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Feasible Compositions for Random Copolymerizations

RAYMOND L. SMITH* and MICHAEL F.MALONE

Department of Chemical Engineering


159 Goessmann Laboratory
University of Massachusetts Amherst
Amherst, MA 0 1 003

Using the attainable region approach, feasible compositions and conversions for
random copolymers are determined, along with alternatives for the related reactor
configurations. This analysis attempts to find all of the possible compositions that
can be produced by any system of reactors and mixing. The average copolymer
compositions are bounded by the feed composition and the instantaneous copoly-
mer composition produced at the initial conditions. Since the instantaneous
copolymer composition can be found through the Mayo-Lewis equation, that case
and the feed composition mark the limiting feasible compositions. The results can
also be used to determine the range of feed compositions for which a specific
copolymer product composition is possible. If the addition of monomer at any point
in the reactor system is possible, e.g., by side-feeding, the analysis indicates that
any desired copolymer composition can be obtained.

INTRODUCTION BACKGROUND
n designing a process to produce a copolymer it is
I useful to know the range of feed compositions which
can give a desired product, as well as the range of
The attainable region approach is a geometric
method for determining the feasible limits of additive
quantities in a system composed of reaction and mix-
product compositions one can obtain for any given ing processes. W i c a l additive quantities are concen-
feed. This information can be employed to generate trations, enthalpies, residence times, or moments of a
process designs which can make a single product distribution. Here, they are the average compositions
composition for various feeds and make a range of for a copolymer product.
product compositions for specified feeds. In either The attainable region concept was first articulated
case, it is interesting to know what is feasible and the by Horn (2).Glasser et al. (3)developed an approach
reactor systems that can achieve the limits of feasibil- to find these regions. Smith and Malone (1)used the
ity. approach for homopolymerizations to find the feasible
Because copolymer composition is such an impor- molecular weights and the corresponding limiting re-
tant factor in determining properties, it is interesting actor configurations.
to know the feasible limits for compositions. To deter- Mathematical and geometric representations of
mine these limits the attainable region approach, reaction and mixing processes are employed in the
used previously for homopolymers (1) is developed construction of regions of feasible compositions. The
here for random copolymers. The attainable limits of construction consists of finding the largest area (or
product compositions depend on several parameters, volume in three dimensions) that is (a) convex and
including the feed compositions and on whether the that (b) can not be extended by reaction. The reactor
feed composition is fixed or if one of the comonomers models and construction procedures described in lhis
can be added to alter the feed composition during the paper are based on the analyses of Hildebrandt and
course of polymerization. Both scenarios will be con- Biegler (4) and Feinberg and Hildebrandt (5).The
sidered here. reader is referred to these papers and references there-
in for more in-depth descriptions.
The reactors used in the construction of a feasible
region always include continuous stirred-tank reac-
'Corresponding author. Current address: U S . Environmental Protection Agency tors (CSTR) and plug-flow reactors (PFR). In some
26 W. Martin Luther King Drive M S 466 Cincinnati. OH 45268. smithray- cases, it is also necessary to include differential side-
mond@epa.gov(5131 569-7161 fax: (5131 569-7111. I h e work described ln this
paper has been presented at the 1999 National Meeting of the American Institute
stream reactors (DSR). For instance, Godon- et al. (6)
of Chemical Engineers. review the use of DSR reactors for three dimensional

POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2001, Vol. 41, No. 2 145
Raymond L. Smith and Michael F. Malone

problems, and in this work the DSR is used to adjust One reason it is difficult to guarantee that the full
concentrations in the reaction system while maintain- attainable region is found is the possibility for isolated
ing a fured feed composition. The CSTR is modeled as solutions (7). In the literature, necessary conditions
for finding the attainable region have been deter-
ci - ci0 = ri(c)t (11 mined, while sufficient conditions have not. Therefore,
where ciand ri are the concentration and the rate of while all the points which we determine to be part of a
production of i, respectively: ci0 is the feed concentra- region are feasible, this does not preclude the possi-
tion, and t is the reactor residence time. The PFR bility that a point outside the feasible region could be
model is obtained.
Important reactions which occur during free-radical
dci copolymerizations include initiator decomposition,
-= ri(c)
dt radical initiation, propagation, and termination. The
"terminal model" will be used to describe propagation
and the DSR model is
in this work. In the terminal model the reactivity of a
_
dCi - growing chain depends only upon the type of repeat
- ri(c) + a(c: - ci) (31 unit on the growing chain end and the type of mono-
dt
mer unit to be added (8).A typical scheme for copoly-
where CO is the concentration of the side-feed stream merizations is
and OL is the volumetric rate of side-feed added per
unit volume of reactor. The DSR is a PFR reactor that Initiation
has additional side-feed points along its length. For
practical purposes the side-feeds would be added at 1% 2R (4)
discrete points, but the mathematical model describes
the limiting case as a differential process.
R+M-%Pl (5)
We should point out that it is much simpler to find
candidates for the attainable region than to guarantee Propagation
that the entire region has been found. In fact, there is
no general method that can guarantee that a candi-
date is, indeed, the full attainable region. Therefore,
we use the term "feasible region" (or "candidate re-
gion") to denote a region of compositions that can be
obtained even though a larger attainable region may
exist. Nevertheless, many useful results can be gained
from examining the candidates and the corresponding
reactor types. Furthermore, all of the points in the
feasible regions can be obtained, and if these suggest
new reactor configurations or product compositions,
the main benefits of the exercise are gained.
To find the feasible region one employs a construc- Termination
tion procedure that begins with a feed and follows
paths generated from the reactor model equations
above for various increasing residence times. The fea-
sible regions are extended with additional reactors
and made convex by mixing. (Mixing is represented in
composition space as a line connecting two feasible
points.) To determine whether a convex re@on is the
feasible region, points along the boundaries are
checked to see if a reactor with that feed could extend
the region. The region can be extended if a "reaction Here, I is initiator, R is a primary radical, M is mono-
vector" (a vector made up of the rates of formation) mer, P,, and D, are growing chains and dead chains of
points outside of the region there. A reactor is added length n, respectively. Numbers in parenthesis refer to
at such a point. and once the region is convex (with monomers and chain ends of a particular type. When
added mixing lines if necessary) then the boundaries no parenthesis are present, either type of monomer
are checked again to see if reaction extends the re- unit or chain end is applicable. The symbols are used
gion. This process is repeated until the convex region above to represent molecules in the reaction scheme,
can not be extended, and therefore we have found the and later as concentrations. The reaction rate coefi-
best available candidate for the feasible region. cients are & for decomposition, k, for initiation, $ for

146 POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2001, Vol. 41, No. 2
Feasible Compositionsfor Random Copolymerizations

propagation, and for termination (by disproportiona- which in dimensionless form and in terms of conver-
tion). Note that one can easily add transfer reactions sions is
and other termination reactions to the scheme (9).
The long chain approximation allows the equations kp(12)A&l)(M(&- x2 - XI )
= kpcz l)G(2)(M($f (2 1)
for the monomer concentrations to be written in a With this approximation one can substitute fior A&,) or
simple form that includes only propagation reactions. A&,) in Eqs 16-1 9. Substituting for A:,,), the equations
For the isothermal PFR, are then divided through by A:(2), which is incorpo-
rated into the residence time as T = A&2) t. The result-
ing equations for the PFR are
kp(21) (M(:U- xd2 +

k p ( l l ) k p o( M & - 4

where t is the residence time and Aou) is the zeroth


moment of the molecular weight distribution for live
chains with a j-type unit on the chain end. The
monomer concentrations (in Eqs 1 3 and 1 4 ) can be
written in terms of the conversions of the monomers. kP(ZZ)(M& - XZ))(M(llf + M(21f) I231
The total conversion of both monomers is
which are equivalent to the Mayo-Lewis equ,ation for
M(1i.r - Y1) + %).r - Mm instantaneous copolymer compositions (IL 1). The
x, = x, + x, = (15) Mayo-Lewis equation is normally written in differen-
4 v + M(2U M(l)f+ M(2U tial form as dM(I,/dM(2,which is obtained by dividing
where M(i)f is the feed concentration of monomer i. Eq 22 by Eq 23.
The total conversion is used in gel effect correlations For the CSTR the equations are
(10).Equ~tions13 and 1 4 can be written in terms of
conversions as
Xl - x1.0 =

x, - x2.0 =

3)+
Equations 22-25 are autonomous: the results depend
only on the conversions of the two monomers, the ini-
where * indicates that the variable is scaled by the tial concentrations, and the reactor temperature.
total feed concentration of the monomers, M(llr + M(2F In discussing the feasible compositions it is useful
For isothermal CSTR the corresponding model to relate them to the monomer concentrations and ki-
equations are netic coefficients. The traditional method of express-
ing the kinetic coefficients is in the form of reactivity
ratios

where qois the conversion fed to the reactor.


A common assumption is that the total radical con- Dotson et al. (8) review the qualitative behavior in
centration and the concentration of radicals of each copolymerizations for various values of the reactiviiy
type remain at a quasi steady state, with the amounts ratios, e.g., r, > 1, r, 5 1; r, < 1, r2 < 1 and the effects
of each type of radical depending only on the cross of r, and r2 on the relationship between comonomer
propagation steps (8).Thus, and copolymer compositions. These reactivity ratios
are used to determine instantaneous copolymer com-
kP(1 2 h I)M(2)= kP(21) A W ) M (1) (20) positions in the Mayo-Lewis equation

POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2001, Vol. 41, No. 2 14.7
Raymond L. Smith and Michael F. Malone

where JcO is the mole fraction of component i in the


feed. Equation 28 is an instantaneous solution to the
differential form of Eqs 22 and 23.

FEASIBLE REGION FOR FREE-RADICAL


COPOLYMERIZATIONS
The feasible region for the compositions of copoly-
mers is found in terms of the conversions of both
monomers, x, and %. From these, x I / % gives the av-
erage molar ratio of monomer 1 to monomer 2 in the
copolymer while xl/xT gives the mole fraction of 1 in
the copolymer. (The feasible regions could be devel-
oped in terms of the concentrations of the monomers,
but conversions are more convenient.) x
MMA
We will consider two cases: 1) the initial feed to the
reactor system is fixed and only this feed can be
mixed during the construction of the region, and
2) the initial feed to the reactor system is set, but a
degree of freedom is added s o that either of the
monomers can be mixed individually at any point in
the reactor system in order to extend the attainable
products.
The example systems are isothermal copolymeriza-
tions of methyl methacrylate with vinyl acetate and
styrene with acrylonitrile. The kinetics for the methyl
methacrylate/vinyl acetate system have been taken
from Hamer et aL (10)with initiator decomposition ki-
netics for azobis(isobutyronite) (AIBN) from Schmidt
and Ray (12). For the styrene/acrylonitrile system the
kinetics were taken from Lin et al. (13)with the AIBN
initiator kinetics from Schmidt and Ray (12).

Specific Feed Compositions


For the case where the feed to the reactor system is
set (i.e., the feed composition can not be changed
from the initial composition) the feasible region is gen- Fig. 1 . Feasible regions for methyl rnethacrylate/vinyl
erated with CSTR and PFR reactor profiles and mixing acetate. Polymerization conditions are T = 70°C isothermal,
lines. Glasser et al. (3) explain that for regions con-
9 = 0.30 wt. AIBN. and monomer feed molefractwns, fi,o, of
a) 0.30, b) 0.50, and c) 0.70 methyl methacrylate.
structed in two dimensions, only mixing and CSTR
and PFR reactors are needed. The reactor profiles are
generated with Eqs 22-25 and in terms of the conver-
sions of the two monomers for a given mole fraction of
component 1 in the feed, fi.o.Examples of the feasible each part of the figure a PFR generates compositions
region for copolymerizations are shown as the shaded with the highest mole fraction of methyl methacrylate.
regions in Fig. I for the bulk isothermal copolymeriza- Figure 2a shows a PFR reactor system.
tion of methyl methacrylate (l)/vinyl acetate (2). The To show the maximum conversions for obtaining
reactor profiles start at the origin and proceed until all given desired copolymer compositions the results of
of the monomers are reacted. The slope of a line from Fig. I b are plotted in a different form in Fig. 3. At each
the origin passing through a point in the feasible re- point in the feasible region the total conversion is
gion describes a product composition in terms of the simply the sum of x,, and xvAc. Thus, it is easy
amounts of each monomer in the product. Figure I to transform the feasible region into a graph of co-
shows that the feasible copolymer compositions change polymer composition versus total conversion. The
dramatically with the feed composition. However, in shaded area in Fig- 3 corresponds to the feasible

148 POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2001, V O . 41, No. 2


Feasible Compositionsfor Random Copolymerizations

OR

Fig. 2. Reactor systems that define the boundaries of thefeasible region.

region of Fg.1 b. Therefore, conversions up to the PFR An interesting difference in these feasible regions is
profile on the edge of the shaded area in Fig. 3 can be that the curvature of the reactor profiles has changed:
obtained for given xMMA/xTvalues. Note that the where in Fig. 5a the profiles are curved downward, in
shaded area in Flg. 3 is not convex because one can- Fig. 5b the profiles are curved upward.
not mix conversions (i.e., concentrations) and mole The maximum conversions for obtaining desired
fractions on the same basis. copolymer compositions corresponding to the feasible
To show the attainable products over a wide range region of Fig. 5b are shown in Rg. 6. This iqure is
of feed compositions the maximum and minimum similar to Q. 3 for methyl methacrylate/vinyl acetate,
copolymer compositions are taken from diagrams except that the copolymer compositions obtained are
such as Fig. 3 and put together into one Figure (Q. lower in styrene than the mole fraction of styrene in
4). On this figure the feasible products are shown for the feed. This change in the orientation of the copoly-
particular values of the feed composition. One can mer composition versus total conversion Figure is a
also use this figure in the reverse manner by choosing reflection of the change that occurs in the feasible re-
a copolymer composition and finding the range of feeds gions (i.e., the above described change in curvature of
that are able to produce it. Examples where reactor the reactor profiles). More evidence of these changes
system design alternatives are developed for given de- are seen in Fig. 7, which shows a composite graph of
sired copolymer compositions are presented by Smith the feasible copolymer compositions for given feeds (or
(9). range of feeds for a desired copolymer composition).
Before discussing general results, a second example The crossing of the equal monomer and copolymer
system of styrene (1) and acrylonitrile (2) is consid-
ered. The feasible region for a copolymer rich in acry-
lonitrile is shown in Ftg. 5a, in which one can see that
-
composition line by the curve of limiting compositions
(atfm,.o 0.60) is known as an “azeotrope”because
the feed and product compositions do not change
the conversions of acrylonitrile are much higher than from this point by reaction (in analogy to azeotropes
those for styrene, and so the products with this feed in vapor-liquid equilibrium whose compositions do
composition,fsrr.o = 0.15, will have more acrylonitrile not change on boiling). The result in the feasible re-
in them. A different picture is available when the feed gions is seen in the change in curvature of the PFR
composition is rich in styrene, fmo = 0.80 (Fig. 5b). profiles for the two cases shown in Fig. 5 , whei-e

POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2007, Vol. 47, NO. 2 149
Raymond L. Smith and Michael F. Malone

X
T
Fig. 3. Product compositions that arefeasible at various conversionsfor afeed molefraction ofJMm,o = 0.50 methyl rnethacylate.

Fg.4. Thefeasible copolymer compositions of methyl methacrylate/vinyl acetatefor different feeds, or thefeed molefractions which
can produce a particular product composition.

150 POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2007, Vol. 41, No. 2
Feasible Compositionsf o r R a n d o m Copolymerizations

the curve of limiting copolymer compositions in Fig. 4,


a s well a s the corresponding curve in Fig. 7 for
styrenelacrylonitrile (rl = 0.386 and r2 = 0.06). Thus,
the Mayo-Lewis equation can be used to find the same
limiting copolymer compositions as the feasible re-
gion. The reason the results are the same is that the
feasible region analysis found that PFR reactors near
zero conversion generate the highest compositions,
while the Mayo-Lewis equation gives the instanta-
neous compositions, which are exactly the same. In
fact, the differential form of the Mayo-Lewis equations
(Eqs 22 and 23) are our PFR reactor equations. If the
X
reactivity ratios (i.e., propagation rate coefficients)
STY changed with conversion, as previously suggested and
then refuted by O’Driscoll et al. (14),it is possible that
CSTR reactors (shown in Fig. 2b) would generate
points on the boundaries of copolymer feasible re-
gions. in other words, because a CSTR reacts every-
thing at the same conditions, it can exploit any extreme
in the reactivities, just as it exploited low termination
rate coefficients to generate high molecular weights for
homopolymers (1).We have not found any copolymer-
ization systems where there is a substantial change in
the reactivity ratios with conversion.
The point of maximum conversion on the feasible
region and composition versus conversion figures
can also be easily obtained. The point of miaximum
conversion in the feasible region, Figure 1 b, is in
the center of the diagram where xM = xVAc= 0.50.
X The copolymer composition (as given by the slope
ACR xm/xvAc) at this point of complete conversion is the
Fg. 5. Feasible regions for styrene/acrybnitrik. Poiymeriza- same as the feed composition. In other worcls, when
tion conditions are T = 70°C isothermal, r/ = 0.30 wt.AlBN, both monomers react completely, the feed composi-
a n d monomerfeed mole fraction. fi,o.of a)0.15 and b) 0.80 tion is regained-for the copolymer compositicln. How-
styrene.
ever, the distribution of compositions can bc narrow
or broad depending on whether a CSTR or PFR, re-
spectively, is used (15).This point, where the copoly-
mer composition matches the feed composition at
complete conversion, is shown at the far right in F‘ig 3
the copolymer compositions are initially close to the (xMm/xT = 0.50). In both figures one can mix the
azeotropic composition and then move away toward comonomer feed into the product and obtain lower
the feed composition. total conversions. This mixing of feed with the effluent
A n example of the opposite curvature in the feasible of a PFR or CSTR is shown in Fig. 2c. Thus, the diago-
regions is seen for reactivities rl > 1 and rz > 1 shown
nal mixing line in Fig. I b between complete conver-
in Fig. 8. Dotson et al. (8) indicate that examples sion and the origin and the horizontal line in Fig. 3
where both reactivities are greater than one for free- are obtained with minimal effort. More effort is needed
radical copolymerizations are rare, so we have used to find the upper boundary of the feasible region,
the styrene/acrylonitrile kinetics from Lin et al. (13) which in all of our examples is a PFR reactoi- profile.
with rl = 10 and r, = 20. Notice that the reactor pro- Generating the feasible region provides results on the
files start near the edges of the diagram and work in maximum conversions at which one can obtain de-
towards the feed composition, as opposed to Fig. 5 sired copolymer compositions (for given feeds, e.g..
where the reactor profiles start near the center and Fig. 3).
work outwards.
After constructing a number of copolymer feasible Mixing of Additional Monomer Streams
regions, we can anticipate some general results. In
particular, it is interesting to see how simply some In a second case we generate the feasible region
points of the region can be obtained. For instance, using a specified feed composition and then add a de-
solving Eq 28, the Mayo-Lewis equation, for various gree of freedom by allowing the pure monomer(s)to be
feed compositions for the methyl methacrylate/vinyl mixed into the reactor system. While this monomer
acetate system (rl = 22 and r, = 0.04) one obtains feed could be added at discrete points in the reactor

POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2001, Vol. 41, No. 2 151
Raymond L. Smith and Michael F. Malone

X
STY

X
T
Fig. 6. Product compositions that arefeasible at various conversionsfor afeed molefraction of fsry..o = 0.80 styrene.

X
STY

X
II’

J3g. 7. The feasible copolymer compositionsfor styrene/acylonitrilefor different feeds, or the feed molefractions which can produce
a particular product composition.

152 POLYMER ENGINEERING AND SCIENCE, FEBRUARY 2001, Vol. 41, No. 2
Feasible Compositionsfor Random Copolymerizations

CONCLUSIONS
The feasible region for free-radical copo1,periza-
tions h a s been developed for the conversions of
monomers in the system. Examples of copolymeriza-
tions between methyl methacrylate/vinyl acetate and
styrene/acrylonitrile show the approach. The feasible
region figures show how the different propagation ki-
netics affect the feasible products. For a specific feed
composition methyl methacrylate/vinyl acetate copoly-
mers are always richer in methyl methacrylate than
the ratio given in the feed (or equal to the feed at com-
plete conversion), while styrene/acrylonitrile copolly-
X
Z mers tend to cross propagate and so favor products of
intermediate composition.
For a specific feed composition the limiting copoly-
mer compositions are simple to determine. The aver-
age copolymer composition at complete conversion is
the same as the feed composition, because everything
is reacted, although the composition distribution
could be broad. The other limiting copolymer compo-
sition was found to be generated by PFR reactors at
small conversion. This is the same result a s an in-
stantaneous copolymer composition based on the
monomer concentrations. The common method for
determining the instantaneous copolymer composi-
tion is to use the Mayo-Lewis equation, and therefore
the limiting composition can be determined alge-
X braically. While both the complete conversion and in-
2 stantaneous copolymer compositions give the limits of
Fig. 8. Feasible regions for a system with r, = 10 and r, = feasibility, the feasible region is needed to determine
20. Polymerization kinetics taken from styrene/acrylonitrile the maximum conversions at which a desired copoly-
with reactivity ratios shown T = 70°C isothennat, I 0.30 mer composition is possible. As a result of this analy-
wt. AlBN, and monomer feed molefractions, fi,o o j i 0.25
and b) 0.90. sis it was determined that PFR reactors form the
boundary of the feasible compositions, and therefore,
a PFR obtains the highest copolymer compositions.
By allowing for the addition of pure monomers to
the reactor system it was determined from the feasible
region that any copolymer composition could be
system, the continuous limit is a differential side- achieved for the systems studied. I t appears that this
stream reactor (DSR),which is represented by Fig. 2d. is a general result of using differential side-stream or
[Note that in an analogy to the mathematically similar the mathematically equivalent semibatch reactors.
PFR and batch reactors, the corresponding reactor for Finally, with the attainable region approach1 for the
a DSR is a semibatch reactor.) Since a DSR is a PFR feasible copolymer compositions one can determine
with a changing feed composition along its length, we
whether a specific feed will generate a desired prod-
can use Eqs 22 and 23 where the monomer feed con- uct, or whether different or additional feeds are neces-
centrations, M(,u.+ M(,lf. are adjusted by the monomer sary. This approach also finds the maximum conver-
side-feed. Note that this also affects the conversions sions for desired copolymer compositions. Finding
as given by Eq. 15. This is expected since conversion these composition and conversion limits is a first step
is based on the total feed to the reactor system. in the conceptual design of copolymerizationprocesses.
The consequence of the ability to have any mono-
mer composition in a DSR at any point, is the feasible
region shown in Fig. 9. Any copolymer composition is REFERENCES
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POLYMER ENGlNEERlNG AND SCIENCE, FEBRUARY 2001, Vol. 41, No. 2 163
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X
2

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