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Viscosity-Temperature Relationships For Poly (Vinyl Chloride) - Tetrahydrofuran Dilute Solutions
Viscosity-Temperature Relationships For Poly (Vinyl Chloride) - Tetrahydrofuran Dilute Solutions
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
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 where l'/o is the viscosity of THF, r and r0 the flow times
ible to be certain of chain flexibility, although PVC and p and p0 the densities of solution and solvent respect
macromolecules are usually regarded as flexible and ively.
THF as a good solvent for PVC. On the other hand, The densities of THF and of the PVC fraction with
the ratio between the unperturbed dimensions and Mw = 153,000 were determined gravimetrically in the tem
the dimensions of the freely rotating chain suggests perature range 15--45, temperature being controlled within
some stiffuess of PVC molecules. Study of the visco 0.02.
The densities of the polymer solutions with concen
sity of dilute PVC-THF solutions may provide evi trations up to 1 g/dl and for temperatures between 15 and
dence about PVC chain stiffness in solution. 40 were calculated from the densities of polymer and sol
For this reason, we studied viscosities of PVC-THF vent assuming additivity:
solutions at temperatures from 10 to 45 and concen p = 0.8875 + 3.72 x 10-3-c
trations up to 1 g/dl. + 1.036 x 10- 3 (20 - t) g/cm3 (5)
where c is the solution concentration and t is the tempera
2. EXPERIMENT AL
ture.
The concentrations of the solutions were determined by
The viscosities of PVC-THF solutions were measured weighing at 20; for the other temperatures, corrections
for three fractions of a Geon-suspension PVC (M, 63,000; for the temperature dependence of the volume were made.
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 3. RESULTS AND DISCUSSIONS
Ubbelohde-type viscometer with suspended bulb level; the
temperature was controlled within 0.02. The Hagen Moore and co-workers [6--11] have shown that the
bach-Couette correction was applied for the flow times viscosity of dilute polymer solutions varies with tem
so that the viscosity, nc- was calculated from: perature according to an Arrhenius-type law:
Chain 102K,
flexibility Polymer Solvent Jdl/gmol Ref.
-0.1 10
0
!3'
I"' {
6
)(
9
"'
Q
-0,3
;;;,. =63,ooo
;;;,. '63,ooo
0
2.1
<!
_g,-1 70 Q.
U 2.0
<i
1. 9
1.e
- 1.75'----'---........L---'----'----'--........,.. _.
Fig. 3. Concentration dependence of the pre-exponential 0.1 0.2 0.3 0.4 0.5 0.6 0.7
which differ from those given in the literature. Equa et al. [16], 0.766 by Freeman and Manning [17] and
tions (11) and (13) are equivalent, (13) arising from 0.54 by Koboyashi [18], characteristic for flexible
(11) by expanding the exponential factor and retaining chains.
no terms beyond those in the square of the concen Moderate stiffness of PVC chains in THF is sug
trations. Consequently the K02 value, evaluated from gested also by a value of 1.83 quoted by Kurata and
the A - c2 plot, must be equivalent to the product Stockmayer [19] for the ratio between the square of
of K01 A0 (see Table 2). the unperturbed average end-to-end distance and the
However we must note that Eqns. (11) and (13), dimensions of the freely-rotating chain; this ratio is
and especially Eqns. (12) and (14), were deduced for also between the values characteristic for flexible and
a large scatter of the experimental data; for reliable for stiff chains.
conclusions, measurements over a more extended
range of concentrations and molecular weights are
necessary. REFERENCES
The coefficients of the equations (7), (8) and (9}-{14),
I. P. J. Flory and T. G. Fox, J. Am. chem. Soc. 73, 1904
deduced from the slopepf the lines in Figs. 1-4 and (1951).
from th1: plots k, - Mw, lg k01 - lg M; and lg 2. J. Brandup and E. H. Immergut (Editors), Polymer
k02 - lg Mw, are listed in Table 2. Handbook, Interscience, New York (1966).
The values of both y1 and y2 suggest that the pre 3. C. Vasile, A. Onu and I. A. Schneider, Rev. Roumaine
exponential factor should be expressed by: Chim., 15, 1935 (1970).
4. C. Carvayal, K. J. Tolle, J. Smid and M. Szwark, J.
A= A0exp[-K.i"(Mc)2]. (15) Am. chem. Soc. lf7, 5548 (1965).
2
The value of 2.25 x 10- found for K. is in the 5. D. J. Metz and A. Glines, J. phys. Chem. 71, 1158
(1967).
range of values established by Moore and Uddin [9] 6. W. R. Moore and A. M. Brown, J. Colloid. Sci. 14,
for bisphenol-A polycarbonate in various solvents I (1959).
and lies between the K. values for flexible polymers 7. W. R. Moore and A. M. Brown, J_ Colloid. Sci. 14,
and for cellulosic derivatives. Taking into account 343 (1959).
also the exponential dependence of A on concen 8. W. R. Moore and G. D. Edge, J. Polym. Sci. 47, 469
(1960).
tration, it seems that there is some stiffness of the
9. W. R. Moore and M. A. Uddin, Europ. Polym. J. 3,
PVC chains in THF. This conclusion agrees with 673 (1967).
the greater values of the exponent in the Mark-
852 N. AELENEI and I. A. SCHNEIDER
10. W. R. Moore, R. J. Fort, R. J. Hutkinson and M. 16. A. Takahashi, M. Ohara and J. Kagawa, Kogyo kwa
Murphy, Polymer, A35 (1963). gaku zasshi (J. chem. Soc. Japan, Ind. chem. Soc.), 66,
11. W. R. Moore and H. Pathan, Indian J. Technol. 3, 960 (1963).
392 (1965). 17. M. Freeman and P. P. Manning, J. Polym Sci. A2,
12. W.R. Moore, Nature, (Lond.) 206, 184 (1965). 2017 (1964).
13. H. K. Johnston and S. Sourirajan, J. appl. Polym. Sci. 18. T. Koboyashi, Bull. chem. Soc. Japan, 35, 726 (1962).
17, 3717 (1973). 19. M. Kurata and W. H. Stockmayer, Fortschr. Hoch
14. H. Batzer and A. Nisch, Makromolek. Chem. 22, 131 polym. Forsch. 3, 196 (1963).
(1957). 20. S. H. Maron and M.-S. Lee, J. Macromol. Sci.-Phys.
15. H. Inagaki and J. Nakazawa, (quoted in Ref. 2). 87, 61 (1973).