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Chemical Engineering Science, Vol. 43, No. 3, pp. 429-442. 1988. ooo5-2509/88 s3.00 + 0.

00
Punted in Great Britain Q 1988 Pcrgamon Journals Ltd.
ANALYSIS OF THE ROLE OF STRIPPING AGENTS IN
POLYMER DEVOLATILIZATIONt
K. RAVINDRANATH and R. A. MASHELKAR
Polymer Science and Engineering Group, Chemical Engineering Division, National Chemical Laboratory,
Pune 411008, India
(Received 4 October 1986; accepted in revised form 25 May 1987)
Abstract-A comprehensive model has been developed to analyse the process of polymer melt devolatiliz-
ation in the presence of a stripping agent, which performs the function of enhancing the molecular diffusion
of the desorbing monomer and reducing the interfacial concentration. The problem leads to a coupled set of
non-linear partial differential equations with time dependent boundary conditions. This problem has not
been solved in the literature so far. The model enables the prediction of the influence of diffusivity ratios,
relative volatility, hydrodynamic conditions, etc. on the devolatilizer performance and provides useful
guidelines for the selection of a suitable stripping agent. The strategy developed in this work can be also used
for related problems of multicomponent desorption in other systems.
1NTRODUCTlON
The problem of polymer devolatilization is frequently
encountered in polymer synthesis and polymer proces-
sing operations. Generally the aim is the removal of
residual volatile monomer present in the polymer
(Biesenberger and Sebastian, 1983). Invariably the
polymer contains solvents, water and low molecular
weight compounds. All these volatile components
must be removed to improve the product quality,
reduce the product cost and eliminate health hazards.
When the concentration of monomer is rather high
polymer devolatilization is generally carried out by
using flash evaporators. During this stage volatile
components are removed through the formation of
vapour bubbles. Newman and Simon (1980) and
Amon and Denson (1984) have developed effective
models for analysis this stage of devolatilization. In the
final stages of polymer devolatilization, the concen-
tration of monomer is further reduced to the desired
level (usually to the ppm level). During this stage, the
rate of monomer removal is limited by diffusional
limitations. Therefore, single screw extruders and twin
screw extruders, which can generate high interfacial
areas and promote convective mixing, are widely used.
A number of models have been developed for analys-
ing the process of devolatilization in single screw
extruders (Latinen, 1962; Coughlin and Canevari,
1969; Roberts, 1970; Biesenberger and Kessidis, 1982)
and in twin screw extruders (Todd, 1974; Collins et al.
1985; Secor, 1986). All these models provide valuable
guidelines for determining the efficiency of monomer
removal rate. In addition, these models have been used
for estimating the effective transport coefIicients and
for examining the influence of screw extruder design
parameters on the devolatilization process.
In many industrial operations, stripping agents (also
known as carrier substances) are added to the polymer
t NCL Communication No. 4150.
to improve the devolatilization performance. For
instance, for removing styrene from polystyrene,
Werner (1980) found that addition of 3 / , water helped
in reducing the styrene content from 820 to 420 ppm
under otherwise identical conditions. The effectiveness
of addition of water as a stripping agent on desorption
of ethylene from low density polyethylene melt in
partially filled twin screw extruder can be seen from the
data presented in Fig. 1 (Werner, 1980). In such cases
desorption of the two volatile components occurs
simultaneously and the simplified models developed in
all the references cited in the foregoing cannot be used
since they have not taken into account two major
factors. In the presence of a stripping agent, the
fractional free volume of the polymer is increased,
which can lead to a significant increase in the diffusivity
of the monomer which is supposed to be removed.
Similarly, the partial pressure of the monomer is also
reduced which again helps in removing the residual
monomer. We will elaborate on these later.
It is important to mention here a recent interesting
paper by Vrentas et al. (1985) which tackles a related
problem. They developed a model for devolatilization
occurring in a film. In their model the film is initially
assumed to contain a small amount of monomer and
the film is then exposed to a gas stream containing a
stripping agent. During this process the absorption of
stripping agent and the desorption of the monomer is
assumed to take place simultaneously. After a par-
ticular time the gas stream is replaced by an inert
stream, so that desorption of both the components can
take place. They found that the stripping agent can
substantially aid the monomer removal process. Their
model is not directly applicable, when the stripping
agent is added in the beginning of devolatilization
process.
The devolatilization of a polymer melt is generally
carried out in a partially filled screw extruder under
high vacuum and the stripping agents are added in the
beginning of the operation itself. In such a case, the
429
K. RAVINDRANATH and R. A. MASHELKAR
16
i I I Illll I I
10' 2 3 5 102 2 3 5 10s
PRESSURk,mbar
1. Enhancement of devolatilization of low density polyethylene by using a stripping agent (Werner.
1980).
exact extent of vacuum applied plays an important role
and the interfacial concentrations cannot be assumed
to be zero or for that matter to have a constant finite
value independent of time. In fact the interfacial
concentrations will change with time and a time
depedent boundary condition at the interface has to be
used. An additional complication arises due to the
great sensitivity of the value of molecular diffusivity of
small solutes in polymeric media to small changes in
the concentration of volatiie components. Indeed a
small change in the fractional free volume in the
molten polymer as a result of the presence of a small
molecular weight monomer can alter the diffusivities
by an order of magnitude (Duda and Ni, 1978).
A realistic model for monomer removal from poly-
mer melts in the presence of a stripping agent requires
incorporation of al! the above-mentioned complexities,
whereas none of the earlier papers consider these
aspects. There are no guidelines available in the open
literature regarding selection of suitable stripping
agents. The influence of the concentration of the
stripping agent, diffusivity and the vapour pressure of
the stripping agent on the devolatilization process has
not been quantitatively examined in the past. We
believe that our work provides important guidelines in
this regard.
There are two additional motivations behind this
work. Ravindranath and Mashelkar (1984, 1985, 1986)
have analysed the final stages of polycondensation
involved in the manufacture of polyethylene tereph-
thalate. They show that in the presence of side
reactions, the rate of polycondensation is actually
enhanced, rather than reduced. This is essentially due
to the augmentation of the desorption of the key
volatile component in the presence of other volatile
components which are formed as a result of side
reactions. One expects similar phenomena to occur in
the presently considered case of simultaneous desorp-
tion of two volatile species from a polymeric melt.
Additionally, and perhaps more surprisingly, there
appear to be no prior analysis of the case of simul-
taneous desorption of two volatile species even in the
case of low molecular weight systems. The present
study thus serves the general purpose of providing
framework for analysing these cases too.
MATHEMATICAL MODEL FOR DEVOLATILIZATION IN A
MOLTEN POLYMER FILM
Any model developed for devolatilization in a single
screw or a twin screw extruder should incorporate the
following specific aspects:
-Desorption from the flowing melt pool and from
the film deposited on the barrel wall
-The presence ofcirculatory flow of the polymer melt
- The influence of backmixing.
Stripping agents in polymer devolatilization 431
In the present work a mathematical model will be
developed mainly for the process involved in the first
step mentioned above, namely devolatilization in a
thin stagnant film. This model can then be used for
developing a complete model for single screw or twin
screw extruders.
Consider a thin stagnant molten polymeric film of a
finite thickness placed on a solid impermeable surface.
Initially the polymer film has a thickness L and it
contains a small amount of monomer (pl 0) and
stripping agent (pzO). At time t = 0, the polymer film is
exposed to vacuum, which assigns a specific value of
concentration of monomer and stripping agent at the
interface (x = L). The thickness of the film is assumed
to be very small. Hence the monomer and the stripping
agents are assumed to be removed only through the
interface. In the present analysis of ternary diffusion
process, it is assumed that p, and p2 are sufficiently
small so that the cross diffusion coefficients can be
neglected compared to the principal diffusion coef-
ficients (Vrentas et al., 1985). Then the mass balance
equations for unsteady state diffusion in a finite film
can be written as
a~, a apI
-=- D,-
at ax
( >
ax
dP2 a
-=_
at dX
( >
D dp2
2 ax
(1)
Here p1 is the mass density and D, is the diffusivity of
component 1. Subscript 1 refers to the monomer and
subscript 2 refers to the stripping agent. The boundary
conditions are
p, = p,,; p2 = p20; t = 0, 0 Q .X 6 L
(3)
3PI
-=o; +o: t>o,x=o
at
(4)
PI = Pli; P2 = PZii
t > 0, x = L.
(5)
pIi and pzi refer to the concentration of components 1
and 2 at the interface. The gas phase resistance is
assumed to be negligible due to the low pressures
employed in the devolatilization process. The concen-
tration of the monomer and the stripping agent will be
assumed to be small. Therefore the variation of film
thickness with time is neglected. The self diffusion
coefficients D1 and D2 depend on the concentration of
the diffusing species. These are given by Vrentas et al.
(1985).
exp -
(WI @:
+w,P:
D, = D,,exp -
(WI p: &/<I 3 + WI2 p;I + w3 Vf 523)
VFFilY
V
FH-
Y
- +,, + T- T,,)w,
+f+& + T-T&w,
++(K2 + T- T&w,.
(8)
Here D, 1 is the pre-exponential factor for component
I, w1 is the mass fraction of component I and @ is the
specific critical hole free volume of component I for a
jump. Here subscript 3 refers to the polymer. P,, is the
average free volume per gram of mixture and y is the
overlap factor for free volume. The parameters K, ,,
K
21, K~I. Kzz, K,,
and K2, are free volume par-
ameters, which can be determined from the solvent and
polymer viscosity data (Duda et a[., 1982). T is the
temperature and T,, is the glass transition temperature
for component I. 5 1 3 and tz3 are the ratios of critical
molar volume of components 1 and 2 to the critical
molar volume of jumping unit of polymer.
Equations (lk(5) are nondimensionalised using the
following variables
B = D;/D:
0: = D, (pl = 0; ,u2 = 0)
0; = Dz(pl = 0; pr = 0).
Equations (l)-(5) are now converted to
(13)
(14)
(15)
(18)
aM*
---=Q
aM2
all
-=Q e>o; q=o
3T
(19)
The mass fractions of component 1 and 2 were
calculated by using the following equations:
Ml
W
=M,+M,+M,
M,
w2 = M,+M1+M3
(21)
(22)
where Mj = V,. (23)
To proceed with the actual calculations, the initial
mass fractions of component 1 and 2 were fixed and
pIo and pzo
are calculated from the following
432 K. RAVINDRANATH and R.A. MASHELKAR
expression:
WlO
PI0 =
w20
Pzo = -
v/lw,.+ Vzw,,+ Psw,,'
w
The solution of eqs (16) to (20) can be found, once the
values of the following parameters are known: PI, P:,
K>,/Y (K>,+ T-T&~,,,<z~, B,w~~/w~~,w~*/w~,P~i
and pZi. Vrentas et al. (1985) have discussed the
possible range of values for 8,, fit, K J y (K2, + T
- r,,), 5 1 3 and
tz3 and these have been used in the
present work (see Table 1). The value of p depends on
the type of stripping agent used. w10/w30 and w20/w30
are the input parameters. pli and pZi depend on the
applied vacuum.
Cakulation of interfacial concentrations (p ,i and p,,)
In the limit of very low concentrations of p ,iand pZi,
we assume that the Flory-Huggins theory for binary
mixtures (Biesenberger and Sebastian, 1983) can be
used to describe the theormodynamics of the ternary
system. Then the partial pressure of component 1 and
2, in the simplified form, can be written as
PI =P?+I exp(l+X,)=P~P,p,iexp(l+X,) (26)
p2 = Pz$Z exp(1 +x,) = PT vZ pZi exp(l +x,). (27)
Here Py is the pure component vapour pressure, 41 is
the volume fraction and x1 is the polymer-solvent
interaction parameter for component I. Rearranging
eqs (26) and (27) and expressing p1 and pz in terms of
the applied vacuum (P), we get
and
(29)
where CL = PI Pye +XI and 6 = Pyel+xz/Pyel +x1.
While analysing the devolatilization process of a
single component, all the previous workers (Latinen,
1962; Coughlin and Canevari, 1969; Denson, 1983)
have assumed p ,i to zero. With such an assumption, the
exact effect of vacuum on devolatilization cannot be
analysed. In addition for a fixed applied vacuum, pli
and pzr are not constant for the case of desorption of
Table 1. Typical properties of monomer, stripping agent and
polymer (Vrentas et al., 1985).
Property
Stripping
Monomer agent Polymer
1 2 3
P: (cm3/d
0.90 0.90
3; (cm3/g)
0.80
1.20 1.20 0.90
K,,lY w,, + T- T,,)
(cm/iz) 0.40 0.40 0.05
513 0.75 0.75 -
x1
0.5 0.5
Table 2. Some typical systems where simultaneous desorp-
tion of two comoonents is encountered
System
Desorbing volatile
components
1.
II.
Removal of reaction
byproducts
(1) Polyethylene
terephthalate
(2) Polybutylene
terephthalate
(3) Nylon 6
Removal of residual
monomer
(1) Polystyrene
(2) Polymethyl
methacrylate
(3) Low density
polyethylene
Ethylene glycol, water and
acetaldehyde
Butanediol, water and
tetrahydrofuran
Caprolactum and water
Styrene and water (stripping
agent)
Methyl methacrylate and
water (stripping agent)
Ethylene and water (stripping
agent)
two components. Indeed they vary with time. The
interfacial concentrations (eqs 28 and 29) depend on
the vapour composition, which is in turn determined
from the desorption rates of components 1 and 2. But
the individual desorption rates can vary with time due
to the continuous change in diffusivity value and also
due to the continuous change in the concentration
profile of the components in the film. Therefore, p1,
and pZi will change with time. We now propose a new
procedure for calculating pl, and pzi as a function of
time. If p 11 and pZi values at time f3 are known, p li and
pr, at 0 + A8 can be determined by proceeding the
following steps.
(1) Assume p ,, and pZ, values at 8 + A6, based on the
values at time 8.
(2) Calculate the desorption rates of components 1
and 2 from the following equations.
N, =;
s
t+At
_-D ap, dt
@fAO
L?x
= ___ __
f x=L
(3)
(4)
D, aM,
--~
0: h- q=,
d6, (30)
s
t+At
OfAO
____
I
(31)
Because of the sharp gradients at the interface a
specially developed method (described in the
Appendix) is used for calculating N, and N,.
With these values of N 1 and N z, calculate the mole
fraction of the components in the vapour phase
from
N1
= N,+N2
N2
y2 =Nl+N,
Calculate p ,i and pzi using eqs (28) and (29).
(32)
(33)
Stripping agents in polymer devolatilization
(5) If the calculated and assumed values of p ,, and pzi
are not within a prescribed error bound ( 4 0.1 /,),
repeat steps (1) to (4).
While writing eqs (32) and (33), it is assumed that the
vapours are removed at the same rate as they are
formed and there is no backmixing in the vapour
phase. This is true only for devolatilization in a thin
stagnant film considered in the present work. For
devolatilization in an extruder, the calculation of p li
and pZi is more involved, since the vapours formed at
time f are mixed with those formed at time t + At.
Therefore the vapour at the outlet or the extruder will
represent as average composition of the vapours
formed at different times. This important fact has to be
taken into account for developing a complete model
for screw extruders.
RESULTS AND DISCUSSION
It has been customary to analyse the performance of
a devolatilization process in terms of the fraction of
extractable components remaining unextracted, fi 1.
6
1
= PI-Pli
PlO -P,,
(34)
As we have already pointed out earlier, pi, is assumed
to change with time. Hence eq. (34) is not useful for
presentation of the results. Therefore we shall analyse
the effectiveness of the devolatilization process in
terms of the following parameters.
433
s
1
M, =
MI dv; (35)
0
1
iii, =
s
Mzdv.
0
(36)
Here A, represents the fraction of the monomer
remaining in the polymer. R, represents the ratio of
the amount of stripping agent in the polymer to the
initial amount of monomer. In the present work, all the
calculations are performed assuming that the polymer
contains initially one percent of monomer (w,~/w~~
= 0.01).
influence of stripping agent on desorption (a = 0)
As mentioned earlier, the previous workers have
assumed pli to be zero, which is equivalent to the
assumption of c1 = 0 in the present work. The effect of
the initial concentration of a stripping agent on i\;i, is
shown in Fig. 2 for cc = 0 and p = 0. When /I = 0, the
diffusivity of the stripping agent is zero and it is not
removed from the system. With an increase in the
initial concentration of the stripping agent, the free
volume of the polymer increases (see eq. 6), hence
D, /Dy also increases. Therefore, R, decreases dra-
matically with an increase in the stripping agent
concentration as shown in Fig. 2.
However, such a dramatic reduction cannot occur
when the finite diffusivity of the stripping agent is
taken into account (p # 0). The influence of the
molecular diffusivity of stripping agent is shown in
Fig. 2. Effect of stripping agent concentration on fi,, u = 0, fi = 0.
434 K. RAVINDRANATH and R.A. MASHELKAR
0 0.1 0.2 o-3 o-4 O-5 0.6 0.7 0.6 0.9 1.0
8
Fig. 3. Effect of diffusivity ratio (8) on M,; M,, = 2, x = 0.
Fig. 3 for the specific case of a = 0 and for a fixed
initial concentration of the stripping agent. Larger
values of /3 imply faster removal of the stripping agent
too. Such rapid removat implies in turn that the
contribution of the stripping agent towards the in-
crease of overall free volume would decrease as time
progresses. This would mean that the favourable
influence of the presence of stripping agent in enhanc-
ing the diffusivity of the monomer would reduce too.
One concludes that stripping agents with large values
of p offer no long term advantage, and stripping agents
which have low to moderate values of ,!I must be used.
In the latter case, the stripping agent will remain in the
molten polymer for extended periods and aid in the
process of monomer removal. Note that this obser-
vation is valid only in the case of OL = 0. When 01 is finite,
we get different results depending on the devolatiliz-
ation time, as we shall see later.
Influence of applied vacuum or desorptionfor a single
component system (a =fi ni l e)
In Figs 2 and 3, the effect of applied vacuum on M, is
not taken into account. Its influence on M, is now
shown in Fig 4. The value of cr depends both on the
applied vacuum as well as on the pure component
pressure (eq. 28). For typical polystyrene-styrene
system, the value of cc changes from 0.001 to 0.01 at
171C (Biesenberger and Sebastian, 1983), when the
applied vacuum is varied from 1 to 10 kPa (which are
typical operating pressures of single screw extruder).
As intuitively expected, increasing the vacuum (lower
values of a) helps in decreasing A, at a faster rate.
Depending on the applied vacuum (u), the final value
of M, at longer times is fixed due to equilibrium
considerations. For obtaining very low values of M,,
the devolatilization process has to be operated at high
vacuum.
Simultaneous itxjiuence of applied vacuum and stripping
agent on desorption
ti, can be reduced effectively by adding small
amounts of stripping agents. This is shown in Fig. 5 for
a fixed applied vacuum (x = 0.003). M, decreases
continuously with an increase in &?,,. The addition of
stripping agent leads to a decrease in the effective
partial pressure of monomer in addition to influencing
the overall free volume of the polymer. This aids the
desorption process. However, the concentration of the
stripping agent cannot be increased continuously since
the heat input for vaporizing the stripping agent in the
devolatilizer will also increase. The effect of a stripping
agent on the devolatilization process for different
values of a is shown in Fig. 6. It can be seen that the
influence of stripping agent is more pronounced at
lower levels of vacuum (higher c() in comparison to that
at higher levels of vacuum (lower r). This important
observation can be explained as follows. At higher
values of CL, the stripping agent is effective both in
Stripping agents in polymer devolatilization
3
I I
2
o*oi
0 o- 1 0.2 0.3 0.4 0.5 0.6 0.7 O-6 0.9 1.0
Fig. 4. Effect of operating vacuum on 8,; MzO = 0
1-o
s
3
2
xi, 0.1
5.
3
o-01
0 0. 1 0.2 0.3 o-4 O-5 O-6 0.7 O-8 0.9
Fig. 5. Effect of stripping agent concentration on M,; o! = O.W3, fl = I,6 = 1.
CES 43:3-c
436 K. RAVI NDRANATH and R. A. MASHELKAR
2
0.01
0
o-1 o-2 o-3 0.4 o-5 O-6 o-7 0.6 o-9 I .0
0
Fig. 6. Effect of operating vacuum on ml with (-- ) and withouttPPP) stripping agent; Mzo = 2, p = 1,
6 = 1.
increasing the free volume of the polymer and in
reducing the partial pressure of monomer. As c( -+ 0, p ,i
approaches zero and the stripping agent is effective
only in increasing the free volume of the polymer.
Therefore the stripping agent is less effective as c( + 0.
The effectiveness of stripping agent in reducing the
monomer concentration to a very low level can be seen
from Fig. 6. For instance at 6 = 1 (fixed residence time
in extruder) and c( = 0.001 (fixed vacuum) we can
reduce A, from 0.113 to 0.06 by addition of a stripping
agent.
Influence of the diffuusit;ity of stripping agent on
desorption
Another important parameter in the devolatilization
process is the ratio (fi) of the diffusivity of-the stripping
agent to the diffusivity of the monomer. Earlier (see
Fig. 3), we examined the influence of /? for a = 0. There
we concluded that stripping agents with low values of p
are preferable. Now the influence of fi for the case of
finite LY ( = 0.003) is shown in Fig. 7. When b = 0, we see
that &f, reduces rapidly initially and then reaches a
plateau of A, = 0.237. The initial rapid decrease is
ascribed to the increased diffusivity of the monomer
due to the enhanced free volume contribution by the
stripping agent. However, when p = 0, the stripping
agent is not removed from the system and the contri-
bution of the stripping agent towards the reduction of
partial pressure is zero. Thus at longer times (Q > 0.4)
the minimum value of n;i, is determined by
vapourliquid equilibrium considerations alone and
reaches a plateau.
For moderate values of fi( = 0.1 and l), the stripping
agent also continuously desorbs from the system.
While it is present in the system it contributes both to
enhancement of free volume (leading to enhanced
diffusivity of monomer) and also to reduction of
partial pressure of the monomer, the latter effect is
predominant particularly at longer time scales. Hence
M, continues to decrease continuously. For high finite
values of p( = lo), we have a curious observation. Due
to the high diffusivity of the stripping agent in
comparison to that of the monomer, it is rapidly
removed at short times. Its effectiveness, therefore, in
contributing to the enhancement of monomer desorp-
tion rate is negligible.
The above observations offer important clues for the
selection of a stripping agent, in that agents with very
low or high values of/i should not be selected but those
with moderate values of ,8( = 0.1 to 1) are the preferred
ones.
Influence of stripping agent in the very low concen-
tration regime
In the results discussed so far, we have considered
the effect of stripping agent both on the free volume of
the system (leading to a change in the diffusivity of the
monomer) and also the change in partial pressure.
Stripping agents in polymer devolatilization
Fig. 7. Effect of diffusivity ratio (fi) on &f,; A?,, = 2, OL = 0.003, 6 = 1.
Recent environmental regulations imply that one has
to reduce the monomer concentration to very low
levels (few ppm). In such cases, the amount of stripping
agent added itself will be negligible and its influence on
the free volume of the system will also have to be
neglected. It is instructive to consider such a case.
When the free volume contribution of the stripping
agent is neglected D, E 0: and D, = D;.Now the role
of the stripping agent is only in decreasing the partial
pressure. When the diffusivity of the stripping agent is
less than the diffusivity of monomer (namely p < 1),
the partial pressure contribution of the stripping agent
is not significant as compared to the case when @ = 1.
Therefore &f , values for /? = 0.1 are always higher in
comparison to those for p = 1 as shown in Fig. 8. For
j? = 10, the contribution of the stripping agent is
maximum up to a certain time and j%f 1 becomes smaller
when compared to the results for j3 = 1. During this
time, most of the stripping agent is removed and its
contribution at longer times decreases. In the case of
p = 1, the contribution of the stripping agent is
significant even at longer times. Therefore L@, is
minimum for /Y = 1 even at longer times compared to
the corresponding results obtained with finite p values
considered in this work. For selecting the stripping
agent, not only its diffusivity but also the time for
devolatilization should be taken into account. There is
a limiting design value for p in such cases, in that the
diffusivity of the stripping agent should
equal to the diffusivity of the monomer.
be at least
Znfluence of vapour pressure of the stripping agent
(6 + 1)
In all the previous calculations, the ratio of vapour
pressures of stripping agent to the monomer is taken as
unity (i.e. 6 = 1). The influence of change of 6 on ti, is
shown in Fig. 9. In the case of 6 + 0, the stripping agent
has very low vapour pressure and therefore it con-
tinues to remain in the system. The qualitative trend in
this case is similar to the one in the case of p + 0
including the attainment of a plateau. On the other
hand for finite values of 6, as expected, the desorption
is more rapid.
I nfluence of periodic mixing of the-film
So far, the film was considered to be stagnant (or
unmixed) during the devolatilization process. In actual
practice, the film is mixed at definite intervals (depend-
ing on the screw speed in the extruder). Therefore it is
important to examine the influence of mixing on the
devolatilization process.
We assume that the film remains stagnant and it is
exposed to the vacuum for a fixed interval of time (@,),
and then the film gets mixed. At the end of each such
mixing operation, the average concentration of the film
was calculated by averaging over the length of the film.
438 K. RAVINDKANATH and R. A. MASHELKAR
O-01
0 0.1 o-2 0.3 o-4 0:5 0.6 0.7 O-6 o-s 1-o
8
Fig. 8. Effect of diffusivity ratio (8) on A%, without considering free volume contribution; MZO = 2,
a=0.003,6= 1.
3
2
O-01 I 1
0 0.1 0.2 0.3 o-4 0.5 O-6 0.7 O-6 0.9 t-0
8
Fig. 9. Effect of vapour pressure of the stripping agent on M,; M,, = 2, a = 0.003, 6 = 1.
Stripping agents in polymer devolatilization
0.01 \
0 0. 1 0.2 0.3 o-4 0.5 O-6 0.7 0.0 0.9 1. 0
8
Fig. 10. Effect offilm mixing on M, ; MzO = 2, a = 0.003, fi = I,6 = 1; (a) ideal&d penetration theory; (b, c,
d) present model.
This average concentration provided the starting con-
centration for the next intervals. The results obtained
are shown in Fig. 10. In all the cases examined here
mixing is shown to help in decreasing the A, value. By
mixing at regular intervals, large concentration
gradients are created at the interface, which are
essential for attaining high desorption rates.
It may be mentioned that recently Sector (1986) has
developed a mass transfer model for a twin screw
extruder by using periodic mixing of a film. The
calculations provided here can be easily incorporated
in such a model to enable the development of a
complete model for a devolatilizing extruder (see,
however, the discussion on the limitations of such an
approach in certain regimes presented later).
The rol e of ti me dependent boundary condi ti ons i n the
two component desorpti on probl em
As pointed out earlier, the concentration of the
monomer (pJ at the interface is expected to change
with time. When B = 0, however p ,i remains constant
(Fig. 1 l), since the stripping agent does not contribute
towards reduction of the partial pressure of the
monomer. Similarly for /3 = I, p 1, remains constant
since the desorption rates of the monomer and the
stripping agent at any time remain proportional to the
initial concentrations of the monomer and stripping
agent. For /I < 0.1, p Li increases in the beginning and
then decreases as shown in Fig. 11. The desorption
rates of monomer and stripping agent depend on the
value of difTusivity and on the concentration gradient
at the interface. In the beginning, for p = 0.1, the
desorption rate of monomer is greater than that of the
stripping agent. The mole fraction of monomer in the
vapour phase increases and hence p ,i increases (see eq.
28). When a part of the monomer is removed from the
system the rate of desorption of monomer will be less
than the rate of desorption of the stripping agent.
Therefore, p li will then decrease as shown in Fig. 11.
Similar explanation can be offered in the case of the
results obtained with B = 10 also.
In desorption processes occuring in low molecular
weight systems, the influence of stripping agent on free
volume is negligible and only the diffusivity ratios (p)
and vapour pressure ratios (6) for the two components
need to be considered. When /3 - 1 and 6 - 1 the
problem is decoupled and the time invariant boundary
conditions at the interface can be safely used. However,
in the case when the diffusivities or the vapour
pressures of the two components are not equal (p # 1,
6 # 1) the interfacial boundary conditions will change
as a function of time, and then the methods developed
in this work have to be used,
Li mi tati ons of the penetrati on theory approach
A majority of the workers (Latinen, 1962; Roberts,
440 K. RAVINDRANATH and R. A. MASHELKAR
I - C )-
I-
i
,_
I
p 0.1
10
5 I-
3
2
0.01 L
/ I 1
1 I I
/
0 o-1 o-2 o-3 o-4 o-5 0.6 0.7 O-6 C
8
Fig. 11. Effect of diffusivity ratio (/?) 017 M,, pl,/p,o; = 2, a = 0.003, 6 = 1.
1970; Denson 1983; Secor, 1986) analysing the per-
formance of the devolatilization equipment have used
the penetration theory. It is instructive to compare the
model results of the present work with those obtained
by using the penetration theory. The penetration
theory predicts that the rate of desorption is given by
(37)
Here t, is the exposure time, a is the interfacial area,
and D, is the diffusion coefficient of the desorbing
monomer. D, can be assumed to be constant only in
the case of very low monomer concentration regime.
D, otherwise will be a function of monomer concen-
tration. Hence it is both time and position dependent.
The interfacial concentration /3,i is constant only
for the single component desorption process and it is
determined by the applied vacuum alone. For a two
component desorption process, p ,i will vary with time
depending on the diffusivity of the second volatile
component. In fact most of the previous workers
(Latinen, 1962; Roberts, 1970; Secor, 1986) have as-
sumed pli to be equal to zero for analysing the
devolatilization data. What errors can such simplified
assumptions introduce in the model predictions? This
can be illustrated by using D, = 07 and p ,i = 0.
Equation (37) for the rate of desorption then reduces
to
J
40:
y.
e
Following Secot (1986) the material balance for vol-
atile component 1 after the first exposure is given by
p*o = p: + t,N,.
(39)
Substituting eq (38) in (39) gives
Pt _l_ 40,
PlO :-
7t
(40)
where 0, = DytJ L. Assuming that the film is mixed
after every exposure, the concentration of volatile
component after n exposures is given by
ii;&_ /40,\
PI0 \ \i 7t /
where n = 0/G,.
The left hand side of eq. (41) is equal to ti, by
definition (eq. 35). We now plot the predictions from
eq. (41) in Fig. 10 for Be = 0.01. Wecompare the results
of eq. (41) with our results for 0, = 0.01. When
Q -C 0.15, eq. (41) predicts higher values of &?f, com-
pared to our results and for 8 > 0.15 the reverse is true.
This observation can be explained as follows. At small
Stripping agents in polymer devolatilization 441
values of 8, we have D1 > 0: due to the free volume
contribution of the monomer and the stripping agent.
The rate of desorption calculated based on our model
is higher compared to that calculated from eq. (38).
Therefore &Ii, values are lower for our model in the
beginning. At longer times p r -+ /, ti because of equilib-
rium considerations and the rate of desorption ap-
proaches zero. Hence ti, reaches a plateau level. In the
derivation of eq. (41), p ,i is taken as zero. Therefore the
rate of desorption is significant even at longer times
and ti, values continues to decrease.
Subscript zero indicates the initial
values
distance in the x-coordinate
polymer-solvent interaction par-
ameter for components 1 and 2
mole fraction of monomer and strip-
ping agent
CONCLUSION
Stripping agents are commonly added to aid the
process of devolatilization in polymer melts. These
agents have a dual function of enhancing the molecular
diffusivity of the desorbing monomer and also in
reducing the interfacial concentration of the monomer.
Proper incorporation of these factors leads to a set of
coupled equations with time variant boundary con-
ditions, a problem that has not been tackled in the
prior literature. The present work develops a mathe-
matical model and also a solution strategy which could
be used in a broad range of problems. More specifically
the model results can be used for ascertaining the
influence of diffusivity ratios, relative volatilities, etc.
on the process of devolatilization and consequently
also for selection of suitable stripping agents. The
present model can be easily incorporated in more
comprehensive models of total systems, such as twin
screw devolatilizers.
a
DI, Dz
fim
n
NI, N,
NOTATION
interfacial area
diffusion coefficients for monomer
and stripping agent
limiting values of D, and Dz at p1 = 0
and p2 = 0
thickness of the film
dimensionless parameters as defined
in eqs (9), (10) and (23).
fraction of monomer remaining in the
polymer
ratio of the amount of stripping agent
present in the polymer to the initial
amount of monomer
value of M, at 0 = 0
number of exposures
desorption rates of monomer and
stripping agent
average desorption rate
applied vacuum
vapor pressure of monomer and strip-
ping agent
devolatilization time
exposure time
molar volume of monomer, stripping
agent and polymer
weight fraction of monomer, stripping
agent and polymer, respectively.
Greek symbols
cc
PI? P2
3;
Subscripts
0
i
1
2
3
parameter as defined in eqs (28) and
(29)
parameter as defined in eq. (13)
parameter as defined in eq. (29)
dimensionless film thickness ( = x/L)
dimensionless time as defined in eq.
(12)
dimensionless exposure time
( = D:t,/L2)
mass density of monomer and strip-
ping agent
average mass density of monomer
after n exposures
values at H = 0
values at the interface (x = L)
monomer
stripping agent
polymer
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1
-J
~+A@D, akf, s+AeaM,
-__
Secor. R. M.. 1986. A mass transfer model for twin screw
AtJ B 07 aq =I
dt, =A
JJ
---ddBdq
0 B
ae
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1
=-
s
A0 o
(Ml le+ao -MI I s) ds WV
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D:P,o 1
J

30, 449945 16.
Wcrncr, H., 1980, in Deuofntilization of Plastics, pp. 99-131.
Verrin Deutscher Ingenieure Dusseldorf. VDI-
Gesselschart Kunststoftechnik.
N,=p-
(A3)
L.
W,le---Mle+& dtl.
A0 o
Similarly by integrating eq. (17). We obtain
P
4
e+AO D2 dM1
-__
APPENDIX A@ * DZO atl g=1
dH = &
s
I
(Mz Iti+Ae - Mz le)drl
0
Equation (16) can be integrated with respect to n leading to
(A4)
and

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