'l~nermodynamics of polymeric-glass-solvent systems 2051

21. T. M. BIRSHTEIN, E. V. ANUFRIEVA, T. N. NEKRASOVA, O. B. PTITSYN and T. V.

SHEVELEVA, Vysokomol. soyed. 7: 372, 1965 (Translated in Polymer Sci. U.S.S.R.
7: 2, 412, 1965)
22. F. T. WALL, J. Airier. Chem. Soc. 66: 2050, 1 9 4 4
23. F. TREDVELL and V. GOLL, Kurs a~aliticheskoi khimii (Course on Analytical Chemis-
try). Ob"emnyi i gazovyi analiz (Volumetric and Gas Analysis), ONTI, 1935

THE CORRESPONDING STATES THEORY OF POLYMER SOLUTIONS

AND THE THERMODYNAMICS OF POLYMERIC-GLASS-SOLVENT
SYSTEMS

D. PATTERSON and A. A. WAGER

Centre de recherches sur les macromolecules, Strasbourg, France
Department of Chemistry, Ural State University, Sverdlovsk, U.S.S.R.
(Received 13 March 1967)

THE feeling seems to exist among polymer chemists that accepted polymer
solution theory deals adequately with all essential features of polymer solution
behaviour, and t h a t future progress will be confined to details. However, phe-
nomena have been discovered recently which are at variance with the predictions
of the usual theory, as for instance: (a) the change of the Flory-ttuggins polymer-
solvent interaction parameter X1 with concentration [1] (Fig. 1); (b) a negative,
exothermic heat of mixing a liquid polymer and a solvent has been observed,
not only in polar systems, b u t also for non-polar polymers with non-polar solvents
[2-3]; negative entropies and heats of dilution are also found [3]. Very large
negative heats and entropies of dilution are observed in systems involving
a glassy polymer [4] as will be discussed later. (c) Even non-polar polymer-sol-
vent systems separate into two phases when the temperature is increased suffi-
ciently as well as when it is lowered [3, 5]. Thus solvent "quality" does not
increase monotonically with temperature as expected from the quasi-lattice
theories, b u t passes through a maximum and then decreases.
The typical phase diagram in Fig. 2 shows this recently discovered phase
separation occurring at temperatures above a lower critical solution temperature
(LCST), and the well-known separation below the upper critical solution temper-
ature (UCST). For a polymer of infinite molecular weight, the latter temperature
is the Flory 0-point. :Both coexistence curves in Fig 2 are strongly asymmetrical,
that is, the critical concentration ~o2 is small. With increase of the molecular

* Vysokomol. soyed. A9: No. 8, 1814-1825, 1967.

2052 D. PATTERSON and A. A. TAGER

weight of the 10olymer the UCST increases and the LCST decreases, hence the
domain of complete miscibility decreases.
The new LCST has now been studied in a number of systems [3, 5] and is
predicted [6] to occur in all polymer-solvent systems below the vapour-liquid
critical temperature of the solvent. I"Iowever, it usually lies above the normal
boiling point of the solvent, which explains why it escaped attention before
this. Nevertheless, the LCST is not purely of academic interest but is of general
importance in polymer solutions because at temperatures far below the LCST the

t'51 ////~2
//~i//J
i'O i ~ 5
8
~LC$T
0"5
I ~ UGST(O)
I I
/0•
o'q o.5 0.8 i.O
%
FIG. 1 Fio.2
FIG. 1. Xz vs. (a2 for the systems natural rubber-acetone (1), methylethyl ketone
(2), ethyl acetate (3), benzene (4); polystyrene-acetone (5), n-propyl acetate (6),
polyisobutylene-benzene (8); polybutadiene-chloroform (10). The dashed line
is the saturation curve zt/~l= 0.
Fie. 2. Typical phase diagram for polymer-solvent solution.

solvent "quality" can actually be getting worse with increase of T, contrary to

usual ideas.
A negative heat, A/t 1 and entropy, AS1 of dilution is a necessary condition for
the existence of the LSCT, and negative values of these quantities are in fact
observed either near the LCST [7] or even at a temperature far below it. For
instance, polyisobutylene mixes with the low n-alkanes already at room temper-
ature with a negative heat [2] and LCST of these systems lie in the range of
75°C to 215°C [Sa] (pentane to octane).
All these facts are unexplained b y the Flory-I-Iuggins theory. This theory,
and many other solution theories, are based on the quasi-crystalline model of
the solution. This model has a number of shortcomings. One, pointed out b y
Flory and collaborators [8] is that it artificially supresses the most important
property of a liquid, the irregularity in the distribution of molecules about one
another. Another assumption of the theory is that it applies to nonathermal
 Thermodynamics of polymeric-glass-solvent systems 2053

mixtures the equation for ASm obtained for athermal systems. The heat of mixing
leads to preferential arrangements of the molecules in solution, t h a t is, it leads
to values of A S M which are different from the values corresponding to complete
molecular disorder. An improvement here is given by the "quasi-chemical"
approximate theory.
However, it appears t h a t the most serious fault of the lattice theories is
their neglect of the effect of volume changes in the process of mixing. Constancy
of volume is a direct consequence of the model, as one of the essential assump-
tions is t h a t the motion of a component molecule about its equilibrium position
does not change when mixing occurs. This assumption limits the entropy of
mixing to the combinatorial or geometric contribution which is due to the number
of combinations of arranging the molecules of the different kinds on the lattice
sites of the solution. I n fact, during the mixing of the polymer with a low mole-
cule liquid, contraction usually occurs, that is, the volume of the solution is less
t h a n the sum of the volumes of the components [9].
The only theory which takes into account the change of volume during the
mixing is the Prigogine theory [10]. One of the most important ideas of this
theory is the idea of a difference in free volume between a polymeric and a mono-
meric liquid. This idea is very similar to the idea about the effect of a difference
in density of packing between the polymer and its hydrogenated monomer, which
is developed in the works of Kargin's school [11].
One of the characteristic differences between an amorphous or liquid polymer
and a small molecule liquid is due to the presence of the very strong, and not
easily expanded covalent bonds between the segments in the polymer, the
dimension of which is less t h a n the dimension of intermolecular bonds in the
liquid. Therefore the process of polymerization is always accompanied by a con-
traction [1 la]. Furthermore, the free volume of the polymer is always less than the
free volume of its low molecule analogue due to the bonds between the segments.
The difference in the free volumes of polymeric and monomeric liquids is
parallelled by the difference in their coefficients of thermal expansion which is
considerably larger with the latter. Therefore at ordinary and even more at
high temperatures the monomeric liquid is greatly expanded compared with the
polymer. The "expanded" solvent mixing with the polymer is rather like a com-
pressed gas condensing into the polymer, and this gives rise to a negative contribu-
tion to the heats of mixing since one gets back part of the "heat of vaporization"
when the solvent contracts in making the mixture. During mixing, the free vol-
ume changes of the polymer and the solvent are opposite in sign, as the free volume
of the solvent decreases and the free volume of the polymer increases. But these
changes will not balance to give a zero A V M, which remains negative.
This new negative contribution which seems to be the result of the interac-
tion between molecules of the solvent, adds to the well-known dispersion inter-
action between the non-polar polymer and non-polar solvent. As the result of
this, the total heat of mixing can become negative (AHM<0). Such a case takes
2054 D. PA~rEI~SON and A. A. TAG~R

place during the mixing of polyisobutylene with the low normal alkanes [2a], or
of polydimethylsiloxane with short chain oligomers [2b]. Furthermore, the nega-
tive A V~ can give a negative contribution to AS M producing the thermodynamic
conditions necessary to the LCST, namely that the heat and entropy of dilution
are negative. It is this latter negative contribution to AS M which causes the phase
separation of the solution at the LCST, as distinct from the UCST caused by
a positive AH~. (The negative contribution to the entropy is more important
than that to the heat, so t h a t the over-all contribution of the volume change
i n the f~ee energy is positive.)
The LCST in polar and hydrogen-bonded solutions takes place through
a quite different mechanism. Here, strong dipole-dipole interactions of hydrogen
bonds can be accompanied by the negative values of AS1 and AH 1 necessary
to the LCST.
These qualitative presentations in the Prigogine theory are confirmed by the
quantitative calculation. In their earlier work Prigogine and his collaborators
used the quasi-crystalline lattice or cell model for the polymer solution; however,
the rigid lattice incapable of volume changes is replaced by a lattice of dells whose
volume can change with pressure, temperature and the composition of the solu-
tion.
The later average potential polymer solution theory of Prigogine is independ-
ent of any detailed lattice assumption, and uses a law of corresponding states
which should be obeyed by chain-molecule liquids if certain assumptions are valid.
Pure liquids of chain molecules [12]. For a chain molecule one considers the
molecule as a succession of quasi-spherical segments ("hard spheres"), which
can differ in chemical composition and in geometrical structure. In the following
presentation, however, we assume the segments to be identical. The segments
in a chain-molecule liquid exert on each other two different kinds of forces, the
valence forces, and the intermolecular Van der Wa~ls forces, which differ appre-
ciably in strength and range. The properties of a liquid, which depend only on the
valence forces or on the internal degrees of freedom are called the internal pro-
perties. The properties of a liquid depending on the intermolecular interactions,
or on the external degrees of freedom are called the external or configurational
properties. Thus in a chain molecule the nuclear and electronic motions and the
stretching and bending vibrations are internal motions. The translations and
rotations of the molecule as a whole are replaced in the liquid state by low frequen-
cy, high amplitude vibrations; they and any free internal rotations are external
motions. A hindered internal rotation, according to Hijmans [121, should be
considered as a succession of transitions between different states of rotational
isomerism on which twisting vibrations are superimposed, the former baing
external--the latter internal motions. The internal rotations in the chain molecule
are influenced by the packing of the molecules and hence by the volume. In general
the internal properties of liquid depend only on the temperature; the external--
on the temperature and volume.
 Thermodynamics of polymeric-glass-solvent systems 2055

In the Prigogine theory only external properties are considered. Therefore

one m a y picture a chain-molecule liquid as an assembly of quasi-free segments,
interacting only through t h e i r Van der Waals forces. There remain, however,
several differences between such an assembly and an assembly of spherical mole-
cules. The existence of chemical bonds will affect the behaviour of the segments
in several respects, viz.:
1) The surface around a segment is only partly free for intermolecular inter-
action, the remaining part being blocked b y the adjacent segments in the same
molecule.
Let us suppose that the molecule is composed on n chain atoms, b u t m a y be
considered as a succession of r quasi-spherical segments, q, the number of external
contacts of these r connected segments will be equal to the number presented b y
a rather smaller number, q, of independent spherical molecules. In the lattice
theories the relation between q and r is given by:
qz----r(z--2)-k 2 . (1)
In a n y case we expect that q is of the same order as r.
2) Each segment of the chain contributes less than the 3 external degrees of
freedom it would have if it were an independent spherical molecule I f the number
of external degrees of freedom is 3c then c is the number of equivalent spherical
molecules.
I t is assumed that the same form of interaction potential characterizes all
the external contacts between segments:
q~(r)----e* ~*(r/r*) (2)
where t * - - t h e contract energy, when the liquid is at 0°K and r*--is the inter-
molecular distance, at which the maximtun interaction takes place; ¢*--is some
function, possibly that describing the often used 6-12 potential.
Then a chain-molecule liquid can be characterized b y means of these two
segment parameters as well as the three parameters related to the whole molecule
which are of the nature of effective numbers of segments; q, r and c.
I f one assumes that the molecule, consisting of r segments, and hence having
3r degrees of freedom, has free inner rotation between segments then there are
(r--1) stretching vibrations, and (r--2) bending vibrations. All in all the number
of the inner degrees of freedom in such a molecule is equal to (2r--3). ~Ience the
number of the external degrees of freedom is 3 r - - 2 r ~ - 3 = r ~ 3 . Then
ac----r+3 (r~2). (3)
For a n y monomeric liquid, for which the inner degrees of freedom are absent,
3r----3c. Then, r = l , c : 1 and c / r : 1 . For a series of homologues such as the
normal alkanes, when r-.oc, i.e. moving from methane up to polyethylene,
c/r decreases asymptotically to a constant value:
c 1
lim - - * - . (4)
r~o r 3
2056 D . PATTERSON a n d A. A. TAGER

This would be 1/3 if the chain is completely flexible, that is if there are free internal
rotations between segments as in equation (3) If the chain molecules is a comple-
tely rigid rod, the number of degrees of freedom per molecules is 3c----5 and

c/r----O. Thus the parameter - depends on the flexibility of the chain molecule and
r
1 e c
it changes from 0 up to ~ . The ratio - : - is called the structural factor and
r q
it plays an important role for polymers and polymer solutions.
The cohesive energy is proportional to ze* for a monomer, b u t for a chain-mo-
lecule to qze*, where z is the coordination number of liquid, and qz--the number
of external contracts made b y the r segments.
I f in'the system there are N chain molecules, the cohesive energy of liquid
is proportional to Nqze*, its volume to N(r*) ~ and its entropy to Nck where
k--is Boltzmann constant.
The values
Uo:qe*N; Vo=r(r*)aN and So----ckN (5)

are called the molecular units. They are most important to the process of reducing
thermodynamic functions.
The law of corresponding states and the chain-molecule liquids. The principle
or the Law of Corresponding States was formulated for the first time for the real
gases. It says that a corresponding temperatures and corresponding pressures the
corresponding wolumes of substances must be the same.
The corrsponding state of two substances is such a state when the substances
have the same reduced pressure, temperature and volume. (The reduced quanti-
ties are the dimensionless quantities which are usually obtained b y dividing the
temperature, volume and pressure of a givin gas b y the critical parameters.)
Pitzer [13] and later on Guggenheim [14] have shown that for all liquids with
spherical molecules the Law of Corresponding States is valid. Thus, a universal
equation od state P* (V*, T*), valid for any of these substances, is obtained when
the pressure, the volume and the temperature are replaced b y reduced quantities,
(designated here b y an asterisk).
Prigogine and his collaborators have extended the principle of corresponding
states to liquids consisting of chain molecules [10b], and the principle has been
tested for a variety of such liquids [15]. The configurational energy, volume, en-
tropy etc. of a chain-molecule liquid are functions of temperature and of the
number n of chain-atoms in the molecule (V(T, n); U(T, n); S(T, u), etc). The
reduced quantities are functions only of the reduced temperature. The reduction
parameter should be a function only of the nature of the substance, that is, for
the series of homologues it should depend only on the number n of chain-atoms.

V*(T*)= V(T, ~)/Vo(n) (6a)

 Thermodynamics of polymeric-glass-solvent systems 2057

U*(T*)= U(T, n)/Uo(n) (6b)

S*(T*)----S(T, n)/So(n ) (6e)
U*, V*, S*, etc.--are the reduced configurational energy, volume and configura-
tional entropy respectively. All of them are functions of reduced temperature
only
T*:T/T o ; T o = Uo/S o . (7)

The reduction parameters are given b y eqn. (5). In the case of the entropy we will
omit from consideration the combinatorial of the entropy due to number of com-
binations of arranging the flexible chain-molecules on the liquid lattice. Thus only
the "non-combinatorial" entropy will be considered due to the interactions
between segments and their neighbours.
The reduction parameter T0(s ) increases asymptotically as the number of
chain backbone atoms n goes to infinity. Typical values indicate t h a t T o for
a high polymer is about 1.5-2 times T Ofor a monomeric solvent. Thus the temper-
ature affects configttrational quantities of high polymer liquids as if divided by
a factor of 1.5 or 2 as evidenced by the much greater density of these liquids
compared with solvents.
The reduction procedure m a y be carried out in m a n y different ways. For
instance, one reduction procedure consists of plotting log V against log T on
separate sheets for the different liquids. Then, by shifting the sheets in the x
and y directions, all of the curves m a y be brought into juxtaposition with the
curve for one of the liquids which m a y be taken as a reference liquid. The extent of
the shifts required give values of the ratio of V0 and T o to those quantities
Vo,R and T0m--for the reference liquid taken by Hijmans to be heptane. For all
n-alkanes Hijmans got a single curve V*(T*) [12].
All the thermodynamic properties, calculated from these equations are the
external and so-called configurational properties t h a t is, the properties which
depend only on the intermolecular interactions. Thus the energy of eqn. (6b) is the
configuration (intermolecular) energy. It is the energy of the liquid minus t h a t
of the substance in the perfect gas state. It is thus a negative quantity, and
equal to the negative of the energy of vaporization or to the negative of (heat of
vaporization minus RT).
Similarly to the above reduced quantities, we shall use below the reduced
configurational heat capacity

C* (T *)= Cp(T,n) (8)

~o (n)
and the reduced free Gibbs energy
G (T,n)
G*(T*)=--~ (9)
Uo (n)
2058 D . PATTERSO~ a n d A. A. TAGER

Thermodynamics of chain-molecule mixtures. The Prigogine theory pre-

dicts that the molar thermodynamic quantities of mixtures obey the same law of
corresponding states as a pure liquid. The most simple system is the molecular
mixture, formed by the components, the molecules of which are the members of
one series of homologues, i.e. e* and r* are the same. This is the case of mixing of
an amorphous liquid polymer with the low molecular analogue, or its hydro-
genated monomer. In this simple case the reduction parameters for the mixture
are simple mole fraction averages, that is:

< Vo>= x 1 (Vo,1)-{-x2 (Vo.2) (10a)

<Uo>----x, (Uo.1)-l-x 2 (Uo.2) (10b)

where x, and x, are the mole fractions of the components.
Similarly
<q> =x, q,+x~ q2 (11)
<c>= x l c~ + x2 c2 .

Then, according to eqn. (7), the reduced temperature of mixture:

T </c~kT (x 1 c , + x 2 c~) R T x 1 c1 RT x~c2 RT

<T*> . . . . (12)
<To> = \ q / - ~ = (xlql+x2q2) e* x, ql+x2q2 e* + x l q i + x 2 q ~ ~*

I f every item is multiplied and divided by ql and q2 respectively, we obtain:

<T*>=X, T~ ~-X 2T: (13)

where

Xl - Xl ql (14)
x, q, + x2 q2

represents the "surface fraction" of component 1, that is, the ratio of the num-
ber of external contracts made by molecules of that component to the total
number of external contacts in the solution. This fraction should be almost
equal to the fraction of all segments which are of t~Te 1. In other words one
expects that q_~r, so that X I = ~ , , and

< T * > ~- ~1 T* + ~2 T* (15)

where T~ and T~--the reduced temperatures of the pure components and ~1
and q2--their volume fractions in the solution.
Everything mentioned above allows to calculate the volume, heat and en-
tropy of mixing and the excess dynamic quantities. Thus, the volume of mixing
/IV.,= Vsol--x 1 V , - - x 2 V2. Substituting the reduced quantities, one obtains

zf VM ----<Vo>V *(<T *>)-- {x~ Vo,, (T*)-}-x2 Vo,2 V * (T:) }

 Thermodynamics of polymeric-glass-solvent systems 2059

We assume that the ratio

xl Vo,1 _ x l Vo,1 . x~ Vo, 2 = ~2 Vo,2

<Vo> xl Vo,l+x2 Vo,2 ' <Vo> xl Voa+X~ Vo,2
are equal to the volume fractions ~ot and ~o2.
Then
V*(T*)}. 06)
In Fig. 3 the curve of temperature dependence of reduced volume for
the serie of homologues is given. The reduced volumes at T* and T~ for a short
homologue (solvent) and a long homologue (polymer) are shown. The point B
denote the reduced volume of the mixture, and the point A - - t h e additive sum of
the reduced volumes of the pure components. I t is shown that the difference
A Vi should be negative. This is in agreement with the intuitive consideration
and with the experimental data.
Similarly one can calculate the energy of mixing, almost identically equal
to the heat of mixing in these systems

z ~ V M : V s o l - - X 1 V l - - X $ Ur~<Uo>[U*(<T*>)--q~ 1 U*(T~)--qJ 2 U*(T*)]. (17)

A number of models of the liquid state and empirical data for the n-alkanes
[16] show that the curvature o£ U * ( T * ) is also concave upwards, at least at
higher temperatures, and hence in this case .dU M is also negative.
Thus the l~rigogine theory predicts, that in the processes of mixing of poly-
mers, even when the "chemical" difference between components are small or
absent (polymer--hydrogenizated monomer), both values A V M and A H M are
found to be different from zero. This is only due to the difference in the lengths of
the chains and to the difference in the coefficients o£ thermal expansion. This
contribution in the thermodynamic function only due to the difference in the
lengths of molecules is called the structural effect in the Prigogine theory; it
c
depends on the structural factor --.
q
The negative values of A V M are also the main reason for the negative con-
tribution to the entropy of mixing A S M. It is important to notice, however,
that this negative contribution to A S M is found, experimentally and theoreti-
cally, to be more important than the negative contribution to A H M. In fact
according to one model, the smoothed potential cell model, these two contribu-
tions are related b y TASM-----2JHM . Thus the final contribution to AGM is positive,
and this effect of free volume changes on mixing is the cause of phase separation
at high temperatures (LCST). i n absolute terms, of course, A V M and A H M are
small quantities for the solution of a liquid polymer in a solvent because the
curvature of V * ( T * ) is in fact quite small; the polymer increases its free volume
while the solvent decreases its free volume and these two changes almost balance
due to the small value of the curvature of V* (T*).
2060 D. PATTERSON and A. A. TAGER

Thermodynamics of polymeric glass solutions. Simha and collaborators [17]

have shown t h a t the law of corresponding states is approximately valid for
polymeric glasses. They used the same reduction parameters as for liquid poly-
mers if the temperature is sufficiently below Tg. In the glass state, of course
V*(T*) is not merely an extrapolation of V*(T*) of the liquid state, but lies
above this as shown schematically in Fig. 4. It should be noted that the glass
transition temperature for the different polymer corresponds only approximate-
ly to a single reduced glass temperature T * . As a first step, however, we as-
sume t h a t the correspondence is exact, and we now apply the corresponding
states theory to systems containing a polymeric glass and a solvent. These
systems have been studied b y one of us and present a number of striking
features [4].
For instance, the heat of dilution AH 1 of a solution in the glass state is essen-
tially constant, negative (exothermic) and very large ~ - - 1 0 c a l / g . When a
critical concentration of solvent is reached, the solution changes from the glass
state to the liquid state, and the heat of dilution drops to a value typical for
the dilution of liquid solutions, i.e. about 10-10 3 times less [4].

v77-'
V'(T')
u'(r')
17,.
. /~
GlaSS / ,$"
"
/ /
T~ T* 7*
FIG. 3 FIG. 4 FIG. 5

F I e . 3. Temperature dependence of reduced volume for polymers above Tg.

FIG. 4. Temperature dependence of reduced volume for polymers above a n d
belov Tg.
F i e . 5. T e m p e r a t u r e dependence of reduced energy.

This order of magnitude difference is surprising at first sight since the specific
volume of the solvent is not as far different from t h a t of the glass as from that of
the polymeric liquid, l-Iowever it is evident that here the loose packing of the
glass has changed the situation [11]. In fact the curvature of V*(T*) over the
whole curve (Fig. 4) and of H*(T*) (Fig. 5) are much greater than if the polymer
were in the liquid state throughout the whole range of reduced temperature.
Qualitatively it is evident that a large negative value of A VM, and hence of
ztHM would be expected. Experimentally a very large negative value of AS 1
 Thermodynamics of polymeric-glass-solvent systems 2061

is found when the solution is in the glass state, and so one might expect phase
separation to occur as in a liquid polymer solution at the Lower Critical Solution
Temperature, where A ~ is negative, b u t much smaller than in the present case of a
glass solution. In fact, however AG 1 is not very different from the value in a
normal liquid solution at ordinary temperatures. Thus the negative contribution
to AS 1 furnished b y A VM must almost exactly balance AH 1 in the case of a glass
solution unlike the case of a liquid solution.
We would like to explain this qualitative difference between liquid systems
and systems containing a glass and a liquid and to confirm with quantitative
calculations.
Calculation of AH M. For our semi-quantitative calculation we assume a
single reduced curve of V*(T*) and U*(T*), i.e. the principle of corresponding
states is assumed to hold in the region of the glass temperature as well as else-
where. Also we completely neglect the curvature of U*(T*) above and below
Tg, i.e. C* above and below the glass transition is taken to be constant, equal
to, respectively, C* z and C~g.
*
From Fig. 5 it follows that for any reduced temperature
T*>T*
Ug -t-C~z ( T * - - T * ) (18)
For a n y reduced temperature
<T*> <T* ,

U *---- Ug*-5 C~g* ( T * - - T * ) . (19)

At the glass transition the reduced temperature of the solution is equal to
the reduced glass transition temperature
<T*>----T*.
Then, using the eqn. (13) one m a y calculate the concentration, at which the
solution changes from glass to liquid
Tg -- T 2 . T 1 -- Tg (20)
~lg ~ , , , ~P2g- , , "
T z -- T u TI -- T 2

Let us consider mixing N 2 molecules of glass-state loose-packed polymer with

-/~1 molecules of law molecular liquid and divide the problem into cases: when
~2< ~g and when q2> q2g.
Case I ~z<~2g (liquid solution). We shall calculate Z~HM~--zJUMusing the
eqn. (17) and putting in it the values U*(T*) and U*(T*), obtained from eqn.
(18) and the values U*(T*) obtained from eqn. (19). The reduced temperature
of solution is calculated using eqn. (15). Then
AHM=N<q>e*[U*+C;* ~ * * * [U:+C~ * *
--,q'2 [ U*-{-Cpg (T~--T~)]. (21)
2062 D. PATTERSON and A. A. T A G E R

The value of the parameter <q> is expressed through the values q, and q~,
using the eqn. (11). After some transformation, we obtain

% z/c* (T*--T*) (22)

where
z/c; = % -c;, .
Then

Z/HI= OZ/ttM= 0 (23)

3N~
and
AH--2= OZ/HM
aN-----~=--NAq28* zfC;* (Tg* --T~)
* (23a)

where _hr~=Avoga~lro's number.

Equation (23a) may, however, easily be transformed to eliminate the re-
duced quantities
Z/H2-= -- Z/C~ (Tg-- T) (24)

where JC~ is the molar quantity Cp~--Cpg for the polymer. The same expression
also serves for the specific quantities (per g)

Z/h2-------ACp(Tg--T). (24a)

Case II q2> ~g (solution in glass state).

We must now use eqn. (19) for both T* and <T*> and eqn. (18) for T~. Then
we obtain:
(25)
Z/HI= -- N ~ q,e * z/C* (T~--T*) (26)

Z/H2=0. (26a)

Thus, the Prigogine theory predicts very sharp alterations of the values
A H 1 and AH2 at the transition of solution from the glass state to the liquid one.
The theoretical curves of the alterations of the values AH 1 and AHa with the
concentration axe represented in Fig. 6a; they are similar to the experimental
curves (Fig. 6b). Dividing eqn. (26) by eqn. (23a) and using eqn. (20), we obtain:

A H 1 (Case II) ql ep~g

(27)
AH~ (Case I) q2 ~lg ,
 Thermodynamics of polymeric-glass-solvent systems 2063

and for specific quantities

Ahl (Case II) m2 ¢2g ~ ~g

= - - - - _ (2s)
A/~ (Case I) ml ~Olg ~Plg

where, m 1 and m 2 are the masses of the segments in the solvent and polymer
molecules. These m a y be equal as in the case when the polymer and solvent
are from the same homologous series. Then,

Afh (Case II) ~lg=Ah2 (Case I) ¢2g. (29)

I t means t h a t the areas indicated in Fig. 63 are equal.

Using a typical value of ACp----0.1 cal/deg and Tg~ 100 ° we have Ah2 (Case I)
-- -- 10 cal/g.

oaL
tO- h

-aa, 8
6

4
-ag
2

0
% °e=l 0~2 0~ O6 O8 ~2

Fro. 6. Dependence of Ah-~and Ahl: a--theoretical; b--experimental curves.

AGM Calculation. For the calculation of the non-combinatorial part of the

free energy of mixing we can use Gibbs-I-Ielmholz equation in reduced form

G
T *' F- * T* -- f U ( ~ , )2 d T * + K (30)

where K is a constant of integration.

For a n y reduced temperature T* > Tg*
G * ----(Ug--C~
* * T~)-t-k~T* - - C ~ l* T* In T* . (31)

For a n y reduced temperature T* < T*

G*= Ug*--C~g*Tg*~ Kg T*--C*g T* In T * . (32)
The free energy of mixing
AG~ = <G*> (solution)-- rpl G1* -- ~2 G2* • (33)
2064 D. PATTERSON and A. A. TAGER

Substituting the values of (G*>, G~ and G~ from eqns. (31) and (32), and using
the same relation as in the calculation of ztH M, we obtained the expression
for AGM.
A relation between the two constants of integration is obtained b y the re-
quirement that G* be continuous at T~. I t is found that all terms of the same

order as AH M vanish. The next terms remaining are of higher order in ( T ~ - - T ~ )

are of the same order as those occurring for liquid solutions, and which have
been neglected here. To the accuracy required here, therefore, we find that
AG~ (non-combinatorial)-~ 0. (34)
I f the heat and entropy of mixing are negative such a result is possible only on
condition that
T A ~ 1 (non-combinatorial)=AH 1 . (35)
In this case of a polymeric glass and a solvent which mix to give a solution in
the glass state, the large negative A VM produces a large negative contribution
to AS~. However, it is cancelled b y the negative AHM, and so does not lead to
phase separation as in the case of a liquid polymer solution at high temperature
(LCST).
CONCLUSIONS
(1) The basic principle of the Prigogine solution theory is considered, and
the possibility of application of the Law of Corresponding states to the loose
packed glass state polymer solution in their hydrogenated monomers is shown.
The heat and free energy of mixing are calculated.
(2) It is shown that at a high concentration of polymer in' solution when the
solution is in the glass state, AIt~=O and A H 1 is finite, constant and negative.
For the liquid solution, AHI=O and AH~ is finite, constant and negative. The
critical concentrations at which the values A H 1 and A H 2 change were calcul-
ated. The coincidence of theoretical curves for the alteration of A H 1 and A H 2
with concentration and the absolute value of A I t 2 with the experimental data
is satisfactory.
(3) It was shown that the non-combinatorial part of the free energy in the
processes of mixing loose packed glass state polymers with their hydrogenated
monomers or with other oligomers of the same chemical structure are close to
zero. This is possible on condition of balance of the large negative values of
AH1 and T A ~ 1.
Translated by D. PATTERSON (Co-aubhor)
REFERENCES
1. C. BOOTH, G. GEE, G. HOLDEN and G. R. VCILLIAMSON, Polymer 5: 343-367, 1964
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Farad. Soc. 58: 2116, 7, 1962
 S y m p o s i u m on macromolecular chemistry 2065

3. C. H. BAKER, W. B. BROWN, G. GEE, J. S. ROWLINSON, D. STUBLEY a n d R. E.

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1965
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1964
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Chemical Technology Series 1: 135, 1958
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Zh. fiz. khim. 27: 1217, 1958
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REPORT

SYMPOSIUM ON MACROMOLECULAR CHEMISTRY*

N. A. PLATE

TKE Scientific Council of High-Molecular W e i g h t Compounds a t t a c h e d to the General and

Technical Chemistry D e p a r t m e n t of t h e U.S.S.R. A c a d e m y of Sciences, with the A c a d e m y
of Sciences of the Armenian S.S.R., held a symposium in Yerevan from 29th October to 4
November 1966 on the problem of Kinetics a n d F o r m a t i o n and Transformation Mechanism
of Macromolecules.
These problems are of interest because the t h e o r y of polymerization a n d the whole
field of p o l y m e r synthesis are a t present passing through a period of development due to

* Vysokomol. soyed. A9: No. 8, 1826-1828, 1967.