European Polymer Journal. Vol. 12, pp. 849 to 852. Pergamon Press 1976. Printed in Great Britain.

VISCOSITY-TEMPERATURE RELATIONSHIPS
FOR POLY(VINYL CHLORIDE)-TETRAHYDROFURAN
DILUTE SOLUTIONS
N. AELENEI and I. A. SCHNEIDER
Physical Chemistry Department, Polytechnic Institute of Jassy, R-6600 Jassy, Roumania

(Received 5 February 1976)

Abstract-The viscous flow parameters for dilute PVC-tetrahydrofuran solutions were determined in
the temperature range 10---45. The temperature dependence of the viscosity of the solutions obeys
an Arrhenius-type equation. The concentration and the molecular weight dependence of the pre
exponential factor of this equation is given by the following relationship:
A= A0exp[ -Ka(cMw)2J.
Both the values of the viscous flow parameters and the mathematical expression of the pre-exponential
factor indicate, by comparison with other results, some stiffness of PVC chains in tetrahydrofuran.

I. INTRODUCTION at the working temperature, r0 the flow time and i'1r0 the
Hagenbach-Couette correction (in accordance with the
According to Flory and Fox [1], the exponent "a" recommendations for use of the viscometer). The tempera
of the Mark-Houwink-Sakurada equation ture dependence of the viscosity of the stabilized-THF in
the range 15 to 45 can be expressed as
[17]=KM" (1)

3
must lie between 0.5 and 0.8 for macromolecules with lg110 = -1.656 + \11 in cP) (3)

; 0
flexible chains without draining effects in dilute solu
tions; the lower limit applies to tightly coiled chains which agrees satisfactory with equations given by Carvajal
in theta solvents, and the upper to highly swollen et al. [4] and Metz and Glines [SJ.
The viscosities of the polymer solutions were measured
chains in very good solvents. Values greater than 0.8 using a dilution viscometer with suspended level; the kin
are usually regarded as evidence for draining effects etic energy corrections were negligible. The viscosities were
of the solvent through the macromolecular coil, or calculated from:
of chain stiffness in solution. T. p
The literature contains contradictory results for the 11=110-- (4)
To Po
exponent for the PVC-tetrahydrofuran (THF) system,

ranging from 0.56 to 0.92 [2]. Therefore it is not poss
ible to be certain of chain flexibility, although PVC
macromolecules are usually regarded as flexible and
THF as a good solvent for PVC. On the other hand,
the ratio between the unperturbed dimensions and
the dimensions of the freely rotating chain suggests
some stiffuess of PVC molecules. Study of the visco
sity of dilute PVC-THF solutions may provide evi
dence about PVC chain stiffness in solution.
For this reason, we studied viscosities of PVC-THF
solutions at temperatures from 10 to 45 and concen
trations up to 1 g/dl.
2. EXPERIMENT AL
The viscosities of PVC-THF solutions were measured
for three fractions of a Geon-suspension PVC (M, 63,000;
108,000 and 153,000) characterized previously [3]. THF
stabilized with 0.05% hydroquinone was used.
The viscosity of the solvent was measured using an
Ubbelohde-type viscometer with suspended bulb level; the
temperature was controlled within 0.02. The Hagen
bach-Couette correction was applied for the flow times
so that the viscosity, nc- was calculated from:
where l'/o is the viscosity of THF, r and r0 the flow times
and p and p0 the densities of solution and solvent respect
ively.
The densities of THF and of the PVC fraction with
Mw = 153,000 were determined gravimetrically in the tem
perature range 15--45, temperature being controlled within
0.02.
The densities of the polymer solutions with concen
trations up to 1 g/dl and for temperatures between 15 and
40 were calculated from the densities of polymer and sol
vent assuming additivity:
p = 0.8875 + 3.72 x 10-3-c
+ 1.036 x 10- 3 (20 - t) g/cm3 (5)
where c is the solution concentration and t is the tempera
ture.
The concentrations of the solutions were determined by
weighing at 20; for the other temperatures, corrections
for the temperature dependence of the volume were made.
3. RESULTS AND DISCUSSIONS
Moore and co-workers [6--11] have shown that the
viscosity of dilute polymer solutions varies with tem
perature according to an Arrhenius-type law:

1'/o = k(ro - Mo)'Po (2) 17 = A-exp(Q/R T) (6)

where k is the viscometer constant, p0 the density of THF

849 where 17 is the viscosity of the solution, Q the apparent
 850 N. AELENEI and I. A. SCHNEIDER

Table 1. Values of the K. constant for some polymer-solvent systems

Chain 102K,
flexibility Polymer Solvent Jdl/gmol Ref.

Poly(vinyl acetate) -chloroform 0.836 [10]

Great Poly(methyl methacrylate) -chloroform -1.467 [10]
Poly(vinyl formate) -chloroform 0.946 [10]
Bisphenol-A polycarbonate -chloroform 2.68
,, Moderate
-ethylene dichloride
-methylene chloride
2.39
1.42 [9]
-tetrahydrofuran 1.76
-dioxane 2.39
Cellulose acetate -acetone 9.80 [15]
Cellulose nitrate -acetone 4.61 [8]
Small -n-amyl methyl ketone 10.05 [8]
-methyl acetate 8.38 [8]
-n-butyl acetate 5.86 [8]
-cyclohexanone 11.3 [8]
The pre-exponential factor, A, depends also on the concentration and the molecular weight
of the polymer but, as compared to Q, it is much more sensitive to experimental errors.
activation energy of viscous flow and A a pre Moore [12] in terms of the activation entropy change
exponential factor. of viscous flow. Thus, for flexible chain polymers in
The apparent activation energy of viscous flow is dilute solutions:
a function of the nature of the polymer-solvent sys

tem, of the solution concentration and of the molecu

lar weight of the polymer. A linear dependence of
the apparent activation energy on the concentration
was found for all polymer-solvent systems studied:
Q = Qo + kc' c (7)
Q0 being the activation energy of viscous flow of the
pure solvent and k; a coefficient depending on the
molecular weight of the polymer. The coefficient k.
generally increases with molecular weight according
to:
k, = K.Mw (8)
and data analysis for many systems indicates that K.
depends on the chain flexibility of the polymer in solu
tion; for flexible polymers in good solvents, K. is by
1-2 orders lower than for stiff chain molecules, e.g.
cellulosic derivatives (see Table 1).
It seems, however, that the dependence of A on
molecular w.eight and concentration is connected with
the chain flexibility in solution; it was interpreted by
A= A0 + K.M"c (9)
while for stiff chain polymers:
A= A0exp(-KMPc) (10)
In these equations, A0 represents the pre-exponential
factor for the pure solvent and K0, K, o: and fJ are
constants depending on the nature of the polymer
solvent system. A dependence similar to that in Eqn.
(9) was found also for a polymer with moderate stiff
ness of the chain [9].
For the PVC-THF solutions considered here,
Eqns. (6), (7) and (8) were verified: thus, as seen from
data presented in Fig. 1, the plot lg r, vs (1/T) gives
straight lines for all concentrations and fractions used.
Also, the dependence of the apparent activation
energy on concentration is linear (Fig. 2).
The plots lg A vs c2 (Fig. 3) and A vs c2 (Fig. 4)
indicate that the dependence of the pre-exponential
factor on concentration may be expressed thus:
A=A0exp(-k.(c2) (11)
with:
(12)
II

-0.1 10
0

!3'
I"' {
6
)(
9
"'
Q
-0,3

7aL-o1 J.-o3 J.-o5-oso1-oe

0
- 1,5 3.20 3.25 3.30 3.35 3.40 3.45 3.50
IOo/T, K-1
Fig. 1. Typical diagrams of lg '1 vs (1/T) for PVC-THF c, g/dl
solutions, for various concentrations and molecular Fig. 2. Dependence of the apparent activation energy, Q,
weights of the polymer. on the concentration and molecular weight of the polymer.
 Viscosity-temperature relationships 851

;;;,. =63,ooo
;;;,. '63,ooo
0
2.1

<!
_g,-1 70 Q.
U 2.0

<i
1. 9

1.e
- 1.75'----'---........L---'----'----'--........,.. _.

0 01 02 0 3 0.4 0.5 0.6 0.7

r?, cf/dl2

Fig. 3. Concentration dependence of the pre-exponential 0.1 0.2 0.3 0.4 0.5 0.6 0.7

factor, A, (Eqn.: lg A = lg A0 - k01 c 2

). c 2
g fdl2
2

Fig. 4. Concentration dependence of the pre-exponential

factor (Eqn.: A = A0 - k02 c ).

Table 2. Viscous flow parameters for dilute PVC-THF solutions

---------
10-3k, 102K, 103. k.2 103 A0 k.1
MW Jdl 10-3Qo Jdl k.1 cPdl2 cPdl2 102 A0
Fr. g/mol gmol J/mol g" dl2/g2 l010K01 Yi 7- -gi- 1012.K.2 {'2 cP

1 63,000 1.314 0.0618 l.40 1.36

2 108,000 2.489 7,544 2.25 0.269 I.OS 2.15 5.78 5.94 4.85 1.97 2.208
3 153,000 3.409 0.345 7.36 7.61

or Houwink-Sakurada equation found by Batzer and

2 Nisch [14] (0.92), Inagaki and Nakazawa [15] (0.83)
A = A0 - k02 c (13)
and Maron and Lee [20] (0.851) which are specific
with: for polymers with stiff chains or with permeable coils.
However for the PVC-THF system, other authors
(14)
found values smaller than 0.8, e.g. 0.69 by Takahashy

which differ from those given in the literature. Equa
tions (11) and (13) are equivalent, (13) arising from
(11) by expanding the exponential factor and retaining
no terms beyond those in the square of the concen
trations. Consequently the K02 value, evaluated from
the A - c2 plot, must be equivalent to the product
of K01 A0 (see Table 2).
However we must note that Eqns. (11) and (13),
and especially Eqns. (12) and (14), were deduced for
a large scatter of the experimental data; for reliable
conclusions, measurements over a more extended
range of concentrations and molecular weights are
necessary.
The coefficients of the equations (7), (8) and (9}-{14),
deduced from the slopepf the lines in Figs. 1-4 and
from th1: plots k, - Mw, lg k01 - lg M; and lg
k02 - lg Mw, are listed in Table 2.
The values of both y1 and y2 suggest that the pre
exponential factor should be expressed by:
A= A0exp[-K.i"(Mc)2].
2
The value of 2.25 x 10- found for K. is in the
range of values established by Moore and Uddin [9]
for bisphenol-A polycarbonate in various solvents
and lies between the K. values for flexible polymers
and for cellulosic derivatives. Taking into account
also the exponential dependence of A on concen
tration, it seems that there is some stiffness of the
PVC chains in THF. This conclusion agrees with
the greater values of the exponent in the Mark-
et al. [16], 0.766 by Freeman and Manning [17] and
0.54 by Koboyashi [18], characteristic for flexible
chains.
Moderate stiffness of PVC chains in THF is sug
gested also by a value of 1.83 quoted by Kurata and
Stockmayer [19] for the ratio between the square of
the unperturbed average end-to-end distance and the
dimensions of the freely-rotating chain; this ratio is
also between the values characteristic for flexible and
for stiff chains.
REFERENCES
I. P. J. Flory and T. G. Fox, J. Am. chem. Soc. 73, 1904
(1951).
2. J. Brandup and E. H. Immergut (Editors), Polymer
Handbook, Interscience, New York (1966).
3. C. Vasile, A. Onu and I. A. Schneider, Rev. Roumaine
Chim., 15, 1935 (1970).
4. C. Carvayal, K. J. Tolle, J. Smid and M. Szwark, J.
(15) Am. chem. Soc. lf7, 5548 (1965).
5. D. J. Metz and A. Glines, J. phys. Chem. 71, 1158
(1967).
6. W. R. Moore and A. M. Brown, J. Colloid. Sci. 14,
I (1959).
7. W. R. Moore and A. M. Brown, J_ Colloid. Sci. 14,
343 (1959).
8. W. R. Moore and G. D. Edge, J. Polym. Sci. 47, 469
(1960).
9. W. R. Moore and M. A. Uddin, Europ. Polym. J. 3,
673 (1967).
852 N. AELENEI and
10. W. R. Moore, R. J. Fort, R. J. Hutkinson and M.
Murphy, Polymer, A35 (1963).
11. W. R. Moore and H. Pathan, Indian J. Technol. 3,
392 (1965).
12. W.R. Moore, Nature, (Lond.) 206, 184 (1965).
13. H. K. Johnston and S. Sourirajan, J. appl. Polym. Sci.
17, 3717 (1973).
14. H. Batzer and A. Nisch, Makromolek. Chem. 22, 131
(1957).
15. H. Inagaki and J. Nakazawa, (quoted in Ref. 2).
I. A. SCHNEIDER
16. A. Takahashi, M. Ohara and J. Kagawa, Kogyo kwa
gaku zasshi (J. chem. Soc. Japan, Ind. chem. Soc.), 66,
960 (1963).
17. M. Freeman and P. P. Manning, J. Polym Sci. A2,
2017 (1964).
18. T. Koboyashi, Bull. chem. Soc. Japan, 35, 726 (1962).
19. M. Kurata and W. H. Stockmayer, Fortschr. Hoch
polym. Forsch. 3, 196 (1963).
20. S. H. Maron and M.-S. Lee, J. Macromol. Sci.-Phys.
87, 61 (1973).