Sunteți pe pagina 1din 33

Polymer-Plastics Technology and Engineering

ISSN: 0360-2559 (Print) 1525-6111 (Online) Journal homepage: http://www.tandfonline.com/loi/lpte20

Controlled Degradation of Polypropylene: A


Comprehensive Experimental and Theoretical
Investigation
C. Tzoganakis , Y. Tang , J. Vlachopoulos & A. E. Hamielec
To cite this article: C. Tzoganakis , Y. Tang , J. Vlachopoulos & A. E. Hamielec (1989)
Controlled Degradation of Polypropylene: A Comprehensive Experimental and Theoretical
Investigation, Polymer-Plastics Technology and Engineering, 28:3, 319-350, DOI:
10.1080/03602558908048602
To link to this article: http://dx.doi.org/10.1080/03602558908048602

Published online: 04 Oct 2006.

Submit your article to this journal

Article views: 27

View related articles

Citing articles: 34 View citing articles

Full Terms & Conditions of access and use can be found at


http://www.tandfonline.com/action/journalInformation?journalCode=lpte20
Download by: [Technical University of Crete]

Date: 14 September 2015, At: 08:34

P0LYM.-PLAST. TECHNOL. ENG., 28(3),319-350 (1989)

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

1.

INTRODUCTION

The chemical structure of polypropylene is generally influenced by the kind of


the polymerization system used during its production. The conventional polymerization process is canied out in an inert hydrocarbon medium at moderate
pressures and temperatures using Ziegler-Natta catalyst systems [ 11, Generally, PP resins produced by this method have broad molecular weight distributions as a result of the broad distribution of active sites on the catalyst. For the
purpose of improving application and processing characteristics, the MWD
can be modified in a postreactor stage by means of reactive extrusion. Reactive
extrusion combines two operations: chemical reaction for the formation or
modification of polymer molecules and processing of the produced polymer for
the purpose of structuring the polymer molecules into shaped plastic products
[ 2 ] .In the present work, reactive extrusion involves chemical modification of a
commodity PP resin to produce a specialty polymer with superior processing
properties. The peroxide-promoted degradation is a very economical postreactor process used for the production of controlled-rheology (CR) polypropylene
resins with tailor-made MWD [3-61. Interest in PP degradation via peroxides
began with melt stabilization studies [7-81. A technique was developed to
promote degradation by means of a peroxide initiator and was used to determine the degree of stabilization at various stabilizer amounts. Early patents [3]
and publications [9] on this process appeared in the 1960s. By means of this
method cleavage of the polymer chains is accomplished by highly reactive
peroxide radicals created by the decomposition of suitable peroxides [ 101. The

i
i
FF

Powder

peroxide

peroxide

(very high concentration)

Crosslinked

&
Narrow MWD

FIG. 1. General approach to production of narrow MWD and/or crosslinked poly-

propylene.

kd

Initiation
I

kl

Chain Scission
P

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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

FIG. 2. (a) General reaction scheme. (b) Chain scission reaction.

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)

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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 .

II. REACTION MODELING


Despite the great industrial importance of the peroxide-promoted degradation
of PP only few modeling studies have been presented. Hudec and Obdrzalek
[5] have presented a simple relation describing the changes of the weight
average (A?,) and number average ( f i n )molecular weights of the polymer
MWD. Very recently Tzoganakis et al. [ I l l proposed a general reaction
scheme and developed a plug flow model that can predict the MWD of the
polymer in terms of the average molecular weights. The model was successful
in predicting experimental results obtained from industrial and laboratory scale
experiments. In the model, only the initiation and chain scission reactions have
been considered and the equations that describe the time variation of the
peroxide concentration and of the first three moments of the MWD are the
following:

dl
dt

- = -kdI

CONTROLLED DEGRADATION OF PP

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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

The average molecular weights were calculated by the equations

111.

EXPERIMENTAL

Experiments were carried out in a Killion single-screw extruder with 38 mm


diameter and a LID of 241 1. The peroxide used was 2,5-dimethyl-2,5-di(tbuty1peroxy)hexane (Trigonox 101j and was provided by Akzo Chemie. The
polypropylene used was KY6100 from Shell. The peroxide was premixed with
the polypropylene powder before feeding into the extruder. A master batch
(5%) was used for the preparation of the various concentration PP-peroxide
mixtures. Extruder runs were performed at 220C and 20 rpm. The peroxide
concentration in contrast to previous studies [ 1 1 ] was extended to high levels.
The concentration range was 0.01-0.6 wt%.

TZOGANAKIS ET AL.

324

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

The MFI of the produced polymers was measured according to ASTM


D1238-65T using a Monsanto capillary rheometer. The shear viscosity of the
polymers was measured with an Instron 321 1 capillary rheometer at different
temperatures using three dies with L/D equal to 8, 16, and 40. Bagley and
Rabinowitch corrections were applied to the data [ 131.
The MWD of the degraded polymers was measured by high temperature
size exclusion chromatography (SEC). Two linear styragel columns were used
with 1,2,4-trichlorobenzene (TCB) at 140C.

IV. MEASUREMENT OF EXTENSIONAL VISCOSITY


The extensional viscosity ( q E )of the produced controlled-rheology PP resins
was calculated using the converging flow analysis of Cogswell [14]. In the
analysis, it is assumed that the polymer melt adopts a coni-cylindrical flow
pattern when flowing from a reservoir into a die and that the melt takes up the
pattern that corresponds to minimum entrance pressure drop. The velocity at
the outer boundary of this pattern is assumed to be zero and the total entrance
pressure drop is taken to be equal to the sum of those due to shear and
extensional flow. Also, it is assumed that the shear viscosity (11) of the polymer
melt can be described in terms of a power-law model, n being the power-law
index. In the present work, measurements of the pressure drop occurring
during the flow of the CR resins through three capillary dies with different L/D
were performed. The entrance pressure drop was calculated using the equation

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

where the apparent shear rate is

YA

4Q

3
7TR

Q being the volumetric flow rate and R the capillary radius. The extensional
strain rate (&) was calculated using the following

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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.

V. RESULTS AND DISCUSSION


As was expected, the MWD of the polymer was found to become narrower as a
result of the action of the peroxide radicals. In Fig. 3 the MWD of the
polypropylene resins, extruded under different peroxide concentration levels,
are presented. It is noted that increasing the initiator concentration changes
dramatically the distribution. In particular, the whole distribution is shifted to
0.5

0.4

ai
0.0
6.0

8.0

10.0

12.0

14.0

16.0

In IM)

FIG. 3. Effect of peroxide concentration on the MWD of the polymer produced.

TZOGANAKIS ET AL.

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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

Peroxide Concentration (wt%)

FIG. 4. Variation of number-average molecular weight with peroxide concentration.

0.0

4.0

Model

3.0

M e a s u r e d by

SEC

LD

z
*

2.0

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

15

1 .o

..---

- -- -0-

-0 - - -0- I

0.0
0.00

--.

0.20

0.40

0.60

Peroxide Concentration (wt %)

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

FIG. 6. Variation of z-average molecular weight with peroxide concentration.

0.80

TZOGANAKIS ET AL.

328

800.

.' 6 0 0 .
z
.
E

2.30 C

2.16 K g
5.00 K g

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

0)
X

7
-5

400.

U
w
-

200.

0.
0.0

0.2

0.4

0.6

Peroxide concentration ( w t 46)

FIG. 7 . Effect of peroxide concentration on the MFI of the resins produced.

5 kg weights. The MFI is increasing linearly with concentration up to about


0.2% and then it starts to level off at a concentration of about 0.4%.Similar
results have been obtained by other researchers [lS]. It seems that at high
concenti-ations recombination of peroxide radicals prevents further chain scission reactions. It must be pointed out that starting from a commodity resin with
MFI = 2-3, resins with up to 100 times higher melt indices can be produced by
properly varying the peroxide content. In Fig. 8 , the change of the polymer
flow curve with peroxide concentration is given. The viscosity was measured at
190C. It is clear that resins produced at high concentrations exhibit a flatter
viscosity curve as a result of their Newtonian-like behavior. Based on these data
a constitutive equation for the shear viscosity was derived. This equation
expresses the shear viscosity as a function of shear rate, weight average
molecular weight, and temperature. This equation is given in Table 2 . The
variation of the viscosity with peroxide concentration is plotted in Fig. 9 for
different apparent shear rate values. It is noted that the rate with which the
viscosity decreases is higher in the 0-0.05% peroxide concentration range,
especially at low shear rates. Experimental measurements of the intrinsic
viscosity of the CR resins were also performed and the results are presented in

0.8

4.0

-.-E

3.0

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

-.->x

;2.0

1.o
0.5

1.5

1.0

2.0

2.5

3.0

Loglo (Shear Rate)

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(+)),

+ A,T + A,T2 + A,T

+ A, (ln(if,)I2 + A, In(+) In(M,) + A,T In(if,)


~

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

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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

Peroxide concentration (wt %)

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

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

.-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

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

Iu

0.7

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

0.6

0.4

0.3
0.00

0.05

0.10

0.15

Peroxide concentration (wt

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

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

3.5

2.5

1.5
0.0

0.2

0.6

0.4

0.8

Peroxide concentration (wt %)

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

FIG. 14. Variation of consistency index with weight-average molecular weight at


three temperature levels.

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

FIG. 15. Bagley plot of the starting PP resin at 190C.

12
10
8.

4.

2.
0.

-8.0

0.0

8.0

16.0

24.0

32.0

40.0

48.0

L/ D

FIG. 16. Bagley plot of the resin produced using 0.1%peroxide ( T

190C).

10.

8.

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

6.
4.

2.
0.
0.

800.

400.

1200.

1600.

Apparent Shear Rate (s-')

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

Peroxide Concentration (wt %)

FIG. 18. Effect of peroxide concentrationon the Bagley correction of the produced
resins.

8.

6.

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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.

Extensional Strain Rate (s-)

FIG. 20. Extensional viscosity of the resins produced as a function of the strain
rate. (Calculations using Cogswells method [ 141.)

TZOGANAKIS ET AL.

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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

where Y and p are defined as

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

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

aPj

The matrix of the derivatives of Y with respect to p is called the sensitivity


matrix. Sensitivity coefficients indicate the direction and the magnitude of
change of the model outputs (Y) due to perturbations in the parameter values
(p). A positive sensitivity coefficient indicates that a positive variation of the
corresponding parameter causes an increase in the output variable while a
negative coefficient indicates decrease in the output variable. Following the
method of Atherton et al. [20] and Thomas et al. [21], the sensitivity equations
that describe the time variation of the sensitivity coefficients can be derived by
means of the formula:

The initial conditions for Eq. (18) are


+.. =

if pj is not an initial condition

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.

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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)

FIG. 21. Effect of initiator efficiency perturbations on the model outputs ( T =


220C,f = 0.6, I,, = 0.9764E - 3 mol/m3).

5.

35.0

30.0
yI

25.0

t 8

.g
E
0

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

e>

20.0

5c 15.0
..c

i?J 10.0

5.0

0.0
0.

1.

2.

3.

5.

4.

Time (min)

FIG. 22. Effect of temperature perturbations on the model outputs ( T = 220C,f


0.6,I . = 0.9764E - 3 mol/m3).

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)

FIG. 23. Effect of initiator efficiency perturbations on the average molecular


weights (T = 220"C,f = 0.6, I,, = 0.9764E - 3 mo l h3).

5.

342

TZOGANAKIS ET AL.

0.0
-1

.o

c
v)

.-2u
.-

-2.0

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

ur

c
..E
c
.-

-3.0

v)

5 -4.0

v)

-5.0

-6.0

FIG. 24. Effect of temperatureperturbation on the average molecular weights ( T =


- 3 mol/m3)).

220C,f = 0.6, I , = 0.9764E

sensitive to parameter fluctuations, mainly during the first minute of the


reaction. This was expected to happen since due to the fast decomposition rate
of the peroxide, the reaction has almost been completed in less than 2 min.
Finally, the effect of parameter perturbations on the second moment ( Y4) of the
polymer MWD is shown in Fig. 25.
Let us now try to give a quantitative interpretation to the presented sensitivity results. As an example, consider the effect of inaccuracies in the
initiator efficiency cf)on the second moment (Y4). From Fig. 21 it can be seen
that for a value of p42 equal to 0.6 we have

For a small perturbation in f (i.e., 1%) this equation can be written as

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

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).

This means that a 1% variation in f could result in 0.6% variation in the


predicted Y4 value. This shows that we can afford small inaccuracies in the
value of the initiator efficiency used in the simulations.
Similarly, from Fig. 22, for p43 equal to 5, we have
d Y 4-T
pd3=5= aT Y,

For a 1% perturbation in T , we have


-AY4
= - p , , =AT
- X X = ~ %1
y4

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.

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

VII. CONCLUDING REMARKS


Some new results obtained during controlled degradation experiments of polypropylene have been presented. The experiments were carried out in a singlescrew extruder using a peroxide to promote chain scission. Peroxide concentration levels were in the range 0.01-0.6 wt%, and it was verified that as peroxide
increases, the molecular weight distribution of the polymer becomes narrower
and it is shifted to lower molecular weights. As a result the melt flow index of
the resin increases dramatically while the shear and elongational viscosities
decrease considerably. Based on measurements of the MWD and of the shear
viscosity of the resins at different temperatures, a correlation describing the
shear viscosity as a function of shear rate, temperature, and weight average
molecular weight was developed. By using the shear viscosity data and following Cogswells analysis of converging flows, the extensional viscosity of the
produced CR resins was estimated as a function of strain rate. These estimations along with preliminary experimental results suggest that these PP resins
exhibit better performance in fiber spinning.
A previously developed kinetic model was used successfully to predict the
changes of the molecular weight distribution during the degradation reaction.
A statistical sensitivity analysis of the model equations indicated that temperature perturbations during the reaction can distort the model predictions, especially during the first minute of the reaction, this being due to the very fast
decomposition of the peroxide initiator.

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

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

CONTROLLED DEGRADATION OF PP

Monomer molecular weight


Number average molecular weight
Viscosity average molecular weight
Weight average molecular weight
z-average average molecular weight
Power-law index
Bagley correction
ifh moment of polymer distribution
Volumetric flow rate, m3/s
Die radius, m
Time, s
Temperature, K
Dimensionless variables in equation (16)

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)

Application of the sensitivity equations (18) yields the following differential


equations for the sensitivity coefficients:

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

For the decomposition rate constant, k,:

(1.9)

For the initiator eflciency, f


d +-i 2

(1.10)

-kd+,*

dt

(1.11)

432
- -++I*

--

dt

- F,(l -

02 2
Y I ) -QO
s44

QI.O

Qi.0

+ F,(1 - Y I ) -QoS 5 &0


Qi.0

+ 2k,-(110
Qi.0

(1.12)

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

CONTROLLED DEGRADATION OF PP
347

For the temperature, T:

(I. 14)

348

TZOGANAKIS ET AL.

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

(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)

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

APPENDIX I1
The average molecular weights of the polymer distribution can be calculated
by the formulae:
(11.1)

(11.2)
(11.3)

The normalized sensitivity coefficients of the molecular weights are de-

(11.4)

(11.5)
(11.6)
(11.7)

(11.8)

TZOGANAKIS ET AL.

350

REFERENCES

121

Downloaded by [Technical University of Crete] at 08:34 14 September 2015

131
141

I201
[211

H. P. Frank. Polypropylene, Gordon and Breach Science Publishers, New York,


1968.
J. A. Biesenberger and D. H. Sebastian, Principles of Polymerization Engineering, Wiley, New York, 1983.
R . E. Green and E. T. Pieski, U.S. Patent 3,144,436 (1964), E. I. du Pont de
Nemours Co.
K. Babba, T. Shiota, K. Murakami, and K. Ono, Japanese Patent 7,379,X51
(1973), Surnitorno Chern. Co.: CA, 80 (1974).
P. Hudec and L. Obdrzalek, Agnew. Makromol. Chem., 89, 41 (1980).
H. G. Fritz and B. Stohrer, Intern. Polym. Proc., 1, 31 (1986).
T. J. Henman, in Developments in Polymer Stubilisation--l ( G . Scott, ed.),
Applied Science Publishers, London, 1979, p. 39.
T. J. Henrnan, in Degradation and Stabilisation of Polyolefins (N. S. Allen,
ed.), Applied Science Publishers, London, 1983, p. 29.
M. Rado, Int. Chem. E n g . , 2 , 482 (1962).
M. Dorn, Adv. Polym. Techn., 5 , 87 (1985).
C. Tzoganakis, J. Vlachopoulos, and A. E. Hamielec, Polym. Eng. Sci., 28. 170
(1988).
H. M. Hulburt and S. Katz, Chem. Eng. Sci., 19, 555 (1964).
C. D. Han, Rheology in Polymer Processing, Academic Press,New York, 1976.
F. N. Cogswell, Polym. Eng. Sci., 12, 64 (1972).
R . N. Schroff, L. V. Cancio, andM. Shida, Trans. Soc. Rheol., 21,429 (1977).
H. M. Laun and H. Schuch, paper presented at the Winter Meeting of the Society
of Rheology, Santa Monica, CA, 1987.
G. Ritzau, 45th Annual Technical Conference of the SPE, 546, 1987.
H.Westmijze, Akzo Chemie Netherlands, Personal communication, 1987.
W. Minoshima, J. L. White, and J. E. Spruiell, Polym. Eng. Sci., 20, 1166
(1980).
R. W. Atherton, R. B. Schainker, and E. R. Ducot, AIChE J . , 21,441 (1975).
I. M. Thomas and C. Kiparissides, J. Appl. Polym. Sci., 29, 2195 (1984).