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A New Improved Method for Estimating


Hansen Solubility Parameters of Polymers

Article in Journal of Macromolecular Science Part B · March 2006


DOI: 10.1080/00222340500522372

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Journal of Macromolecular Sciencew, Part B: Physics, 45:285–290, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0022-2348 print/1525-609X online
DOI: 10.1080/00222340500522372

A New Improved Method for Estimating Hansen


Solubility Parameters of Polymers

FARHAD GHARAGHEIZI AND MAHMOOD TORABI ANGAJI


Department of Chemical Engineering, Faculty of Engineering,
University of Tehran, Tehran, Iran

In this work a new improved method to estimate the Hansen solubility parameters, dd,
dp, and dh, as well as the radius of interaction sphere for a given polymer, is presented
starting from the idea that the solvents that dissolve a polymer have solubility par-
ameters near to that polymer. In this study, using intrinsic viscosities of the polymer
in these solvents and the molar volumes of the solvents, a correlation has been done.
Results fit data quite well.

Keywords Hansen solubility parameters, polymer solubility, intrinsic viscosity

Introduction
Solubility parameters have found their greatest use in the coatings industry to aid in the
selection of solvents. They are used in other industries, however, to predict compatibility
of polymers, chemical resistance, and permeation rates and even to characterize the
surfaces of pigments, fibers, and fillers. Liquids with similar solubility parameters will
be miscible, and polymers will dissolve in solvents whose solubility parameters are not
too different from their own.[1]
The solubility parameter has been used for many years to select solvents for coatings
materials. A lack of total success has stimulated research. The skill with which solvents
can be optimally selected with respect to cost, solvency, workplace environment,
external environment, evaporation rate, flash point, etc., has improved over the years as
a result of a series of improvements in the solubility parameter concept and widespread
use of computer techniques. Most, if not all, commercial suppliers of solvents have
computer programs to help with solvent selection.
The term solubility parameter was first used by Hildebrand and Scott.[2,3] The earlier
work of Scatchard and others contributed to this development.[4] The Hildebrand solubility
parameter is defined as the square root of the cohesive energy density:
rffiffiffiffi
E
d¼ ð1Þ
V

Received 5 October 2005; Accepted 27 October 2005.


Address correspondence to Farhad Gharagheizi, Department of Chemical Engineering, Faculty
of Engineering, University of Tehran, P.O. Box 1365-4563, Tehran, Iran. E-mail: fghara@engmail.
ut.ac.ir

285
286 F. Gharagheizi and M. T. Angaji

V is the molar volume of the pure solvent, and E is its (measurable) energy of vaporization.
The solubility parameter is an important quantity for predicting solubility relations, as can
be seen from the following brief introduction. Thermodynamics requires that the free
energy of mixing must be zero or negative for the solution process to occur spontaneously.
The free energy change for the solution process is given by the relation

DGM ¼ DH M  TDSM ð2Þ

where DGM is the free energy of mixing, DHM is the heat of mixing, T is the absolute temp-
erature, and DSM is the entropy change in the mixing process.
Equation (3) gives the heat of mixing as proposed by Hildebrand and Scott[2,3]:

DH M ¼ w1 w2 VM ðd1  d2 Þ2 ð3Þ

The ws are volume fractions of solvent and polymer, and VM is the volume of the mixture.
Equation 3 is not correct. This equation has often been cited as a shortcoming of this
theory in that only positive heats of mixing are allowed. It has been shown by Patterson,
Delmas, and coworkers that DGM noncomb is given by the right-hand side of Eq. (3) and not
DGM.[5 – 10] The correct relation is

2
DGM
noncomb ¼ w1 w2 VM ðd1  d2 Þ ð4Þ

The noncombinatorial free energy of solution DGM noncomb includes all free energy effects
other than the combinatorial entropy of solution occurring because of simply mixing
the components. Equation (4) is consistent with the Prigogine corresponding states
theory of polymer solutions and can be differentiated to give expressions predicting
both positive and negative heats of mixing.[3,5] Therefore, both positive and negative
heats of mixing can be expected from theoretical considerations and have been
measured accordingly. It has been shown clearly that solubility parameters can be used
to predict both positive and negative heats of mixing. Previous objections to the effect
that only positive values are allowed in this theory are not correct.
A more detailed description of the theory presented by Hildebrand and the succession
of research reports that have attempted to improve on it can be found in Barton’s extensive
handbooks.[11,12] The slightly older, excellent contribution of Gardon and Teas is also
a good source of related information, particularly for coatings and adhesion
phenomena.[13] The approach of Burrell, who divided solvents into hydrogen bonding
classes, has found numerous practical applications.[14] The approach of Blanks and
Prausnitz divided the solubility parameter into two components, nonpolar and polar.[15]
Both are worthy of mention.
A widely used solubility parameter approach to predicting polymer solubility is that
proposed by Hansen. The basis of these so-called Hansen solubility parameters (HSP) is
that the total energy of vaporization of a liquid consists of several individual parts.[16 – 19]
These arise from (atomic) dispersion forces, (molecular) permanent dipole – permanent
dipole forces, and (molecular) hydrogen bonding (electron exchange). The basic
equation that governs the assignment of Hansen parameters is that the total cohesion
energy, E, must be the sum of the individual energies which make it up.

E ¼ E D þ EP þ E H ð5Þ
Estimating Hansen Solubility Parameters 287

Dividing this by the molar volume gives the square of the total (or Hildebrand)
solubility parameter as the sum of the squares of the Hansen D, P, and H components.

E=V ¼ ED =V þ EP =V þ EH =V ð6Þ
d2 ¼ d2d þ d2p þ d2h ð7Þ

To sum up this section, it is emphasized that HSP quantitatively account for the cohesion
energy (density). An experimental latent heat of vaporization is considered much more
reliable as a method to arrive at a cohesion energy than using molecular orbital calcu-
lations or other calculations based on potential functions. Indeed, the goal of such
extensive calculations for polar and hydrogen bonding molecules should be to accurately
arrive at the energy of vaporization.
The object of our work is to describe a more rapid and accurate method to determine
the partial or Hansen solubility parameters as well as the radius of interaction sphere for a
given polymer using the tabulated Hansen solubility parameters of solvents. Intrinsic visc-
osities of a polymer in different solvents and molar volume of solvents were used as
weights of dissolving capacities of polymer. Equations corresponding to a system of
material points placed into a tridimensional space were used, and a computer program
was elaborated.

Common Methods
Determination of Hansen solubility parameters of a polymer by the classical method[1]
consist in testing of polymer solubility in different solvents with known partial solubility
parameters. Solvents which interact with the given polymer (dissolve or swell it) are rep-
resented as points in planes having as coordinates (0,dh,dp), (2dd,0,dp), (2dd,dh,0), and lie
within circles of radius, R, which represents the radius of interaction sphere (Fig. 1).
The coordinates of the center of the sphere represent the Hansen solubility parameters
of the polymer. Any of the three planes can be considered first for drawing of the circle,
which results in different values for R and for the Hansen solubility parameters.

Figure 1. Hansen sphere and circles of solubility.


288 F. Gharagheizi and M. T. Angaji

Hansen’s method[1] for determination of solubility parameters is based on con-


tacting the polymer of interest with 40 to 45 well-chosen liquids. One may then
observe or measure a number of different phenomena including full solution at a
given concentration, degree of swelling by visual observation or by measurement
of weight change, volume change, clarity, surface attack, etc. The object of the
studies is to determine differences in affinity of the polymer for the different
solvents. These differences are then traditionally used to divide the solvents into
two groups, one which is considered “good” and the other which is considered
“bad.” Such data can be entered into the SPERE program as discussed in
Hansen.[1] This program computes the three partial Hansen solubility parameters
and R, the radius of interaction sphere.
One of the more promising methods to evaluate polymer Hansen solubility parameters
for limited data is based on the intrinsic viscosity.[1,20,21] In this paper, a new, simple, and
easy method to estimate the Hansen solubility parameters of polymers is presented. In this
new method HSP is estimated from the intrinsic viscosity of polymer in a number of
solvents and the molar volumes of these solvents.

New Improved Method


The authors of this paper consider that good and limiting solvents of a polymer can be
represented in the three-dimensional space of coordinate dd, dp, and dh as a system
of material points with different weights. The weights of the solvents are determined
by the liquid molar volumes of the solvents and intrinsic viscosities, normalized to
unity, of the polymer in the corresponding solvents, as it is well known that the
intrinsic viscosity of a polymer in a given solvent is a measure of polymer-solvent inter-
actions: the higher the interactions, the greater the values of intrinsic viscosity. The

Table 1
Properties of solvents and properties of solutions
Solvents [h]a dd dp dh Solubility V

Methyl-2-pyrrolidone 0.97 18 12.3 7.2 1 96.5


Dimethyl formamide 0.947 17.4 13.7 11.3 1 77
Diethyl sulfoxide 0.182 18.4 16.4 10.2 1 71.3
gamma-Butyrolactone 0.689 19 16.6 7.4 1 76.8
Morpholine 1 18.8 4.9 9.2 1 87.1
Cyclohexane 0.718 17.8 6.3 5.1 1 104
Diacetone alcohol  15.8 8.2 10.8 0 124.2
Acetone  15.5 10.4 7 0 74
Diethylene glycol  16.2 7.8 12.6 0 118
momomethyl ether
Ethylene glycol  16.2 9.2 14.3 0 97.8
monoethyl ether
Ethylene glycol  15.9 4.7 10.6 0 136.1
monoethyl ether
acetate
a
Normalized intrinsic viscosity data from [h] ¼ [h]i/Max([h]i).[21]
Estimating Hansen Solubility Parameters 289

Table 2
The comparative results between this method and other reported results

Correlation dd dp dh

Ref.[21] 18 11.1 8.8


Ref.[1] 19 11 9
Ref.[1] 20 11 10
This Method 18.1 11.4 8.8

coordinates of the mass center of the system of material points represent the Hansen
solubility parameters of the polymer. It is obvious that the mass center is closer to
solvents with higher weights, the ones with smaller weights being poor solvents for
the polymer. The equations of the coordinates of the mass center, adapted to the
present situation, are:

ddp ¼ Sðddi  ½hvi i Þ=S½hvi i ð8Þ

d pp ¼ Sðd pi  ½hvi i Þ=S½hvi i ð9Þ


dhp ¼ Sðdhi  ½hvi i Þ=S½hvi i ð10Þ

where subscript index p designates the polymer and vi, [h]i are the molar volume of
solvents and intrinsic viscosity of polymer in the ith solvent normalized to unity. Nor-
malization to unity was done by dividing by the maximum obtained intrinsic viscosity.
Once the coordinates of the interaction sphere (dd, dp, and dh) are determined, the sep-
arating distances from its center to the points corresponding to good and limiting
solvents, Ri, are computed. The highest value of Ri is the well-known Hansen’s relation:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Ri ¼ 4ðddi  ddp Þ2 þ ðd pi  d pp Þ2 þ ðdhi  dhp Þ2 ð11Þ

Using this method to compute the Hansen solubility parameters of a polymer, all the good
and limiting solvents are included in the interior of the sphere or are at least on its surface.
The intrinsic viscosity of a sample of polyesterimide in 11 solvents was measured by
Segarceanu and Leca.[11] The normalized values of these data and the Hansen solubility
parameters of these solvents are shown in Table 1. Some of these solvents thus dissolve
the polymer and have an intrinsic viscosity, and some of them do not dissolve the
polymer and do not have any value of intrinsic viscosity.
The results of this improved method and the values reported by Hansen[1] and
Segarceanu and Leca[21] are compared in Table 2.
The results with this method fit the experimental data well.

Conclusion
1. This method is a very promising method of arriving at the polymer Hansen solubility
parameters with limited data.
2. The method is simple, uses literature data on solvents and polymers, and can be easily
implemented on a computer.
3. The equations used to determine the Hansen solubility parameters are simple and do
not imply special processing.
290 F. Gharagheizi and M. T. Angaji

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