Znd. Eng. Chem. Res.

1996,34, 1501-1516 1601

REVIEWS

Phase Equilibria in High-pressure Polyethylene Technology

Bernard Folie
Exxon Chemical International, 20 Canadastraat, B-2070 Zwyndrecht, Belgium

Maciej Radosz"
Exxon Research and Engineering Company, Annandale, New Jersey 08801

This is a review of the phase equilibria in supercritical monomer solutions of ethylene

homopolymers and copolymers, such as low-density polyethylene (LDPE), linear low-density
polyethylene (LLDPE), poly(ethy1ene-m-methacrylate) (EMA), poly(ethylene-co-vinyl acetate)
(EVA), poly(ethylene-co-methacrylicacid) (EMAA), and poly(ethy1ene-m-acrylicacid) (EM). The
knowledge of such phase equilibria underlies the high-pressure polyethylene (HPPE) technology.
The ability to estimate such phase equilibria allows for smooth and robust process optimization
during grade transitions. This is important because the HPPE technology makes it possible t o
minimize the product cross-contamination and, hence, to make higher-value, fluctuating-demand
speciality polymers. Experimental data, phase diagrams, and patterns of phase disengagement
presented in this paper are related to the reactor system, the high-pressure separator (HPS),
and the high-pressure recycle system. These data and diagrams are used to characterize the
monomer-polymer miscibility defined as a cloud point transition. The cloud point pressures in
such systems are found to depend on thermodynamic parameters, such as temperature and
composition, and on the dissimilarity between the polymer and the monomer. This dissimilarity
is characterized in terms of the differences in molecular weight and density (e.g., for LDPE and
LLDPE), in polarity (e.g., for EVA and EMA), and in association (e.g., for EA4 and EMAA).

Introduction flow diagram of the HPPE process is shown schemati-

Understanding the phase behavior of polymer solu-
tions in supercritical fluids (SCFs) is of great theoretical
and practical interest. Predicting phase boundaries
(e.g., cloud points) and phase compositions (e.g., solu-
bilities) for such systems is difficult because (i) they are
highly nonideal at high pressures, (ii) the polymer and
solvent greatly differ in size, thus critical conditions, and
(iii) commercial polymers are composed of many mol-
ecules differing in molar mass and chemical composi-
tion. Nevertheless, the phase boundaries and compo-
sitions are required for the safe and efficient operation
of polymer processes such as the high-pressure poly-
ethylene (HPPE)process, where the bulk polymerization
reaction and the main polymer-monomer separation
step are carried out in supercritical The
objective of this work is to review the phase equilibria
of ethylene-based polymers and copolymers in sub- and
supercritical monomer fluids, which underlie the HPPE
technology.
The High-Pressure Polyethylene Process
Low-density polyethylene (LDPE) is one of the most
widespread plastic materials, synthesized commercially
at relatively high temperatures (180-300 "C) and high
pressures (1000-3000 bar) by free-radical bulk polym-
erization in supercritical ethylene.1>2The polymeriza-
tion is carried out in a well-stirred single-stage or
multistage autoclave or a tubular reactor. A generic
* Corresponding author. Current address: Department of
Chemical Engineering, Louisiana State University, Baton
Rouge, LA 70803.
0888-588519512634-1501$09.00/00 1995 American Chemical Society
cally in Figure 1. In brief, fresh ethylene, after primary
compression, is combined with recycled ethylene and,
optionally, with a comonomer. This stream is pressur-
ized to the desired reactor pressure in a second com-
pression stage. Polymerization of the monomers is
initiated by adding free-radical initiators (e.g., organic
peroxides); in tubular reactors, oxygen from air is also
used as initiator. The heat of reaction is removed by
either controlling the rate of initiator addition in auto-
clave reactors or by through-wall heat transfer in
tubular reactors. The polymer molecular weight (MW)
is controlled by adjusting the reactor temperature and
pressure and, optionally, by adding a chain-terminating
agent. In this process, ethylene is both the reactant and
the solvent for the polymer. Due to the short reactor
residence time (30-90 s), the monomer conversion is
relatively low, between 10 and 20 wt % in autoclaves
and up to 30 wt % in tubular reactors. The reactor
effluent stream is depressurized across a pressure-
reduction valve down to 150-250 bar to allow separa-
tion of the product from the unreacted ethylene in a
high-pressure separator (HPS). The overhead monomer-
rich stream is cooled and recycled back to the reactor
whereas the bottom polymer-rich stream undergoes a
second separation step at near atmospheric pressures
in a low-pressure separator (LPS). The LPS overhead
is recycled back to the reactor, whereas the residual
ethylene and comonomers dissolved in the molten
polymer can optionally be stripped under vacuum in a
devolatilizing extruder. Finally, the extrudate is pel-
letized under water, and the pellets are dried and stored
in silos that are continuously purged with warm air.
Recently, Exxon Chemical retrofitted the HPPE pro-
1502 Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995

I COMONOMER

PRIMARY

e
COMPRESSOR

ETHYLENE

COMONOMER
I
CATALYST

t 1I
b-, LPS

HIGH-PRESSURELOOP 1
WITH
SUPERCRITICAL ETHYLENE

-
TO EXTRUDER AND
FINISHING
Figure 1. Simplified flow diagram of the HPPE process.

HIGH-PRESSURE LLDPE MADE WITH METALLOCENECATALYSTS: polymerizing ethylene with a polar comonomer (e.g.,
vinyl acetate, methyl acrylate, and acrylic acid). LL-
CH2=CH2 NARROW MWD DPE, on the other hand, is made of linear molecules of
NARROW CD similar sizes (MWD = 2) to which short-chain branches
LINEAR MOLECULES
(SCB) can be added by polymerizing ethylene with
various higher a-olefins (e.g, 1-butem and 1-hexene).
APOLAR COMONOMERS
Due to the large diversity of polyolefins that -can be
produced via the HPPE process today, it is essential to
HIGH-PRESSURE LDPE MADE WITH FREE-RADICAL INITIATORS: understand the effect of the polyolefin size, microstruc-
ture, and chemical composition on the phase behavior
in supercritical solvents, for example, the phase bound-
BROAD MWD aries in the reactor and the phase compositions in the

$+ BROAD SCBD
./CH2=CH2
LCB
.POLAR COMONOMERS
NARROW-BROAD CD
high polymers + oligomers
Figure 2. Schematic diagram illustrating the differences in
microstructure and chemical composition between LDPEs and
LLDPEs made in the HPPE process.
cess to allow for commercial production of linear low-
density polyethylene (LLDPE) using single-site homo-
geneous metallocene catalyst^^-^ in high-pressure
autoclave reactors. The LLDPE produced this way has
different microstructure and chemical composition com-
pared to LDPE. As illustrated in Figure 2, LDPE is
made of branchy macromolecules differing in size (mo-
lecular weight distribution (MWD) or polydispersity
(Mw/Mn)between 5 and 20) and in branch size (from
short to long chain branches) and density (number of
branches per 100 backbone carbons). Polar pending
groups can be incorporated into the LDPE backbone by
HPS.
Thermodynamic Issues in the HPPE Process
The phase state of the reaction mixture controls the
polymerization kinetics and, therefore, the polymer
structure and end-use properties. In a stirred autoclave
reactor, the exothermic polymerization reaction is usu-
ally carried out in a single-phase region to facilitate the
reaction heat removal and hence ensure adequate
reaction temperature control and to avoid fouling and
forming cross-linked materials. Moreover, the presence
of a viscous polymer-rich phase increases the probability
of forming hot spots in the reactor and hence initiating
explosive runaway reactions via the autoacceleration or
? ~ effect is illustrated sche-
Trommsdorf e f f e ~ t . ~This
matically in Figure 3. In brief, when phase separation
occurs, polymer-rich microdroplets are formed. Termi-
nation of the live macroradicals entrapped in those high-
viscosity regions becomes severely diffusion-controlled,
resulting in a rapid increase of the ratio of the propaga-
tion rate constant (K,) to the termination rate constant
The resulting increase in polymer MW, combined

n molecules (the so-called “waxes”) that can have rela-
LOW VlSCOSrPl
BULK PHASE
MACRORADICALS
HIGH VISCOSITY
MICRO-DROPLET
TERMINATION BECOMES DIFFUSION-CONTROLLED
kp I kt INCREASES RAPIDLY
II
FORMATION OF “HOT SPOTS + ETHYLENE DECOMPOSITION
Figure 3. Schematic diagram illustrating the autoacceleration
(Trommsdorf) effect.
with the high exothermicity of such a vinyl polymeri-
zation reaction, can eventually lead, locally, to cross-
linking, visible as tiny gels in films, to reactor fouling,
and, in the worst instances, to the decomposition
reaction of ethylene.
Nevertheless, in some instances, it is desirable to
carry out the polymerization reaction in a two-phase
region. Phase separation in autoclave reactors is typi-
cally achieved by lowering the pressures or by adding
an inert antisolvent, such as N2, to the reaction mix-
t ~ r e .As
~ reported by Bogdanovic et a1.,8 LDPE pro-
duced in a two-phase system exhibits superior film
properties because of narrower MWD and less long-
chain branches (LCB). However, ethylene polymeriza-
tion in a two-phase system requires higher initiator
cons~mption.~Since the entropy of mixing (AS,)
decreases as polymerization proceeds in the reactor, the
supercritical polymerization mixture has a tendency to
split into two phases.1° An example of an undesirable
phase transition in high-pressure tubular reactors is
polymer precipitation due to cooling of the reaction
mixture (through-wall heat transfer) that leads to the
deposition of polymer films on the tube inner wall. This
impairs heat transfer and hence requires continuous on-
line def~uling.~,~ Therefore, it is crucial to know the
temperature, pressure, and mixture composition corre-
sponding to the demixing point (the cloud point). As it
is discussed later, the cloud point curve (binodal)
depends to a large extent on the polymer size, structure,
and chemical composition.
For separating the polymer from the unreacted mono-
mers, a combination of phase transitions is used,
including fluid-fluid equilibria in the HPS, which we
will refer to as liquid-liquid (LL) equilibria even if one
of the phases is supercritical with respect to the solvent,
vapor-liquid (VL) equilibria in the LPS and extruder,
and solid-vapor (SV) equilibria in the silos. The
polymers produced in this process are always polydis-
perse (MWD > 1.0) and contain a fraction of low MW
Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995 1503
tively high solubility in the HPS monomer-rich phase.
This leads to recurrent fouling of the heat exchangers
in the high-pressure recycle system. Therefore, some
processes include one or more additional phase separa-
tion steps, solid-liquid (SL) or LL, in the recycle system
to remove the waxes from the recycled monomer stream.
In fact, one faces a difficult optimization problem
whereby the pressure in the HPS should be high enough
to reduce the ethylene recompression cost but, at the
same time, low enough to reduce the wax solubility in
the monomer-rich phase and the monomer solubility in
the polymer-rich phase.
Generic Phase Diagrams
(i) Solvent-Solvent Systems. Although polymer-
solvent mixtures are multicomponent systems by virtue
of the polymer polydispersity, their phase behavior can
be related to those of true binaries whose components
differ in size, structure, and p01arity.ll-l~ Pressure-
temperature (P-T) projections of generic pressure-
temperature-composition (P-T-X) phase diagrams for
binary mixtures of increasing degree of molecular asym-
metry are shown in Figure 4.
In Figure 4a (type A behavior), characteristic of
binaries with a low degree of molecular asymmetry, a
continuous critical locus joins the critical points (Cl and
C2) of the pure components which terminate their
respective vapor pressure curves. Also depicted in
Figure 4a is a region of liquid-liquid immiscibility at
low temperatures, bounded by a liquid-liquid-vapor
(LLV)line ending at an upper critical end point (UCEP)
and, at higher pressures, by the upper critical solution
temperature (UCST) curve, along which increasing
temperature induces transition from two liquid phases
to a single liquid phase. For the record, type A behavior
shown in Figure 4a, is referred to as type I (with no
LLV curve) or type I1 in the classification of van
Konynenburg and Scott.14 Type B behavior shown in
Figure 4b is characteristic, for instance, of hydrocarbon
binaries with a high degree of molecular size asym-
the critical locus is discontinuous and is
represented by two separate dashed curves: one con-
nects the lower critical end point (LCEP) to the heavy
component critical point (Cz), while the other connects
the higher UCEP to the light component critical point
((21). Type B behavior corresponds to type IV or type V
(special case with no LLV curve) in the classification of
van Konynenburg and Scott. For ethane and propane,
for example, the change from type A to type B phase
behavior (without a known LLV curve, however) occurs
at c18 and between c29 and C30, re~pective1y.l~~ The
type C P-T projection shown in Figure 4c (correspond-
ing to type I11 in the classification of van Konynenburg
and Scott) is typical of binaries with a very high degree
of molecular asymmetry. In this case the LLV line
intersects the critical locus only once at the UCEP. The
other part of the critical locus starts at C2 and rises with
pressure without ever meeting the LLV line or C1. As
this second part of the critical locus is shifted toward
higher temperatures (see Figure 4c), it progressively
becomes smoother until it loses its pressure minimum
and maximum. Such critical loci are characteristic of
gas-gas (GG) equilibria of the first (type y ) and the
second (type b) kind.14
(ii) Polymer-Solvent Systems. In general, poly-
mer-solvent mixtures exhibit phase behavior patterns
similar to those depicted in Figure 4 for binary mixtures
1504 Ind. Eng. Chem. Res., Vol. 34,No. 5,1995
TEMPERATURE -
8
(b)
\ 1 PHASE
TEMPERATURE - UCEP. Also depicted in Figure 5 are two three-phase
I$)
I
I\
\,\
\
- iGG- 1
1
2 PHASES \ 0 “1.
TEMPERATURE -
Figure 4. Two-dimensional P-T projections of generic P-T-X
phase diagrams for binary mixtures of increasing degree of
molecular asymmetry, going from a to c, between component 1
(light) and component 2 (heavy). The dashed curves represent the
mixture critical loci.
of small molecules, except that the polymer vapor
pressure curve is usually not shown in P-T diagrams,
because polymer vapor pressures are very low and
polymers decompose before they reach their critical
temperatures (Ca shown in Figure 4 does not exist for
polymers). A qualitative example of a P-T isopleth
(constant polymer volume fraction) phase diagram typi-
cal of a monodisperse and amorphous polymer-solvent
mixture with a high degree of molecular asymmetry
(type B behavior) is shown in Figure 5. In most cases,
there is a pair of LL boundaries, one at higher temper-
atures, labeled the lower critical solution temperature
(LCST) curve, and one at lower temperatures, labeled
the UCST curve. These curves are not critical loci but
are labeled LCST and UCST because they correspond
to the LCST and UCST boundaries in T-X coordinates.
In a P-T projection, these boundaries intersect the
M : molecular weight
TEMPERATURE -
Figure 5. P-T isopleth typical of an amorphous and monodis-
perse hydrocarbon polymer-solvent binary system showing the
effect of increasing degree of molecular asymmetry between the
polymer and the solvent. The cloud point pressure (at constant
temperature) increases, and the UCST and LCST curves merge
into one single curve (U-LCST) with increasing differences in
molecular weight (AM-)and density (&) for nonpolar systems, with
increasing differences in polarity (Ap) for polar nonassociating
systems and with increasing differences between self-association
and cross-association (AA)due to specific chemical forces (e.g.,
hydrogen bonding) for polar associating systems.
mixture VL curve near, respectively, the LCEP and
regions (LLV), one below the UCEP temperature and
one above the LCEP temperature. In general, the
mixture VL curve is close, but not identical, to the
solvent vapor pressure curve and typically extends up
to 3-5 “C above the solvent critical point. Therefore,
the LLV curve is extended toward higher temperatures
with increasing solvent critical temperature. For poly-
disperse polymers, LLV is not a single curve but a
band.15a The line between the UCEP and the LCEP
represents the bubble-point side of the mixture VL
curve.
As the degree of molecular asymmetry between the
polymer and the solvent increases, the LCST and UCST
curves approach each other and eventually merge into
a single curve with a minimum, labeled the U-LCST
curue16J7(type C behavior), as shown in Figure 5. In
this case, as in Figure 4c for binaries of small molecules,
there is only one three-phase LLV line which extends
all the way to near the solvent critical point. For
polyethylene-solvent mixtures relevant to the HPPE
process, the degree of molecular asymmetry between the
polymer and the solvent can be characterized in terms
of the difference in molecular weight (AM)and density
(A@)for nonpolar systems, in terms of the difference in
polarity (Ap) for polar nonassociating systems, and in
terms of the difference between self-association and
cross-association (AA) due to specific chemical forced2
(e.g., hydrogen bonding) for polar associating systems.
These effects are illustrated qualitatively in Figure 5
for an amorphous polymer-solvent mixture.
In addition to P-T isopleths which allow one to
determine the number of phases present at given T, P,
and overall mixture composition, one often needs phase
composition diagrams, such as T-X or P-X. These
diagrams are illustrated in Figure 6 as cuts of a
qualitative P-T-X phase diagram for a monodisperse
and amorphous polymer-solvent mixture exhibiting a
U-LCST critical locus. For the polyethylene-solvent
systems of interest here, increasing pressure always

@ P1
T curve.
U-LCST
crlllcal I o w a
WT U POLYMER
T E
WT X POLYMER
T where point L and V are located on the coexistence
WT X POLYMER
Figure 6. Three-dimensional P-T-X phase diagram typical of
an amorphous and monodisperse polymer-solvent system exhibit-
ing a U-LCST critical locus. At elevated pressures (PI), the LL
miscibility gap in T-X coordinates is continuous with a maximum
(UCST);at intermediate pressures (Pz), it becomes discontinuous
with a maximum (UCST) and a minimum (LCST); at pressures
(P3)lower than the minimum critical pressure, an hourglass-
shaped T-X diagram is obtained, without critical point.
induces mixing because of a negative excess volume of
mixing (AVm < 0). This pressure-induced mixing is
illustrated qualitatively with P-X isotherms in the
P-T-X phase diagram in Figure 6. The maximum on
each isotherm is a critical point, called the upper critical
solution pressure (UCSP). While these isotherms have
similar shapes a t all temperatures, the T-X isobars
shown on the right-band side in Figure 6 change their
shape depending upon pressure. At elevated pressures
(e.g., PI), the miscibility gap in T-X coordinates is
continuous with a maximum a t UCST; a t intermediate
pressures (e.g., P2), it becomes discontinuous with a
maximum a t UCST and a minimum a t LCST; a t
pressures lower than the minimum critical pressure
(e.g., P3),it becomes an hourglass-shaped miscibility gap
without critical points. In the latter case, the system
is immiscible a t all temperatures within a limited
concentration range.
(iii) The Polydispersity Effect. Several features
distinguish a typical P-X phase diagram for polymer-
solvent systems from those of true binary systems
consisting of small molecules of similar sizes. First, the
cloud point P-X curve is highly asymmetric with the
maximum shifted toward the solvent-rich concentration
end.l0 As the size difference between the polymer and
the solvent decreases, this maximum is shifted to higher
polymer concentrations.16J7For polydisperse polymers,
the critical point (UCSP) does not coincide with the
maximum on the phase boundary (called the precipita-
tion threshold1*) but is shifted to higher polymer
concentrations. Finally, for the true binary systems, the
compositions of the liquid phases in equilibrium, given
by the tie lines, coincide with the binodal compositions
at the same pressure, temperature, and overall compo-
sition. By contrast, for the polydisperse polymers, the
binodal (cloud point) compositions usually do not coin-
cide with the phase compositions which must be mea-
sured independently as tie lines and are given by the
so-called coexistence curves. In addition, the pressure-
composition dependence of the minor phase being
formed at the cloud point is represented by a so-called
Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995 1506
shadow c ~ r v e . The
~ ~ shadow
, ~ ~ curve does not coincide
with either the cloud point curve or the coexistence
These curves are illustrated qualitatively with a
generic P-X phase diagram shown in Figure 7. The
weight fraction ratio of the two phases in equilibrium
can be calculated according the the lever rule. The
weight fraction ratio of the polymer-rich phase t o the
polymer-lean phase (w'lw'') is equal to the ratio of the
l
distance between points F and V to the distance between
points F and L:
curves and point F corresponds to the feed or initial
concentration shown for a bubble-point-type transition
in Figure 7, where the feed concentration is lower than
the critical concentration. A similar approach can be
used for a dew-point-type transition also shown in
Figure 7, where the feed concentration is higher than
the critical concentration. A quantitative example of
the cloud point, shadow, and coexistence curves is shown
in Figure 8 for a LDPE wax-ethylene system.
Thermodynamic Basis of UCST and LCST
Behavior
In general, the thermodynamic requirements to form
a homogeneous solution of two pure components can be
expressed by
AGm = AHm- TAS, < 0 (2)
and
where AGm is the difference in Gibbs free energy
between the solution and the pure components and AH,,,
and ASm are the corresponding differences in enthalpy
and entropy. Since solutions are more random than
pure components, the classical combinatorial A S m is
inherently positive, thus favoring the solution state. On
the other hand, the magnitude and sign of A H m is
governed by the change in intermolecular energy when
a solution is formed. For UCST systems, mixing is
endothermic ( A H m > 0) because the like interactions are
more energetically favorable than the unlike interac-
tions, thus favoring the two-phase state. In fact, ac-
cording to the principle "like-dissolves-like", the more
alike the pure components, the smaller the AHm, On
the other hand, the more dissimilar the solute and the
solvent, the larger the AH,. Hence, for long chains,
A H m dominates the always favorable AS,,,. At high
enough temperatures, the -TM, term compensates for
the positive A H m to give the negative AGm value
required for solubilization. For example, in the system
polyethylene-n-alkane, the cloud point pressure de-
creases substantially with increasing solvent size.21For
these nonpolar systems, the dispersion (London) forces
between polymer segments and solvent are strength-
ened (larger A H m ) as a result of an increase in solvent
polarizability with increasing solvent size.22 This effect
alone would make AG, more positive, resulting in
higher cloud point pressures. In this case, the observed
decrease in cloud point pressure is due to a compara-
tively larger increase in AS,.
1506 Ind. Eng. Chem. Res., Vol. 34,No. 5, 1995

FREE-VOLUME DIFFERENCE Ap
BUBBLE POINT-TYPE TRANSITION: Xi > X,t
(a) LIQUID
-
---- cloud point curve
shadow curve

W
a
3
v)
v)
W
a PHYSICAL INTERMOLECULAR FORCES CHEMICAL INTERMOLECULAR FORCES :AA
R
- Londonor dispersionforces (AM) - hydrogenbonds
-permanent dipole moments (4) - charge transfer complexes
Figure 9. The phase behavior of any polymer-solvent system
ultimately depends upon the balance of physical and chemical
XCrt Xi,i Xi,2 intermolecular forces acting between polymer segment-segment,
POLYMER CONCENTRATION ---+ solvent-solvent, and polymer segment-solvent and upon the
difference in pee volume between polymer and solvent.
DEW POINT-TYPE TRANSITION: Xi < Xcr+
LIQUID
-
---- cloud point curve
shadowcurve I is exothermic ( A H m < 0), thus favoring the solution
existence curve state. In order for the phase separation to take place
ation threshold
upon raising the temperature, A S m must necessarily be
negative in this case. It is now well established that
such a negative noncombinatorial AS, does exist due
t to free-volume (density) dissimilarities between the
solvent and the polymer. In brief, as the system
W
a temperature approaches the solvent critical tempera-
3
v)
v)
ture at a moderate constant pressure, the solvent
W
a molecules tend to take a more expanded gas-like con-
R figuration, resulting in a rapid drop in density with
increasing temperature. Since the polymer density is
still far removed from its hypothetical critical density,
the polymer does not undergo such a dilation effect with
Xi,i Xi,2
POLYMER CONCENTRATION
Figure 7. Typical P-X isotherms for polydisperse polymer-
- increasing temperature. It is precisely this growing
difference in density (A@)between the polymer and the
solvent that induces demixing upon raising the tem-
perature. As it is shown directionally in Figure 5, the
solvent systems exhibiting UCSP behavior. (a) A bubble-point LCEP temperature decreases with increasing 4 values,
transition occurs when the initial polymer concentration (Xi)is
larger than the critical polymer concentration (Xcrt),
whereas (b) either as a result of increasing polymer density or
a dew-point transition occurs when Xi is smaller than Xd. decreasing solvent density. In fact, the polymer has a
contracting effect on the solvent molecules by confining
them to a more rigid matrix (AVm < 0). The negative
60
1 Spahl and Luft (1981)
A S m results from this lesser degree of spatial disorder
for the solvent in such a confined state, compared to
that in an expanded state.
The phase behavior of any polymer-solvent system
ultimately depends upon the balance of physical and
L chemical intermolecular forces driving the polymer
U
J segment-segment, solvent-solvent, and polymer seg-
a30
t ment-solvent interactions and upon the difference in
P
free volume between the polymer and the solvent. As
20 shown in Figure 9, examples of the physical intermo-
10
- cloud point curve
shadow curve
lecular forces are the dispersion forces acting among
nonpolar molecules and the polar forces acting among
- coexistence curves
molecules with permanent dipole or higher pole mo-
"0 10 20 30 LO 50 60 70 80 90 100 ments. Examples of specific chemical forces are hydro-
gen bonding and charge transfer complexing, which can
weight % LDPE lead to self-association that favors demixing or cross-
Figure 8. P-X isotherm (160 "C) for a polydisperse LDPE wax association that favors mixing.
(M,= 1130 g/mol, M , = 4040 g/mol) in ethylene. The coexistence
curves shown correspond to dew-point type transitions with Xi <
Xd (E 40 wt %). The feed compositions are, from left to right, Phase Disengagement Patterns
6.1, 14.0, 18.6,28.0, and 36.5 wt %. These data were taken from
ref 19. The HPPE process is a continuous process. Therefore,
the kinetics of phase disengagement play a crucial role
At temperatures approaching the solvent critical in the design of efficient separators. In order to
temperature, polymer-solvent systems exhibit LCST minimize the separator volume and polymer residence
behavior, characteristic of the temperature-induced time, the phase disengagement patterns and the phase
phase separation. For the LCST phase separation A H m stability have to be taken into account.
 Ind. Eng. Chem. Res., Vol. 34,No. 5, 1995 1507
PATTERNS OF PHASE DISENGAGEMENT

... .
0
1 Phase Dew Point VL

1-Phase Bubble Point VL

Figure 10. Schematic diagram of phase disengagement patterns

upon lowering pressure at constant temperature. The shaded area
represents the polymer-rich phase.
u homogeneoussystem

On a macroscopic scale, there are two patterns of

phase separation, as illustrated in Figure 10. One
pattern is similar to a dew-point separation in vapor-
liquid equilibria (VLE), where one observes the onset
and growth of the high-density phase (liquid) upon
lowering the pressure. The other pattern is similar to
a bubble-point separation in VLE, where one observes
the onset and growth of the low-density phase (vapor)
upon lowering the pressure.16 As shown in Figure 7,
the dew-point transition occurs when the initial polymer
concentration (Xi) is smaller than the critical polymer-
concentration (Xd),whereas the bubble-point transition
occurs when it is larger than Xed. Hence, the type of
the phase disengagement pattern in a particular sepa-
ration process depends on Xi and Xch. Since XCh is
k n o w n to increase with decreasing polymer MW, con-
centrated solutions of high MW polymers (e.g., in HPS)
will tend to separate according to a bubble-point-like
pattern, whereas dilute solutions of low MW waxes (e.g.,
high-pressure recycle separator) will tend to separate
according to a dew-point-like pattern.
Whereas the shape of the Gibbs free energy of mixing
(AGm) curve as a function of composition X determines
the phase state of the system at a given T and P, its
curvature determines the phase stability and hence the
microscopic mechanism by which the system d e m i x e ~ . ~ ~growth mechanism. These mechanisms are illustrated
This is illustrated qualitatively in P-X coordinates in
Figure 11 for a polymer-solvent binary exhibiting a
negative excess volume of mixing (AVm < 0). At
elevated pressures (PI), the system is homogeneous
because the AGm curve has a positive curvature (@AGm/
3x2 > 0) across its entire concentration range, hence,
such a system cannot lower its free energy of mixing at
any composition. At lower pressures (P& the system
demixes because the AGm curve has, locally, a negative
curvature ( @ A G m / t P .c 0). The compositions of the two
phases in equilibrium, given by the double tangent to
the AGm curve, correspond to the binodal compoxi-
tions (X'b and d'b). At these points, the chemical
potential of each species is the same in both phase (&'i
= +"i). The compositions at the two inflection points,
where the curvature of the AGm curve changes from
concave to convex and vice versa, correspond to the
spinodal compositions (dSp and x " ~ ~ )The
. pressure
(UCSP) and composition ( X h )at which these four points
merge into one single point corresponds to the critical
point.
The LL domain, bounded by the binodal, is divided
into two distinct regions: one unstable and one meta-
stable, each region corresponding to a different micro-
scopic separation mechanism.23 In the unstable region,
bounded by the spinodal curve, the system demixes
spontaneously, forming two cocontinuous phases. This
is k n o w n as the spinodal decomposition mechanism. In
the metastable region, nuclei of the new phase must
form and grow into dispersed droplets in a continuous
0.0 xcrt 1.o
Polymerweight fraction
Figure 11. Constructing a P-X phase diagram (binodal and
spinodal) from the shape and curvature of the Gibbs free energy
of mixing (AG,) curve as a function of composition, X,a t constant
temperature.
matrix of the other phase. This energy-intensive de-
mixing mechanism is known as the nucleation and
in 2'-X coordinates in Figure 12. In general then,
crossing the binodal (from a one- to a two-phase region)
is a necessary condition for demixing to occur, whereas
crossing the spinodal is a sufficient condition for spon-
tanous and irreversible demixing. At equilibrium, after
a sufficient settlement time, both mechanisms will
eventually lead to two homogeneous liquid phases albeit
at different rates.
Polymer Solubility in Solvents
Polyethylene solubility in supercritical ethylene de-
pends on temperature and pressure. This dependence,
similar to that of many solutes in SCFS,~ is illustrated
qualitatively in Figure 13. The two solubility isotherms
shown in Figure 13 describe the solubility behavior of
polyethylene in sub- and supercritical ethylene. In the
subcritical pressure (e.g., LPS), where the vapor pres-
sure- and enthalpy-related effects are dominant, the
solubility increases (due to solute evaporation) with
increasing temperature and decreasing pressure. In the
supercritical pressure range (e.g., HPS), the solubility
always increases with increasing pressure, as reported
by LuR and Lindnel.24 for several high and low MW
LDPEs in ethylene. The effect of temperature is not as
straightforward, however. At intermediate pressures,
the free-volume (density) effect is dominant and the
solubility drops with increasing temperature ((a In
XlaT), < 0). At higher HPS pressures and at reactor
pressures, the solubility is controlled by energy-related
1508 Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995

DEW-POINT BUBBLE-POINT
TRANSITION TRANSITION

stable 4

1
t

metastable
POLYMER CONCENTRATION - 3'

t
t

Figure 12. T-X phase diagram typical of a monodisperse and amorphous polymer-solvent binary system, illustrating the difference
between demixing through the spinodal decomposition mechanism and the nucleation and growth mechanism.

enthalpy effects free-volume energy effects

dominant effects dominant dominant
8 - 4 - 0
I

W
U
fn
a.
I
I
0
a
G
5
2
fn
E
>
t
d /I I
m I
3 I
s:a I
I
I
0.1 1 10
PRESSURE (bar)
100 1000

W
B I
3 I Figure 14. Effect of pressure and temperature on PEP790
I solubility in ethylene as predicted by SAFT. kg was fitted to
8 I
experimental cloud point data taken from ref 48.
1
I
I Using the free-volume theory to estimate the solubility
1 of a high MW and polydisperse LDPE (M, = 13 kg/mol,
! PRESSURE MWD = 10) in ethylene, Bogdanovic et reported
al.25926

1 subcritical
a
supercritical
-
an increase in solubility with increasing temperature
in the pressure range 250-290 atm. The opposite
LPS HPS REACTOR temperature effect is shown in Figure 14, which il-
Figure 13. Qualitative diagram showing the effect of pressure lustrates the solubility of a low MW (790 g/mol) model
and temperature on polymer solubility in a subcritical and polyolefin, a nearly-monodisperse, amorphous, and al-
supercritical solvent. ternating ethylene-propylene copolymer (PEP), in eth-
ylene. These curves were calculated from an equation
effects, hence it increases with increasing temperature of state (EOS) derived from statistical associating fluid
((3 In X/aT>, =- 0). Notice that at the crossover point theory (SAFT). In this case, the simulation results
labeled 1 in Figure 13, the solubility is independent of indicate a decrease in PEP solubility with increas-
the temperature. The location of this point is system- ing temperature in the HPS pressure range (200-300
dependent as illustrated by the following two examples. bar).

Polyethylene solubility in ethylene not only depends
upon the HPS temperature and pressure but also
depends upon the polymer yield or conversion in the
reactor and upon its MW and MWD prior t o fraction-
ation. As a rule of thumb, it has been observed that,
as the conversion increases, the polymer solubility
increases while its average MW in the ethylene-rich
phase decreases.% This is expected because the polymer
solubility increases with decreasing MW.
In copolymerizationprocesses, the polymer solubility
can be controlled by tuning the solvent mixture density
not only with temperature and pressure but also with
solvent c o m p o s i t i ~ n . ~ ~
Experimental Approaches
The equilibrium phase behavior of polymer solutions
in supercritical solvents, for example, characterized by
the cloud point curve, the spinodal curve, the coexistence
curves, and the critical point, is usually determined
experimentally in small high-pressure variable-volume
optical batch cells where it is possible t o vary the
pressure and observe the phase transitions at constant
temperature and composition. The cloud points are
determined by light scattering or simply by visual
inspection when there is enough difference in the
refractive index between the two demixed phases.
Modern light-scattering techniques involve irradiation
of a solution of known polymer concentration with a
He-Ne laser and measurement of the scattered light
intensity as the system is brought from the homoge-
neous to the heterogeneous region by a change in
pressure. At the cloud point, the intensity of the
scattered light increases drastically. Such phase transi-
tions can also be observed visually in optical cells
equipped with sapphire windows, by displaying the
window image, via a borescope and a video camera, on
a video screen.16 At the cloud point, the initially-clear
solution becomes turbid.
The phase compositions can be determined by Sam-
pling and analysis of the equilibrated phases. A volu-
metric-gravimetric method combined with gas chro-
matography or mass spectrometry analysis of the light
components, suitable for polymer solutions, was recently
reported.28 Flow that allow continuous sampling
and production of relatively large samples have also
been used for that purpose.
One of the most recent techniques developed to
measure both the spinodal and binodal at elevated
pressures is a pressure-pulse-induced critical scattering
(PPICS) developed by Kiepen and BrochardZ9and Wells
et al.30 PPICS is based on the fact that the reciprocal
of the light intensity (1d-l scattered from a homoge-
neous polymer solution is proportional to the second
derivative of AGm with respect to composition which is
the spinodal. Another, more effective, approach to
measuring the spinodal is through a light-scattering
pressure-jump e ~ p e r i m e n t . ~ ~
The LL critical point can be determined by a method
described by de Loos et al.32 In order t o estimate the
critical temperature, one measures the phase volume
(or height) ratio as a function of the pressure difference
between the separation pressure and the cloud point
pressure at a fixed temperature. The interface rises in
the dew-point region, as the volume of the polymer-rich
phase increases. The interface drops in the bubble-point
region, as the volume of the polymer-rich phase de-
creases. By decreasing the dew-point temperature and
Ind. Eng. Chem. Res., Vol. 34, No. 5,1995 1509
increasing the bubble-point temperature, one converges
around the critical temperature.
Theoretical Approaches
Thermodynamic models applicable to polymer solu-
tions have recently been reviewed by W ~ h l f a r t h .Only
~~
a brief overview of the most popular models, especially
those useful for calculations of high-pressure phase
equilibria, is given here.
The starting point for calculations of phase equilibria
of solutions is usually a model for the excess Gibbs free
energy (P), from which the activity coefficient (yi) of
each component i in the mixture can be estimated, and/
or an EOS, from which the fugacity coefficient (vi)of
each component i can be calculated. With the chemical
potential hi)or fugacity f i of each component i being
equal in all phases at equilibrium, the phase composi-
tions can be estimated by solving the following set of
equations (for two coexisting phases):
,uIi =PI'& or f i = f, (4)
Hence,
(piyip= y p g vi (5)
Bi= 1.0
si = 1.0 (7)
where f i 0 is the standard state fugacity of component i
and xi and yi are the unknown mole fractions of
component i in each phase.
The most popular P model for polymer solutions is
a lattice model first derived by Flory and H ~ g g i n s . ~ ~ J ~ , ~ ~
The Flory-Huggins model is widely used in industry
because of its simplicity. However, it suffers several
important shortcomings, especially for high-pressure
phase equilibria calculations involving polymers in
SCFs. First, it is only applicable to incompressible
liquid solutions, since it assumes that there is no excess
volume of mixing (AV, = 0). Second, it fails to predict
the LCST type phase behavior. In other words, it
neglects the effect of the free volume dissimilarity
between the polymer and the solvent.
Three different approaches have been used t o develop
EOSs for polymer solutions.33The corresponding states
free-volume theory, first developed by P r i g ~ g i n eand ~~
put in practice later by F ~ o $ and~ P a t t e r ~ o ntakes
,~~
into account the dissimilarity in free volume between
the polymer and the solvent as a result of their great
difference in size. The basic deficiency of this theory is
that it is essentially limited to liquid-like densities. The
lattice-fluid models, such as those developed by Sanchez
and L a ~ o m b eand ~ ~Koningsveld and K l e i n t j e n ~ac-
,~~
count for compressibility and excess volume of mixing
by allowing for unoccupied sites (holes)in a rigid lattice.
Those models, with the exception of the lattice-gas
model of Koningsveld and Kleintjens, suffer the same
drawback as the fi-ee-volumemodels; they are only valid
a t liquid-like densities. The third group of EOSs is
those derived from thermodynamic perturbation theory,
such as the perturbed-hard-chain (PHC),39the chain-
of-rotators and the statistical associating fluid
theory (SAFT).40-45These EOSs are useful because
they are generally applicable over a wide range of
densities (from dilute gases to dense liquids) and over
a wide range of molecular sizes (from small to large,
1510 Ind. Eng. Chem. Res., Vol. 34,No. 5,1995
polymeric molecules). Since SAFT is also applicable to
associating molecules and has been demonstrated for
high-pressure polyolefin systems, it is briefly described
below.
SAFT is a molecularly based EOS that incorporates
terms accounting for the molecular size and shape (e.g,
chain length and branchiness), association (e.g., hydro-
gen bonding) energy, and mean-field (e.g., dispersion)
energy. SAFT development and approximations and
tests against molecular simulation data are described
el~ewhere.~O-~~ A SAFT fluid is a collection of spherical
segments that are not only exposed to repulsive (hard
sphere) and attractive (dispersion) forces but can also
aggregate through covalent bonds to form chains (chain
effect) and through hydrogen-like bonds to form short-
lived clusters (association effect). The reference part
of SAFT includes the hard-sphere, chain, and associa-
tion terms. The perturbation part of SAF'T accounts for
the relatively weaker, mean-field dispersion-likeeffects.
The SAFT residual Helmholtz free energy (Ares)relative
to an ideal gas reference state is given by
Ares = Aref + AdiSp
(8)
with
Aref = AhS + AChain
+ Aassoc (9)
Using the thermodynamic relationship (W&)T = -P,
SAFT can be expressed in terms of the compressibility
factor, 2:
i j
where 3 is the reduced fluid density, m is the number
of segments per molecule, is the molar density, v is
the molar volume, XAis the mole fraction of molecules
not bonded at site A, u/k is a temperature-dependent
dispersion energy of interaction between segments, DG
and t are constants, and the summation is over all the
sites. Knowing Ares and 2, vi can be estimated from
the following thermodynamic identity:
In v i= {a(Ares//RT)/ani}r,",~,~~
-In2 (15)
where V is the total volume of the system and ni is the
number of moles of substance i.
In order to extend SAFT to real fluids, one needs three
pure component parameters for nonassociating fluids:
uo, the temperature-independent segment-segment
interaction energy, uoo, the temperature-independent
segment volume, and m, the segment number. Also
needed are two association parameters that characterize
each site-site interaction: E , the energy of association
between sites on a molecule, and K, the reduced volume
of association. The nonassociating parameters are
600
t
- tt
400
A LL . L (DP)
0 50 100 150 200 250
TEMPERATURE ("C)
Figure 15. P-T isopleths for PEP790 (at 15 wt %) in l-butene,
propylene, and ethylene, illustrating the phase behavior shift from
type A to type B to type C, respectively, with decreasing solvent
size and density (data are from refs 16 and 48).
found by fitting SAFT to pure component vapor pres-
sures and saturated liquid densities; these parameters
are found to be well-behaved and hence easy to general-
ize for large molecules.44
In order t o extend SAFT t o real fluid mixtures, one
also often needs a binary parameter, k,, which is used
to fine-tune the unlike-segment interaction energy
estimated from mixing rules. The SAFT mixing rules,
however, are only required for the dispersion term
because the three reference terms can be extended to
mixtures based on rigorous statistical mechanics.
SAFT was applied to many real pure components44
and fluid m i ~ t u r e s including
, ~ , ~ ~ supercritical and near-
critical solutions of polymers, such as PEP and poly-
isobutylene (PIB). For example, SAFT was found to
account for phase transitions in binary and ternary
systems of P E P - a - ~ l e f i n , PVT
~ ~ , ~data
~ ~for
~ ~pure PEP
and the associating effects in binary systems
of monohydroxy and dihydroxy telechelic PIB in non-
polar and polar solvents.50
Amorphous Polyethylene Systems
P-T isopleths were recently reported by Chen et
al.16J7and Gregg et al.48for solutions of PEP in sub-
and supercritical a-olefins, including ethylene. In those
well-defined systems, it was demonstrated that the
greater the size difference (AMI between the polymer
and the solvent (i) the higher the probability of type B
and C phase behavior and (ii) the higher the cloud point
pressure.
An example of each type of phase behavior is shown
in Figure 15 where experimental data are shown for 790
g/mol PEP in three different solvents. The PEP-1-
butene system exhibits type A behavior with no LL split.
The PEP-propylene system exhibits type B behavior
of the LCST type. The PEP-ethylene system, for which
part of the U-LCST curve is shown in Figure 15, exhibits
type C behavior. As expected, the size of the single-
phase region (at pressures above the cloud point curves)
increases with increasing solvent power, which, in this
case, increases with increasing solvent MW and density.
While both LCST and U-LCST transitions were
observed for PEP solutions in propylene, only U-LCST
transitions were observed for PEP solutions in ethylene
in the MW range investigated (790-96 000
This is illustrated in Figure 16 where, for comparison,
 Ind. Eng. Chem. Res., Vol. 34,No. 5, 1995 1511
2000 . . . . . . . . . . . . . . . . . . . . . . . . .
l ' l ' l ' l ' *
P-1 ISOPLETH
(i I S Ut% rolul.)
*
-SAFT
- A LL-*L (BP)
1500 --
z UCST PEP 96k
I

t
P

w
a
3
v)
3
- 500 1 ' PEP 0.79k a
a
200

t LCST
f ,
,
N u
.,
I
C36 0.5k
1.6k

w-- - c20 0.28k LOO

0 50 100 150 200 250

TEMPERATURE ("C)
0
Figure 16. P-T isopleths for semicrystalline LDPEs, amorphous 40 80 120 ieo 200 240

PEPs, and n-alkanes in ethylene showing the shift in phase
transition from LCST type to UCST type with increasing solute
MW. In all the cases, the polymer concentration is close to 15 wt
% (data are from refs 48, 51-55). Not shown in this figure are
the solid-liquid transitions expected at low temperatures for the
semicrystalline LDPEs and n-alkanes.
500
O8k -
28k
15k -
IOk
5.0k -
- successfully predicts the increase in temperature and
700 -
-,
0
-150 -100 -50 0 60 LOO 150 200 250 while the higher a-olefins behave like cosolvents for the
TEMPERATURE ("C)
Figure 17. P-T isopleths for PEPs (at 15 wt %) in propylene,
showing the shift from type B (LCST) to type C (U-LCST) phase
behavior with increasing polymer MW. The curves were calculated
from SAFT (data are from ref 17).
cloud point data for several semicrystalline LDPE-
ethylene and n-alkane-ethylene systems (for which the
SL transitions are not shown) are also i n c l ~ d e d . ~ ~ s ~ lpropylene-diene)
As shown in Figure 16, the slope of the cloud point curve
changes sign with decreasing polymer MW. In the
temperature range shown, the phase transition for high
MW polymers is of the UCST type, while for low MW
polymers, it is of the LCST type. Although the LCST
transitions shown in Figure 16 are the LCST branches
of U-LCST curves, the UCST transitions may or may
not be the UCST branches of U-LCST curves. The latter
will depend on whether or not the critical locus shown
in Figure 4c has a minimum.
The effect of polymer M W on the cloud point curve is
illustrated for various PEP-propylene systems in Fig-
ure 17. As shown, the cloud point pressure at a fxed
temperature increases with increasing polymer M W , as
expected. The phase transition also shifts from type B
to type C phase behavior with increasing polymer MW.
For examples, PEPlOK (and above) exhibits a U-LCST
TEMPERATURE ("C)
Figure 18. P-T isopleths for PEP26k (at 15 wt %) in a mixture
of 1-butene and ethylene, showing the effect of increasing ethylene
concentration (in weight percent on a polymer-free basis) in the
solvent mixture. For 23.4 wt % ethylene in the mixture, SAFT
predicts that the UCST and LCST merge (data are from ref 17).
transition, while PEP5.9K (and below) exhibits an LCST
transition. It turns out that, as the LCEP drops, the
initial LCST slope, (aP/aT)x,increases.I6 In addition,
the phase disengagement is of the dew-point type for
PEP790 and PEP5.912, whereas it is of the bubble-point
type for PEP2612 and PEP96K. For these systems, SAFT
pressure of the U-LCST minimum with increasing
polymer Mw, as shown by the curves in Figure 17.
During production of LLDPE with the metallocenes,
ethylene is polymerized with a higher a-olefin. The
stream entering the HPS consists of a ternary system
LLDPE/ethylene/a-olefin for which the ethylene/a-olefin
ratio depends on such factors as the weight percent
a-olefin incorporated in the polymer and the a-olefin
reactivity ratio. In these mixed olefin cases, Chen et
a1.16 found that ethylene behaves like an antisolvent
polymer. This is illustrated in Figure 18 for a PEP26M
1-butene/ethylene system where the size of the LL
region rapidly increases, hence the single-phase region
decreases, with increasing ethylene concentration in the
mixture.
The monomer density, and consequently its solvent
power, also depends on its molecular structure, as
illustrated in Figure 19 for a low MW (ethylene-
-~~ elastomer in straight, branched, and
cyclic saturated paraffins of the same carbon number
( C S ) . ~The
~ difference in solvent power between the
linear (n-hexane) and the branched parafin (methyl-
pentane) is small, whereas the cyclic compound (meth-
ylcyclopentane) is a much better solvent because of its
higher critical dencity (ec). As the density difference
(he)between the polymer and the solvent increases, the
LCST curve shifts to lower temperatures, which means
that the size of the two-phase region increases.
Semicrystalline Polyethylene Systems
Both LDPE and LLDPE manufactured in the HPPE
process significantly differ from the model PEP com-
pounds in the following ways: (i) they are usually
semicrystalline and therefore precipitate below their
crystallization temperature, (ii) they are polydisperse,
1512 Ind.Eng. Chem. Res., Vol. 34,No. 5, 1995
I I I I I I
1400 I . . . I ' " 1 . ' . I ' . ' i " ' I . . '

1200 .......... :- PA

1000

800
.............. .......................... .......... ........ ......

...............
.............. .......

........
t
W
U
3
cn
600 ...................... .......................... . . . . . . . ................... .......................... 3
U
. . i R
, :
400 - * .. ......; .................. /i
i/
,'
j .6
. . :
. . . . . .; . . . . . . . . j.. ..:... ....... i... .......................................... .........._
: I
e v i
I
200 -1 .................. i..r/ .. .A.......:. .......... ..i . . . . . . . . . ..I I
................... . . . ........... ......................... :-
1 i
I / j
: 0 triple point

-
!
j EPDM-140 k
0 r...i...i...i...i...l...
1 I I 1 I I I

140 160 180 200 220 240 260 280 TEMPERATURE

TEMPERATURE ("C)

Figure 19. P-T isopleths for EPDM (at 6 w t %) in straight,

branched, and cyclic saturated paraffins of the same carbon I Berghmans' critical point (b) I
number (CS), showing the effect of the solvent density on the a polymer melting point
position of the LCST cloud point curve (data are from ref 56). ,/-- L

t
\
\
with polydispersity ranging from narrow for LLDPE
(MWD = 2.0) to broad and very broad for LDPE (MWD
= 5-20), and (iii)they are made of molecules differing w
U
in SCB (comonomer) content and therefore must also 3
I-
be characterized on the basis of their SCB (composition)
distribution, SCBD (CD). Moreover LDPE is not linear W m.p. s
R
but branched with a variable number of LCBs. Hence,
understanding the effects of crystallinity, MWD, SCB, 3I-
SCBD, and LCB on the high-pressure phase behavior
of polyethylene-solvent solutions is key to HPPE
technology.
The system most extensively studied during the past
30 years is the LDPE-ethylene ~ y ~ t e m . The ~ ~ , ~ ~ , ~ ~ I

POLYMER VOLUME FRACTION 1.0

qualitative P-T and T-X phase diagrams shown in O e 0

Figure 20 represent typical phase diagrams for semi-
crystalline LDPE-ethylene systems exhibiting a LL
phase transition of the UCST type. These phase
diagrams were constructed on the basis of Ehrlich's
three-dimensional (P-T-X)phase diagram^^^?^^ for the
same system. Figure 20a shows a P-T isopleth phase
diagram; upon decreasing temperature, the cloud point
curve intersects the crystallization boundary at point
A, beyond which one solid phase coexists with one liquid
phase (SL). Along the crystallization boundary below
point A, three phases coexist, two liquid phases and one
solid phase (SLL). Figure 17b shows a T-X phase
diagram; we see that LL demixing and crystallization
occur side by side and that the polymer melting point
is depressed with increasing solvent concentration. The
cloud point curve intersects the crystallization boundary
at the critical point B (Berghmans's point). According
to the phase rule:
the crystallization temperature is independent of con-
centration only for true binary systems.60 Indeed, if the
number of components, m, is two and the number of
phases, n,three, there is no degree of freedom left (F=
0) when the pressure is fixed. For polydisperse polymer-
solvent systems (m > 2), the crystallization temperature
either decreases with decreasing concentration, as sug-
gested by the data of Condo et al.59for the quasi-binary
HDPE-propane system, or increases with decreasing
concentration, as recently reported by Koningsveld and
BerghmansG0for the quasi-binary HDPE-diphenyl
Figure 20. (a) P-T isopleth phase diagram typical of semicrys-
talline, high M W LDPE-ethylene solutions, showing the intersec-
tion (point A) between the cloud point curve and the crystallization
boundary. Typical operating conditions for the reactor, HPS, and
the recycle separators are also indicated. (b) T-X phase diagram
(constant P ) for the same system as in part a showing the effect
of decreasing pressure and increasing polymer MW on the phase
boundaries.
ether system. In general, point B moves toward higher
polymer concentrations and higher temperatures with
either increasing polymer MW, decreasing pressure, or
both.
Spahl and Luft19,20,61 investigated the phase bound-
aries of LDPE waxes in supercritical ethylene. They
reported a phase boundary with a positive slope ((W
82')~ > 0),typical of the LCST branch of a U-LCST type
phase transition, for an LDPE wax (M, = 1.1 kg/mol)
in ethylene (Figure 21). For comparison, the phase
boundaries of other LDPEs and linear high-density
polyethylene (HDPEs) in ethylene are also included in
Figure 21. These data illustrate the shift from a LCST-
type to a UCST-type phase transition with increasing
LDPE size, as already inferred from Figure 16. Also
worth noticing in Figure 21 is that the cloud point
pressure increases with increasing polymer size, albeit
at a considerably reduced rate for the largest polymers.
Moreover, as the polymer size increases, the cloud point
pressure becomes more and more temperature depend-
ent. This is one possible explanation for the recurrent
fouling observed in high-pressure tubular reactors at
 Ind. Eng. Chem. Res., Vol. 34, No. 5,1995 1513
2000 4 . 1 . ;. . . ; . ..; .. . ; . . .; . .. 1 1 1 I I
Spahl~and Lu(r (1981)- 700
ElWK
1800-

1600-

-
L 1400-- _- I

e
w
!
!
j 1200 8 A
In
A
w
In
g 1000
l3 0
0
800
0
600 0
0 22 8
P 8
4 0 0 6 - 24
100 120 140 160 180
TEMPERATURE ('C)
200

Figure 21. P-T projections for LDPEs and HDPEs in ethylene

(data are from ref 20).
220

200 c 0

the tube entrance during low-temperature start-up or

directly downstream of the cold side-stream injection
Propane
points.20
By comparing the cloud point curves for LDPE and I I I I I I
0
HDPE of similar MW and MWD, others20,62 concluded 0 20 40 60 80 100 120 140 160 180 2
that the presence of LCBs (absent in HDPEs) enhances Temperature ("C)
polymer solubility and, consequently, lowers the cloud
Figure 22. P-T isopleths for PEBs (at 5 wt % in propane) varying
point pressures, as illustrated in Figure 21. However, in 1-butene content but of similar MW, illustrating the effect of
the cloud point data recently collected by Chen,63with the SCB density (branched100 C) on the cloud point pressure (data
nearly-monodisperse linear poldethylene-1-butene) (PEB) are from ref 63).
samples of varying 1-butene content in sub- and super-
critical propane indicate that SCBs play a significant
role in shifting the phase boundaries. As shown in from Hnrch et al. (1993)

Figure 22, the cloud point pressure increases with

decreasing 1-butene content and, hence, with decreasing 2600
SCB density (number of ethyl branched100 carbon
atoms). Moreover, the cloud point curve shifts from an
LCST-type to a U-LCST type with decreasing 1-butene =b
w
2200 \.
content. The data are consistent with the known facts a
3 EMA/58wt%MA/99i * . 4
that the higher the polymer crystallinity (or density),
the less soluble the polymer becomes, thereby requiring
3
a
higher pressures for complete solubilization.
These results also suggest that the higher cloud point
pressures exhibited by HDPEs are probably due to their
lower SCB content and consequentlytheir higher densi- ' P-T isopleth
LL EMA/25wt%MA/75k
ties and, to a lesser extent, t o their lack of LCBs. 'f 5.5 wl% EMA
* ; . . * . ; ' . . .
1000
Looking back at Figure 21, one can see also that, as for
the size effect, branchiness has a more significant effect
on the cloud points of the smaller polyethylene mol-
ecules. In other words, the presence of highly branched
LDPE waxes in the polymer, as indicated for instance
by a broad SCBD, is particularly undesirable with
respect t o recycle fouling because it is likely t o increase
the LDPE solubility in the HPS overhead stream. of Luft,64,65
McHugh,22,66 W~hlfarth,~'-'~ and their col-
laborators. These systems can be divided into nonas-
Polar Ethylene Copolymer Systems sociating and associating.
(i) Nonassociating Systems. Both poly(ethy1ene-
Polymerizing ethylene with polar monomers, such as co-methyl acrylate) ( E m ) and poly(ethylene-co-vinyl
vinyl esters (e.g., vinyl acetate (VA), methyl acrylate acetate) (EVA) are weakly polar polymers whose ester
(MA), and butyl acrylate (BA)),unsaturated carboxylic groups interact electrostatically with each other, be-
acids (e.g., acrylic acid (AA)and methacrylic acid cause of their permanent dipole moments, but do not
(MAA)), or mixtures of these, in the presence of free- hydrogen bond with each other significantly. An ex-
radical initiators, results in polymers with enhanced ample of a P-T phase diagram for EMA in ethylene is
optical, mechanical, and thermal properties compared shown in Figure 23, prepared on the basis of experi-
to traditional LDPE homopolymers. Phase behavior mental data taken by Hasch et The EMAs shown
studies for these polar systems are relatively scarce in in Figure 23 have high MW and varying MA content.
the literature, the most comprehensive ones being those As for the high MW LDPE in ethylene, the cloud point
1514 Ind. Eng. Chem. Res., Vol. 34, No. 5, 1995

1 6 0 0 ' . . . : . . . : . . . : . . . : . . . 1 I 1 I L

- 1400
EVA1: 29.3k10.935 ocm-3

=z
h
2200

2000
1
+
L ' 160
9
'd from Luft and W l n i (1982)
i-

I
+
w
a
3
v) 1800
3a
a
+ 1600
z
2 1400
a
3
5 1200
'""t,
0
180°C
15 vi%EVA

0:2 0:4
EVA3-28MtKVA

ti
0
1000 I
0
15 wI% polymer
I
5
I
10
LL
I . . . . I . . . . l . . . . I . . . . l . . . .

15
1

WEIGHT PERCENT COMONOMER IN POLYMER

20
I
25
I I
30

VA WEIGHT FRACTION (POLYMER-FREE BASIS)
Figure 24. Cloud point pressure vs free VA weight fraction in
+
the solvent mixture (VA ethylene) for three EVAs of varying
VA content and one LDPE homopolymer. M,, and the density are
indicated for each polymer in the upper right corner. The
temperature is constant at 160 "C (data are from ref 71).
curves for EMA are UCST-type phase boundaries. As
shown in Figure 23, however, the cloud point pressure
first drops with increasing MA content (up to 25 wt %)
and then increases again a t higher MA concentrations
in the polymer. The same behavior was reported by
Luft and Wind65for the EVA-ethylene system. This
nonmonotonic dependence can be explained by the
difference in polarity (Ap) between the polymer and the
solvent. Since ethylene has a quadrupole moment, it
is more polar than an LDPE homopolymer. As MA or
VA is incorporated into the backbone, the polymer
becomes more polar and Ap is reduced, favoring more
and stronger polymer segment-solvent interactions.
This results in lower cloud point pressures. At some
higher VA or MA weight percent, however, Ap will start
increasing, requiring higher cloud point pressures again.
In the presence of free VA or MA in the solvent
mixture, the cloud point pressure consistently drops
with increasing MA or VA content in the p ~ l y m e r . ~ ~ in
This is illustrated for several high MW EVAs in Figure
24, where the cloud point pressure is plotted as a
function of the VA weight fraction in the solvent mixture
at constant temperature and polymer concentration (15
w t % polymer). Also illustrated in Figure 24 is the
observation that the polymer and solvent VA content
have a much greater effect on the cloud point pressure
than do small differences in molecular size22,64and
density between the polymer and solvent. Although the
polymer density, and therefore he, increases with
increasing VA content (which should drive the cloud
point toward higher pressures), the cloud point pressure
consistently drops with increasing polymer VA content
at all VA weight fractions. Obviously, the Ap effect is
stronger than the A@effect in this case. The effect of
Ap on the cloud point pressure of the EVA-ethylene-
VA pseudo-ternary system was successfullymodeled by
the SAFT
(ii) Associating Systems. The pending carboxylic
acid groups (COOH)in poly(ethy1ene-m-acrylic acid)
(EAA)and in poly(ethylene-co-methacrylic acid) (EMAA)
can hydrogen bond intra- and intermolecularly. There-
fore, the cloud point pressure of these polymers in
ethylene rapidly increases with increasing acid percent
in the polymer backbone.64 This is illustrated in Figure
25 where the cloud point pressure for EAA-ethylene
Figure 25. Cloud point pressure vs weight percent comonomer
in the polymer backbone for two different polar systems: the
associating EAA-ethylene system and the nonassociating EVA-
ethylene system. The temperatures and composition are as
indicated in the figure (data are from ref 65).
(comonomer-free) systems is plotted as a function of the
polymer AA content at constant temperature and poly-
mer concentration (15 wt % polymer). Also shown in
Figure 25 are the cloud point curves for EVA-ethylene
(comonomer-free) systems. Figure 25 illustrates a
dramatic difference in the phase behavior between
EAAs and EVAs in the presence of supercritical ethyl-
ene.
For the associating systems, to a first approximation,
it is the balance between the self- and cross-association
(AA)which controls the cloud point pressure. In pure
ethylene, as the polymer AA content increases, the
degree of self-association is likely to increase. This is
expected to favor demixing and therefore higher cloud
point pressures. Conversely, in the presence of free AA
in the solvent mixture, the cross-association between
polymer segments and the solvent is expected t o favor
mixing and therefore lower cloud point pressures.
P-T isopleths for several high MW EAAs,73varying
, ~AA
~ content, in pure ethylene are shown in Figure 26
along with a reference LDPE homopolymer and EVA.
In all the cases shown in Figure 26, the cloud point
curves are UCST-type phase transitions. The important
point to notice here is that, as the cloud point curves
are extrapolated toward higher temperatures, the dif-
ferences in the cloud point pressures rapidly diminish.
This can be explained by the fact that the average
potential energy (r,)or energy of attraction between two
species i a n d j due to polarity and hydrogen bonding
rapidly decreases at elevated temperatures.13 At such
temperatures, the phase behavior is primarily controlled
by the dispersion interactions among the polymer seg-
ments and the solvent molecules and by the differences
in free volume. These trends are quantitatively ex-
pressed by the followieg relation for r,:
rli= - c 1 ( ~ 4 / r 6-) c z b i2,uj2/ r6KT) -
c3bi2Qj2/r8hT) ... H - bonding (17) + +
where the first term represents the temperature inde-
pendent dispersion interactions, the second term the
dipole-dipole interactions, and the third one the dipole-
quadrupole interactions (with ,u the permanent dipole
moment, r the intermolecular distance, Q the quadru-
pole moment, K the Boltzmann constant, and ci con-

2400 . ...:. . . .:. . . .:....:..
15 wt% polymer
A
L (4) Folie, B. J.; Turner, H. W.; Canich, J. A. M. High Temper-
t 2200;
e ature Polymerization Process Using Ionic Catalysts to Produce
w
a (5) Sinn, H.; Kaminsky, W. Adu. Oganomet. Chem. 1980, 18,
3
v)
3
a
L
1000
50
4 100 150
. 200 250
TEMPERATURE (“C)
Figure 26. P-T isopleths for three EAAs of increasing AA
content, one LDPE homopolymer, and one EVA (all at 15 wt % in
ethylene), illustrating the rapidly diminishing differences in cloud
point pressures at elevated temperatures (data are from refs 52,
71, and 73). The curves are labeled with weight percent incorpo-
ration and with weight average MW, e.g., 138k (if not given, it
means it is not available).
stants). is related t o the interchange energy of
mixing o as follows:
where z is the number of dissimilar solvent-polymer
segment pairs.
The EM-ethylene phase diagram presented in Fig-
ure 26 can be used to explain the heterogeneity due to
formation of “microgels”in commercial EAA products.
Because AA is much more reactive than ethylene in the
high-pressure free-radical process, a local depletion of
free AA, combined with an excess of AA in the polymer,
can lead to a local phase separation in the reactor. Such
a phase separation, in turn, underlies formation of the
microgel domains in the final EAA products.
Conclusions
All the cloud point curves for commercial semicrys-
talline, polydisperse LDPE-monomer systems are of the
UCST or U-LCST type. For the homopolymer LDPE-
ethylene system, the cloud point pressure increases
while the cloud point curve is shifted t o higher temper-
atures with increasing polymer MW (AM) and crystal-
linity/density (A@). For the polar LDPE-monomer
systems, on the other hand, the difference in polarity
( A p )and the difference in self-association versus cross-
association (AA)control the shape and position of the
cloud point curve..
Acknowledgment
We gratefully acknowledge Professor Gerhard Luft’s
unpublished data that we used to prepare Figures 24
and 26. We thank Doctors David Walsh, Paul Ehrlich,
Ludo Kleintjens, Christopher Gregg, and Richard Shutt
for their helpful comments that enhanced this paper.
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Received for review November 21, 1994
Accepted November 29, 1994@
I39401770
@ Abstract published in Advance A C S Abstracts, February
15, 1995.