JOURNAL OF POLYMER SCIENCE VOL. XI, NO.

LETTERS TO THE EDITORS

Viscosity Characteristics of Polyalkyl Methacrylate Solutions

It has been shown in a number of that the constant k' in the

Huggins equation :
%P/C = I71 + k"r1I2C
is independent of molecular weight for a linear polymer. Kecently, how-
e ~ e r ,it~has
. ~ been found that polystyrene solutions may show an increase
in k' with increasing molecular weight when the latter becomes very high.
The reverse behavior, that is, a decrease in k' with increasing molecular
weight, is now reported for certain polymethacrylates with long side chains.
During the course of experiments on the viscosity-temperature relation
using a variety of polymer-solvent systems, a number of alkyl methacry-
lates have been produced by the method of ester interchange.6 These
ranged from the butyl to the decyl homologue and each has been emulsion-
polymerized using various concentrations of Fe ++-HzOz as initiator.'
In this way, a number of polymethacrylates were available which varied
with respect to both the degree of polymerization and the length of the
alkyl side chain.

Fig. 1. Plot of k' against [77] for solutions of polyalkyl methacrylates in ben-
zeneat25'C.
379
380 LETTERS TO THE EDITORS

The viscosities of these polymers were determined in benzene solution

in concentrations ranging from 0.100 to 0.500 g./100 ml. at 25°C. and in
all cases rectilinear plots of 71 =/c against c were obtained. The values of
k’ and [q] were determined from these plots in the usual way (see, e.g.,
reference 8) and they are shown plotted against each other in Figure 1.
The series of seven octyl polymers shows a marked decrease in k’ to a limit-
ing value of ca. 0.33 as [71] approaches unity. The low molecular hexyl
polymer also has an abnormally high value of k’. In neither case are the
probable errors in k’ sufficiently large to account for these high values,
being f0.03 in the “worst” cases. It is also unlikely that the heterogeneity
of these polymers is responsible for the increase in k’ at low 171 since: (a)
all samples were prepared in a similar way, (b) unfractionated polymers
give similar values to fractionated samples (see, e.g., references 4,8,9), and
(c) values of k’ are not appreciably affected by the molecular weight dis-
tribution of the solute.’O It would therefore appear that benzene is a bet-
ter solvent for the higher than the lower molecular weight samples and this
unusual effect must be attributed to the presence of the hexyl and octyl
side chains. The effect of branching in producing higher values of k’
has been ~ o n s i d e r e d ~only
~ ’ ~ in
~ ’terms
~ of the chain branching arising dur-
ing polymerization. In the case of the low molecular polyalkyl methacry-
lates it would appear that even the short side chains due to hexyl or octyl
groups have a profound en’ect upon the polymer configuration in benzene
solution. The unusual nature of the polymer-solvent interaction in these
cases is reflected also in the fact that only when the side chains are extended
as far as the hexyl homologue do the polymers become soluble in hy-
drocarbon oils.
This work was carried out in the laboratories of the Manchester Oil Refinery Ltd.,
Manchester 17, England.
References
1. M. L. Huggins, J . Am. Chem. SOC.,64,2716 (1942).
2. C. E. H. Bawn, Trans. Faraday Soc., 47,97 (1951).
3. F. Eirich and J. Riseman, J . Polymer Sci.,4,417 (1949).
4. J. A. Manson and L. H. Cragg, Can. J . Chem., 30, 482 (1952).
5. L. H. Cragg and R. H. Sones, J: Polymer Sci.,9, 585 (1952).
6. U.S.P. 2,109,877, March 1938.
7. J. H. Baxendale, M. G. Evans, and G. S. Park, Trans. Faraday SOC.,42, 155
(1946).
8. H. Daoust and M. Rinfret, J . Colloid Sci.,7 , 11 (1952).
9. T. Alfrey, Jr., A. I. Goldberg, and J. A. Price, J . Colloid Sci., 5 , 251 (1950).
10. W. E. Davis, J . Am. Chern. SOC.,69, 1453 (1947).
11. I. Harris, J . Polymer Sci.,8, 353 (1952).
12. W. E. Mochel, J . Polymer Sci.,8, 583 (1952).
S. J. LEACH
Biochemistry Unit
Wool Textile Research Laboratory
Commonwealth Scientific and
Industrial Research Organization
Melbourne
Received June 10, 1953