Progress in Organic Coatings, 8 (1980) 113 - 141 113

@ Elseqier Sequoia S.A., Lausanne - Printed in the Netherlands I

SOLVENT FORMULATION FOR SURFACE COATINGS

J. RAMSBOTHAM
Koninklijke/Shell Laboratorium (Shell Research B.V.), Amsterdam (The Netherlands)

Contents

1 Introduction. ............................................. 113

2 Solvent power and polymer solubility ............................. 114
2 .l Solvent solubility parameters ................................ 114
2.2 Solvent blends and reformulation ............................. 115
2.3 Polymer solubility maps ................................... 120
2.4 Some limitations of solubility parameters. ....................... 126
3 Solvent volatility and loss from coatings. ........................... 127
3.1 Solvent volatility measurement. .............................. 127
3.2 The wet stage of film formation .............................. 130
3.3 Flow in paint films. ...................................... 132
3.4 The dry stage of film formation .............................. 134
4 Solution properties. ......................................... 135
4.1 Flashpoints. ........................................... 135
4.2 Viscosity ............................................. 138
5 Concluding remarks ......................................... 139
Appendix .................................................. 139
References. ................................................ 140

1. Introduction

During the last ten years, considerable advances have been made in the
development of techniques which can assist the solvent formulator in his
work. Many of these have been separately described in the literature.
However, in the majority of cases, the solvent formulator has an interest in a
combination of these techniques rather than in any single one. It is therefore
important to him to have a series of simple, accurate guidelines which allow
him to arrive, without unnecessary trial and error, at a cost-optimised solvent
blend within the constraints he may care to apply. The object of this review
is to present such a series of techniques which we have successfully used for
the past few years for technical service and trouble-shooting work.
Technical criteria for designing a solvent blend for a paint system may
be summarised as follows:
Candidate solvents when combined must have a volatility suitable for
the applicational technique.
114

They must form a true solvent for the polymer or binder system.
Solutions often have to conform to flashpoint regulations and attention
must be paid to other solution properties such as viscosity.
Solvent must evaporate from the paint fihn in such a way as to mini-
mise flow defects such as orange peeling and not cause the resin to
precipitate out of solution.
Unnecessarily high levels of retained solvent in the final film must be
avoided.

The techniques necessary for following the above scheme through are
now discussed.

2. Solvent power and polymer solubility

From the earliest times, formulators have tried to quantify the ‘power’
or ability of their solvents to dissolve things. Many of these traditional
methods were developed for the hydrocarbon extracts used with natural
resins, and factors such as the kauri-butanol number and aniline point are
still widely quoted [l] . However, certain coatings such as shellac, and later
nitrocellulose, required the use of additional oxygenated or chemical
solvents whose power far exceeded that of the hydrocarbons. Other criteria
of measuring solvent power came into vogue [l] and a vast amount of
literature relating to nitrocellulose in particular is found. However, during
the past 20 years, coatings formulators have achieved access to such a wide
range of synthetic resins and polymers that a general method for describing
the power of various solvents towards them is absolutely vital. Such a general
method is provided by solubility parameters.

2.1 Solvent solu bility parameters

An exhaustive review of solubility parameters has recently been
published by Barton L2], although a more general account is available which
lays more emphasis on the applicational aspects [ 31. Solubility parameters
are numbers which attempt to quantify the intermolecular forces between
molecules in a liquid. As there are three distinct types of intermolecular
force (dispersion, polar and hydrogen bonding), modem systems use three
parameters each representing one of these forces. On the basis that the
mixing of liquids is likely to occur if intermolecular forces are of a similar
strength and that a solvent/polymer interaction will also be governed by
these forces, solvent blends having similar intermolecular forces (i.e.
solubility parameters) will have similar solvent powers. This is the basis for
reformulating a solvent blend - one first calculates the three solubihty para-
meters and then produces them in a replacement blend.
At this stage, it has to be realised that unfortunately there are, several
systems of solubility parameters [2, 31 and each has its merits. There is no
doubt that if one system could be adopted as a ‘universal one’, life would be
 115

made much easier. The work of Henry [4] will hopefully help towards this
end. Perhaps the best known parameter systems are those due to Hansen
[ 5 - 71 and Nelson and his co-workers [S, 91.
Using a concept of ‘homomorphs’, Hansen postulated that the cohesive
energy density of a liquid, C - a measure of the total intermolecular forces
- could be related to dispersion, Cd, polar, C, and hydrogen bonding, C.&,
components by :

c = Cd + c, + Ch
The Hildebrand solubility parameter 6 is related to the cohesive energy
density, C = 62, and this then gives rise to the expression:

Hansen derived values for the parameter components and a selection are
summarised for more common solvents in Table 1.
By contrast, the parameter system developed by Nelson and his co-
workers is a much more empirical type of development than that of Hansen.
The Hildebrand solubility parameter is retained together with a fractional
polarity term’proposed by Gardon [lo] and a hydrogen bonding index [ 81.
Values;for these parameters are summarised in Table 2.

2.2 Solvent blends and reformulation

Whichever solubility parameter system is used, the power of a solvent
is described using three parameters. In the case of a blend of solvents,
however, each of these three parameters has to be calculated. The relation-
ship universally applied is:

P= 5 v,P,
x=1

where, for a solvent blend of N components, P is the blend parameter,

P, is the value of the equivalent parameter of component x, and v, is the
volume fraction of component x.
Returning to our earlier remarks, it can be seen that by using the
preceding linear relationship, the solubility parameters of a blend can be
calculated and then reproduced in a replacement reformulated blend. Quite
clearly this last step is most easily carried out using a computer [ 9,l l] .
However, a graphical approach can be used. Figure 1 illustrates this using
Nelson’s system of parameters.
It will be noted that the various classes of solvents (aliphatic and
aromatic hydrocarbons, ketones, esters, glycol ethers and alcohols) occupy
characteristic positions on this type of representation. If one combines two
solvents, such as n-butanol (NBA) and xylene, the solubility parameters of
the blend are situated somewhere on a straight line joining the points
representing the two solvents. Moreover, in the case illustrated in Fig. 1:
116

TABLE 1
Hansen’s solubility parameters - solvents

Solvent type Solvent name

Aliphatic n-hexane 7.3 0 0

hydrocarbons n-heptane 7.5 0 0
cyclohexane 8.2 0 0.1

Aromatic benzene 9.0 0 1.0

hydrocarbons toluene 8.8 0.7 1.0
o-xylene 8.7 0.5 1.5
ethyl benzene 8.7 0.3 0.7

Ketones acetone 7.6 5.1 3.4

methyl ethyl ketone 7.8 4.4 2.5
methyl isobutyl ketone 7.5 3.0 2.0
cyclohexanone 8.7 3.1 2.5
isophorone 8.1 4.0 3.6

Esters methyl acetate 7.6 3.5 3.7

ethyl acetate 7.7 2.6 3.5
n-butyl acetate 7.7 1.8 3.1
isobutyl acetate 7.4 1.8 3.1
Oxitol acetate 7.8 2.3 5.2

Alcohols methanol 7.4 6.0 10.9

ethanol 7.7 4.3 9.5
n-propanol 7.8 3.3 8.5
isopropanol 7.7 3.0 8.0
n-butanol 7.8 2.8 7.7
see-butanol 7.7 2.8 7.1
isobutanol 7.4 2.8 7.8

Glycol ethers methyl Oxitol 7.9 4.5 8.0

Oxitol 7.9 4.5 7.0
butyl Oxitol 7.8 2.5 6.0
methyl Dioxitol 7.9 3.8 6.2
Dioxitol 7.9 4.5 6.0
butyl Dioxitol 7.8 3.4 5.2

Ethers furan 8.7 0.9 2.6

tetrahydrofuran 8.2 2.8 3.9
1,4dioxan 9.3 0.9 3.6
diethyl ether 7.1 1.4 2.5

Nitrogen acetonitrile 7.5 8.8 3.0

compounds nitromethane 7.7 9.2 2.5
2nitropropane 7.9 5.9 2.0
nitrobenzene 9.8 4.2 2.0
ethanolamine 8.4 7.6 10.4
pyridine 9.3 4.3 2.9
aniline 9.5 2.5 5.0
formamide 8.4 12.8 9.3
dimethylformamide 8.5 6.7 5.5
(Continued on facing page)
 117

TABLE 1 (Continued)

Solvent type Solvent name 6d 6, 6h

Sulphur carbon disulphide 10.0 0 0.3

compounds dimethyl sulphoxide 9.0 8.0 5.0

Polyhydric ethylene glycol 8.3 5.4 12.7

alcohols propylene glycol 8.2 4.6 11.4
glycerol 8.5 5.9 14.3
diethylene glycol 7.9 7.2 10.0

Halogenated dichloromethane 8.9 3.1 3.0

hydrocarbons chloroform 8.7 1.5 2.8
carbon tetrachloride 8.7 0 0.3

Others diacetone alcohol 7.7 4.0 5.3

water 7.6 7.8 20.7
acetic acid 7.1 3.9 6.6

TABLE 2
Solubility parameters - Nelson, Hemwall and Edwards

Solubility Fractional Hydrogen

parameter polarity bonding

Individual hydrocarbons
n-Pentane 7.02 0 0
2-Methylbutane 6.75 0 0
n-Hexane 7.27 0 0
Methylpentanes 7.0 - 7.1 0 0
Dimethylbutanes 6.7 - 6.9 0 0
n -Heptane 7.5 0 0
Methylhexanes 7.25 0 0
3 -Ethylpentane 7.37 0 0
Trimethylbutane 6.95 0 0
n-Octane 7.54 0 0
Methylheptanes 7.35 0 0
Ethylhexanes 7.5 0 0
Dimethylhexanes 7.1 - 7.4 0 0
Ethyl methylpentanes 7.3 0 0
Nonane 7.64 0 0
Decane 7.74 0 0
Undecane 7.81 0 0
Dodecane 7.92 0 0
Cyclopentane 8.1 0 0
Ethyl cyclopentane 7.94 0 0
Methyl cyclopentane 7.85 0 0
Trimethyl cyclopentanes 7.3 - 7.55 0 0
Cyclohexane 8.2 0 0
Ethyl cyclohexane 7.96 0 0

(Continued overleaf)
118

TABLE 2 (Continued)

Solubility Fractional Hydrogen

parameter polarity bonding

Benzene 9.2 0.001 4.0

Toluene 8.9 0.001 4.2
Xylene (commercial) 8.85 0.001 4.5
Ethylbenzene 8.8 0.001 4.2
Trimethyl benzenes ca. 9.9 0.001 5.0

Commercial hydrocarbon solvents

White spirit (LAWS) 7.85 0 0.5
Hexane 7.3 0 0
SBP 100/140 7.5 0 0
SBP 140/165 7.6 0 0
SBP 1 7.4 0 0
SBP 2 7.5 0 0
SBP 3 7.7 0 0.25
SBP 4 7.6 0 0.1
SBP 5 7.6 0 0
SBP 6 7.8 0 0.5
SBP 11 7.75 0 0.5
Rubber solvent 7.7 0 0.3
Shellsol A 8.8 0.001 5.0
Shellsol E 8.4 0.001 4.5
Shellsol AB 8.7 0.001 5.3
Shellsol R 8.4 0.001 5.0
Shellsol T 7.6 0 0
Shellsol TD 7.65 0 0
Shellsol K 7.7 0 0.1
Shellsol RA 8.65 0.001 5.5

Ketones
Acetone 10.0 0.695 12.5
Methyl ethyl ketone 9.3 0.510 10.5
Methyl isobutyl ketone 8.4 0.315 10.5
Methyl isoamyl ketone 8.3 0.255 10.9
Cyclohexanone 9.9 0.380 13.7
Ethyl amyl ketone 8.2 0.223 8.5
Pent-o-xone 8.5 0.190 12.5
Diisobutyl ketone 7.8 0.123 9.8
Diacetone alcohol 9.2 0.312 0
Isophorone 9.1 0.190 14.9
Mesityl oxide 9.0 0.332 12.0

Esters
Ethyl acetate (85 - 88%) 9.6 0.182 4.9
Ethyl acetate (99%) 9.1 0.167 8.4
Isopropyl acetate 8.6 0.100 8.5
nPropy1 acetate 8.75 0.129 8.5
set-Butylacetate 8.2 0.082 8.3
Isobutyl acetate 8.3 0.097 8.7
nButy1 acetate (90 - 92%) 9.0 0.118 5.7
(Continued on facing page)
 119

TABLE 2 (Continued)

Solubility Fractional Hydrogen

parameter polarity bonding

n-Butyl acetate (99%) 8.6 0.120 8.0

Amy1 acetate 8.45 0.067 8.2
Methyl amyl acetate 8.2 0.050 8.3
Isobutyl isobutyrate 7.1 0.042 8.0
Methyl (methyl) Oxitol acetate 9.2 0.095 10.5
Ethyl Oxitol acetate 8.7 0.073 10.1

Ethers and glycol ethers

Tetrahydrofuran 9.9 0.075 12.0
Dioxane 10.0 0.006 14.6
Methyl Oxitol 10.8 0.126 0
Ethyl Oxitol 9.9 0.086 0
Butyl Oxitol 8.9 0.048 0
Methyl Dioxitol 10.2 0.058 0
Ethyl Dioxitol 9.6 0.043 0
Butyl Dioxitol 8.9 0.028 0

Alcohols
Methyl alcohol 14.5 0.388 -19.8
Isopropyl alcohol 11.5 0.178 -16.7
n-Propyl alcohol 11.9 0.152 -16.5
secButy1 alcohol 10.8 0.123 -17.5
Isobutyl alcohol 10.7 0.111 -17.9
nButy1 alcohol 11.4 0.096 -18.0
Methyl isobutyl carbinol 10.0 0.066 -18.7
n-Amy1 alcohol 10.9 0.074 -18.2
Cyclohexanol 11.4 0.075 -16.5
2-Ethylhexanol 9.5 0.042 -18.7

Miscellaneous
Dichloromethane 9.7 0.12 1.5
Chloroform 9.3 0.017 1.5
1,2-Dichloroethane 9.8 0.043 1.5
1,2,2,2-Tetrachloroethane 10.4 0.092 1.5
2-Nitropropane 9.9 0.72 4.0
Dimethylformamide 12.1 0.772 18.9
Chlorobenzene 9.50 0.058 2.7

Volume fraction of xylene BX

Volume fraction of NBA = AX

A third solvent can then be added to this ratio and a similar procedure
repeated between point ‘X’ and the point characterising the new solvent.
(In this case solvent fractional polarities would need to be calculated at each
stage.) This approach gives something of a ‘feel’ for which solvents could be
combined to reproduce the solubility parameters of a given existing blend.
120

t9

+5
XILENE (0001,

+3

-3

-6

-9

-12

-15

-18

7 a 9 IO II 12
nlLoE9RlNo SOLUBILITY WRIMETER

Fig. 1. Solvent solubility parameters.

2.3 Polymer solubility maps

The use of solubility parameters to reformulate or ‘copy’ an existing
blend is most convenient. However, this copying process has several dis-
advantages implicit in it, and the more important of these are:
The blend being copied may not be optimal either technically or
commercially.
One assumes that only solvents or blends having a particular set of
solubility parameters are suitable and so unnecessarily restrict the formula-
tion.
Reformulating to optimal cost and other constraints is not always
possible with the solvents available.

Ideally these advantages could be short-circuited if the solubility parameters

of the resin(s) or polymer(s) were known. These could then be reproduced in
a solvent blend - in fact, one could literally follow the saying of ‘like
dissolves like’. Unfortunately, the solubility parameters of polymers and
resins are not directly measurable and they have to be deduced from those of
the solvents which dissolve them. Generally speaking, the solubility para-
meters of a polymer are taken to be those situated ‘in the centre’ of the
points corresponding to those of the true solvents for the polymer.
 121

Fig. 2. Diagrammatic reprisentation of a polymer solubility plot based on Hansen’s

parameter system. The dotted circles represent projections of the ‘sphere of solubility’.

2.3.1 Hansen’s solubility maps

In this respect, Hansen has introduced the very convenient concept of
a sphere of solubility shown in Fig. 2. Polymers and resins are assigned the
parameters given in Table 3 and solvents falling within a sphere of radius
R A0 are compatible with the resin. (Teas [12] has pointed out that this
system can be most conveniently represented on triangular axes because of
the relationship introduced in 2.1:

Unfortunately, the convenience of a ‘sphere’ of solubility is lost.)

Naturally, the strongest solvents for the polymer are those whose para-
meters place them near the centre of the sphere. Mixed binder systems are
easily accommodated by formulating in the areas of overlap of the spheres.
While the concept of a sphere of solubility has an undoubted appeal,
it has proved to be a little over-simplified for more quantitative formulation
work involving synthetic resins in our laboratories. In short, it seems that the
sphere is not always a sphere and that a more flexible approach to the radius
of solubility (RAO) should be adopted to allow for the concentration of dis-
solved resin or polymer, as we will shortly discuss.

2.3.2 Ramsbotham ‘s solubility maps

In an effort to achieve a better standard of quantitative solubility
prediction, Ramsbotham has recently described [13 - 151 how Nelson’s
TABLE 3
Hansen’s solubility parameters - polymers

Polymer type Trade name Supplier Computed parameters

RAO

Poly(ethy1 methacrylate) Lucite 2042 Du Pont 8.60 4.72 1.94 5.20

Poly(methy1 methacrylate) Rohm & Haas 9.11 5.14 3.67 4.20
Epoxy Epikote 1001 Shell 9.95 5.88 5.61 6.20
Long oil alkyd (66% oil length) Plexal P65 Polyplex 9.98 1.68 2.23 6.70
Alcohol soluble rosin resin Pentalyn 830 Hercules 9.79 2.84 5.34 5.70
Poly(viny1 butyral) Butvar B76 Shawinigan 9:09 2.13 6.37 5.20
Polystyrene Polystyrene LG BASF 10.40 2.81 2.10 6.20
Poly(viny1 acetate) Mowilith 50 Hoechst 10.23 5.51 4.72 6.70
Urea-formaldehyde Plastopal H BASF 10.17 4.05 7.31 6.20
Nitrocellulose H23 (lh set) Hagedorn 7.53 7.20 4.32 5.60
Chlorinated polypropylene Parlon PlO Hercules 9.90 3.09 2.64 5.20
Cellulose acetate Cellidora A Bayer 9.08 6.22 5.38 3.70
Pure phenolic Super Beckacite 1001 Reichold 11.37 3.20 4.08 9.70
Phenolic resin (resole) Phenodur 373U Albert 9.65 5.68 7.13 6.20
Modified pentaester of rosin Cellolyn 102 Hercules 10.62 0.46 4.17 7.70
Alcohol soluble resin Pentalyn 255 Hercules 8.58 4.58 7.00 5.20
Blocked isocyanate (phenol) Suprasec F5100 ICI 9.87 6.43 6.39 5.70
Short oil alkyd (34% oil length) Plexal C34 Polyplex 9.04 4.50 2.40 5.20
Saturated polyester Desmophen 850 Bayer 10.53 7.30 6.00 8.20
Styrene-butadiene (SBR) elastomer Polysar 5630 Polymer Corp. 8.58 1.64 1.32 3.20
Acrylonitrile-butadiene elastomer Hycar 1052 B. F . Goodrich 9.10 4.29 2.04 4.70
Isoprene elastomer Cariflex IR305 Shell 8.10 0.69 -0.40 4.70
Poly(isobutylene) Lutonal IC/123 BASF 7.10 1.23 2.28 6.20
cis-Polybutadiene elastomer Bunahuls CBl 0 Huels 8.57 1.10 1.67 3.20
Thermoplastic polyamide Versamid 930 General Mills 8.52 -0.94 7.28 4.70
Ester gum Ester gum BL Hercules 9.60 2.31 3.80 5.20
Hexamethoxymethyl melamine Cymel300 American Cynamid 9.95 4.17 5.20 7.20
Terpene resin Piccolyte S-100 Pennsylvania Ind. Chem. 8.05 0.18 1.39 4.20
Furfuryi alcohol resin Durez 14383 Hooker Chem. 10.34 6.63 6.26 6.70
Petroleum hydrocarbon resin Piccopaie 110 Pennsylvania Ind. Chem. 8.58 0.58 1.76 3.20
Poly(viny1 chloride) Vipla KR (K = 50) Montecatini 8.91 3.68 4.08 1.70
Coumarone-indene resin Piccoumarone 450 L Pennsylvania Ind. Chem. 9.49 2.68 2.82 4.70
124

solubility parameters can be used to construct solubility maps using a

dilution ratio technique. The principle involved is that if a solution of a resin
or polymer in a known solvent is titrated with a diluent, there will be an end-
point in the titration where turbidity is observed and the solubility para-
meters at this end-point can be calculated. If this procedure is performed
using various combinations of solvents and diluents and the points are
plotted onto axes as in Fig. 1 and points of similar fractional polarity are
connected, solubility maps such as those shown in Figs. 3 - 8 are obtained.
In this approach, fractional polarity, instead of being represented as a vertical
axis out of the plane of the paper, is shown as a contour line. These maps
represent the minimum solvent power necessary to dissolve the resin.
If such a map of a resin or polymer is made and the solvents are then
superimposed on it as in Fig. 1, solvents falling ‘outside’ the map are
naturally non-solvents. Solvents or blends whose parameters place them
within the map are true solvents for the resin if their fractional polarity is
lower than that shown as the maximum permissible on the map; they will
only be partial solvents if the polarity constraint is exceeded. Very good
quantitative predictions are obtained usingthese maps by measuring tech-
niques - for instance in Fig. 3, two non-solvents for the epoxy resin
combine to form a true solvent in the ratio BC : AD :xylene :n-butanol.
Blends are built up in an analogous way to that described in Section 2.2.

HYOROGEN BONDING INDEX

.
-12 - NON-SOLVENTS

NON-SOLVENTS

Fig. 3. Solubiiity map for Epikote 1004 (solids > co. 30% wt.).

Fig. 4. Solubility map for Epikote 1001 (solids > ca. 30% wt.).
 125

HYDROGEN BONDING NMX kXO$EN BONDING INDEX

CONTOURS DENOTE MAXIMUM CONTOURS DENOTE MAXIMUM

PERMISSIBLE FRACTIONAL POLARITY PEFMlSSlBLE FRPCTIONAL POLARITY
+9 - FOR TRUE SOLVENT Fa( TRUE SOLVENTS

+6 -

$3 -

SOLVENTS

O-

-3 -

-6 - -6

-9 - -9

-12 - NON-SOLVENTS -12 NON-SOLVENTS

-15

HILDEERAND SOLUEILITY PARAMETER

8 9 IO II 12
MLDEBRAND SOUJBILITY PARAMETER
13

Fig. 5. Solubility map for Epikote 1007 (solids > ca. 30% wt.).

Fig. 6. Solubility map for Epikote 1009 (solids > cu. 30% wt.).

2.3.3 Effect of dissolved solids

It has long been recognised that with a large number of resins, the
power of the solvent necessary to dissolve them at low solids concentrations
is higher than that required at higher solids [ 141. This has been used as a
measure of solvent power in the so-called ‘dilution limit’ [l] but ii more
frequently encountered in the phenomenon of partial solubility, e.g.
solubility behaviour of solid epoxy resin in butyl and ethyl acetates and
short oil alkyds in white spirit type solvents. However, this behaviour is not
general, and particularly with higher molecular weight resins such as nitro-
celluloses, the solvent power required does not decrease as the resin con-
centration increases. Ramsbotham [ 141 recently suggested in arriving at a
simple thermodynamic condition for solvency from the Gibbs equation:
TAS> AH
that the enthalpy term AH could be considered as mainly a function of
the solubility parameters, while the entropy change AS was polymer con-
centration related. He did not develop this hypothesis by applying, for
example, a Boltzmann equation, and work along these lines would be
extremely useful.
126

CONTOURS DENOTE TIE M‘WMUM

+S
CONTOURS DENOTE M&XIMUM PERMIS.WLE FA-
PERMISSIBLE FRACTIONAL POLM,TY POLAQlTY OF SOLVENTS
FOR TRUE SOLVENTS

+4

-4

-0

NON-SOLVENT

-12

APPRBIMI\TE END-POINTS
OF DIL”TK)N RATIO DATA

-16

-20
I I
---- _---_
s 9 10 II 12
HILDEBRAND SOLUBLIN PARAMETER

Fig. 7. Solubility map for Setal 84 (short oil alkyd resin).

Fig. 8. Solubility map for Varcum 6820 phenolic resin (Reichhold) (solids > co. 10% wt.).

In practical terms, this means that when using any solubility map it is
useful to know the minimum solids contents for which it applies to avoid
formulating partial solvents. In the case of mixed binder systems, formula-
tions are conducted in the ‘area of overlap’ of the solubility maps, and the
solids content is taken, for absolute safety, as that of the lowest resin con-
centration.

2.4 Some limitations of solubility parameters

Molecular interactions between paraffin hydrocarbons are of the
dispersion type. Consequently they are described in all solubility parameter
systems using the Hildebrand solubility parameter only. Care has to be taken
for molecules smaller than ca. C4 or larger than ca. Cs since it has been
shown that the Hildebrand parameter can lead to inaccurate indications of
solvent power [l] . Hoy [ 161 has also drawn attention to the fact that the
glycol ethers (Oxitol solvents) can exhibit a ‘chameleonic’ behaviour by
forming internal as well as external hydrogen bonds as shown below:

B-0 - CH2
R .O.CH,.CH,.OH +
k dH,
‘0’
 127

He suggests that this could account for the fact that these solvents are
miscible with water on the one hand (6 = 23.5) and aliphatic hydrocarbons
on the other (6 = cu. 7.5). All solubility parameter systems content them-
selves with one set of values for the solubility parameters, however. In the
majority of cases these serve very well with organic solvent based coatings
with the exception of situations where an Oxitol is blended with a paraffin
hydrocarbon, i.e. an extremely non-polar, non-hydrogen-bonding ‘weak’
solvent. Nunn [ 171 has also examined some anomalous predictions obtained
using solubility parameters. In summary to this section it must be stressed
that poor predictions using solubility parameters/solubility maps are rather
an exception than a rule!

3. Solvent volatility and loss from coatings

Besides combining solvents having an appropriate power, the

formulator must choose them in such a way that the volatility of the solvent
formulation is suited to the end use. In order to do this a practical measure
of solvent volatility is required. Techniques of volatility measurement have
recently been described by Rocklin [ 181. The way in which solvents subse-
quently evaporate from films during the drying process is important, not
only to obtain a good standard of finish, but to ensure that the mechanical
properties of the film are optimal. Solvent is lost from the film in two basic
stages, an initial ‘wet stage’ where the rate of loss is limited by solvent
diffusion to the air through the surface boundary layer of the solution, and
a ‘dry stage’ where solvent is lost at a much lower rate in a process where
solvent diffusion in the bulk film is rate limiting. A review on the topic of
solvent evaporation has been published by Yoshida [ 191 ; Newman and Nunn
[ 201 have recently reviewed the dry stage of film formation in detail.

3.1 Solvent volatility measurement

Experience has shown that criteria such as solvent boiling point or
vapour pressure do not stand up very well in practical paint formulation
[ 211. ASTM.D3539.76 describes the use of the Shell Automatic Evaporo-
meter, which is used to relate the evaporation rates of solvents relative to a
standard of n-butyl acetate.
Relative Evaporation Rate (RO) = (time taken for 90 %w n-butyl acetate
to evaporate)/(time for 90 %w test solvent to evaporate)
(The time taken for 90% rather than 100% of the solvent to evaporate
avoids the introduction of spurious substrate-solvent interactions.) Relative
evaporation rates are summarised in Table 4. Variations on this type of
measurement are possible [ 18, 211, but the values given here are representa-
tive and work extremely well in practice. The relative evaporation rate is a
good guideline when choosing solvents to suit a particular end-use/applica-
tional technique.
128

TABLE 4
Relative evaporation rates of solvents and effective viscosities (n-butyl acetate = 1)

Effective ASTM
viscosity D.3539.76
(cP,20 “C)

Alcohols
Methyl alcohol _ 1.9
Denaturated ethanol 1.05 1.54
Isopropanol (IPA) 1.10 1.5
Normal propanol (NPA) 1.40 0.94
Secondary butanol (SBA) 1.40 0.89
Isobutanol (IBA) 1.80 0.64
Normal butanol (NBA) 1.60 0.47
Methyl isobutyl carbinol (MIBC) 1.8 0.28
Diisobutyl carbinol (DIBC) - 0.036
Hexylene glycol (HG) 0.007

Esters
Methyl acetate 0.42 5.1
Ethyl acetate 0.45 4.2
Isopropyl acetate 0.52 3.5
Normal propyl acetate 0.59 2.14
Secondary butyl acetate 0.65 1.75
Isobutyl acetate (98%) 0.68 1.45
Normal butyl acetate 0.68 1.0
Methyl amyl acetate 0.87 0.47
Amy1 acetate (95% mixed isomers) 0.83 0.38
Ethyl lactate - 0.2

3lycol ethers and glycol ether acetates

Methyl Oxitol 1.20 0.53
Ethyl Oxitol 1.20 0.38
Isopropyl Oxitol _ 0.33
Methyl Oxitol acetate 1.6 0.32
Ethyl Oxitol acetate 1.2 0.20
Butyl Oxitol 2.0 0.08
Methyl Dioxitol - 0.02
Ethyl Dioxitol - 0.017
Butyl Dioxitol 2.15 0.004
Ethyl Dioxitol - <0.003
Butyl Dioxitol acetate - 0.001

Ketones
Acetone (DMK) 0.31 5.6
Methyl ethyl ketone (MEK) 0.41 3.7
Methyl isobutyl ketone (MIBK) 0.55 1.6
Cyclohexanone 2.0 0.32
Ethyl amyl ketone (EAK) 0.8 0.28
Pent-o-xone (ME-6K) 1.2 0.27
Methyl cyclohexanone - 0.2

(Continued on facing page)

 129

TABLE 4 (Continued)

Effective ASTM
viscosity D.3539.76
(cP,20 “C)

Diisobutyl ketone (DIBK) 1.05 0.2

Diacetone alcohol (DAA) 2.00 0.15
Isophorone 2.3 0.026

Miscellaneous
Diethyl ether
Isopropyl ether (IPE)
Methylone dichloride
Tetrahydrofuran
Trichloroethane
Trichloroethylene
1,4-Dioxan
Perchlorethylene
Dichloropropane
2-Nitropropane
Water
- 11.0
- 6.81
- 6.35
- 4.85
- 4.7
- 3.22
- 1.65
- 1.29
- 1.06
- 1.04
- 0.38

Hydrochrbons(‘)
Hexane 7.2
SBP 62162 7.0
SBP 2* 5.7
SBP l* 5.6
Cyclohexane 4.5
SBP 80/110 4.27
Benzene 4.12
SBP 5* 3.92
Heptaue 3.62
SBP 4* 3.51
SBP 3* 2.7
Toluene 2.0
SBP 100/140 1.9
Rubber solvent* 1.12
Xylene 0.76
SBP 140/165 0.59
SBP 6* 0.41
SBP ll* 0.29
Shellsol A 0.2
White spirit (LAWS) 0.19
Shellsol E 0.14
Shellsol TD 0.14
White spirit (115 OF flash) 0.12
Shellsol T 0.1
Shellsol AB 0.06
Distillate* 0.05
Solvent 300* 0.029
Shellsol N 0.02
Shellsal RA 0.017

(Con timed overleaf)

130

TABLE 4 (Continued)

Effective ASTM
viscosity D.3539.76
(CP, 20 “C)

Shellsol K 0.013
Shellsol R 0.013
Solvent 350* 0.011
Shell Ink Solvent 2325 0.007
Shell Ink Solvent 2426 0.003
Shell Ink Solvent 2729 <0.003
Shell Ink Solvent 2831 < 0.003

(l)Many of these are ‘mixed solvents’ and relative evaporation rates quoted should be
considered only as a guide to solvent behaviour rather than absolute values.
*Grades available only in U.K.
Actual viscosities may be used as effective viscosities.

3.2 The wet stage of film formation

The most useful application of relative evaporation rates is not so much
as’indications of pure solvent volatility but in the prediction of so-called
‘solvent balance’. A solvent is said to be ‘in balance’ if, as it evaporates, it
remains a true solvent for the dissolved polymer(s); if the composition
changes so that it becomes a non-solvent then it is said to be ‘out of
balance’. Unfortunately, it is not sufficient to simply compare solvent
evaporation rates and assume that the solvent having the highest rate shown
in Table 4 will be lost most quickly from the blend. Raoult’s law must be
applied to the situation, and without significant loss of accuracy one may
write:
R =R:ylvl +R;y2vp + ...
where R is the evaporation rate of the blend, Ri is the relative evaporation
rate of component X, yX its activity coefficient and v, its volume fraction.
Rearranging this expression leads to a value for the concentration of com-
ponent x in the vapour phase:

Walsham and Edwards [22] have shown that this type of approach
predicts the evaporation characteristics of blends of pure solvents very well.
Moreover, Sletmore [23] pointed out that since the chemical functional
groups of solvents played a far more significant role in determining the
value of the activity coefficient than the hydrocarbon part of the molecule,
solvents could be classed into three major groups, viz. hydrocarbons, ketones
and esters (carbonyl group), and alcohols and glycol ethers (hydroxyl
group).
Figures 9 - 11 illustrate a representative series of activity coeffi-
cients [24] .
 Y ESTERS/KETONES
50

25 25

0 0
0 IO 20 30 40 50 60 70 80 60 100 0 10 2u 30 40 50 6a 70 60 90 100
C HYDROCARBONS (% VOLUME 1 C ESTERS/KETONES (% VOLUME)

Fig. 9. Activity coefficients of hydrocarbons (7) as a function of concentration (C).

Fig. 10. Activity coefficients of esters/ketones (y) as a function of concentration (C).

0
0 IO 20 30 40 50 60 70 60 90 100
C ALCOHOLS/GLICOL ETHERS (%“OLUMEI

Fig. 11. Activity coefficients of alcohols/glycol ethers (7) as a function of concentra-

tion (C).

3.2.1 Calculation of activity coefficients

In a binary solvent blend, one simply reads off a value for the activity
coefficient from the appropriate graph. For example, 20% volume hydro-
carbon in alcohol has an activity coefficient of about 2.6 for the hydro-
carbon (Fig. 9) and nearly 1.2 for the alcohol (Fig. 11). This approach is
most convenient to use alongside the technique of solubility maps when
starting to build up a blend as shown in Fig. 3 and discussed in Section 2.3.
In the case of a multiple component blend the procedure is somewhat
more lengthy and is most easily illustrated by a general example. Let us
132

assume that a blend contains (Y% hydrocarbons, p 7%ketone-type and e %

alcohol-type solvents. The activity coefficient of the hydrocarbons is deter-
mined by looking up values on Fig. 9 corresponding to cu%in both ketone
(K) and alcohol (A). The actual value of the coefficient is taken as:

3.2.2 Corrected evaporation pates

The application of the theory in 3.2 is rather time-consuming,
especially in the absence of a computer. Moreover, possible effects of
dissolved polymer, especially at higher concentrations prior to the onset of
the dry stage of film formation, are ignored [ 19,201. Ramsbotham [ 211 has
indicated that a term Roy --.the corrected evaporation rate - is very useful
when designing blends. Basically, this term gives a very good indication of
how solvents in a blend will behave relative to each other and is used instead
of the relative evaporation rate of the solvent. However, care should be
exercised when using it at volume fractions smaller than ca. 0.15.

3.2.3 Balanced blends and solu bility maps

Returning now to the case illustrated in Fig. 3 of two non-solvents
for a resin being combined to form a solvent blend, in an ideal case one
would hope to find a hydrocarbon-rich blend (reasons of cost) combined
with sufficient alcohol such that it formed an azeotropic or balanced
mixture [ 21, 251. To this would be added less volatile, true solvents to
achieve a good flow and a situation where, as the wet stage proceeded, the
power of the residual solvent increased. The object of this is to ensure that
the polymer or resin molecules are fully extended and free to interact
efficiently with each other. In a borderline solvent, polymer molecules tend
to form compact intramolecular clusters - this topic has been reviewed by
Funke [ 261.
A useful practical rule regarding solvent balance emerges due to the
exponential form of the activity coefficient as a function of concentration.
If, during the wet stage, a particular component starts to decrease in con-
centration relative to the other components, its activity coefficient will
steadily increase. This has the effect of increasing the rate at which it is lost.
In other words, if a solvent blend is initially in balance its balance will
improve as evaporation progresses; if its initial evaporation rates show it to
be out of balance then this will be aggravated as the wet stage progresses.
Because of this type of argument, in practical cases one usually only needs
to consider the initial evaporation characteristics of a blend in balance
considerations.

3.3 Flow in paint films

During the wet stage of film formation, particularly if solvent is lost
rapidly from a film, it is not surprising that defects associated with flow
 133

Fig. 12. Surface tension driven cellular convection (Bhard cell formation).

within the films occur. Very often this so-called cellular convection phe-
nomenon or BCnard cell formation can be minimised by attention to solvent
design. Moreover, these cellular convection currents can also cause pigment
separation. Cellular convection has been reviewed by Hansen and Pierce
[ 27, 281, while Kresse [ 291 and Haselmeyer [ 301 have given practical
treatments of pigment sedimentation phenomena.

3.3.1 Cellular flow

Contrary to the early theories of Rayleigh, who produced the first
mathematical analysis of this phenomenon in 1916, the driving force in films
thinner than about 4 mm is the surface tension (Rayleigh argued that dense
solution at the surface of a film caused by evaporation of solvent sank and
set up so-called “density-driven cellular convection”). In fact, evaporation of
solvent causes cooling and a raising of concentration of dissolved polymer,
these effects raise the surface tension of the film and solution flows from a
low to a high surface tension area. The resulting flow pattern is shown
schematically in Fig. 12 and the well-known ‘orange peel’ defect is imme-
diately seen. This effect is minimised by not exceeding the Marangoni
number and this in turn is a function of the following expression:

dI’
at2 -- dT Iv.13
( )

where a is the temperature gradient across the film, t is the film thickness,
dI’/dT is the change in surface tension as a function of temperature, 17is the
kinematic viscosity, and D is the density.
In practical terms this implies that one must:
reduce a, i.e. avoid a blend composed entirely of highly volatile
solvents,
not attempt to apply excessively thick films,
minimise (dI’/d!I’), and
134

not use excessively low viscosities or densities (thickening agents

such as aerosils can help here) ; solvents and viscosities are discussed in
Section 4.2.

When designing solvent blends, the above set of criteria can be helped
along by ensuring that involatile, true solvents are present in sufficient
quantity to give an adequate degree of flow-out at the end of the wet stage
of film formation.

3.3.2 Pigment defects

Although pigment defects are strictly outside the scope of this brief
review, several of them can at least be reduced by paying due care to the
choice of solvents. If a pigment system contains a mixture of inorganic
pigments they will tend to settle at rates which are a function of the
following expression developed by Stokes [ 311, although some modification
is required if they differ radically in shape [32] :

r2P, -W/s
where r is the radius of the pigment particle, D, and D, are the densities of
pigment and solution and q the viscosity. Pigment sedimentation phenomena
will tend to occur with:
particles of widely differing size (check dispersion or flocculation),
pigments’of differing densities, and
too low a viscosity medium (see Section 4.2).

It will be appreciated that measures taken to reduce cellular flow will

also ease sedimentation or flotation problems [ 29, 301. Efficient dispersion
and pigment wetting are clearly important here and are discussed [ 331 and
reviewed [ 341 elsewhere. In general terms, it can be seen that larger particles
will settle at a higher rate than smaller ones and consequently the paint film
will change colour as it dries. A diagnostic test is to allow one part of a film
to dry without disturbance and constantly massage another portion with the
finger to re-disperse the pigment and compare colours.
Cellular convection currents discussed in Section 3.3.1 can lead to a
separation of pigments around the edges of the BQnard cell illustrated in
Fig. 12. This is intentionally aimed for in hammer-finish effects but is more
often undesirable and cellular flow must be reduced.
Finally, organic pigments in an underlying coat of paint are sometimes
leached into the top coat by retained solvent in this layer. This ‘bleeding’
can be reduced by choosing either alternative pigments or by redesigning
the solvent blend to eliminate the retention of solvent in the dry stage of
film formation as discussed in Section 3.4.

3.4 The dry stage of film formation

When as much as 30% solvent is contained in a film, its rate of loss is
markedly reduced since its release is controlled by the diffusion of solvent
 135

through the bulk film. The pioneer work in this field was published by
Hansen [35] who applied Fick’s laws of diffusion to the process. Much work
has subsequently been done on the topic, the bulk of it using thermoplastic
rather than thermosetting systems [ 201. However, our experience has been
that conclusions for thermoplastic systems seem to hold quite well for
ambient temperature cured thermosetting formulations. Several general
conclusions which have an obvious practical importance can be made:
The mechanism of solvent release in the dry stage is unrelated to the
mechanism of release in the wet stage, i.e., solvents which are very volatile
do not necessarily have high diffusion coefficients.
Solvent retention levels increase as a function of the square of the film
thickness and are concentration-related [ 361.
Inclusion of plasticiser reduces the level of retained solvent.

From the point of view of the solvent formulator, the first of the
preceding points is probably of most interest. While the actual composition
of the solvent blend changes, sometimes radically, in the wet stage of film
formation, it is primarily the shape and size of the solvent molecules that
determines how they will be released during the dry stage. (There are odd
exceptions to this rule where there is an intensely strong affinity between
polymer and solvent, e.g. glycol ethers/nitrocelluloses and benzene/colo-
phonium!) Using this line of reasoning and reviewing all published data
available led Newman and Nunn [ 201 to draw up the list adapted in Table 5.
Although solvents will clearly be retained at differing levels in different
polymers, the degree to which they are retained relative to each other does
not change significantly from polymer to polymer. Table 5 is therefore an
extremely handy guide for selecting solvents for a reformulation where
solvent retention has proved to be a problem. The council of perfection is
to determine the diffusion coefficients of solvents in polymers, but data
currently available appear to be unreliable [ 371.

4. Solution properties

The solvent formulator is often confronted with legislation relating to

his product as it appears in the actual can. For example, the flashpoint is
widely used as a criterion for flammability in both labelling and transport
legislation. Consequently, it is a help if flashpoints can be estimated if not
accurately predicted. Viscosity is more of an applicational parameter and it
is useful when formulating, say, thinners or when encountering certain flow
defects if the viscosity can be varied by choosing appropriate solvents.

4.1 Flashpoin ts
It is unfortunate that there is no prediction technique available for
flashpoints which is so reliable that actual measurements can be largely
dispensed with. Most published techniques, moreover, deal with the solvent
136

TABLE 5
An approximate order of increasing retention for individual solvents

Solvent Evaporation rate Molar volume

(n-butyl acetate (cm3/mole)
= 1.0)

Methanol 1.9 40
Acetone 5.6 73
Methyl Oxitol 0.53 79
Methyl ethyl ketone (MEK) 3.7 90
Ethyl acetate 4.02 97
Ethyl Oxitol 0.38 97
n-Heptane 3.62 146
Butyl Oxitol 0.08 130
nButy1 acetate 1.0 132
Benzene 4.12 88
Methyl OxitaI acetate 0.32 117
increasing Ethyl Oxitol acetate 0.20 135
retention Dioxan 1.65 85
Toluene 2.0 106
2-Nitropropane 1.04 90
Methyl isobutyl ketone (MIBK) 1.6 124
Isobutyl acetate 1.45 133
2,4-Dimethyl pentane 5.6 148
Cyclohexane 4.5 108
Diacetone alcohol 0.15 123
Pent-o-xone 0.27. 143
Methyl cyclohexane 3.5 126
Cyclohexanone 0.32 103
v Methyl cyclohexanone 0.2 122

mixtures rather than actual solutions. A widely applied rule of thumb

states that “the flashpoint of a solvent blend is that of the lowest flashing
component.” While this is a fair approximation in many cases, it can by no
means be relied upon. A better computer-based technique has been described
by Walsham [38] but it is too difficult for routine use. Ramsbotham has
pointed out c13;39] that the empirical relationship below gives fair indica-
tions as to how a flashpoint of a blend will vary, and this is used in our
laboratories:

F=-_
Flu1 +~,vz+ ..I
71 72
where F is the blend flashpoint, F, that of pure component x, u, its volume
fraction and -yx the activity coefficient calculated from Figs. 9 - 11.
Reference [39] contains reference to other work on this topic.
The above expression predicts that the flashpoints of non-ideal com-
binations such as hydrocarbon/alcohol mixtures can fall below that of either
component. This same effect can be observed especially with low concentra-
 137

tions of resin or polymer - solvent structure is broken and the flashpoint of

the solvent blend falls. At higher concentrations flashpoints invariably rise.
However, as results in Table 6 show, even this is a dangerous generalisation!
From the point of view of flashpoint control by solvent formulation,
the above expression implies that the addition of solvents having an
‘infinitely high’ flashpoint to a blend will eventually raise the flashpoint of
the blend. Callaerts [ 401 has published interesting data on ketones dosed
with chlorinated hydrocarbons which are plotted out in Fig. 13, and there is
clearly no straightforward relationship to be drawn regarding the effective-
ness of the individual chlorinated hydrocarbons.
Interesting results are also obtained in solvent blends when low con-
centrations of chlorinated hydrocarbons are added, as the data in Table 7

TABLE 6
Flashpoints of epoxy resin solutions in ethyl Oxitol. Flashpoints measured in ethyl Oxitol
(ethyl glycol ether) using an automatic Pensky-Martens Closed Cup apparatus by ASTM
D93

Resin grade Resin concentration Flashpoint (“c)

(W wt.)

Pure Oxitol 0 41
Epikote 1001 10 44
Epikote 1001 30 31
Epikote 1009 10 44
Epikote 1009 30 30

-20
0 20 40 w W 100
9. VOLUME CHLWNATED
SOLVENT IN KETONE

Fig. 13. Flashpoints of ketone/chlorinated hydrocarbon blends [40].

138

TABLE 7
Influence of non-flammable solvents on flashpoints

Composition of basic solvent Additive to blend (X vol.) Flashpoint (“C)

blend (% vol.) (ASTM D.93)

Ethyl Oxitol/isobutanol/ methylene chloride 0 33

Shellsol A, 30/21/49 5 32

10
15 (“-“,+
l,l,l-trichloroethane 5 32
10 31
15 30
20 29

Ethyl Oxitol water 0 41

5 42
10 36
20
30

+Size of flame increases, no flash recorded.

*Flame extinguished.

show. Similar types of results have been observed with systems containing
water (Table 7). It is tempting to hypothesise that at low concentrations of
water or chlorinated hydrocarbon, the structure of the flammable com-
ponent(s) is broken and the resulting higher vapour pressure leads to a lower
flashpoint. However, it is clear that at higher concentrations combustion is
simply not supported. Without doubt, this aspect of solvent system design
would benefit considerably from a methodical series of studies.

4.2 Viscosity
There have been at least 80 relevant publications on predicting
viscosities since 1965 and clearly these cannot all be dealt with in this short
review. The prediction of the actual viscosity of a polymer solution can be
carried out using the concept of intrinsic viscosity; most recently Bagda has
shown how this could be related to solubility parameters [41]. However, in
many formulations the question is not so much what the actual viscosity will
be but rather, given a choice of a number of solvents, which will give the
lowest viscosity and how will they affect the viscosity relative to each other.
Rocklin and Edwards have recently published details of a technique which
meets this need quite admirably [ 421. These workers use a modified version
of the Kendall equation to predict viscosities:

where 7~is the blend viscosity, u, the volume fraction of component x and
n, is the so-called ‘effective viscosity’ of component x. This effective
viscosity applies mostly to highly structured solvents such as the alcohols
 139

and glycol ethers; other classes of solvent have effective viscosities which are
virtually the same as their ‘normal’ viscosities. The effective viscosity is the
viscosity a solvent would have if most of its (hydrogen-bonded) structure
was broken, as is the case in most solvent blends where the concentration of
-OH containing solvent is < cc. 30%. Values published by Rocklin and
Edwards are given in Table 4.
The philosophy behind using these figures is that if two solvent blends
are both powerful solvents for a polymer or resin, then the blend having the
lower viscosity will give the lower solution viscosities at a given concentra-
tion. In other words, if in doubt, the preceding equation can be used to
predict solvent viscosities. More commonly, it is adequate to simply choose
solvents in a blend having the lowest effective viscosities where this is an
important formulation parameter.

5. Concluding remarks
Many of the preceding techniques involve linear relationships or factors
which can be linearised, and there is no doubt that much work can be saved
by setting up computer programmes to carry out linear optimisation work.
However, this is not an absolute must and, as has been indicated, blends can
be built up starting with a basic pair of solvents and adding to them.
Invariably, formulators use commercial hydrocarbon solvents which are
often mixtures of compounds since they are distillation fractions. Typical
properties of the hydrocarbon solvents referred to in this review are given in
the Appendix.
In producing a review such as this, certain areas of solvent technology
which really would repay further study become clear. Flammability related
legislation involves flashpoints, and a series of practical guidelines which are
more reliable than those presented here would be’a boon to the paint
formulator .
Finally, I would like to thank all my associates in the Shell laboratories
at Amsterdam for their help in making this publication possible.

Appendix
Typical properties of selected hydrocarbon solvents

Grade SG Distill. range Aromatics Kauri Flash

60 “F ASTM D86 content butanol No. point
ASTM % volume ASTM (“C)
D125 IBP DP D1133 PMCC
“C “C

White spirit (LAWS) 0.777 157 198 17 37 39*

Hexane 0.678 65 69 0.01 29 o*
SBP 62182 0.685 65 75 <0.05 30 0*
SBP 80/110 0.711 82 108 0.1 32 o*
(Continued overleaf)
140

(Continued)

Grade SG Distill. range Aromatics Kauri Flash

60 “F ASTM D86 content butanol No. point
ASTM % volume ASTM (“C)
IBP DP
D125 “C D1133 PMCC
“C

SBP 100/140 0.730 106 138 0.1 32 0*

SBP 140/165 0.748 143 165 0.6 30 27*
SBP 1 0.682 44 107 0.1 (w) 32 0*
SBP 2 0.706 71 94 0.02 (w) 33 0*
SBP 3 0.723 100 121 0.3 (w) 32 o*
SBP 4 0.697 48 144 0.6 (w) 33 o*
SBP 5 0.712 92 103 0.3 (w) 33 0*
SBP 6 0.768 138 165 14.0 (w) 36 32
SBP 11 0.775 153 167 16.3 (w) 38 44
White spirit
(115 “F flash) 0.781 165 193 18.8 (w) 36 50
Rubber solvent 9.737 110 156 <13(w) 32 9*
Distillate 0.792 165 231 17.2 34 48
Solvent 300 0.792 157 250 20.8 35 47
Solvent 350 0.785 171 266 8.5 29 55
Shellsol A 0.873 166 184 96 90 43*
Shellsol E 0.858 160 200 83 75 43*
Shellsol AB 0.892 186 215 99 91 63
She&o1 N 0.875 165 255 82 72 52
Shellsol R 0.888 203 263 84 81 78
Shellsol RA 0.910 182 320 99.5 90 62
Shellsol T 0.760 186 214 <0.5 26 52t
Shellsol TD 0.750 170 187 <0.5 26 51t
Shellsol K 0.783 195 245 2.5 27 72
Shell Ink Solvent 2325 0.809 218 251 19.6 31 92
Shell Ink Solvent 2426 0.831 248 270 31.3 32 109
Shell Ink Solvent 2729 0.836 257 286 30.8 28 125
Shell Ink Solvent 2831 0.838 276 304 30.7 26 140

*Abel-Pensky Closed Cup. j-TAG. (w) = % weight.

Dioxitol, Epikote, Oxitol, Pent-o-xone and Shellsol are Shell trade marks.
The proposed Hildebrand units, (cals. cm-3)1/2, have been used for the
solubility parameters as is conventionally accepted.

References

1 Solvent power, Shell Tech. Bull. ICS(x)/79/2.

2 A. F. M. Barton, Chem. Rev., 75 (1975) 731.
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4 F. Henry, Proc. XIV FATIPEC Congr., Budapest, 1978, p. 263.
5 C. M. Hansen, J. Paint Technol., 39 (1967) 104.
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8 R. C. Nelson, R. W. Hemwail and G. D. Edwards, J. Paint Technol., 42 (1970) 636.
 141

9 R. C. Nelson, V. F. Figurelli, J. G. Walsham and G. D. Edwards, J. Paint Technol., 42

(1970) 644.
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35 C. M. Hahsen, Off. Dig., 37 (1965) 57.
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39 Predicting the flashpoint of solvent mixtures, Shell Tech. Bull. ICS(x)/77/5.
40 R. Callaerts, J. Fire Flammability, 9 (1978) 229.
41 E. Bagda, Proc. XIV FATIPEC Congr., Budapest, 1978, p. 137.
42 A. L. Rocklin and G. D. Edwards, J. C&t. Technol., 48 (1976) 68.