Handbook of Solvents - George Wypych - ChemTech - Ventech!

118 Valery Yu. Senichev, Vasiliy V. Tereshatov
# Solvent
D A δ′ δ V1×10 6
(MJ/m 3 ) 1/2
m 3 /mol
19 1-Propanol 11.9 13.4 21.0 24.5 75.2
20 Methyl ethyl ketone 2.3 11.6 18.3 19.0 90.1
21 Cyclohexanone 2.7 11.1 19.5 20.3 104.0
22 Diethyl ether 7.6 12.4 12.0 15.4 104.8
23 Ethylbenzene 0.3 7.3 17.9 18.0 123.1
24 Pyridine 1.9 19.6 21.0 21.8 80.9
25 Propyl acetate 4.8 9.6 16.4 17.8 115.2
26 1,4-Dioxane 8.3 12.9 17.7 20.5 85.7
27 Aniline 6.2 16.8 20.0 22.5 91.5
Table 4.1.4. TDM parameters of some polymers, (MJ/m 3 ) 1/2 . [Adapted, by permission,
from V.Yu. Senichev, V.V. Tereshatov , Vysokomol . Soed ., B31 , 216 (1989)]
Polymer D A δ′ δ
Polymethylmethacrylate 2.5 6.5 18.6 19.8
Polyvinylacetate 4.9 10.4 17.8 19.2
Polystyrene 0.3 7.3 17.9 18.0
Polyvinylchloride 11.6 10.6 16.1 19.5
δ h can be separated into donor and acceptor components using values of enthalpies of
the hydrogen bond formation between proton-donors and proton-acceptors. In the absence
of such data it is possible to evaluate TDM parameters by means of analysis of parameters
of compounds similar in the chemical structure. For example, propyl acetate parameters can
been calculated by the interpolation of corresponding parameters of butyl acetate and ethyl
acetate, 24 parameters of benzene can be calculated by decomposition of δ h into acceptor and
donor components in the way used for toluene elsewhere. 25
The solubility prediction can be made using the relationship between solubility and
the χ 1 parameter (see Subchapter 4.2). The total value of the χ 1 parameter can be evaluated
by adding the entropy contribution:
χ = χ + χ
1
S H [4.1.45]
where:
χS an empirical value. Usually it is 0.2-0.4 for good solvents.
The value of the parameter is inversely proportional to coordination number that is
number of molecules of a solvent interacting with a segment of polymer. The value of the
entropy contribution to the parameter should be included in solubility calculations. The
value χ S = 034 . is then used in approximate calculations.