784 J. Chem. Eng.

Data 1995, 40, 784—791

Vapor-Liquid Equilibria of Copolymer + Solvent and Homopolymer

+ Solvent Binaries: New Experimental Data and Their Correlation
Ram B. Guptaf and John M. Prausnitz*
Department of Chemical Engineering and Chemical Sciences Division, Lawrence Berkeley Laboratory,
University of California, Berkeley, California 94720-1462

Sixty-four isothermal data sets for vapor—liquid equilibria (VLE) for polymer + solvent binaries have
been obtained using a gravimetric sorption technique, in the range 23.5—80 °C. Solvents studied were
acetone, acetonitrile, 1-butanol, 1,2-dichloroethane, chloroform, cyclohexane, hexane, methanol, octane,
pentane, and toluene. Copolymers studied were poly(acrylonitrile-co-butadiene), poly(styrene-co-acry-
lonitrile), poly( styrene-co-butadiene), poly(styrene-co-butyl methacrylate), poly( vinyl acetate-co-ethylene),
and poly(vinyl acetate-co-vinyl chloride). All copolymers were random copolymers. Some homopolymers
were also studied: polyacrylonitrile, polybutadiene, poly(butyl methacrylate), poly(ethylene oxide),
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polystyrene, and poly(vinyl acetate). The composition of the copolymer may have a surprising effect on
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VLE. Normally, deviation from ideal behavior lies between those of the constituent homopolymers,
according to the copolymer composition, as observed for cyclohexane + poly(ethylene-co- vinyl acetate)
and chloroform + poly(styrene-co-butyl methacrylate). However, the strong nonideal behavior observed
for systems containing hydrocarbons and poly(butadiene-co-acrylonitrile) shows that the effect of
acrylonitrile is in excess of that expected from the copolymer composition. The perturbed hard-sphere
chain (PHSC) equation of state was used to represent VLE of the copolymer solutions studied here.

Introduction of a solvent in a polymer solution (Danner and High, 1993).

These include inverse gas chromatography, piezoelectric
Vapor-liquid equilibria (VLE) in polymer + solvent
systems are necessary for a variety of applications includ- sorption, differential vapor pressure, gravimetric sorption,
ing surface acoustic-wave vapor sensors (Ballantine and light scattering, and turbidimetry analysis. We have used
a gravimetric sorption technique because it gives direct
Wohltjen, 1989; Grate et al., 1992), recovery of organic
vapors from waste-air streams using a polymeric mem- measurement of the VLE of polymer + solvent systems.
brane (Baker et al., 1987; Matsumoto et al., 1991), per- This classic method has been described in detail by
vaporation (Maeda et al., 1991) and other polymeric Panayiotou and Vera (1984). Figure 1 gives a schematic
membrane-separation processes, polymer devolatilization of the apparatus. A copolymer or homopolymer sample in
an aluminum pan is suspended by a sensitive, calibrated
(High and Danner, 1990), vapor-phase photografting (Kubo-
ta et al., 1990), and optimum formulation of paints and quartz spring in an evacuated glass chamber. The glass
coatings (Napper, 1983). For rational process and product chamber is kept in a constant-temperature air bath. In a
design, we require experimental data and correlations typical experiment, a known amount (25-50 mg) of poly-
based on molecular thermodynamics. mer is loaded onto the pan and evacuated to remove any
Copolymers are gaining an increasing amount of com- trace moisture, oligomers, or monomers present. Now the
mercial interest because of their unique physical properties. length of the spring is measured with a cathetometer to
World production of copolymers has been continuously find the polymer mass, using a predetermined calibration
rising over the last 20 years (Wohlfarth, 1993). However, curve. Solvent vapor is introduced into the evacuated
published VLE studies for copolymer + solvent are rare. system by quickly opening and closing the solvent valve.
Some experimental results (Bonner and Prausnitz, 1974; The system is allowed to equilibrate for several hours;
Corneliussen et al., 1963; Iwai et al.,1990; Moore and subsequent pressure and spring-length readings yield
Shuttle worth, 1963; Panayiotou and Vera, 1984) describe pressure as a function of polymer-phase composition.
copolymer + solvent VLE for finite solvent concentrations. Readings are taken with increasing pressure. All experi-
By contrast, there are about 1000 data sets published for ments are at pressures below 90% of the saturation vapor
homopolymer + solvent systems (Wohlfarth, 1994). There pressure to avoid solvent condensation in the system.
is a need for more experimental studies for copolymer Quartz springs (Ruska Instruments Corp., Houston, TX)
solutions. This work contributes toward meeting that need. have a sensitivity of 1 mg/mm with the maximum load limit
The purpose of this work is to obtain VLE data for of 250 mg. These springs are equipped with reference
copolymer + solvent binaries and for some of their parent pointers on the top and bottom of the spring. Quartz spring
homopolymer + solvent binaries and to examine the effect calibration (length versus mass, a linear correlation) is
of copolymer composition on VLE. The experimental data
independent of temperature in the range of interest (23—
are correlated using an equation of state based on molec-
80 °C). The buoyancy effect on the calibration was also
ular thermodynamics.
negligible. Spring length was measured using a cathetom-
Experimental Section eter with a precision of 0.05 mm. Hence, mass was
measured with a precision of 0.05 mg. The typical error
Apparatus and Procedure. Several experimental
in the measurements of mass fraction solvent in the solvent
methods are available for measuring the vapor pressure
+ polymer mixture, wi, was about 2%.
*
To whom correspondence should be addressed.
+
Present address: Department of Chemical Engineering, Auburn Pressure was measured using a mercury manometer
University, Auburn, AL 36849. kept at the same temperature as that of the polymer
0021-9568/95/1740-0784$09.00/0 © 1995 American Chemical Society
 Journal of Chemical and Engineering Data, Vol. 40, No. 4, 1995 785

m m
Figure Experimental apparatus for VLE measurement of
1.
cd cd
u ©

polymer + solvent binary solutions. (Here VLE of two polymers © CO CO

with a common solvent can be measured simultaneously.)

solution. There was no solvent condensation on the 0.

E
mercury meniscus as the system pressure was always lower to

than the solvent saturation pressure. The pressure was

measured with a precision of 0.1 kPa, except in the cases
of cyclohexane (23.5 °C), octane (60 °C), and toluene (23.5
°C) where the precision was 0.01 kPa. The temperature
of the air bath was controlled within 0.5 °C of the set point.
The reproducibility of the experimental procedure was
checked by comparing our VLE data with literature values
(Bawn et al., 1950; Kun et al., 1993) for the toluene +
polystyrene system at 35 °C. Good agreement was ob-
served.
Materials. All polymers were supplied by Scientific
Polymer Products (SPP), Ontario, NY, except poly(butyl
methacrylate) which was from Aldrich. These polymers
are listed in Table 1 along with their molecular weight
(Mw), polydispersity (MJMn), and glass-transition temper-
ature (tg). For copolymers, the mass percent compositions
of the two constituent polymer segments are specified. All
copolymers used here were random copolymers. Glass-
transition temperatures for copolymers were calculated w
¿k
from the Fox—Flory equation bpPu
-§Ph ^ co oo to © in©in©©«-tio^coLomtocooo
co co co co © TfoCOOlOOOlCOO^COCO©©
h m in m co coin^HcocoinomcotM>oo
v d
1
Kt%
+ 273.15) =
F/(ígl + 273.15) + F2/(tg2 + 273.15) *c
P

& m^t©ininot>©in©o©©©xco-^coin©
(1) oo&copy;incoao<N&copy;&copy;&copy;oo&copy;coincoH&copy;['-TtC'-t>
Mil I ^ Ml I I
r7l T1
<9
-C
where tg = glass-transition temperature of the copolymer, &copy; i-H rf CO &copy; TH

tgi and tg2

=
glass-transition temperatures of parent sN ^ cd ^ ^ in co

homopolymers, and F\ and F2 = mass fractions of mono- o

&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;
&copy;

&copy;

a
mers 1 and 2, respectively. All temperatures are in degrees
&copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy;

&copy; &copy; in&copy; &copy; -sf- 00 in&copy; &copy; &copy;

r-l 00 00 in 00 co i-i
Celsius.
&copy; &copy; &copy;

&copy;HH CO rH CO CO rH
in
Ontario,

Both copolymers and homopolymers had polydisperse

molecular weights. These were used without further -S
cd

fractionation because the polymer molecular weight has 9 9 0 to

—V
to
o
^o x
o
.2 .2 .2
negligible influence on the VLE behavior provided the § § to
Products,

to to *3
molecular weight is above about 10 000 (see, for example, 9 "É 9 c P
C P to
.2 .2 E
: jp -c
“

e c
-0-0-0 O
' ce *£ >
Kun et al. (1993) and Bonner and Prausnitz (1974)). 000
o -a
ce
—
>) 6 ó ó
*·
&copy; &copy;

V V V to o v V V V
Solvents were used after degassing by a freeze/thaw p
to 3
-r
cd 9 .

-µ
V i
_

cd
to
cd
_to _to
cd cd
V
to
cd
Polymer

"E "E 'E &

^
¿ *?
procedure described by Panayiotou and Vera (1984). 3 E •2
-3 “
3
®
V
IP
&copy;

£ 3
cd
to to to to

Experimental Data. Table 1 gives a summary of all

&copy;,Z>

i9 & & &

•Sj¡ g to
V
to
c i 1
P
^
ce
to -r·
to >> p
«e
>>
—

9 9 9 9
d d d d

the new data obtained in this study. Table 2 gives 1 e

Scientific

to to to
5 Cd Cd Cd
cd e > '> "> ’> ’>

lli
=

experimental VLE data for polymer + solvent binary ^co ^m ^ ^ ^ #

"

« H CO rl SÍ &copy; &copy; &copy; CO &copy;

systems. Most of the experiments were performed at a g co co m

315 S >>>>>!
co ^ m > &copy; co m t> h
SPP
3* Z1 >>>>>>>>
temperature higher than the glass-transition temperature S.S.S.S.S.S.S.S.B.S.S.S.S.S.S.S.S.Í
of the polymer. A total of sixty-four data sets were obtained
786 Journal of Chemical and Engineering Data, Vol. 40, No. 4, 1995
Table 2. New Experimental Vapor-Liquid Equilibrium Data for Polymer + Solvent Systems (u>i =
Mass Fraction
Solvent in Polymer Phase, t =
Temperature, and P =
Pressure)
P/kPa wi P/kPa wi P/kPa w i P/kPa wi P/kPa w\ P/kPa wi P/kPa wi P/kPa ici
Acetone + Poly(styrene-co-butadiene) 1-Butanol + Poly(vinyl acetate)

Acetone + Poly(5% styrene-co-butadiene) t 80 °C

=

2.7 0.005 8.0 0.036 12.3 0.092 15.2 0.012

t = 50 °C 5.2 0.018 10.8 0.081 13.9 0.011
13.7 0.003 45.3 0.067 51.1 0.078 59.6 0.115
26.5 0.023 46.5 0.072 52.3 0.079 59.7 0.110 1-Butanol + Poly(vinyl acetate-co-ethylene)
36.3 0.040 47.2 0.067 53.3 0.080 61.3 0.120
41.5 0.056 47.3 0.066 55.2 0.091 1-Butanol + Poly(9% vinyl acetate-co-ethylene)

Acetone + Poly(23% styrene-co-butadiene) t =

80 °C
2.7 0.006 8.0 0.017 12.3 0.031 15.2 0.036
i = 50 °C 5.2 0.012 10.8 0.027 13.9 0.034
26.5 0.024 46.5 0.075 52.3 0.088 59.6 0.125
36.3 0.049 47.3 0.058 53.3 0.091 59.7 0.120 1-Butanol + Poly(vinyl acetate-co-vinyl chloride)
41.5 0.061 51.1 0.085 55.2 0.100 61.3 0.130
45.3 0.071 1-Butanol + Poly(12% vinyl acetate-co-vinyl chloride)

II
CD o °C t 80 °C
=

12.7 0.009 54.8 0.062 81.3 0.128 91.5 0.183 2.7 0.007 8.0 0.022 12.3 0.040 15.2 0.046
26.4 0.021 68.5 0.092 84.8 0.147 97.9 0.231 5.2 0.016 10.8 0.033 13.9 0.044
40.7 0.037
1,2-Dichloroethane + Polyacrylonitrile
Acetone + Poly(styrene 45%-co-butadiene)
t = 70 °C
t = 50 °C 16.3 0.025 30.8 0.043 40.7 0.050 46.0 0.058
13.7 0.004 45.3 0.074 51.1 0.088 59.6 0.137 21.2 0.031 36.5 0.046 43.9 0.054 49.1 0.061
26.5 0.022 46.5 0.078 52.3 0.092 59.7 0.130 26.7 0.040
36.3 0.046 47.2 0.074 53.3 0.095 61.3 0.141
41.5 0.061 47.3 0.071 55.2 0.105 t =
80 °C
22.4 0.017 36.3 0.024 50.1 0.044 59.5 0.057
II
o O 27.3 0.020 45.7 0.038 57.6 0.053 60.7 0.060
12.7 0.009 54.8 0.069 81.3 0.140 91.5 0.197
26.4 0.023 68.5 0.101 84.8 0.163 97.9 0.258 1,2-Dichloroethane + Polystyrene
40.7 0.044
t = 70 °C
Acetone + Poly(50% styrene-co-butyl methacrylate) 16.3 0.064 30.8 0.152 40.7 0.244 46.0 0.306
21.2 0.092 36.5 0.209 43.9 0.289 49.1 0.352
t =
60 °C 26.7 0.127
8.9 0.005 43.3 0.044 81.7 0.133 95.9 0.201
16.8 0.013 51.6 0.053 85.3 0.144 98.7 0.224 t = 80 °C
23.5 0.022 60.3 0.071 90.4 0.164 100.4 0.254 22.4 0.070 36.3 0.125 50.1 0.257 59.5 0.360
34.7 0.027 67.6 0.090 27.3 0.090 45.7 0.221 57.6 0.331 60.7 0.377

Acetonitrile + Polyacrylonitrile 1,2-Dichloroethane + Poly(70% styrene-co-acrylonitrile)

t 60 °C
=
t = 70 °C
6.7 0.011 18.3 0.032 32.5 0.061 37.9 0.076 16.3 0.009 30.8 0.139 40.7 0.243 46.0 0.296
13.3 0.022 23.2 0.041 21.2 0.026 36.5 0.196 43.9 0.281 49.1 0.339
26.7 0.048
Acetonitrile + Poly( acrylonitrile-co-butadiene)
t 80 °C
=

Acetonitrile + Poly(21% acrylonitrile-co-butadiene) 22.4 0.009 36.3 0.090 50.1 0.279 59.5 0.376
27.3 0.039 45.7 0.251 57.6 0.348 60.7 0.389
t 60 °C
=

6.8 0.011 26.1 0.065 34.1 0.112 39.3 0.187 Chloroform + Poly(33% acrylonitrile-co-butadiene)
13.7 0.026 30.1 0.085
t =
60 °C
Acetonitrile + Poly(33% acrylonitrile-co -butadiene) 13.6 0.080 26.9 0.172 52.8 0.372 66.3 0.485
26.8 0.170 39.6 0.262 59.9 0.424 73.3 0.563
t =
60 °C
6.7 0.023 18.3 0.065 32.5 0.148 37.9 0.206 Chloroform + Poly(cis-l ,4-butadiene)
13.3 0.043 23.2 0.091
t =
60 °C
Acetonitrile + Poly(51% acrylonitrile-co-butadiene) 13.6 0.114 26.9 0.228 52.8 0.444 66.3 0.548
26.8 0.224 39.6 0.336 59.9 0.494 73.3 0.615
t 60 °C
=

6.8 0.021 26.1 0.111 34.1 0.182 39.3 0.293 Chloroform + Poly(butyl methacrylate)
.

13.7 0.047 30.1 0.144

t =
70 °C
Acetonitrile + Poly(c¿s-l,4-butadiene) 13.3 0.093 40.1 0.268 65.5 0.434 86.0 0.566
26.4 0.176 53.6 0.347 78.8 0.520
t =
60 °C
6.7 0.010 18.3 0.017 32.5 0.030 37.9 0.039
13.3 0.010 23.2 0.024
 Journal of Chemical and Engineering Data, Vol. 40, No. 4, 1995 787
Table 2. (Continued)
P/kPa W1 P/kPa W1 P/kPa Wl P/kPa W1 P/kPa Wl P/kPa Wl P/kPa wi P/kPa ¡Cl

Chloroform + Polyethylene oxide) Cyclohexane + Poly(51% acrylonitrile-co-butadiene)

t 60 °C
=
t 60 °C =

14.0 0.082 53.2 0.459 66.1 0.540 79.2 0.585 13.7 0.007 26.1 0.024 32.0 0.032 39.7 0.060
28.1 0.276 58.4 0.497 72.3 0.567 87.1 0.609 19.1 0.011 26.4 0.024 35.6 0.047 43.1 0.091
40.1 0.379 19.6 0.015

Chloroform + Poly(50% styrene-co-butyl methacrylate) Cyclohexane + Poly(cis-l,4-butadiene)

t 70 °C
= t =
60 °C
13.3 0.078 40.1 0.222 65.5 0.369 86.0 0.512 13.5 0.082 26.9 0.189 33.6 0.272 38.1 0.338
26.4 0.148 53.6 0.292 78.8 0.455 20.3 0.134

Chloroform + Poly(styrene-co-butadiene) Cyclohexane + Poly(styrene-co-butadiene)

Chloroform + Poly(5% styrene-co-butadiene) Cyclohexane + Poly(5% styrene-co-butadiene)

t = 50 °C t =
60 °C
8.5 0.040 31.6 0.272 47.6 0.489 53.7 0.580 4.8 0.027 19.9 0.120 29.5 0.189 37.6 0.276
16.3 0.106 38.3 0.341 50.0 0.537 56.4 0.638 10.5 0.057 24.8 0.152 33.7 0.233 40.7 0.323
25.5 0.204 45.5 0.457 16.9 0.103

Chloroform + Poly(23% styrene-co-butadiene) Cyclohexane + Poly(23% styrene-co-butadiene)

t = 50 °C t =
23.5°C
8.5 0.046 31.6 0.270 47.6 0.482 53.7 0.566 2.00 0.015 4.53 0.074 7.64 0.197 10.03 0.328
16.3 0.111 38.3 0.338 50.0 0.514 56.4 0.621 2.99 0.035 6.83 0.141 9.03 0.276
25.5 0.206 45.5 0.449
t = 60 °C
Chloroform + Poly(45% styrene-co-butadiene) 4.8 0.018 16.9 0.088 29.5 0.168 37.6 0.244
10.5 0.052 24.8 0.136 33.7 0.208 40.7 0.287
t 50 °C
=

8.5 0.043 31.6 0.272 47.6 0.500 53.7 0.592 Cyclohexane + Poly(45% styrene-co-butadiene)
16.3 0.107 38.3 0.343 50.0 0.534 56.4 0.650
25.5 0.205 45.5 0.463 t = 23.5 °C
2.00 0.011 4.53 0.063 7.64 0.176 10.03 0.301
Chloroform + Poly( vinyl acetate) 2.99 0.028 6.83 0.127 9.03 0.253

t 60 °C
= t 60 °C =

14.0 0.088 53.2 0.334 66.1 0.416 79.2 0.466 4.8 0.021 19.9 0.103 29.5 0.163 37.6 0.240
28.1 0.150 58.4 0.371 72.3 0.444 87.1 0.490 10.5 0.050 24.8 0.130 33.7 0.200 40.7 0.282
40.1 0.245 16.9 0.087

Chloroform + Poly( vinyl acetate-co-ethylene) Cyclohexane + Poly(vinyl acetate-co-ethylene)

Chloroform + Poly(9% vinyl acetate-co-ethylene) Cyclohexane + Poly(25% vinyl acetate-co-ethylene)

t = 60 °C t =
80 °C
14.0 0.031 53.2 0.147 66.1 0.196 79.2 0.235 7.5 0.011 39.7 0.140 55.5 0.238 64.1 0.300
28.1 0.067 58.4 0.168 72.3 0.216 87.1 0.253 14.4 0.037 54.9 0.228 60.7 0.277 70.4 0.369
40.1 0.104 26.5 0.074

Chloroform + Poly(25% vinyl acetate-co-ethylene) Cyclohexane + Poly(50% vinyl acetate-co-ethylene)

t = 60 °C t =
80 °C
13.9 0.062 39.9 0.228 59.9 0.358 73.1 0.441 7.5 0.005 39.7 0.104 55.5 0.170 64.1 0.225
26.7 0.140 53.2 0.320 66.5 0.401 79.3 0.481 14.4 0.025 54.9 0.159 60.7 0.205 70.4 0.287
26.5 0.046
Chloroform + Poly(50% vinyl acetate-co-ethylene)
Cyclohexane + Poly(70% vinyl acetate-co-ethylene)
t = 60 °C
13.9 0.098 39.9 0.303 59.9 0.439 73.1 0.512 t 80 °C =

26.7 0.202 53.2 0.398 66.5 0.477 79.3 0.552 7.5 0.004 39.7 0.081 55.5 0.133 64.1 0.191
14.4 0.026 54.9 0.123 60.7 0.156 70.4 0.242
Chloroform + Poly(70% vinyl acetate-co-ethylene) 26.5 0.042

t = 60 °C Hexane + Polyacrylonitrile
13.9 0.059 39.9 0.287 59.9 0.450 73.1 0.526
26.7 0.161 53.2 0.403 66.5 0.489 79.3 0.573 t = 60 °C
12.4 0.001 25.1 0.007 36.0 0.007 43.3 0.009
Cyclohexane + Poly( acrylonitrile-co-butadiene)
Hexane + Poly( acrylonitrile-co-butadiene)
Cyclohexane + Poly(21% acrylonitrile-co-butadiene)
Hexane + Poly(21% acrylonitrile-co-butadiene)
t 60 °C
=

13.7 0.030 32.0 0.114 35.7 0.176 39.7 0.216 t = 60 °C

19.6 0.062 35.6 0.177 38.1 0.210 43.1 0.283 12.9 0.025 38.8 0.082 50.8 0.134 63.7 0.236
26.4 0.084 25.6 0.044 44.5 0.104 57.5 0.170 64.9 0.251
788 Journal of Chemical and Engineering Data, Vol. 40, No. 4, 1995

Table 2. (Continued)
P/kPa Wi P/kPa W1 P/kPa w i P/kPa W1 P/kPa wi P/kPa w i P/kPa w\ P/kPa w\
Hexane + Poly(33% acrylonitrile-co-butadiene) Pentane + Poly{acrylonitrile-co-butadiene)

t =
60 °C Pentane + Poly(21% acrylonitrile-co-butadiene)
12.4 0.002 25.1 0.017 36.0 0.026 43.3 0.037
t = 60 °C
Hexane + Poly(51% acrylonitrile-co-butadiene) 22.8 0.008 65.5 0.033 97.3 0.055 124.8 0.078
36.0 0.016 84.0 0.046 113.3 0.070 137.6 0.089
t =
60 °C 46.8 0.021
12.9 0.018 38.8 0.029 50.8 0.041 63.7 0.062
25.6 0.020 44.5 0.033 57.5 0.044 64.9 0.062 Pentane + Poly(33% acrylonitrile-co-butadiene)

Hexane + Poly(cis-l,4-butadiene) t 60 °C
=

13.3 0.009 64.7 0.027 89.7 0.036 115.7 0.050

t 60 °C
=
26.9 0.014 77.5 0.032 101.7 0.044 130.1 0.055
12.4 0.036 25.1 0.078 36.0 0.115 43.3 0.146 53.5 0.025

Hexane + Poly( styrene-co-butadiene) Pentane + Poly(51% acrylonitrile-co-butadiene)

Hexane + Poly(23% styrene-co-butadiene) t 60 °C

=

22.8 0.010 65.5 0.019 97.3 0.022 124.8 0.027

t 70 °C
—
36.0 0.009 84.0 0.022 113.3 0.026 137.6 0.034
13.9 0.014 38.5 0.063 61.5 0.162 75.2 0.262 46.8 0.013
27.3 0.043 48.8 0.110
Pentane + Poly(czs-l,4-butadiene)
Hexane + Poly(45% styrene-co-butadiene)
t 60 °C
=

t = 70 °C 13.3 0.012 64.7 0.061 89.7 0.095 115.7 0.134

13.9 0.016 38.5 0.061 61.5 0.155 75.2 0.249 26.9 0.024 77.5 0.082 101.7 0.117 130.1 0.155
27.3 0.038 48.8 0.103 53.5 0.046

Methanol + Poly (vinyl acetate) Pentane + Poly( styrene-co-butadiene)

t =
80 °C Pentane + Poly(23% styrene-co-butadiene)
13.6 0.021 39.9 0.041 65.7 0.062 79.1 0.080
28.4 0.030 52.5 0.053 t = 60 °C
22.8 0.008 65.5 0.033 97.3 0.055 124.8 0.078
Methanol + Poly(10% vinyl acetate-co-vinyl chloride) 36.0 0.016 84.0 0.046 113.3 0.070 137.6 0.089
46.8 0.021
t = 80 °C
13.6 0.029 39.9 0.032 65.7 0.037 79.1 0.038 Pentane + Poly(45% styrene-co-butadiene)
28.4 0.030 52.5 0.037
t 60 °C
=

Octane + Poly( acrylonitrile-co-butadiene) 22.8 0.010 65.5 0.019 97.3 0.022 124.8 0.027
46.8 0.013 84.0 0.022 113.3 0.026 137.6 0.034
Octane + Poly(21% acrylonitrile-co-butadiene)
Toluene + Poly(styrene-co-butadiene)
t = 60 °C
2.90 0.036 5.08 0.064 6.91 0.111 8.41 0.158 Toluene + Poly(23% styrene-co-butadiene)
4.19 0.052 5.91 0.079
t =
35 °C
Octane + Poly(51% acrylonitrile-co-butadiene) 0.90 0.029 3.04 0.032 4.83 0.037 5.48 0.038
2.08 0.031 4.36 0.037
t 60 °C
=

2.85 0.007 5.08 0.013 6.91 0.021 8.41 0.026 Toluene + Poly(5% styrene-co-butadiene)
4.19 0.010 5.91 0.015
t =
35 °C
Pentane + Polyacrylonitrile 0.93 0.043 3.04 0.184 4.83 0.416 5.48 0.513
2.08 0.099 4.36 0.319
t 60 °C
=

13.3 0.005 64.7 0.010 89.7 0.010 115.7 0.011

26.9 0.007 77.5 0.010 101.7 0.010 130.1 0.011
53.5 0.011

by varying the solvent, copolymer composition, and tem- theory successfully reproduces all types of observed liquid-
perature. liquid equilibrium phase diagrams, including upper or
lower critical solution temperatures (UCST or LCST), or
Brief Summary of Theory for Correlation. To model
VLE of copolymer solutions, we have used a perturbed both, and closed partial-miscibility loops (Song et al.,
1994c).
hard-sphere chain (PHSC) equation of state (Song et al.,
1993, 1994a—c). For ordinary VLE at low pressures, it is The PHSC equation of state is applicable to fluid
often possible to use the Flory—Huggins theory for a mixtures containing any number of components over the
reasonable correlation of polymer + solvent VLE data, but entire range of fluid conditions. Since the PHSC equation
we would like to use a model that can describe both upper of state uses molecular parameters that have physical
and lower critical solution temperatures and VLE phase significance, it provides a potentially useful method for
diagrams at high pressures and account for solvent com- predicting thermodynamic properties outside the range of
pressibility. For binary polymer solutions, the PHSC available data.
 Journal of Chemical and Engineering Data, Vol. 40, No. 4, 1995 789
The PHSC equation of state for heteronuclear chains is

—-=1+i=lj=l
££* */ k=ll=l
-

m ri—1 mm ri rj

*; ^,µ+i
i=l k=l
-u- ^ ^ ^(2)
i=l/=l A:=1Z=1

where p = pressure, 71 = absolute temperature, = number

density, m = number of components, x = mole fraction,
= Boltzmann constant, a = attractive energy parameter,
b = second virial coefficient of hard spheres, r = number
of hard spheres per chain, andg = pair radial distribution Figure 2. VLE for cyclohexane + poly(ethylene-co-vinyl acetate)
solutions: w\, mass fraction cyclohexane; points, new experimental
function of hard spheres at contact. The subscript ij,kl
denote the pair containing the &th segment of component data; lines, calculation using PHSC equation of state parameters
[cyclohexane + polyethylene, 0, A = -0.0344; cyclohexane +
=

i and the Zth segment of component j. Parameters a and b

poly(vinyl acetate), =
0, A = -0.005; poly(vinyl acetate) +
are temperature-dependent as given by the Song—Mason
polyethylene, = 0, =
-0.164],
(1989) method. For pure solvents and homopolymers, these
are

a = (2/3 ) 3 eFa(k B T/e) (3)

b =
(2/3WFb(kBT/e) (4)

where distance of separation at the minimum potential

=

energy, well depth of the pair potential, and Fa and

e =

are universal functions.

Parameters a and b for a pair of dissimilar segments A
and B are given as 0 0.1 0.2 0.3 .0.4 0.5 0.6
wi
°ab =
(2/3) 3 £ · , (& 77€ ) (5) Figure 3. VLE for chloroform + polystyrene, poly(styrene-co-butyl
methacrylate), and poly(butyl methacrylate) solutions: wi, mass
&ab
=
(2/3) 3AgF(6) fraction chloroform; points, experimental data; lines, calculation
using PHSC equation of state parameters [chloroform + polysty-
rene, = 0, A = -0.025; chloroform + poly(butyl methacrylate),
where =
0, A = -0.05; polystyrene + poly(butyl methacrylate), 0, A =

=
-0.04],
=
(1/2)( + Ug)(l A^) (7)
—

0ab
binary parameters ( and A), are needed for the mixture;
eAB
—
(1 KAB^ (8) these can be determined from experimental mixture prop-
erties.
Parameters and eA pertain to segment A; kab and Aab
are adjustable intersegmental parameters. Results and Discussion
The pair correlation function is
The PHSC equation of state has been applied to some
data sets from the Experimental Section. The experimen-
1 2 ^ij,ki 1 ^ijM tal molecular weights of the polymers were used in the
+
,

Sum
=
--: --= +
,
-
'
'

(9)
3 (1 2 (1
(1 v) ? calculations; however, if these were not available, a 100 000
-

)2
- -

molecular weight has been assumed because molecular

where the packing fraction is weight has a negligible effect on the VLE for high-
m n
molecular-weight polymer solutions. Pure-component mo-
lecular parameters (r, e, and ) were obtained from pure-
=
( /4) ^k=l6¿=1
(10) component properties (Lambert, 1995; Song et al., 1995).
Figure 2 shows pressure versus weight fraction solvent
and in the polymer phase for the system cyclohexane + poly-
(ethylene-co-vinyl acetate) at 80 °C. At a given pressure,
1/3 m n solvent absorption in the copolymer increases as its eth-

^ij,kl i=1 k=l

> 2/3
(11) ylene content rises. This rise is expected because the
hydrocarbon segments of cyclohexane are better liked by
the similar hydrocarbon segments of ethylene, whereas
In summary, each pure solvent or homopolymer is polar segments of vinyl acetate are disliked by the solvent
characterized by three molecular constants: r, segment molecules. The solubility of cyclohexane falls in proportion
number per molecule; a, segment size; and e, nonbonded to the vinyl acetate concentration in the copolymer. All
segment pair interaction energy. These molecular con- binary parameters were set equal to zero, whereas three
stants are obtained from readily available pure-component A binary parameters were regressed using the experimental
data for thermodynamic properties such as vapor pres- data. The PHSC equation of state can accurately correlate
sures, densities, and compressibilities (Song et al., 1994b). the experimental data.
Pure-component parameters for 77 solvents and for 22 Figure 3 shows VLE for a system containing chloroform
polymers have been collected by Lambert (1995). For each and the copolymer poly(styrene-co-butyl methacrylate) and
unlike pair of segments, usually one and only rarely two chloroform with the parent homopolymers polystyrene and
790 Journal of Chemical and Engineering Data, Vol. 40, No. 4, 1995

wi wi

4. VLB for cyclohexane + poly(cis-l,4-butadiene) and poly- Figure 6. VLB for pentane + poly(butadiene-co-acrylonitrile)
Figure
(butadiene-co-acrylonitrile) solutions: w i, mass fraction cyclohex- solutions: un, mass fraction pentane; points, new experimental
ane; points, new experimental data; lines, calculation using PHSC data; lines, calculation using PHSC equation of state param-
equation of state parameters [cyclohexane + polyacrylonitrile, eters: [pentane + polyacrylonitrile, 0, -0.06; pentane +
= =

=
0.082, —

-0.08; cyclohexane + poly(czs-l,4-butadiene), * = 0, poly(c¿s-l,4-butadiene), = 0, —0.085; poly(c¿s-l,4-butadiene)

—

+ polyacrylonitrile, =
0.027, =
0].
=
-0.021; poly(c¿s-1,4-butadiene) + polyacrylonitrile, =
0.027,
=
0.0],
has negligible solubility in polyacrylonitrile due to strong
repulsion between nonpolar cyclohexane segments and
highly polar acrylonitrile segments. Binary parameters for
the PHSC equation of state were regressed from the VLB
data for cyclohexane in polybutadiene and poly(butadiene-
co-21% acrylonitrile) as shown in Figure 4. VLB for
cyclohexane in poly(butadiene-co-51% acrylonitrile) were
predicted; the prediction is in excellent agreement with the
experimental data.
Figure 5 shows results for hexane + poly(butadiene-co-
acrylonitrile). In this case, VLB behavior is similar to that
for cyclohexane + poly(butadiene-co-acrylonitrile) shown
in Figure 4. The solubility of hexane decreases dramati-
Figure 5. VLB for hexane + poly(c¿s-1,4-butadiene) poly(buta- cally with the acrylonitrile content in the copolymer. PHSC
diene-co-acrylonitrile) solutions: wi, mass fraction hexane; points, can successfully correlate this behavior with adjustable
experimental data; lines, calculation using PHSC equation of state binary parameters given in Figure 5. The predicted VLB
parameters [hexane + polyacrylonitrile, = 0.168, = -0.33; for hexane + poly(butadiene-co-51 % acrylonitrile) is in good
hexane + poly(cis-l,4-butadiene), = -0.023; = -0.02; poly(c¿s-
1,4-butadiene) + polyacrylonitrile, = 0.027, =
0.0]. agreement with experiment.
Finally, Figure 6 shows results for pentane with poly-
poly(butyl methacrylate). Figure 3 shows relative pressure (butadiene-co-acrylonitrile). Results are similar to those
P/Psat (PSat= saturation pressure of the solvent at the given for hexane (Figure 5) and cyclohexane (Figure 4). The
temperature) instead of P because data at 50 °C are solubility of pentane decreases dramatically with acryloni-
trile content in the copolymer. The PHSC equation of state
compared with data at 70 °C; normalizing pressure with
can successfully correlate the data for pentane with only
Psat tends to eliminate the temperature effect in a small
one binary parameter for each pair as shown in Figure 6.
temperature range such as here. Going from polystyrene
to poly(50% styrene-co-butyl methacrylate) to poly(butyl Polybutadiene + polyacrylonitrile binary interaction pa-
rameters were the same as those used in Figures 4 and 5.
methacrylate) increases the solubility of chloroform because
of favorable polar interaction between chloroform and butyl
methacrylate segments. Chloroform also has some polar
Conclusions
interaction with styrene segments, but these are not as New VLB data have been obtained for 43 copolymer +
strong as those with the butyl methacrylate segments. The solvent binaries and for 14 homopolymer + solvent bina-
solubility of chloroform rises in proportion to the butyl ries, using a gravimetric absorption technique. “Expected”
methacrylate content in the polymer. nonideal behavior has been obtained for systems such as
For the system shown in Figure 3, all binary parameters cyclohexane + poly(ethylene-co-vinyl acetate) and chloro-
were set equal to zero. Solvent + homopolymer form + poly(styrene-co-butyl methacrylate). However,
parameters were obtained from their VLB experimental strong nonlinear nonideal behavior has been observed for
data. The polystyrene + poly(butyl methacrylate) pa- systems containing hydrocarbons and poly(butadiene-co-
rameter was obtained from the copolymer + solvent VLB acrylonitrile).
data. With only one adjustable parameter for each data
The perturbed hard-sphere chain (PHSC) equation of
set, the PHSC equation of state can correlate the VLB state for mixtures of heteronuclear chains can represent
behavior.
vapor—liquid equilibria of real copolymer solutions using
Figures 4-6 show VLB data for hydrocarbons with poly- one or at most two binary parameters for each pair of
(butadiene-co-acrylonitrile) at 60 °C. For these systems, unlike segments.
solubility is not a simple function of copolymer composition.
Figure 4 compares VLB data for cyclohexane + poly- Acknowledgment
(butadiene-co-aciylonitrile) with theory. At a given pres-
sure, progressing from polybutadiene to poly(butadiene- For experimental assistance, the authors are grateful to
co-12% acrylonitrile) to poly(butadiene-co-51% acrylonitrile), Gary Yeung, Bin W. Zhao, and Kathy Yi. Helpful discus-
the solubility of cyclohexane decreases dramatically with sions with David Soane, Toshiaki Hiño, Yuhua Song, and
the acrylonitrile content in the copolymer. Cyclohexane Stephen Lambert are much appreciated.
 Journal of Chemical and Engineering Data, Vol. 40, No. 4, 1995 791
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