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INTRINSIC VISCOSITY-MOLECULAR WEIGHT RELATIONS(TIP?

FOR POLYISOBUTYLENE1’2
THOMAS G FOX, .Jr., and PAUL ,J. I'LORY
Goodyear Tire and Rubber Company, Akron, Ohio

Received August 19, 1948

During the past five years the intrinsic viscosities from no less than ten polymer
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series (8) have been shown experimentally to depend on molecular weight

according to the simple relationship
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=
KMa (1)
where K and a are constants for a given polymer-solvent pair. This relationship
applies within the limits of accuracy of experiment over wide ranges in molecular
weight, which in some cases are several hundredfold in extent. In a '‘good”
solvent for any given polymer a generally assumes a value between 0.05 and
0.80. Values of K for different polymer series are similar in magnitude. These
similarities suggest that the same theoretical interpretation of the dependence of
[ ] on M may be applicable to virtually all linear polymers.
Recent theories dealing with this problem fail to yield a relationship of the
above simple form. The various functional dependences predicted, on the
other hand, are of a nature that can be closely approximated by the exponential
form (3, 12) over a rather wide range in molecular weight. The Debye-Bueche
and the Kirkwood-Riscman treatments call attention to the influence of the
effective degree of permeation of the flowing solvent medium through the
randomly kinked polymer molecule. Over fairly wide ranges in molecular
weight the dependence of the intrinsic viscosity on molecular weight predicted
by their treatment can be satisfactorily approximated by equation 1. However,
the gradual decrease in the degree of permeation of the domain of the polymer
molecule as the molecular tveight increases should manifest itself in a decrease
in the empirical value of a, provided the molecular weight range covered is
adequately large.
Recently we have sought to take into account the increase in the volume of
the randomly kinked chain resulting from the interferences between distantly
connected segments of the polymer chain, a factor which is believed to outweigh
in importance the one mentioned above. Again the form of the predicted
dependence of intrinsic viscosity on molecular weight can be approximated by
Presented at the Twenty-second National Colloid Symposium, which was held under the
1

auspices of the Division of Colloid Chemistry of the American Chemical Society at Cam-
bridge, Massachusetts, June 23-25, 1948.
Contribution No. 156 from the Research Laboratory of the Goodyear Tire and Rubber
Company.
2
The work presented in this paper comprises a program of fundamental research on rub-
ier and plastics being carried out under a contract between the Office of Naval Research
md the Goodyear Tire and Rubber Company.
197
 198 THOMAS FOX, Jit., AND PAt'L J. FLORA

equation 1 over limited ranges. This factor, however, should bring about an
increase in the apparent value of a with increase in M.
These considerations underline the importance of securing experimental
data on the dependence of intrinsic viscosity on molecular weight over the
widest possible range. An unusually broad range is covered by previously
published data on the intrinsic viscosities of polyisobutylene in diisobutylene (5).
Throughout the molecular weight range investigated (5600 to 1,300,000),
equation 1 applies within the experimental error. In the present investigation
these observations have been extended to include polyisobutylenes of lower
molecular weight. In addition, the effects of solvent type and temperature on
the intrinsic viscosity-molecular weight relationship for this ideally non-polar
polymer have been investigated.

TABLE 1
Separation of low-molecular-weight pohj'isobuit/iene by molecular distillation*
DISTILLATE No. TEMPERATURE RANGE APPROXIMATE YIELD REMARKS

1 ................... 110-150 1 Contaminated with original

2 ................... 150-200 1

3 ................... 200-250 1

4 ...................
10 Residue
*
Distillation carried out at a pressure of at. 0.0005 mm.

EXPEIU-UEXTAL

1. Materials
Four polyisobutylenes with molecular weights ranging from 7000 to 1,000,000
were fractionated from benzene with acetone by a single precipitation technique
described in detail elsewhere (7).“'” A polyisobutylene of lower molecular
weight (3000) was extracted first with hot acetone and then with a 1:1 mixture
of benzene and acetone at room temperature. The undissolved portion was
dissolved in benzene and fractionally precipitated in the usual manner. The
second extract, i.e., the portion insoluble in hot acetone but soluble in the
benzene-acetone mixture, was then separated into four fractions by molecular
distillation, the details of which are given in table 1.
All fractions except those obtained by distillation were dried first on a steam
bath and then in vacuo at 60°C. Each of the individual fractions represented
from 5 to 25 per cent of the whole polymer from which it was separated.
Determination of intrinsic viscosities
2.

The intrinsic viscosities were determined using a Ubbelohde No. 1 viscometer

Many of the fractions employed here were identical with those used in the previous
3

investigation (7).
The polyisobutylene was supplied by the Standard Oil Company of New Jersey. We are
4

indebted to Mr. D. W. Young of the Esso Laboratories, who made available to us two labora-
tory samples of low molecular weight.
 INTRINSIC VISCOSITY OF POLYISORUTYLENE 199

(flow' lime for benzene at 25°C. equaled 71 sec.) calibrated for kinetic energy-
corrections. Measurements were carried out in water thermostats regulated
within =fc0.03°C. of the desired temperature. The value of In (í?rei)/c for a
relative viscosity „ of 1.2, obtained by interpolation or extrapolation of data
for several concentrations, was taken as the intrinsic viscosity [ ]. As has been
pointed out previously Í5), this value differs only slightly from the infinite
dilution value. The intrinsic viscosity values generally are reproducible
within ±2 per cent.
Three of the solvents employed (benzene, cyclohexane, and diisobutylene)
were purified by distillation. Carbon tetrachloride was washed successively
with concentrated sulfuric acid, a 10 per cent solution of sodium bicarbonate,
and water, after which it was dried and distilled. Toluene was dried over
calcium chloride.
Molecular weight determinations
3.

Molecular weights of the polyisobutylene fractions above 4000 (table 3) were

computed either from their intrinsic viscosities in diisobutylene (DIB) at 20°C\
employing the equation (o')
!>] =
3.00 X 10"4 .l/0·*4 (2)
or from their intrinsic viscosities in carbon tetrachloride at 30°C., making use
of the relationship applying to this solvent as established below (table 4).
Molecular weights of the lower fractions were obtained from ervoscopic measure-
ments in pure cyclohexane. The cyclohexane was prepared by hydrogenation
of thiophene-free benzene over Raney nickel. The product was treated for
several days with concentrated sulfuric acid at 100°C. and distilled. The
observed freezing points of two cyclohexane fractions thus obtained were 6.3G°C.
and ü.48°C., as compared with the literature value of 6.5°C. The ervoscopic
measurements were made in a conventional manner, employing vigorous stirring.
At least two and usually three freezing-point measurements xvere made on each
solution, the reproducibility of the average value being ±0.01°C.
Results of the ervoscopic measurements are given in table 2. The molecular
weights were calculated from the van’t Hoff equation, employing values of AT¡c
extrapolated to zero concentration. This extrapolation was made by drawing
parallel lines through the data for the respective fractions on plots of AT/c vs. c
RESULTS

The intrinsic viscosities for polyisobutylene fractions covering a wide molecular

weight range in a variety of solvents at several temperatures are given in table 3
(see also table ). A log-log plot of the intrinsic viscosity for a given solvent
and temperature against the molecular weight is linear (dashed lines of figures 1
and 2), in accordance with equation 1, within the experimental error over a wide
range in M. The values of K and a deduced from the linear plots are given in
table 4. At molecular weights below 2000, however, the observed values of [ ]
deviate from the above simple relationship.
It is well known (4, 11) that benzene and toluene at room temperature are
200 THOMAS G FOX, JK., AND PAUL J. FLOKY

TABLE 2

Cryoscopic data on polyisobutylene fractions

.
C, GRAMS/100
POLYMER G, OF A7'° ( /c) .1/
SOLVENT

Distillate No. 1......... ... 2.80 0.685 0.244

1.45 0.335 0.231
0 Extrapolated : 0.224 890 ± 50*

Distillate No. 2......... 3.71 1.475 0.398

1.86 0.720 0.387
0.90 0.345 0.386
0 Extrapolated 0.377 530 ± 25

Distillate No. 3......... 2.33 0.660 0.283

1.51 0.405 0.268
0.67 0.180 0.268
0 Extrapolated 0.265 755 ± 40

No. 4 (residue)........ 5.60 0.755 0.135

3.22 0.425 0.132
1.99 0.250 0.126
0.97 0.120 0.124
0 Extrapolated 0.115 1730 ± 80

*
This fraction was contaminated with residue, due to spattering during distillation.

TABLE 3
Intrinsic viscosities for poly isobutylene fractions

'
'CYCLO- BON DIISO- 1
TOLU- TOLU- TOLU TOLU- TOLU- j TOLU- TOLU- j BLN- BEN- j BEN-
'
BEN-
Itetra- ! EXE ENE ; ENE
'

ENE ! ENE ZENE j ZENE ! ZENE

¡
¡ ZENE
CHLO- LENE j
AT ¡ AT , AT : AT AT
1
AT i AT AT
AT RIDE AT
1

30°C.
|
AT 20°C.
90°C. | 60°C. 50r'C 30°C. I 15°C. ! 0°C. -10°C. 60°C. , 40°C. 1
30°C. 1
2S°C.
| ! . I
¡ 30eC.

1,260,000 :4 .75 [4.30 .2.90 3 .16 .18 ¡3 2.69 ,2.36 1.86 1.57 12.87 ¡2.20 ¡1.77 il.45
463,000 ¡2 .33 2.06 .1.53 1 .47 .40 1 1 .40 1.29 1.13 ¡0.96 ¡
1.34 ¡1.10 0.89 ¡0.80
110,000 0.78 0 .53 0 .52 ;o ,56 0.49 ¡0.44 0.38 ¡0.57 .48 .43 ¡0.39
92,700 0 .75 ¡0.73 0.57
48,000 ¡0 .47 ¡0.43 0.36 .34 0 .33 ¡0 .34 0.32 0.30 0.28 0.33 0.29 0.26 ¡0.26
10,200 0.15 0 .106
),0
.098 0 103 0.103 0.102,0.103 .

9,550 ¡0 14c>0.138 0.127 0 ,087•!0 .0880 .094 0.0890.088,0.091

. ,0.1150.111 0.107,0.106
7,080 ¡0 .lit 10.115 0.105 0 .080 0 .0810 .088
1,730 0..056 0.056 0.056>

890 . 04C10.045 0.045 0.037 0.034,0.034 0.034

755 0 .033 ¡0.034 0.037
1 0.0260.0280.027 0.027
530 ,0. 027 0.031 0.033 0.0250.024,0. 023 0.023

poor solvents for polvisobutylene, while, cyclohexane and carbon tetrachloride

may be classified as comparatively good solvents for this polymer. In order to
obtain an indication of relative solvent power, acetone, a non-solvent, was
 INTRINSIC VISCOSITY OF POLYI.SOB CTYLKNE 201

added at 30°C. to 0.5 per cent solutions of high-molecular-weight polyisobutylene

( =
1,260,000) in each of these solvents. Comparison of the amounts of
acetone required to produce permanent turbidity (table 5) indicates that the
solvent power decreases in the order: cyclohexane, carbon tetrachloride, diiso-
butylene, toluene, and benzene. The low solvent power of toluene and benzene
for polvisobutylene is further illustrated by the onset of precipitation of this

TABLE 4
1 'iscosity-mo lecular weight relationships

SOLVENT lEUPERATURL
TFUpruvruBF M FOR fraction
K X 10 a
, 0F Jf =
1,260,000

°C.

Cyclohexane......... ...
30 4.75 2.65 0.69 ± 0.02
Carbon tetrachloride. .. . 30 4.30 2.9 0.68
Toluene.................. 90 3.16 1.26 0.72
Toluene................ 60 3.18 1.35 0.71
Toluene................. 30 2.0 0.68
Diisobutvlene............ 20 2.90 3.6 0.64
Benzene............... 60 2.87 2.6 0.66
Toluene............... 30 2.69 2.0 0.67
Toluene................ 15 2.36 2.4 0.65
Benzene................. 40 2.20 4.3 0.60
Toluene................. 0 1.86 4.0 0.60
Benzene................. 30 1.77 6.1 0.56
Benzene................ 25 1.45 8.3 0.53

TABLE 5
Comparison of viscosities and precipitabilities of high-molecular-weight polyisobutylem
( 1,260,000) in various solvents
=

CONCENTRATION
OF ACETONE
M

BIDITY 25°C. 30°C. 4G°C. 60°C.

CC. i ‘IOC cc. solution

CsHn.............. 53 4.78 4.75 4.81 4.83

CCL........... 39 4.25 4.30 4.30 4.38
MB............ 31 2.98 2.90 3.03 2.95
CTLCH:............ 17 2.69 3.18
C6H6............. 5,5 1.45 1.77 2.20 2.87

same polyisobutylene fraction from these solvents at 18°C. and +23°C., —

respectively.
Almost ten years ago Huggins, in consideration of the effects of the heat of
interaction between the solvent and polymer molecules on the size of the polymer
nolecule in solution, suggested that at a given temperature the intrinsic viscosity
if a polymer solution should increase with increasing solvent power (9, 10).
Vlfrey, Bartovies, and Mark (1) suggested further that the viscosity-temperature
oefficient should have a large positive value for a poor (endothermic) solvent, a
202 THOMAS G FOX, JR., A XI) PA VR J. FLUKY

large negative value for a very good (exothermic) solvent, but that in a thermally
neutral solvent (zero heat of dilution) the viscosity should be independent of
temperature at least over a limited range. These predictions were verified by
Alfrey ct al. (1) for several polymers, including polystyrene dissolved in toluene
and in mixtures of toluene and methanol. Recently Gragg and Rogers (2).
working with solutions of GR-S in mixtures of x’arious soh'ents with methanol in
varying proportions, found these predictions to be essentially correct. The
present data (tables 3 and 5), xvlierein the solvent- poxver is altered simply by
changing soh’ents rather than by the addition of a non-solvent, arc in agreement
with these predictions, assuming that the heat of solution of polyisobutylene in
cyclohexane and in carbon tetrachloride is small. Thus for a given polyisobutyl-
ene the intrinsic viscosity in a poor solvent, (benzene or toluene) is considerably
loxx'er than in a good solvent (cyclohexane or carbon tetrachloride) and the
temperature dependence is much more pronounced in the former ease. Inspec-
tion of table 4 reveals fun her that in general the better the solvent the higher
the x’alue of a in equation 1; exceptions to this order of the -x’alues in the table
are not beyond the experimental error.

DISCUSSION’

/. Theoretical
The specific viscosity ^relative x’iscosity minus one) of a sufficiently dilute
solution of polymer molecules may be written
,,, =
]’e

where X is the number of molecules per cubic centimeter, lb is the effective

volume of each molecule, and is a hydrodynamic factor (3). If M is the
molecular xveight and c is the concentration in grams per 100 ec., the intrinsic
X’iscosity max’ be expressed correspondingly as
[] -=
tap/eje-,,)
=
(1 c/'4/) / LOO v3)

Kuhn (13) surmised that, long-chain, irregularly coiled polymer molecules would
offer least resistance to flow of the solution if the encompassed solvent moved
xx’ith the polymer molecule. The polymer molecule would then act as a giant
sphere many times larger than the actual volume of the polymer molecule
itself; hence lb should correspond, roughly at least, to the x’olume pervaded
by the randomly coiled chain. In place of , Kuhn inserted the Einstein factor
2.5 for a suspension of impenetrable spheres. Recently Debye and Bueche (3)
hax’e introduced a hydrodynamic factor , which depends on the extent to which
the velocity field of the solvent penetrates the random coil. In the limit of very
high molecular weight (relatively low permeation), approaches 2.5. Kirkxx’ood
and Riseman (12) have given an alternative treatment with somewhat more
explicit results xx’hich, hoxvever, may be expressed in equix’alent form.
The ex’aluation of lb is of critical importance for the deduction of a relationship
expressing the intrinsic xd.seositv in terms of molecular parameters. In the
approximation usually employed in treating the spatial configuration of a
 INTRINSIC VISCOSITY OF POLYISOBVTYLKNK 203

polymer molecule, each successive segment of the chain is considered to be free

to assume an orientation relative to its immediate predecessor in the chain which
is independent of the situation of all other segments of the chain. In other
words, the angle of rotation about a given bond is considered to be independent
of the arrangement of all other bonds. The configuration problem then reduces
to the treatment of the path described in space by a particle undergoing a series
of unrelated displacements, the direction of each displacement being subject
entirely to chance and independent of the direction of all other displacements.
In this “random flight” approximation, the distance between ends of the chain
should be proportional to the length of each segment and to the square root of
their number. Other linear dimensions are similarly proportional to the square
root of the chain length, or number of segments. Hence, Ye should be pro-
portional to the three-halves power of the chain length, or to M '", and the
intrinsic viscosity should be given by
hi -
Const. .!/ o

i.e., the intrinsic viscosit}· should be proportional to the square root of the
molecular chain length modified by the functional dependence of the hydro-
dynamic factor on the chain length (3).
Occurrence of steric (or other) interactions between near-neighbor segments
does not lead to alteration of the form of the dependence of the volume occupied
by the molecule on the chain length. The same does not apply to interactions
between remotely related elements of the structure, however. The random
flight approximation fails to exclude impossible configurations in which two
distantly connected segments are assigned to the same location. Statistical
considerations show that a large fraction of The hypothetical random flight
configurations for a long-chain polymer molecule will be ruled out on account of
these long-range 'interferences” between segments. Since interferences will
occur less frequently in more expanded configurations, the average dimensions
of the actual polymer molecule will be greater than Those computed for the
hypothetical random flight chain.
The random flight approximation may nevertheless be employed as a first
approximation on which there is superimposed a correction for the influence of
long-range “interferences” between two segments of the same molecule. Thus,
the average effective volume of the polymer molecule will be proportional to
° A where a expresses the alteration in linear dimensions due to interference.
Then

[?? |
=
1'~ (4)
Kuhn (13) has pointed out that the 1‘volume filling effect” of real polymer
molecules (as distinguished from hypothetical chains having negligible cross-
sectional dimensions and hence obeying the random flight approximation) must
ead to an apparent dependence of the effective volume Ye on a power of M
treater than 3/2. On this basis Kuhn predicted that the exponent a in equation
should be between 0.(1 and 0.9. In the present terminology, Kuhn’s prediction
 204 THOMAS G FOX, JR., AND PAUL J. FLORY

is equivalent to a postulated dependence of a' on a power of M between 0.1

and 0.4.
Recently one of the authors (6) derived from statistical-thermodynamic
considerations the relationship
a‘ —

a =
(' ( 1
—

2µ ) 1'~ (5)
where Z is the number of equivalent segments in the chain, C\ is a parameter
somewhat dependent on the particular polymer and solvent, but which generally
should lie in the range from 0.1 to 1, and µ is the energy of interaction parameter
given by
µ =
IiW/RT
where B is the cohesive energy density constant for the polymer-solvent pair and
IT is the molar volume of the solvent. Thus, equation 5 takes into account
not only the configurational interference of the polymer chain with itself, but it
also includes the influence of energy interaction of the polymer with the solvent.
Letting
2/tV. /.’ =

and avoiding specification of the size of the equivalent segment (which will
depend on the stiffness of the chain and local steric interaction) by replacing
CZ1'2 with where C" is a new constant:
of"’ -

a =
C(l ~

/ )3 '’2 ((>)

Correspondence is indicated between and the absolute temperature at which

precipitation sets in for a solvent which mixes endothermally with the polymer;
for a solvent which mixes exothermally will be negative.
Equation 6 can be replaced by
a =
Const. Ma' (7)
where
a' —
d In a /d In .1/

According to equation G, a' (and the constant of proportionality in equation 7

as well) will exhibit a comparatively small variation o\rer fairly wide ranges in
molecular weight. The value of a' to be employed will depend of course on the
mean value of the quantity on the right side of equation 6. In a good solvent
for which C"(l —

/ ) is large, a' will approach 0.3 at large values of 31; in a

poor solvent medium for which / is near zero, a' should approach zero.
.1
—

Thus, aside from the contribution of the dependence of on M, the value of the
exponent a in equation 1 should lie in the range from 0.8 to 0.5, the former value
being approached in good solvents at sufficiently high molecular weights.
Experimentally observed values of a generally occur in this range; indeed,
valid exceptions are unknown among polymer series for which the intrinsic
viscosity-molecular weight correlation has been extended to include high-
molecular-weight polymers. This fact suggests that variation of the hydro-
 INTRINSIC VISCOSITY OF POLYISOBUTYLENE 205

dynamic factor with molecular weight may be relatively unimportant through-

out the high-molecular-weight range; presumably is near its asymptotic
limiting value. The data of this paper have been treated on the basis of the
postulate that may be treated as a constant over the molecular weight range
covered.
It is to be noted nevertheless that the combined variations of a3 and of with
M are such as to compensate to some extent for the deviations from equation 1
which would ensue if either factor alone were to vary with M while the other
remained strictly constant . As the molecular weight decreases, d In a3/d In M
decreases. At sufficiently low molecular weights, however, d In / In M must
increase appreciably with further reduction in M (3). Hence, these two factors
may mutually preserve the empirical relationship given by equation 1 over a
wider molecular weight range than would be observed if either one alone were
present.
2. Comparison of experimental data with theory
The results of the above treatment are expressed by equations 4 and G.
Choosing a for the variable to be eliminated from these two equations, the
dependence of the intrinsic viscosity on molecular weight and temperature is
specified in terms of four parameters, , Ku, C, and . If the hydrodynamic
factor is constant (as postulated above), the product 0 may be handled as a
single parameter, thus reducing the number to three. 0 should be independent
of molecular weight, solvent type, and temperature. The value of will depend
on the interaction forces characteristic of the given polymer-solvent pair. The
third parameter C contains all of the uncertainties inherent in the statistical
treatment of the thermodynamic properties of high-polymer solutions in terms
of the lattice model. It may be expected to vary somewhat with solvent type
but it should be independent of molecular weight and of temperature.
Applying intrinsic viscosity-molecular weight data for a given solvent at a
fixed temperature to the simultaneous solution of equations 4 and 6, the quantity
may be evaluated. In this way for polyisobutylene was found to be
equal to 1.10 X 10~3 (± 10 per cent) for all of the solvents investigated, irrespec-
tive of temperature and molecular weight (for > 48,000 at any rate).
The strong temperature dependence of the intrinsic viscosity in benzene and
toluene permits fairly accurate determination of the 6’s for these poor solvents.
The following procedure may be employed. Having found , a may be
computed from the intrinsic viscosity using equation 4. Plotting values of
(a3
—

a)/M1:2 obtained for a given solvent against 1 /T, and C are obtained.
For benzene and toluene the best values of are 295 (±5) and 255 (±5)°K.,
respectively. The precise agreement between and the incipient precipitation
temperature for each of these solvents (see above) may be to some extent
'ortuitous. Of perhaps greater significance is the fact that the observed de-
jendence on the temperature is accurately in accordance with theory (cf. seq.).
tallies obtained for C are 1.30 X 10~2 and 0.75 X 10~2 for benzene and toluene,
espectivelv.
206 THOMAS G FOX, JR., AXD PAUL J. FLORY

The temperature coefficient of the intrinsic viscosity in the better solvents is

too small for precise characterization from the present measurements. Further-
more, other factors which are neglected here, such as the greater effective freedom
of rotation about chain bonds as the temperature is raised, may amount to an
appreciable fraction of the small temperature coefficient in these cases. Hence,
we have arbitrarily taken C 1.0 X 10'2 for the better solvents, a value
=

intermediate between those for benzene and toluene. Values of were then
deduced from equations 4 and 6. It should be pointed out that the value for C
is sensitive to small variations in 0 and and to experimental errors in the
intrinsic viscosity. Conversely, calculated values of the intrinsic viscosity are
relatively insensitive to the choice of C.
Values of the parameters obtained by the methods outlined above are given in
table 6. To illustrate the measure of agreement between the observed and
calculated viscosities, the intrinsic viscosities calculated from the above para-
meters (solid lines) are compared with the. experimental data in figures 1, 2, 3, 4.
and 5. The agreement over wide ranges in the molecular weight for the various

TABLE 6

Best rallies for the parameters occurring in equations f and ß

solvent A'o X 10s C X 10= o

Cyclohexane................... 1.10 1.0 155

Carbon tetrachloride.......... 1.10 1.0 185
Toluene........................ ! . 10 0.75 255
Benzene........................ 1.10 1.3 295

solvents and temperatures is good. Although the calculated log-log plots in

figures 1 and 2 are slightly curved, they may be approximated by straight lines
over fairly wide ranges in . The observed data seem to agree somewhat better
with the theoretical curves than with straight lines (toluene excepted), although
the data are not sufficiently accurate for a definite decision in this regard. At any
rate, large deviations from the theoretical curves are confined to the very low
molecular weight range where the theory, based on statistical considerations of
chain configuration, is no longer valid. It is obvious that the theoretical
equations necessarily must fail at sufficiently low molecular weights in considera-
tion of the fact that, the '‘intrinsic viscosity” of the monomer (isobutylene)
doubtless would be negative in each of the solvents used. Data of Kemp and
Peters (11) on the intrinsic viscosities in benzene at 2o°C. of the trimer, hep tamer,
and nonamer of isobutylene are included in figure 1 for the purpose of illustrating
the more rapid change of intrinsic viscosity with molecular weight in the very
low range.
In order to illustrate the sensitivity of the size of the polymer molecule in
solution to the nature of the solvent and the temperature, values of a3 calculated
from equation 6 using the parameters of table 6 are presented in table 7. For the
polymer of highest molecular weight the ratio (a) of the effective volume of the
 INTRINSIC VISCOSITY OF POLYISOBUTYLENE 207

molecule to its “random flight” volume, unperturbed by interference and the heat
of mixing of polymer and solvent, varies from 1.19 in benzene at 25°C. to 3.97 in

LOG M
Flea 1. Log hi vs. log M for polyisobutylene fractions in various solvents at several tem-
eratures. For convenience each set of data has been shifted vertically by the addition of
n arbitrary constant C. The solid lines have been calculated from theory. The dotted
nc for diisobutylene (DIB) at 20°C. was drawn according to equation 2 (5). The data of
emp and Peters (11) for the trimer, heptamcr, and nonamer of polyisobutylene in benzene
:2ó°C. (indicated by €5) are included for comparison.

mlohexane at 00°C. Smaller variations in a3 occur for the polymers of lower

olecular weight.
208 THOMAS G FOX, JR., AND PAUL J. FLORA

The availability of three independent parameters in equations 4 and 0 may

arouse skepticism regarding the significance of the agreement obtained above
between experimentally observed intrinsic viscosities and those calculated from
these equations. It is to be noted that the same value for one of the parameters,
0, has been used for all of the solvents. Furthermore, the values of 5 for two

LOG M
Fig. 2. Log M vs. log M for polyisobutylene fractions in toluene at several temperatures.
For convenience each set of data has been shifted vertically by the addition of an arbitrary
constant C. The solid lines are drawn according to theory.

of the solvents appear to be obtainable from independent measurements of the

precipitation temperature. The observations of C-ragg and Rogers (2) on the
approximate equivalence of intrinsic viscosity values for a given GR-S polymer
in different solvent media at incipient precipitation suggest that the same
connection may apply generally. While the precipitation temperatures for
polyisobutylene in carbon tetrachloride and in cyclohexane doubtless are too low
for measurement it is possible that 5-values for these solvents may be independ-
,
 INTRINSIC VISCOSITY OF POLYISOBUTYLENE 209

entlv deduced from thermodynamic measurements on their mixtures with

polvisobutylene. Finally, the values assigned to C for the various solvents
are similar. With the above values of the parameters not only is it possible to
duplicate intrinsic viscosity-molecular weight data, but the unique dependence

Fig. 3. The int rinsic viscosity vs. temperature for a high-molecular-weight polyisobutyl-
ene fraction in various solvents. The solid lines arc drawn according to theory.

on temperature in the poorer solvents is accurately predicted (see figures 3,

f, and 5).
The assumption that the hydrodynamic factor is constant cannot be justified
oy the dependence of the intrinsic viscosity on molecular weight alone. An
nerease in with M could be compensated by a smaller value of C, which would
210 THOMAS G FOX, JR., AND PAUL J. FLORA

lead to a slower change of a with M. It is impossible, however, to reconcile an

appreciable variation of with the observed dependences of the intrinsic viscosity
on both molecular weight and temperature. If is assumed to possess a value
appreciably less than its asymptotic limit, it must increase with *1/ and decrease
with temperature in a poor solvent (since the molecule will be more susceptible
to permeation by solvent as it assumes a more expanded configuration). The
value of a3 increases both with M and with T. Hence, a reduction of (?' for the

Fig. 4. The intrinsic viscosity r.s. temperature for benzene solutions of several polyiso-
butylene fractions. The solid lines are drawn according to theory.

purpose of compensating the effect of an assumed increase in with M would

accentuate the difficulty of accommodating the concomitant decrease in with
T in a poor solvent.
The present results provide good evidence for the approximate constancy of
the hydrodynamic factor throughout the greater part of the molecular weight
range. The dependence of the intrinsic viscosity on solvent type, temperature,
2
and molecular weight (apart from the df1 factor) is largely embodied in the
expansion factor a. The present results do not, however, preclude the existence
of a significant variation of with molecular weight at molecular weights below
50,000.
 INTRINSIC VISCOSITY OF POLYISOBUTYLENE 211

Fig. 5. The intrinsic viscosity vs. temperature for toluene solutions of several polyiso
butylene fractions. The solid lines are drawn according to theory.

TABLE 7
The expansion factor, a3, for polyisobutylene fractions in various solvents

MOLECULAR Carbon tetrachlo-

WEIGHT Cyclohexane Toluene Benzene

30T. acre. 30°C. 60°C. o°c. 30°C. 6QeC. 25°C. 30°C. 00°C.
: j

1.260,000 3. SI 3.97 3.44 .3. SO 1.55 O'! O CO

2.43 1 .19 1.42 2.27
463.000 3.04 2.76 4.37 1.74 1 .99 1.13 1.28 1.87
110.000 2.06 1 .21 1.42 1.58 1 .07 1.16 1 .50
92.700 2.18 1

2.00
48,000 1.92 1.77 1.15 1.31 1.42 1 .05 1.10 1.35
10.200 1.42 1 .08 1.17 1.23
9.550 1.50 1.41 1.07 1.17 1.22 : 1 .02 1.05 1.20
212 THOMAS G FOX, JR., AND PAUL J. FLORY

SUMMARY

Intrinsic viscosities of polyisobutylene fractions covering a wide molecular

weight range have been measured in cyclohexane, carbon tetrachloride, diiso-
butylene, toluene, and benzene at various temperatures from 10°C. to 90°C.
—

The intrinsic viscosity for a given polymer in different solvents at the same
temperature decreases regularly from the best to the poorest solvent for the
polymer, the order in which they are given above. The intrinsic viscosity in the
poorest solvents, benzene and toluene, increases rapidly with temperature;
in the other solvents a low temperature coefficient is observed. Log-log plots of
the intrinsic viscosity vs. the molecular weight in a given solvent at a particular
temperature are approximately linear over a wide molecular weight range; the
slope of the line increases with increasing solvent power from 0.53 for benzene at
25°C. to about 0.70 for the best solvents.
The results have been compared with recent theoretical interpretations of
intrinsic viscosities of high polymers. They are in agreement with the postulate
that the intrinsic viscosity reflects directly the effective volume of the molecule
in dilute solution, the hydrodynamic factor expressing the interaction of the
equivalent sphere with the solvent remaining very nearly constant except,
perhaps, at low molecular weights. The dependence of the intrinsic viscosity on
the molecular weight, solvent power, and temperature is in agreement with
theoretical predictions.

The authors wish to acknowledge the assistance of Mr. Robert E. Marshall

in carrying out the experimental work.
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