Dissolution o f Polyethylene in a Mixture of Two Nonsolvents

Polyethylene (PE), though notoriously insoluble in any single solvent a t near room temperature,
was reported' by the authors to dissolve in a mixture of two nonsolvents (xylene-CSz and cyclo-
hexane-CSz) a t and below room temperature. The work has now been extended, and it has been
found that not only xylene and cyclohexane but quite a few other solvents, viz., benzene, toluene,
carbon tetrachloride, tetrahydrofuran (THF), and chloroform form good cosolvent mixtures for P E
in conjunction with CSz.
These pairs also exhibit a minimum in cloud temperature (T,) as in the previously reported cases,'
and in the case of CHC13 and THF, T, is quite below room temperature. The cosolvent mixture
corresponding to this minimum T,is the optimum solvent composition (OSC). That this is a true
OSC is also corroborated by the fact that the [q]is also maximum a t this minimum ( T c ) . Some
representative data are presented in Figure 1to illustrate the above points.
The viscosity behavior of all such systems are atypical in the sense that the qsPlc vs. c curves have
consistently negative slopes, and in one case, 50:50 cyclohexane-CS2 a t 30°C, the slope is found to
be quite steep, somewhat similar to the behavior of polyelectrolytes (Fig. 2). In this case [q]had
to be obtained by a Fuoss-type plot? i.e., by plotting t/splc against c1I2 from which straight lines are
obtained. Attempts have been made to obtain the Mark-Houwink constants iq the cosolvent
mixtures using both the unfractionated and the fractionated samples, whose moleculgr weights have
been obtained by osmometry in xylene a t 60°C. Results for different PE samples and fractions in
five cosolvent mixtures at 30,34, and 37°C show a large spread in a values from as low as 0.12 to almost
unity and also show a high sensitivity to temperature. Evidently the viscosity behavior of such
systems are too anomalous to be fitted into existing theories.
These systems are, however, theoretically quite interesting because most of them do not satisfy
Gee's3 criteria of cosolvency, viz., dnonsolventl > bpoiymer > dnonsolventz

30 50 70 25 50 75
VOLUME PERCENT C s 2 - VOLUME PERCENT C S 2 +

Fig. 1. Plots showing corroboration of [q]and T, for fraction 2-cosolvent systems.

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18,3315-3317 (1980)

Q 1980 John Wiley & Sons, Inc. 0360-6376/80/0018-3315$01.00
3316 J. POLYM. SCI.: POLYM. CHEM. ED. VOL. 18 (1980)

06 -

07 -

0'6 -

03 -
t
Q
<
&-

03-

Fig. 2. Plot of qsp/cvs. c for fractionated and unfractionated P E in 5050 cyclohexane-CSz.

The more sophisticated equation of Deb and Palit* is also not helpful for predicting OSC because
the latter equation is very sensitive to changes in 6 values. I t can, however, be used in the reverse
way to calculate 6, the cohesive energy density of polyethylene from the optimum solvent composi-
tions. Thus calculated, the 8 for PE comes out between 9 and 9.6 which compares favorably with
the literature value of 9 (estimated).
Attempts to obtain the unperturbed dimension from these viscosity data was successful by using
the Stockmayer-Fixmad plot in the sense that linear Stockmayer-Fixman plots were obtained.
The values of unperturbed dimension ( ( P 2 ) ~ / M ) 1using
/ 2 various fractions a t different temperatures
and a t different cosolvent media were within the range of (900-1100) X lo-" cm g-1'2 against
the literature value6 of (950f 40) X lo-" cm g-'I2

References
1. N. Das and S. R. Palit, J.Polym. Sci.Polym. Chem. Ed., 11,1025 (1973).
2. R.M.Fuoss and V. P. Strauss, Ann. N. Y. Acad. Scz., 51,836 (1949).
3. G.Gee, Trans. Faraday SOC.,40,463,465,468(1944).
4, P. C. Deb and S. R. Palit, Makromol. Chem., 128,123 (1969).
 NOTES 3317

5. W. Stockmayer and M. Fixman, J. Polym. Sci. C, 1,137 (1963).

6. M. Kurata and W. Stockmayer, Hochpolym. Forsch., 3,196 (1963).
NITAVIDYARTHI
SANTIR. PALIT
Department of Physical Chemistry
Indian Association for the
Cultivation of Science
Calcutta 700 032
India
Received September 11,1979
Accepted May 12,1980