Handbook of Solvents - George Wypych - ChemTech - Ventech!

114 Valery Yu. Senichev, Vasiliy V. Tereshatov
Polymer
δ,
(MJ/m 3 ) 1/2
δd,
(MJ/m 3 ) 1/2
δp,
(MJ/m 3 ) 1/2
δh,
(MJ/m 3 ) 1/2
Polyacrylonitrile 25.10 18.19 15.93 6.74
Polyvinylchloride 21.41 18.68 10.01 3.06
Polymethylmethacrylate 20.18 17.72 5.72 7.76
Polystyrene 19.81 19.68 0.86 2.04
Polytetrafluoroethylene 13.97 13.97 0.00 0
Polyethyleneterephthalate 21.6 19.5 3.47 8.58
A large number of data were accumulated for different solvents and polymers (see Tables
4.1.1, 4.1.2). A variation of the Hansen method is the approach of Teas. 33 He showed
for some polymer-solvent systems that it was possible to use fractional cohesive energy
densities plotted on a triangular chart to represent solubility limits:
2
2
2
δ δ
d
p δh
E d = , E p = , E h =
[4.1.24]
2
2
2
δ δ δ
0
2 2 2 2
where δ0 = δd + δp + δh
Teas used fractional parameters defined as
0
0
100δ 100δ d
p
100
fd =
, fp =
, fh
=
[4.1.25]
δ + δ + δ δ + δ + δ δ + δ + δ
d p h
d p h
d p h
This representation was completely empirical without any theoretical justification.
Some correlations between components of solubility parameters and physical parameters
of liquids (surface tension, dipole moment, the refraction index) were generalized elsewhere.
11
2 2 2
−13
/
δ + 0. 632δ + 0. 632δ = 13. 9V
γ
d p h 1 l
2 2 2
−13
/
δ + δ + 006 . δ = 139 . V γ
d p h 1 l
2 2 2
−13
/
δ + 2δ + 0. 48δ = 13. 9V
γ
d p h 1 l
non-alcohols [4.1.26]
alcohols [4.1.27]
acids, phenols [4.1.28]
where:
γl surface tension.
Koenhan and Smolder proposed the following equation applicable to the majority of
solvents, except cyclic compounds, acetonitrile, carboxylic acids, and multi-functional alcohols.
34
2 2
−13
/
δ + δ = 13. 8V
γ
d p 1 l
[4.1.29]
They also proposed a correlation between polar contribution to the solubility parameter
and refractive index: