Macromolecules 1994,27, 6671-6672 6671
Notes
Effect of Chain Architecture on the Cloud incompressible system by V = VA + VB,and considering
Point Curves of Binary Blends of Star uo as unity AG can be written as
Polymers
George Garas and Marios Kosmam' . '
. I
Chemistry Department, University of Ioannina,
451 10 Ioannina, Greece
Received April 15, 1994
Revised Manuscript Received July 27, 1994
The Flory-Huggins expression of the free energy of The diagrams of one loop describing two point correlations
mixing of two polymers i = A and B, of molecular weights between Gaussian chains are easily determined.8 At the
and volume fractions Ni and cpi = VJV, respectively, is critical dimension d = 4 they yield an expression of AG
given by1 AGlkTVluo = (VA/NA) ~ ( C C A+
) ((PB/NB) of the form
+ X(PA(PB. It describes an incompressible system of total
+
volume V = VA VB, with Vi = niNiuo the volume of the
two species, ni the number of chains of the two polymers,
and uo a reference monomer volume considered for
simplicity to be the same for the two monomeric units.
The last term is quadratic in the volume fractions of the
two components and comes from the interactions between
pairs of chains. The x parameter is not a constant at a
specific temperature as initially considered but depends
on the molecular weights and volume fractions of the two
species2because of the correlations between two or more
polymer chains at long chain distances. Starting with a
continuous molecular model and keeping interactions
between two or more chains,3 the dependence of the x
parameter not only on volume fractions and molecular
weights4*5but also on the architecture of the chains can
be seen. Experimentally, architecture effects are seen in
the cases with a lower critical solution temperature where
the critical temperatures of mixtures of stars with an
enhanced macromolecular topology, with linear chains,
are found higher than those of mixing of linear chain^.^^^
The connection of AG with molecular models and the
determination of the effects of the chain correlations are
therefore necessary for the proper description of systems
of chains of complicated architectures and the explanation
of their experimental behavior. We show in this paper
that, keeping correlations between the chains even, the
quadratic dependence of AG on volume fractions can
explain experiments.
ln(2) - 1, M = MA + MB, x =
MA
If w = J dr (1- exp[-V(r)/kTlj is amolecular parameter (2)
MA+ MB
describing the intensity of interactions between ap-
proaching monomeric units, to first order in w, only single where F depends solely on the architectural parameters
encounters between different chains are taken into account which in the present case of stars are the number fi of the
and the x parameter is equal to w, leading to an branches of the two stars and the molecular weight ratio
independence in the case of stars from the chain molecular x = MA/(MA + MB). At the fixed point value w* = €14,
weights and architecture. To second order in w, correla- with t = 4 - d , where d is the dimensionality of the space,
tions between the chains turn in and the cases of stars the exponentiation of the series 1- w[2 ln(M) + f l + ...
differentiate. If fi and Ni are the numbers of branches = M-'/2e+F/4 takes place8 and the M dependence comes
and the molecular weights per branch of the two polymers,
then the star molecular weights are Mi = f,Ni. The volumes
of the two species are given by Vi = njMiuo and that of the
-
from the ln(M) term, yielding an exponent in the limit of
large M equal to -t/2, x M+12. This critical exponent
is the same for stars and linear chains as well as for chains
0024-9297/94/2227-6671$04.50/00 1994 American Chemical Society
6672 Notes Macromolecules, Vol. 27, No. 22, 1994
topology takes place. This agrees with the experimental
observation of a 12O elevation in the cloud point curve of
a mixture of a four-armed star polystyrene with linear
poly(viny1methyl ether) relative to the cloud point curve
of a mixture of linear polystyrene and linear poly(viny1
methyl ether).6 This is of course with the reservation of
the simplification we made considering the two different
monomeric units to be of equal effective length.
For the determination of the critical point the second
derivative of ApA with respect to c p must
~ also vanisha2Apd
Qe am2 = 0, and this provides another condition which
042 Q,h Q .B combined with eq 3 yields the critical value w c = (e9f4/
Figure 1. Spinodal lines of stars of the same molecular weights 2iW-'4[1 + 2[x(1 - ~ ) I l / ~ / x-( lx ) ] . The critical tem-
M = lo', IC = MrJM = 0.2, but different numbers f A and fB of perature T, = b/(a - w,) is then given by
branches: (-) f A = 1, fB = 1; (-) f~ = 1, fB = 4; (- - -) fA = 4,
fB = 4; (* * *) f A = 5, fB = 4. 2 b x ( l - x)M"'~
T, = (4)
2ax(l- X ) M ' - ' / ~ -[l + 2[x(1- x)]1/2]e9/4
We plot these critical temperatures in Figure 2, and we
see that enhanced topologies yield larger critical tem-
120 t; peratures coming from the dependence on the architecture
factor F. This explains the difference of 4 O between the
minima of the cloud point curves of a mixture of 22-armed
star polystyrene and linear poly(viny1methyl ether) and
a mixture of linear polystyrene and linear poly(viny1methyl
ether) seen e~perimentally.~ These experiments have been
i I done with molecular weights of a rank of magnitude higher
24 M 60 a0 100 than those of four-armed stars, and the smaller difference
Figure 2. Critical temperatures T, ("C)as a function of the can also be explained by means of relation 4 where we see
molecular weight parameterM in thousandsfor various numbers that upon increasing the molecular weight M the archi-
and fB of branches of the two species: I-) f A = 1,f B = 1;5-) tectural effects from F decrease. This reduction of the
- -
fA
fA = 1, fB = 4; (- -!f! = 4, fB = 4; (' ' ') f A = 5; fB = 4. All 1lneS architectural effects on increasing M is general, and from
tend to the same limit T, = b/a for M a. eq 4 a special limit is revealed that of Tcfor M m where
the critical temperatures of mixing of all macromolecular
of other architectures, and it is in agreement with previous
results on linear ~ h a i n s . ~Notice
J that the exponent -c/2
corresponds to ideal chains of dense systems like those of
value T, = b/a for M m. -
systems regardless of their architecture tend to the same
melts or concentrated solutions, and it is different from Acknowledgment. We thank the Greek General
the exponent -44 which characterizes expanded chains Secretary of Research and Technology for partial support
like those of dilute solutions in good solvent^.^ of this work.
The spinodals are obtained by applying the criterion
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