definitions in Eiq. (16) are
taken into account, it can be concluded that the actual values of the model
dimensional outputs will decrease. Also it is seen that the values of the
coefficients are small, which means that small uncertainties in the efficiency
value can be tolerated. The effect of the temperature perturbations on the
model outputs is shown in Fig. 22. It is obvious that the values of the sensitivity
coefficients are much higher than those presented in Fig. 2 1. This indicates that
the model predictions are more sensitive to temperature fluctuations during the
reaction. The effects of peroxide efficiency and temperature on the average
molecular weights of the polymer are presented in Figs. 23 and 24, respectively. Inspection of these plots reveals that an increase in efficiency or
temperature decreases all molecular weight averages with M zbeing the most
sensitive. It must be pointed out that the model predictions appear to be very
1.2
1 .o
.-0
.-
0.8
0.2
0.0
0.
1.
2.
3.
4.
Time (min)
5.
35.0
30.0
yI
25.0
t 8
.g
E
0
e>
20.0
5c 15.0
..c
i?J 10.0
5.0
0.0
0.
1.
2.
3.
5.
4.
Time (min)
0.0
3.
4.
-0.1
c
UI
.C
-0.2
.-c>
5
E
-0.3
0)
v)
-0.4
-0.5
0.
1.
2.
Time (min)
5.
342
TZOGANAKIS ET AL.
0.0
-1
.o
c
v)
.-2u
.-
-2.0
ur
c
..E
c
.-
-3.0
v)
5 -4.0
v)
-5.0
-6.0
0.
1.
2.
3.
4.
Time (min)
FIG. 25. Effect of parameter perturbations on the second moment of the polymer
MWD ( T = 2 2 0 " C , f = 0.6, I , = 0.964E - 3 mourn3).
100
Hence, it is clear that temperature perturbations are more important and can
introduce larger e m r s in the model predictions.
5.
344
TZOGANAKIS ET AL.
Acknowledgments
Financial assistance from the Natural Sciences and Engineering Research
Council of Canada is gratefully acknowledged. Also, the authors would like to
thank Shell Canada for providing the polypropylene resin, Akzo Chemie for
providing the peroxide, and Dr. J. Armonas of Modchrom, Inc., for the SEC
measurements.
NOMENCLATURE
D
f
I
kd
Die diameter, m
Peroxide decomposition efficiency
Peroxide concentration, mol/m?
Peroxide decomposition rate constant, sDie length, m
CONTROLLED DEGRADATION OF PP
Greek Letters
Apparent shear rate, s-1
Entrance pressure drop, Pa
Extensional strain rate, s-l
Shear viscosity, Pa- s
Extensional viscosity, Pa- s
Normalized sensitivity coefficient
Shear stress at the die wall, Pa
Sensitivity coefficient
APPENDIX I
345
TZOGANAKIS ET AL.
346
where
5 = 2fk,l,
(1.5)
(1.9)
(1.10)
-kd+,*
dt
(1.11)
432
- -++I*
--
dt
- F,(l -
02 2
Y I ) -QO
s44
QI.O
Qi.0
+ 2k,-(110
Qi.0
(1.12)
CONTROLLED DEGRADATION OF PP
347
(I. 14)
348
TZOGANAKIS ET AL.
(1.20)
(1.21)
where
(1.22)
(1.23)
(1.24)
(I. 25)
(1.26)
(1.27)
(1.28)
(1.29)
(1.30)
(1.31)
(1.32)
CONTROLLED DEGRADATION OF PP
349
(1.33)
(1.34)
APPENDIX I1
The average molecular weights of the polymer distribution can be calculated
by the formulae:
(11.1)
(11.2)
(11.3)
(11.4)
(11.5)
(11.6)
(11.7)
(11.8)
TZOGANAKIS ET AL.
350
REFERENCES
121
131
141
I201
[211