Article No : a09_055

Drying Oils and Related Products

ULRICH POTH, BASF Coatings AG, M€unster, Federal Republic of Germany

1. Definitions . . . . . . . . . . . . . . . . . . . . . . . . . 621 7.2. Cross-Linking by Reaction with Oxygen . . 628

2. History. . . . . . . . . . . . . . . . . . . . . . . . . . . . 622 7.3. Influence of Catalysts on Cross-Linking . . 629
3. Chemical Compositions . . . . . . . . . . . . . . 623 7.4. Yellowing . . . . . . . . . . . . . . . . . . . . . . . . . . 630
4. Sources and Types . . . . . . . . . . . . . . . . . . 623 8. Modifications . . . . . . . . . . . . . . . . . . . . . . . 630
4.1. Linseed Oil . . . . . . . . . . . . . . . . . . . . . . . . 623 8.1. Boiled Oils . . . . . . . . . . . . . . . . . . . . . . . . . 631
4.2. Perilla Oil . . . . . . . . . . . . . . . . . . . . . . . . . 624 8.2. Stand Oils . . . . . . . . . . . . . . . . . . . . . . . . . 631
4.3. Tung Oil . . . . . . . . . . . . . . . . . . . . . . . . . . 624 8.3. Blown Oils . . . . . . . . . . . . . . . . . . . . . . . . . 631
4.4. Oiticica Oil . . . . . . . . . . . . . . . . . . . . . . . . 624 8.4. Factice, Sulfurized Oils . . . . . . . . . . . . . . . 632
4.5. Fish Oils . . . . . . . . . . . . . . . . . . . . . . . . . . 626 8.5. Isomerized Oils . . . . . . . . . . . . . . . . . . . . . 632
4.6. Safflower Oil . . . . . . . . . . . . . . . . . . . . . . . 626 8.6. Copolymers . . . . . . . . . . . . . . . . . . . . . . . . 632
4.7. Sunflower Oil . . . . . . . . . . . . . . . . . . . . . . 626 8.7. Maleinized Oils . . . . . . . . . . . . . . . . . . . . . 632
4.8. Soybean Oil . . . . . . . . . . . . . . . . . . . . . . . 626 8.8. Oil Boiling with Rosin, Copal, and Amber 633
4.9. Cottonseed Oil . . . . . . . . . . . . . . . . . . . . . . 626 8.9. Oil Boiling with Phenolic Resins . . . . . . . . 633
4.10. Dehydrated Castor Oil . . . . . . . . . . . . . . . 626 8.10. Modifications by Transesterification . . . . . 633
4.11. Tall Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . 627 8.11. Modifications Based on Fatty Acids . . . . . . 634
5. Production . . . . . . . . . . . . . . . . . . . . . . . . . 627 9. Application, Importance, and Future Aspects 634
6. Testing and Specifications . . . . . . . . . . . . . 628 References . . . . . . . . . . . . . . . . . . . . . . . . . 634
7. Film Formation . . . . . . . . . . . . . . . . . . . . . 628
7.1. Properties of Drying Oils for Film Formation 628

1. Definitions the molecule. Triglycerides containing a suffi-

Drying oils are fatty oils (! Fats and Fatty
Oils) from different natural sources, which are
able to form coating films by reaction with
atmospheric oxygen. The reaction may take
place with the original, unmodified oils or after
modification. Oils which are able to form films
on their own, without being modified, are called
drying oils in the narrow sense. Oils which are
able to form films if they are modified or mixed
with other film-forming components are called
semidrying oils. Nondrying oils are also used to
produce binders for coatings formulations, but
these oils and there modifications are not able
to form films by reaction with atmospheric
oxygen.
The reaction with atmospheric oxygen (au-
toxidation) takes place with unsaturated fatty
acids containing more than two double bonds in
cient amount of these fatty acids are drying oils in
the narrow sense. Triglycerides with a significant
content of fatty acids with two double bonds are
semidrying oils. Oils containing predominantly
fatty acids with only one double bond are not able
to dry.
Drying oils in the narrow sense are linseed oil,
perilla oil, tung oil, oiticica oil, and different fish
oils. Semidrying oils are cottonseed oil, soybean
oil, sunflower oil, safflower oil, hemp oil, poppy
oil, walnut oil, sesame oil, maize oil, grape
seed oils and the oils of Euphorbia, Coriander,
Brassica, and Limanthes species. Peanut oil,
castor oil, palm tree oil, olive oil, and almond
oil are nondrying oils.
Tall oil is not a triglyceride, but a mixture of
mainly unsaturated fatty acids and rosin. Tall oil
is formed as a byproduct in kraft (sulfate) pulping
(! Tall Oil). Refined tall oil can be used in the

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a09_055
622 Drying Oils and Related Products
same way as fatty acids from soybean oil in the
coating industry.
Dehydrated castor oil is a drying oil. Dehy-
drated castor oil is prepared from castor oil by
dehydration with sulfonic acids or at high tem-
peratures. Dehydrated castor oil contains a rather
high amount of 9,11-linoleic acid.
2. History
It was in the Stone Age that humans began to
grow plants and the early advanced civilizations
developed an agricultural system. Important was
the cultivation of flax to produce linen, but
linseed was also used for production of linseed
oil. First documents which give information on
the growing of flax are dated to the third dynasty
in the Egyptian ‘‘Old Empire’’ (Pharaoh Snofru,
approx. 2650 B.C.). These documents only
describe the use of linseed oil as food and for
lamps, there is no indication that they were
used for painting. But it can be assumed that
oils were used as binders for pigments in addi-
tion to inorganic binders, albumin, waxes, glues,
and blood.
First paintings were artistic paintings for
religious objects or for objects representing
those in power. In the classic period of ancient
Greece paints were also used to protect objects.
Wooden ships were painted with varnishes pre-
pared from mixtures of waxes, rosins, and oils
(semidrying oils).
The first written document how to prepare oil
varnishes dates back to the 11th century. The
monk RODGERUS OF HELMARSHAUSEN named THEO-
PHILUS PRESBYTER described in his ‘‘Schedula
diversarum artium’’ [1] how to prepare a varnish
by melting amber (lat. glassa) together with
linseed oil. In the Middle Ages drying oils were
combined with metal oxides (white lead, red lead
or minium, brown stone) not only to prepare
different colors, but also to improve drying (early
13th century, HERAKLIUS, ‘‘De coloribus et artibus
Romanorum’’ [2]). Furthermore, it was found by
empirical experiments that the drying properties
of oil varnishes could be improved if the oils were
exposed to sunlight (stand oil), or cooked (boiled
oil). Use of other driers (metal vitriols) in oil
varnishes was introduced. The knowledge to
prepare advanced oil varnishes was kept as an
important secret [3].
Vol. 11
In 1298 MARCO POLO reported the use of tung
oil as raw material in paints for the ships in the
Chinese Empire. But it was not until the late 19th
century that tung oil was shipped to Europe for
production of advanced oil varnishes.
In the beginning of the 15th century the use of
turpentine oil (prepared by the new technique of
distillation, developed in the Oriental Empires)
was introduced into the preparation of oil
varnishes (VAN EYCK brothers in Brugge and
Gent). This invention formed the basis for the
works of the most famous painters in the Nether-
lands at that time.
In the 16th century the first Chinese and Japa-
nese painted articles were imported to Europe
and the Europeans started to copy those techni-
ques by using oil-based coatings. The demand for
painted articles became larger and the first coat-
ing manufactories were founded in France and
later in Germany. In the 18th century the method
to produce sheet metal was developed in Eng-
land. The coatings for the articles from sheet
metal consisted of drying oil varnishes modified
with furnace soot and asphalt. At the end of the
18th century the coating technique was also in-
troduced in France and Germany. The develop-
ment of traffic gave a new impetus for founding
and extension of paint industries, because of an
increased demand for coatings for horse coaches
and ships. In the 19th century the industrial
production of coatings and paints started in Eng-
land, the Netherlands, and in Germany. Raw
materials for the oil based coatings were linseed
oil, tung oil, amber, copals, and different types of
rosin. The English varnish processing plants
were famous.
When the natural raw materials became rare
(mainly amber and copals), chemists started to
look for synthetic replacements. The first syn-
thetic resins which were combined with oils were
the phenolic resins. Later so-called oil-reactive
phenolic resins were prepared. The alkyd resins
formed the most important group of synthetic
resins which combined the air drying of oils or
oil-derived fatty acids with the physical drying of
a polyester molecule. Alkyds became the most
important group of resins for paints and coating
from the 1930s to the 1980s and nearly totally
replaced the older varnishes based on oils
combined with amber, copals, and rosins.
Currently alkyds are also being replaced by other
binder systems.
Vol. 11
3. Chemical Compositions [5]
Fatty Acids with Isolated Double Bonds.
Important contents of drying oils are the
fatty acids with isolated double bonds, i.e., lino-
leic, linolenic, arachidonic, and clupanodonics
acid.
Linoleic Acid [60-33-3], all-cis-9,12-octade-
cadienoic acid, Mr 280.45, mp
5.0  C, bp
(1333.2 Pa) 224  C, iodine value 181 %, acid
number 200. Various oils, which are used for
the production of air-drying coatings, contain a
significant amount of linoleic acid: safflower oil,
sunflower oil, cottonseed oil, and soybean oil.
Linoleic acid is also the main component of tall
oil and a constituent of other semidrying oils
which are used for specialties or artist paints.
Linolenic Acid [463-40-1], all-cis-9,12,15-
octadecatrienoic acid, Mr 278.44, mp
5.0  C,
bp (1333.2 Pa) 225  C, iodine value 274 %, acid
number 202. Linolenic acid is the main constitu-
ent of linseed oil and perilla oil.
Arachidonic Acid [7771-44-0], all-cis-
5,8,11,14-eicosatetraenoic acid, Mr 304.47, mp

49.5  C, iodine value 334 %, acid number
184, and clupanodonic acid [2548-85-8], all-
cis-4,8,12,15,19-dodecosapentaenoic acid, Mr
330.52, mp
78.0  C, bp (666 Pa) 236  C, io-
dine value 384 %, acid number 170. These fatty
acids are components of fish oils, which have
nearly the same properties (for coatings and
varnishes) as linseed oil.
Fatty Acids with Conjugated Double
Bonds. Also fatty acids with conjugated double
bonds are important constituents of industrially
used drying oils, i.e., a-eleostearic acid, a-lica-
nic acid, and conjugated linoleic acid.
Drying Oils and Related Products 623
a-Eleostearic Acid [4337-71-7], 9-cis,11-
trans,13-trans-octadecatrienoic acid, Mr
278.44, mp þ 49  C, bp (1560 Pa) 235  C,
iodine value 274 %, acid number 202, is a com-
ponent of tung oil.
a-Licanic Acid, 9-cis,11-trans,13-trans,
trans-4-ketooctadecatrienoic acid, Mr 292.40,
mp þ 75  C, iodine value 260 %, acid number
202, is a constituent of oiticica oil.
Conjugated Linoleic Acid, all-trans-9,11-oc-
tadecadienoic acid, Mr 280.45, iodine value
260 %, acid number 202, is prepared by isomeri-
zation of 9,11-linoleic acid (see Sections 8.5) or
by dehydration of ricinolic acid form castor oil
(see Section 4.10).
There are other high unsaturated fatty acids in
Boleco oil, Isano oil, in the oil of Marigold and in
the oils of Balsaminaceae species but until now
they did not find any industrial use.
4. Sources and Types [6], [7]
The composition of important drying oils is
shown in Table 1. Properties of commercial
drying oils are listed in Table 2.
4.1. Linseed Oil [8], [9]
Linseed oil is a drying oil. It is the oil of the seed
of flax (Linum usitatissimum) which has been
cultivated by humans since the Stone Age. Flax is
mainly grown to produce fibers (linen) and is
cultivated in the Baltic states, Canada, USA,
Argentina, India, and since the nineties also
(again) in middle Europe. The seed consists of
624 Drying Oils and Related Products Vol. 11

11 – 17
22 : 5.6

6 – 18
6 – 18
32 – 43 % oil, the main fatty acids are linoleic
acid and linolenic acid. Linseed oil is mainly used
as a raw material for paints (varnishes, stand oils,
alkyds, combinations with phenolic resins, mal-

1 – 16
0–2
1–6
22 : 1

einized oils, urethane oils, styrolized oils) and

glaziers putty and to produce linoleum, normally
not for foods. Films from linseed oil are stable to

13 – 19a
13 – 29a
water and other agents but they are not sufficient-
20 : 4.5

6–9
ly light-stable and have a tendency for yellowing.
9 – 15
1–2
2–8

4.2. Perilla Oil

20 : 1

Perilla oil is prepared from the seeds of Perilla

fructescens (Labiatae species), grown in India
77 – 86b
73 – 83c
35 – 60
5 – 11
traces
traces
0–3

0–1
0–1
0–2
18 : 3

and Indochina. The seed consists of 30 – 51 %

oil. The composition of Perilla oil is similar to
that of linseed oil. The oil is of local importance.
33 – 58
43 – 56
44 – 68
73 – 79
17 – 24

11 – 25
8 – 10
1–4
0–1
1–3
18 : 2
number of C-atoms : number of double bonds

4.3. Tung Oil [10–16]

13 – 44
15 – 33
14 – 33
13 – 21
12 – 34
17 – 22
13 – 16
10 – 16

8 – 13

Tung oil is isolated from the nut-like seeds of the

4–9
18 : 1

tung tree (Aleurites fordii, Euphorbiaceae spe-

cies) in China and Japan. Tung trees are also
cultivated in USA, Malawi, and Argentina. The
7 – 10
8 – 12
traces
0–2

6–9
16 : 1

seed consists of 25 – 45 % oil. 80 % of the oil

consists of the triple unsaturated, conjugated a-
eleostearic acid. Tung oil is easy to polymerize
traces
24 : 0

and is still being used for coatings. Tung oil is

used for preparation of stand oils, for alkyds, and
in combinations with phenolic resins. Tung oil is
0–1
22 : 0

often mixed with linseed oil. Oxygen uptake

during drying is lower than that of linseed oil.
Films from tung oil are more elastic than those
0–1
0–3
0–1

0–1

from linseed oil and more stable to yellowing.

20 : 0

Products based on tung oil and its modifications

Table 1. Composition of drying oils (figures are given in %)

are used for water-resistant paints (marine

varnishes) and corrosion protection. A special
1–4
2–6
1–5
1–4
2–5
1–3
3–4
2–4
1–3
4–5
18 : 0

use is the preparation of wrinkle finishes. These

finishes dry very fast in the presence of driers and
form regularly wrinkled surfaces (paints for ma-
17 – 29

17 – 19
16 – 19
7 – 11

8 – 13
3–7
3–6
4–6

3–4
6–7
16 : 0

chine facings).
traces
traces
traces

4.4. Oiticica Oil [17]

0–2

3–8
7–8
6–8
14 : 0

a-Eleostearic acid.

Oiticica oil is isolated from the seeds of Licania

a-Licanic acid.

rigida (Chrysobalanaceae species) in Brazil. The

Cottonseed oil

Menhaden oil

and C 18 : 4.
Sunflower oil
Safflower oil
Name of oil

Soybean oil

Oiticica oil
Linseed oil
Herring oil

Sardine oil

seed consists of 50 – 60 % oil, which consists

Tung oil

mainly of licanic acid. Like a-eleostatic acid

licanic acid contains three conjugated double
a
b
c
 Vol. 11

Table 2. Properties of drying oils (commercial, refined)

Name of Color Acid Iodine Saponification Unsaponifiables Viscosity Titer a,  C Refractive i Density at Specifications
oil Gardner number value number (max.), % at 20  C, ndex nD
20 20  C, g/cm3
(max.) (max.) (Wijs) mPa  s

Cottonseed oil 4 1 110 – 120 188 – 196 1.5 approx. 60 30 – 37 0.918

[8001-29-4]
Soybean oil 2 0.4 120 – 141 188 – 195 1.5 approx. 60 20 – 24 1.472 – 1.477 0.917 – 0.925 DIN 55938 ASTM D
[8001-22-7] 1462 BS 5170
Sunflower oil 2 1 125 – 135 188 – 196 1.5 approx. 60 16 – 24 1.475 0.920
[8001-21-6]
Safflower oil 2 1 140 – 150 188 – 196 1.5 approx. 60 16 – 17 1.475 – 1.478 0.923 – 0.926 DIN 55942
[8001-23-8]
Linseed oil 4 0.6 160 – 200 188 – 195 1.5 approx. 60 19 – 21 1.4785 – 1.4825 0.926 – 0.933 DIN 55933 DIN 55934 ISO
[8001-26-1] 150 BS242 BS 243
Fish oil 6 4 190 – 205 188 – 194 1.5 approx. 50 25 – 31 1.482 0.930
[8016-13-5]
Tung oil 8 5 160 – 180 189 – 195 1.0 200 – 400 36 – 37 1.511 – 1.522 0.930 – 0.940 DIN 55936 ASTM D
[8001-20-5] 12 ISO 277 BS 391
Oiticia oil 11 10 145 – 155 186 – 193 1.5 44 – 47 1.510 0.977 – 0.988 ASTM D 601
[8016-35-1]
a
Temperature range where the oil becomes turbid during cooling.
Drying Oils and Related Products
625
626 Drying Oils and Related Products
bonds and has a keto group in addition. That is
why oiticica oil has nearly the same properties as
tung oil. It is of local interest.
4.5. Fish Oils [18–21]
The various fish oils originate from different
organs of fish and differ in their composition.
Oils from herring, menhaden, and sardine are of
industrial interest. All of these oils contain fatty
acids with 18 to 22 carbon atoms and with up to
fife isolated double bonds. The drying properties
of fish oils are comparable with those of linseed
oil. Fish oils have a specific odor, the same holds
true for products from fish oil. Fish oils are used
for varnishes and alkyds for anticorrosive coat-
ings and primers.
4.6. Safflower Oil [22], [23]
Safflower oil is a semidrying oil. It is obtained
from the seeds of Safflower (Carthamus tinctor-
ius, Compositae species), which is grown in
Egypt, Turkey, and North America. The pure
seed consists of 46 – 50 % oil. The oil contains
approx. 70 % linoleic acid. Safflower oil is for
high-quality foods and in the coating industry
mainly for nonyellowing alkyds.
4.7. Sunflower Oil [24], [25]
Sunflower oil is also a semidrying oil. It is
isolated from seeds of sunflower (Helianthus
annuus), which is grown in Eastern Europe,
China, North America, Middle America,
Australia, and Eastern Africa. The seeds consist
of 42 – 63 % oil. The oil contains approx. 60 %
linoleic acid. In the coating industry sunflower oil
is applied in high quality alkyds (nonyellowing)
and in artists’ paints.
4.8. Soybean Oil [26], [27]
Soybean oil is a semidrying oil. Soybeans are
the fruits of soy (Glycine max, Leguminosae
species) which is mainly grown in China, Ar-
gentina, Brazil, and USA. The beans consist to
18 – 20 % of oil. The oil contains approx. 50 %
Vol. 11
linoleic acid. Soybean oil is mainly used for
foods, the paint industry uses only a small part of
the large quantities of soybean oil produced.
Fatty acids from soybean oil are used for alkyds.
Also stand oil are prepared from soybean oil.
Soybean oil is much slower drying than linseed
oil. But the films are more durable and stable to
yellowing.
4.9. Cottonseed Oil
Cottonseed oil is also a semidrying oil. It is
obtained from the seeds of the cotton plant (Gos-
sypium arboreum, G. hirsutum, G. barbadeuse,
and other species), which are located on the
cotton fibers. Cotton is mainly cultivated in
Egypt, China, Japan, North, and Middle America.
The seed kernels consists of 14 – 25 % oil. The
oil contains approx. 40 % linoleic acid. Cotton-
seed oil is used for foods and a raw material for
fatty acids for alkyds (nonyellowing).
4.10. Dehydrated Castor Oil [28–30]
Castor oil consists of a mixture of fatty acids
which contain up to 90 wt % ricinoleic acid (12-
hydroxy-9-octadecanoenic acid). Castor oil is
isolated from the bean-like seeds of the castor
plant (Ricinus communis), which is cultivated in
Brazil, India, the Philippines, South Africa, and
Southeast Europe. The seed consists of 50 –
60 wt % oil. Castor oil is a nondrying oil. In the
paint industry castor oil is used for polyurethane
coatings, alkyds, and for the preparation of
dehydrated castor oil and its fatty acids.
Dehydrated castor oil is prepared by dehydra-
tion of castor oil with sulfonic acids and remov-
ing the crystalline hydrates. Dehydrated castor
oil consists mainly of conjugated 9,11-linoleic
acid and some 9,12-linoleic acid. During dehy-
dration polymerization may occur as side reac-
tion. Dehydrated castor oils are available with
different viscosities. Dehydrated castor oil is a
drying oil. The film forming properties are simi-
lar to those of tung oil, but the drying velocity of
dehydrated castor oil is lower. The films are
stable against yellowing, are elastic and water
resistant. Dehydrated castor oil is used for oil
varnishes – often combined with other oils – for
pigment pastes and for printing inks.
Vol. 11
4.11. Tall Oil (! Tall Oil) [31–37]
Tall oil is a byproduct of the kraft (sulfate)
pulping process. Crude tall oil consists of a
mixture of fatty acids (45 – 55 wt %), rosin
(30 – 40 wt %), and unsaponifiable components
(10 – 13 wt %). The fatty acids can be separated
and used as components for alkyds. Tall oil has a
similar fatty acids composition as soybean oil,
but normally the content of oleic acid is higher.
Furthermore, tail oil fatty acids contain unusual
isomers, e.g., octadecadienoic acids with double
bonds in the 5-,9-, and 5-,12-positions.
5. Production
The industrial production of oils from vegetable
materials (oilseeds) and animal materials (select-
ed fish organs) by pressing (cold and hot) and
extraction is described in detail in ! Fats and
Fatty Oils.
Refining. [6], [38] (! Fats and Fatty Oils,
Chap. 6.). Some of the trace components con-
tained in fatty oils are accepted for use of oils in
foods. But when used in coatings the trace com-
ponents may negatively affect the film forming
properties. The impurities extracted together
with fatty oils include gums, phosphatides, car-
bohydrates, proteins, colorants, and waxes.
The classic refining procedure consists of the
following sequential, stepwise treatments of the
oil: degumming, bleaching, deacidizing, and, if
necessary, deodoration and dewaxing.
Degumming is performed by adding approx-
imately 0.1 wt % of phosphoric acid or the equiv-
alent amount of citric acid and subsequent agita-
tion of the oil for approx. 30 min at 80 – 90  C.
The acids coagulate the gums and the coagulate is
removed by filtration or by centrifugation. The
process can be supported by a treatment with
fuller’s earth.
Bleaching removes the vegetable colors,
such as chlorophyll and carotene, autoxidation
products, soaps, traces of heavy metals, residues
of phosphorus-containing materials, and odor-
ants. In bleaching solid adsorbents, such as acti-
vated fuller’s earth and in special cases activated
carbon, are added. Bleaching is carried out in
Drying Oils and Related Products 627
closed, agitated tanks under partial vacuum at
80 – 90  C in the presence of 1 – 5 wt % fuller’s
earth for up to 30 min. Afterwards, the oil is
filtered over filter presses.
Deacidizing Crude oils may contain 1 –
3 wt % of free fatty acids. This content can be
lowered to below 0.1 wt % by deacidizing. In the
older process equivalent amounts of caustic soda
(sodium hydroxide) are added which convert the
free fatty acids to sodium soaps at 90  C. The
process is carried out under slow stirring to avoid
emulsifying. The sodium soaps are separated in
form of an aqueous, concentrated soap solution
(soap stock). The soap stock is separated and
removed and the oil is dried under vacuum. The
process is problematic regarding the residual
soap contents in the oil and the oil losses by
saponification.
In the newer process the fatty oils are deaci-
dized by distillation (physical deacidizing). The
oil, which is free from other impurities, which
may form decomposition products during the
process, is vacuum steam-distilled at 210 –
270  C and the fatty acids are distilled off. The
final acid content is 0.01 wt %. This process
includes also a deodorization step. The process
avoids contamination of the oil with soaps and
the loss of neutral oil is lower than in the older
process.
Deodorization is essentially a vacuum steam-
distillation, by which odorous volatile com-
pounds, mainly aldehydes and ketones, are
driven from the nonvolatile oils. Other volatiles,
such as free acids, sterols and tocopherol, are also
removed. Deodorization is carried out with steam
under reduced pressure at 1.0 – 2.5 kPa and
180 – 220  C for 2 – 6 h.
Dewaxing Linseeds and sunflower seeds are
covered with a thin layer of wax. Particles of this
wax were dissolved during oil pressing and ex-
traction. Wax dissolved in the oil crystallizes
during storage, especially during cooling and the
oil becomes turbid. The wax contents would
result in film defects in the coatings. Dewaxing
consists of cooling the oil to 4 – 10  C and
holding it at this temperature until the crystalli-
zation process is finished. Then the wax is
removed by filtration.
628 Drying Oils and Related Products
6. Testing and Specifications [39]
The properties of drying oils are tested in specific
tests. The methods and target values are defined
in national (DIN, DGF, ASTM, BS) and interna-
tional (ISO) standards and specifications. Oils are
characterized by color, acid number, saponifica-
tion value, amount of unsaponifiable contents,
iodine number (amount and activity of double
bounds), viscosity, refractive index, and specific
density (! Fats and Fatty Oils, Section 11.3., see
Table 2). The fatty acid composition is deter-
mined by gas and liquid chromatography [40].
7. Film Formation
7.1. Properties of Drying Oils for Film
Formation
Besides their ability to dry by reaction with
atmospheric oxygen, drying oils have other spe-
cific properties. Due to the long aliphatic chains
of the fatty acids and their double bond content,
the coatings based on oils and related products
have a low viscosity and excellent wetting prop-
erties on different types of substrates (metals,
wood) and pigments. That is why drying oils can
form the base for ‘‘high-solids’’ paints, corrosion
protection paints, pigment pastes, fillers, and
artist’s paints (! Artists’ Colors). In addition,
drying oils have an excellent solubility in a broad
variety of solvents, including simple aliphatic
hydrocarbons, which are low cost solvents, odor-
less, and physiologically safe. Also the oils
themselves are no hazardous products. Their
molecular structure imparts excellent flow and
leveling properties during film formation. When
cross-linking is finished the films still contain
mainly aliphatic structures, which are hydropho-
bic and rather stable to water and some water-
soluble agents. A disadvantage is their sensitivity
to basic agents, which will saponify the ester
groups. That is why oils and related products are
not the optimum bases of waterborne coatings.
But in principle the hydrophobicity of the fatty
acids is an advantage also for waterborne coat-
ings, if the drying oils are incorporated well and
protected from saponification (e.g., in aqueous
polyurethane dispersion based on alkyds with
unsaturated fatty acids). Another disadvantage
is that drying requires much time and cannot be
Vol. 11
accelerated sufficiently by higher temperatures
and catalysis.
7.2. Cross-Linking by Reaction with
Oxygen
The mechanisms of film formation of drying oils
have been studied in investigations on oil mole-
cules and appropriate model substances [41]. The
process occurs in different overlapping steps and
the total reaction sequence and the molecular
structure of the film forming polymers are com-
plex [42], [43]. Different reaction mechanisms
are followed, depending on the type of double
bonds and the use of catalysts.
Oils with Nonconjugated Double Bonds.
The initial autoxidation step in the case of oils
with nonconjugated double bonds is the forma-
tion of hydroperoxides in allyl position to the
double bonds [44–48]. Since the 11-position of
linoleic and linolenic acids and – in the case of
linolenic acid also the 14-position – are activated
by two double bonds, the reactivity of these
positions is the highest. First a radical is formed
at these positions by dehydrogenation, then oxy-
gen is added and a hydroperoxide is formed by
recombination with the hydrogen radical. The
reactivity of drying oils is based on the meso-
meric stabilization of the radical intermediate:
the unpaired electron is delocalized over several
carbon atoms along the chain, and less energy is
required to eliminate the hydrogen radical [49].
Additionally isomerization may take place,
analytical investigation on esters of linoleic acid,
for example, showed higher amounts of conju-
gated unsaturated 9- and 13-hydroperoxides
besides hydroperoxides in 8-, 10-, 12- and 14-
position [50–53].
Since the next steps of film forming lead to
different higher molecular products, the analysis
of these products is much more complex. De-
composition products of the film in different
states, byproducts of the film-forming reaction,
were investigated by mass spectroscopy [54–56].
Time-laps infrared spectroscopy was used to
follow the process [57]. The analytical result led
to the interpretation that the next important step is
the formation of peroxy radicals by decomposi-
tion of the hydroperoxide (bimolecular dispro-
portionation at higher concentration). Then a
Vol. 11 Drying Oils and Related Products 629

free-radical chain process is started by formation
of oxygen bridges between fatty acid molecules
and by activation of C-radicals and formation of
C–C bridges. The reaction is terminated by re-
combination of different radicals.
The reaction is strongly influenced by tem-
perature, light, and traces of substances which
may act as catalysts or inhibitor. For example, at
lower temperatures more C–O–C bonds are pro-
duced than at higher temperatures, where forma-
tion of C–C bridges is favored [58].
Oils with Conjugated Double Bonds. react
differently from those with isolated double
bonds. Tung oil for example absorbs less oxygen
during drying, 12 wt % instead of 16 wt % in
case of linseed oil [49], [59–61]. Analysis shows
that the starting reaction is not the formation of
hydroperoxides, but of cyclic peroxides formed
by direct oxygen attack on the conjugated bond
system [62]. Reaction of the peroxides with
allylic methylene groups or dissociation leads to
radicals. The radicals initiate a radical chain
reaction, yielding C–O–C bonds and C–C
bridges [63]. Due to the easy 1,4-addition of
radicals to conjugated double bonds, formation
of C–C bridges is preferred. The reaction is
terminated by recombination of radicals or
disproportionation.
undergo redox reactions. The degree of activity
may be also influenced by the molecular com-
patibility of the metal ion with the double bond
system. Examples of metals in active driers, in
order of decreasing activity, are:
Co > Fe > Mn > Ce > Pb > Zr
The metals are added to drying oils and related
products (drying alkyds) at a concentration of
0.005 – 0.2 wt %. The driers speed up two reac-
tion steps of the drying process, the activation of
methylene bonds to form hydroperoxides and,
more important, the redox reaction in which
radicals are formed from the hydroperoxides
[69–75]. If the hydroperoxides are transformed
faster to radicals, the radical chain polymeriza-
tion takes place more efficiently. The films are
more homogeneous and become stable to disso-
lution in a shorter time. The metal ions are
reoxidized during the process. A simplified illus-
tration of the reaction of a drying oil with oxygen
in the presence of cobalt driers is shown in
Figure 1.

7.3. Influence of Catalysts on

Cross-Linking

All oxidative drying systems are formulated by

adding small amounts of catalysts for drying, the
so-called driers. Driers (siccatives) are oil-solu-
ble metal salts of organic acids. The soaps with
best solubility are obtained from 2-ethylhexanoic
acid and naphthenic acids, in earlier times rosin
acids and linoleic acid were in use [64], [65].
The soaps are produced from metal oxides or
hydroxides and the acids, either by fusion or by
precipitation [66]. The driers are usually dissolved
in aliphatic or aromatic hydrocarbons, water-
emulsifiable versions are available [67], [68].
The driers are classified in two groups, distin-
guished by the mode of action: active driers and
auxiliary driers.

Active Driers. consist of metals occurring Figure 1. Simplified reaction of a drying oil with oxygen in
in several oxidation states and being capable to the presence of a cobalt drier
630 Drying Oils and Related Products
Suitable combinations of metals allow syner-
gistic improvement of the total drying effect.
Thus, in the past most siccatives consisted of
combinations of cobalt and lead. Cobalt pro-
motes the formation of hydroperoxides rather
fast on the film surface. This is connected with
the risk that the surface is cross-linked more
quickly than the other coating layers. Thus,
oxygen cannot diffuse into the film and wrinkles
can be formed. Lead promotes hydroperoxide
decomposition and accelerates polymerization
and ensures that the film is formed evenly over
all coating layers. Also zirconium ions form
complex compounds with hydroperoxides that
decompose slowly [76], zirconium has the same
effect as lead. Since lead is defined as a hazardous
component, most of the new drier compositions
consist of mixtures of cobalt and zirconium. But
also cobalt is in discussion as possible health risk.
Because no real alternative to cobalt exist, the
newer formulation contain smaller amounts of
cobalt driers.
Auxiliary Driers are soaps of metals which
form only one oxidation degree but which acti-
vate the primary active driers. They do not cata-
lyze autoxidation by themselves. Auxiliary driers
are added in higher concentration than the pri-
mary driers, up to 0.6 wt % of metal. Examples of
metals for auxiliary driers are calcium, barium,
and zinc. The effect is explained by the basic
reaction of these driers, which mainly compen-
sate the effect of acid groups present the oil,
and thus prevent precipitation of the active
drier metals [77]. Auxiliary driers can also be
absorbed on surfaces, e.g., from pigments
instead of the active driers and the active driers
are not involved in the process [78]. Barium is
more toxic than lead and should no longer
be used.
If the total content of metals in a film is rather
high, they will be active indefinitely, causing
oxidative breakdown of the film. Therefore, the
amount of driers used must be carefully balanced
to achieve a high degree of cross-linking but to
avoid an early film decomposition.
During storage of wet paints reaction with
oxygen must be avoided. The addition of oximes
(methyl ethyl ketoxime) stabilizes against skin
formation by reaction with oxygen in the con-
tainer [79]. But now also methyl ethyl ketoxime
Vol. 11
is defined as a toxic substance and has to be
substituted.
7.4. Yellowing
Films of highly unsaturated oils and related
products with isolated double bonds tend to
yellow under specific conditions. Films of lin-
seed oil and related products yellow in the dark,
but the yellowing will largely disappear if the
film is exposed to light. Irreversible yellowing
takes place if films from linseed oil and related
products are aged or baked at higher tempera-
tures. The yellowing is caused by formation of
colored polyenes or quinone structures, starting
from conjugated unsaturated hydroperoxides via
ketones as intermediates [80–82]. The formed
1,4-diketones may also react with ammonia
(farmhouses, stables, and rest rooms) to yield
substituted pyrroles that can form colored pro-
ducts by oxidation [83], [84]. For white and other
light colors linseed oil should be replaced by less
yellowing products from semidrying oils, or
better, alkyds based on these oils.
But also the driers (manganese, cobalt) can
form complexes with oximes, which may cause
discoloration in films, mainly by aging [85].
8. Modifications
The rather effective cross-linking of drying oils
by reaction with atmospheric oxygen suffers
from the disadvantages of a low viscosity of the
unsaturated triglycerides, and the fact that the
drying process has to proceed to a significant
extent until a rather hard solvent- and chemicals-
resistant coating film is formed. This process
requires a lot of time. Early in history the painters
tried to improve the drying properties of oils. One
way was the combination of the chemical drying
of oils with products which form films by physi-
cal drying (waxes, rosins, amber). When the
compatibility or solubility constituted a problem,
the components were heated to form stable mix-
tures. Furthermore, it was found that addition of
particular pigments to the oils improved the
drying velocity of the coating films. If oils were
stored in glass bottles in the sun light or heated in
the absence of oxygen the oil became more
viscous. The higher viscosity of these oils results
also in a reduction of drying time.
Vol. 11
When rosins, copals, and amber became rare
or were too expensive, various synthetic resins
were developed as combination partners for oils.
In the beginning mainly phenolic resins were
used. Phenolic resins were later replaced by
alkyds, which combine the chemical drying of
double bonds of fatty acids with physical drying
of a phthalic polyester.
8.1. Boiled Oils
Boiled oils are combinations of drying oils and
stand oils with siccatives. To accomplish a
homogeneous distribution of the driers in the oil,
the oxides or salts of the driers are incorporated
by heating the mixture to higher temperatures
( 100  C, boiling). The metal oxides or salts
form salts with part of the fatty acids by saponi-
fication. The main bases for boiled oils is linseed
oil. The driers may consist of 0.1 – 0.3 wt %
cobalt or about 0.4 wt % lead, sometimes com-
bined with 0.1 wt % of manganese.
Boiled oils are used for varnishes, mainly
lithographic varnishes, and printing inks (pig-
ment pastes).
Currently it is easier to produce varnishes in a
cold process, i.e., by mixing oils and stand oils (or
their mixtures with other resins) with solutions
of metal driers.
8.2. Stand Oils
Stand oils are drying oils with increased viscosi-
ty. The viscosity increase results from heating of
the oils in the absence of oxygen. During heating
an intermolecular polymerization process
occurs. The main reaction is a Diels – Alder
reaction between unsaturated fatty acids, acting
as partly as dienes and partly as dienophiles [86],
[87]. The step that controls the reaction rate of
oils with nonconjugated double bonds (linseed
oil) is the isomerization into conjugated double
bonds with concurrent trans rearrangement
[88–90]. Therefore, oils with conjugated double
bonds react very fast. Stand oils consist of esters
of polymeric fatty acids, containing a significant
amount of cyclic polymeric fatty acids [91]. The
reaction may be catalyzed by the addition of
small amounts of anthraquinone [92].
Drying Oils and Related Products 631
The process used for manufacturing of stand
oils must be adjusted to the reactivity of the
drying oils. Stand oils of linseed oil and soybean
oil are produced in agitated stainless steel reac-
tors at 280 – 300  C in an inert gas stream
(carbon dioxide, nitrogen). The reactor may be
heated by heat-transfer oils, superheated steam,
electrical induction, or resistance heating. The
reactor should be equipped with water cooling
facilities (half-pipes outside the reactor wall or
internal cooling coils). The process is controlled
by temperature and time, the progress of reaction
is determined by measuring the viscosity and the
acid number of samples. A linseed stand oil needs
40 – 45 h at 280  C to attain viscosities of about
10 – 15 Pa  s. Viscosity increase of soybean oil
is much slower. Decomposition products of the
production of stand oils are removed by distilla-
tion, under vacuum if necessary.
Tung oil is heated in small batches (20 –
50 kg) rapidly to 260  C, held for 7 – 12 min
at that temperature (exothermic reaction takes
place) and then flash-cooled with minimum the
same amount of cold tung stand oil.
Stand oils are used in varnishes, oil paints,
enamel varnishes, and fillers. Stand oils dry more
homogeneously than their starting oils and give
more elastic and water-resistant coating films.
Although stand oils dry more slowly than drying
alkyds, stand oils are used in combination with
alkyds to raise the solids of paints to reduce the
amount of solvent to evaporize. Linseed stand oil
has a lower tendency for yellowing than linseed
oil. Tung stand oil and soybean stand oil are even
more stable to yellowing than linseed oil. Tung
stand oil is superior to linseed stand oil in forming
hard and water-resistant films, but the films are
more brittle. Thus, linseed stand oil is often
combined with tung stand oil in varnishes.
8.3. Blown Oils
For production of blown oils, drying oils are
blown with air at 90 – 120  C. During this pro-
cess, hydroperoxides are formed and decompose
into radicals which lead to increase in molecular
mass by a radical chain transfer reaction. In
addition, keto groups and hydroxy groups
are formed. Blown oils have viscosities up to
3 Pa  s and are much more polar than stand oils.
The drying properties are reduced.
632 Drying Oils and Related Products
Blown oils from linseed oil and soybean oil
are used as plasticizers for polymers which dry
physically, for printing inks, for putties, and
sealings. Blown linseed oil is used for core
binders for casting.
8.4. Factice, Sulfurized Oils
Factice is a mixture of drying oils with sulfur or
disulfur dichloride. Like oxygen, sulfur is able to
react with the double bond system in a radical
chain reaction. The polymerization occurs very
effectively over the whole film layer. Varnishes
containing factice oils can be applied in a wet-on-
wet process.
8.5. Isomerized Oils
During isomerization isolated double bonds are
transferred into conjugated double bonds and cis
double bonds are converted into trans double
bonds. The process is carried out with metal
catalysts at 100 – 140  C. Linseed oil and saf-
flower oil are isomerized in the presence of a
nickel catalyst, finely distributed on diatoma-
ceous earth or active carbon [93–95]. Isomerized
oils take up less oxygen during drying than the
corresponding starting oils and form elastic films
with higher water resistance.
The alkali isomerization process is carried
out with the methyl ester of fatty acids to afford
fatty acids with conjugated double bonds.
They are used in alkyds, mainly for stoving
enamels [96–98].
8.6. Copolymers
Copolymers of drying oils are produced by heat-
ing unsaturated oils with unsaturated monomers
[99], [100], preferably styrene. Additionally,
vinyltoluene [101], a-methylstyrene, dicyclo-
pentadiene [102], pentadiene, and indene [103]
are used as monomers, also methylmethacrylate
is described. Copolymerization is carried out at
higher temperatures, catalysts are peroxides, e.g.,
di-tert butyl peroxide [104]. The process may be
run in bulk or in solution. A feed process for
monomer dosing is preferred for most exother-
mic reactions to guarantee a reproducible pro-
Vol. 11
cess. Unreacted monomers are distilled off after
the process. The content of styrene in styrenated
oils is 20 to 45 wt %. During the polymerization
of nonconjugated oils and styrene, grafting of
styrene molecules to chains onto oil molecules
occurs. Starting from the active methylene
groups of the oil, polysterene bridges are formed
[105], [106]. It is important to avoid the forma-
tion of styrene homopolymer, because it is not
compatible with the oil. Conjugated oils form
Diels – Alder adducts connected by short
bridges of polystyrene, the viscosity increases
more rapidly than the viscosity resulting from the
grafting nonconjugated oils [107], [108]. The
compatibility of styrenated oils with other poly-
mers is limited. Using vinyltoluene, a-methyl-
styrene, or dicyclopentadiene gives copolymers
with a much better compatibility and solubility.
Cyclopentadiene and indene form only Diels –
Alder adducts both with conjugated and noncon-
jugated oils.
Copolymers of oils have improved drying
properties, the resulting films are harder and
more resistant to water and chemical agents than
the films from drying oils and alkyds.
8.7. Maleinized Oils [109–112]
Maleic anhydride is a dienophile and easily
reacts with conjugated double bonds in a Diels –
Alder reaction to form a substituted cyclohexane
dicarboxylic anhydride. The process is carried
out at 80 – 120  C [113], [114]. Nonconjugated
unsaturated oils react with maleic anhydride in a
ene reaction via the active methylene groups to
form substituted succinic anhydride derivatives
[115], [116]. But also Diels – Alder reactions
may take place if the isolated double bonds are
converted into conjugated during the process.
The reaction is carried out at 180 – 240  C.
Maleinized oils with 5 – 8 wt % of maleic
anhydride (less than 1 mol per triglyceride) are
esterified with glycerol and other polyols to form
oil-modified polyesters. Their properties are sim-
ilar to those of alkyds, and oil-modified polye-
sters dry faster than the original oils and form
harder and more water-resistant films.
Maleinized oils with 16 – 24 wt % maleic
anhydride are reacted with water or alcohols to
yield maleinized oils with high acid numbers
(100 – 200). After neutralization of the acid
Vol. 11
groups with ammonia or – more preferably –
amines, the maleinized oil becomes water-thin-
nable [117]. The product is combined with
phenolic or amino resins [118–120]. These wa-
ter-thinnable combinations are mainly used as
anticorrosive primers for electrodeposition. In
electrodeposition the part to be coated is
immersed in a tank and direct current is applied.
In the process the binder systems (together with
pigments and additives) are coagulated on the
anode, which is the surface of the substrate to be
coated [121–123]. The coagulated film can be
rinsed with water and is then stoved at 175 –
180  C for 20 – 30 min. The process ensures
that film formation takes place on all parts which
are immersed in the tank. Starting in the 1960s,
such systems gained importance as corrosion
protective primers in the automotive industry.
In the late 1970s the systems were mainly
substituted by a resin system for a cathodic
deposition process. But the maleinic oils are still
in use for industrial primers.
8.8. Oil Boiling with Rosin, Copal, and
Amber
In the past oils – and also drying oils – were used
as solvent for different natural resins. The target
was to convert the natural resins into a suitable
form for application and to combine the film
properties of the natural resins with the drying
properties of the oil. The higher the melting point
of the natural resins, the better the film properties.
Copals were better than rosins, and amber was
better than copals. To improve the properties of
rosins, rosins were transferred into rosin salts
with calcium and zinc, into rosin esters with
glycerol and pentaerythrol, and maleinized and
esterified (! Resins, Natural, Section 5.5.). It
was not easy to melt the high molecular natural
resins (copals and amber) and starting in England
special know-how was gathered for this process.
The combinations of oils, different natural
resins and related products and siccatives formed
the basis for the oil varnishes, the first industrially
used coatings.
8.9. Oil Boiling with Phenolic Resins
When the natural resins became rare the investi-
gation to prepare synthetic resins began. The first
Drying Oils and Related Products 633
synthetic resins used for industrial coatings were
the phenolic resins (! Phenolic Resins). But the
normal phenolic resins (resols) are not compati-
ble with oil. The first step to overcome the
problem was the combination of rosin-modified
phenolic resins with drying oils [124]. The sec-
ond step was the preparation of so-called alkyl-
phenolic resins (from alkyl-substituted phenols)
[125], [126]. These alkylphenolic resins are able
to react with oils, preferable tung oil, to yield
adducts between the double bond system and the
methylol and OH group of the phenolic resin
[127]. The process is carried out at 240  C, using
a mixture of 2 – 4 parts tung oil and 1 part
alkylphenolic resin. The reaction products have
good drying properties and the films are highly
resistant to water and chemicals. The product
were used for industrial coatings and especially
for yacht varnishes. For this application they
were much more suited than alkyd varnishes.
These combinations are often replaced by poly-
urethane coatings, but yacht varnishes are
still available.
8.10. Modifications by
Transesterification
If drying oils are heated with an excess of
polyols, glycerol, pentaerythrol, or dipentaery-
throl at 230 to 260  C, mono- and diglycerides
[128–131] are obtained. The alcoholysis (trans-
esterification) is an equilibrium process. Salts of
alkali or alkaline-earth metals serve as catalysts.
To avoid the formation of incompatibilities of
the catalyst in the reaction mixture or the final
product, the use of lithium salts is preferred. The
reaction is controlled by the added quantity of
polyols, the reactivity of the OH groups, the
temperature, and the time. The progress of the
reaction is determined by measuring the solu-
bility of the reaction mixture in methanol or
ethanol. Transesterification products are starting
materials for production of alkyds, urethane oils,
and urethane alkyds.
Alkyds. (! Alkyd Resins) are prepared by
reaction of the transesterification products and
phthalic anhydride. The process was developed
in 1927 and was the first important process for
production of air-drying alkyds.
634 Drying Oils and Related Products
Urethane Oils [132], [133] are prepared
from the transesterification products and toluy-
lene diisocyanate. Products obtained by reaction
of the transesterification products with mixtures
of phthalic anhydride (first esterified) and toluy-
lene diisocyanate are called urethane alkyds.
Urethane oils and urethane alkyds dry faster than
alkyds to give harder and more resistant films, but
the films are not weather-resistant. Urethane oils
and urethane alkyds are used for wood coatings,
preferably for parquet varnishes.
8.11. Modifications Based on Fatty
Acids
Fatty acids are produced from drying oils by
saponification. The fatty acids are the basis for
the production of alkyds (! Alkyd Resins) and
epoxy esters. In contrast to oil varnishes and
paints, alkyds and epoxy esters based on unsatu-
rated fatty acids are still important coating
materials.
9. Application, Importance, and
Future Aspects
Oil varnishes and oil paints have been largely
replaced by more modern systems, mainly al-
kyds, but there are still some oil paint products on
the market. For people, who want to use natural
raw materials, oil-based paints are still of interest
for furniture coatings (mainly for ‘‘do-it-your-
self’’-applications), but there is nearly no indus-
trial use. Products derived from drying oils, i.e.,
air-dryings alkyds and epoxy esters, and malei-
nized oils, still play a more important role in the
paint industry. In Germany the market volume of
solventborne coating materials is estimated to be
approximately 300 000 t in 1999. Oil paints and
oil varnishes have a share of only 0.6 %, but this is
approximately 12 % more than in 1998. Coatings
based on air-drying alkyds made up nearly 20 %
of this volume, but the amount is decreasing in
comparison to 1998 [134].
Advantages of oil-based or fatty acid-based
coating materials are: excellent wetting of pig-
ments and surfaces, easy application, good flow
and leveling, low health risks, environmental
compatibility, and optimum hydrophobicity of
Vol. 11
films. However, they suffer from two important
disadvantages: (1) Oil- or fatty acid-based
coating materials need too much time for film
formation by air drying to be used in advanced
industrial coatings application processes (e.g.,
automotive coating application) and (2) these
coating materials are not easy to transfer into
water-based systems – to avoid organic solvents
for ecological and economical reasons – due to
the sensitivity to react by saponification. On the
other hand, since the 1980s there has been grow-
ing interest to increase the use of natural renew-
able raw materials. Drying oils and related
products meet this demand. Several institutes
started to investigate the possibility to decrease
the agricultural food production in Europe and to
replace growing of plants for food partly by
growing of plants which produce raw materials
for industrial use [135–140]. There are new
proposals to grow plants which contain drying
or semidrying oils or plants which contain fatty
acids plus other chemically reactive groups.
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Vol. 11
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28 G. W. Priest, J. D. v. Mikusch, Ind. Eng. Chem. 32 (1940)
1314.
29 N. A. Ghanem, Z. H. Abd El-Latif, J. Paint Technol. 39
(1967) 144.
30 C. I. Atherton, A. F. Kertess, J. Oil Colour Chem. Assoc.
49 (1966) 340.
31 W. Sandermann: Naturharze, Terpentin€ ol, Tall€ol,
Springer Verlag, Berlin 1960.
32 W. Asche, Farbe þ Lack 68 (1962) 448 – 453, 518 –
525.
33 H. W. Chatfield, Paint Oil Colour J. 141 (1962) 1262.
34 G. Eick, Farbe þ Lack 69 (1963) 616.
35 W. M. Kraft et al., J. Am. Oil Chem. Soc. 42 (1965) 96.
36 K. B. Gilkes, T. Hunt, J. Oil Colour Chem. Assoc. 51
(1968) 389.
37 J. T. Geoghegan, H. G. Arlt, C. O. Myatt, J. Paint
Technol. 40 (1968) 209.
38 R. V. V. Nicholls, W. H. Hoffman, Off. Dig. Fed. Paint
Varn. Prod. Clubs 24 (1952) no. 4, 245 – 260.
39 H. P. Kaufmann: Analyse der Fette und Fettprodukte,
Springer Verlag, Berlin 1958.
40 DIN 53 782 and DIN 55 957.
41 G. H. Hutchinson, J. Oil Colour Chem. Assoc. 56 (1973)
44.
42 P. O. Powers, Ind. Eng. Chem. 41 (1949) 304.
43 J. R. Chipault, E. C. Nickell, W. O. Lundberg, Off. Dig.
Fed. Paint Varn. Prod. Clubs 23 (1951) no. 11, 740.
44 L. Dulog, Congr. FATIPEC 8th, (1966) , 17 – 25.
45 H. R. Rawls, P. J. Van Santen, J. Am. Oil Chem. Soc. 47
(1970) 121.
46 R. Criegee, Justus Liebigs Ann. Chem. 522 (1936) 84.
47 A. Rieche, Angew. Chem. 50 (1937) 520.
48 E. H. Farmer, Trans. Faraday. Soc., 38 (1942) 340.
49 H. P. Kaufmann, Fette, Seifen, Anstrichm. 59 (1957)
153.
50 F. Hasbeck, W. Grosch, Lipids 18 (1983) 706.
51 E. N. Frankel, C. D. Evans, D. G. McConnell, E. Selke, et
al., J. Org. Chem. 26 (1961) , 4663.
Drying Oils and Related Products 635
52 F. Haslbeck, W. Grosch, J. Firl, Biochim. Biophys. Acta
750 (1983) 185.
53 F. Haslbeck, W. Grosch, Fette, Seifen, Anstrichm. 86
(1984) 408.
54 A. M. Gaddis, R. Ellis, G. T. Currie, J. Am. Oil Chem.
Soc. 38 (1961) 371.
55 J. H. Skellon, J. Oil Colour Chem. Assoc. 46 (1963)
1001.
56 R. Clement, Congr. FATIPEC 14th, 1978, 177 – 182.
57 J. H. Hartshorn, J. Coat. Technol. 54 (1982) no. 687,
53 – 61.
58 P. S. Hess, G. A. O’Hare, Ind. Eng. Chem. 42 (1950)
1424.
59 M. Dyck, Farbe þ Lack 67 (1961) 442.
60 H. Wexler, Chem. Rev. 64 (1964) 591.
61 W. Treibs, Fette Seifen 54 (1952) 3.
62 R. N. Faulkner, J. Appl. Chem. 8 (1958) , 448.
63 L. A. O’Neill, Chem. Ind. (London) 1954, 384.
64 W. J. Stewart, Off. Dig. Fed. Paint Varn. Prod. Clubs 26
(1954) no. 6, 413 – 425.
65 DIN 55 901.
66 J. Skalsky, Prog. Org. Coat. 4 (1976) 137.
67 R. Hurley, F. Buono, J. Coat. Technol. 54 (1982) no. 694,
55 – 61.
68 R. G. Middlemiss, J. Water Borne Coat. 8 (1985) no. 11,
3 – 9.
69 C. E. H. Bawn, Discuss. Faraday Soc. 14 (1953) 181.
70 E. R. Mueller, Ind. Eng. Chem. 46 (1954) 562.
71 N. Uri, Chem. Ind. (London) 1956, 515 – 517.
72 C. E. H. Bawn, J. A. Sharp, J. Chem. Soc. 1957,
1854.
73 F. W. Heaton, N. Uri, J. Lipid Res. 2 (1961) 152.
74 M. Allard, Double Liaison 18 (1971) no. 194, 503 –
523.
75 N. S. Baer, N. Indictor, J. Coat. Technol. 48 (1976)
no. 623, 58 – 62.
76 M. Giesen, Dtsch. Farben Z. 20 (1966) 236.
77 E. Krejcar, K. H
ajek, O. Kol
ar, Farbe þ Lack 74 (1968)
115.
78 G. Rieck: Congr. FATIPEC 10th, 1970, 239.
79 M. Giesen, Congr. FATIPEC 7th, 1964, 349.
80 F. Franks, B. Roberts, J. Appl. Chem. 13 (1963) 302.
81 A. C. Elm, Off. Dig. Fed. Paint Varn. Prod. Clubs 29
(1957) no. 4, 351 – 385.
82 O. S. Privett, M. L. Blank, J. B. Covell, W. O. Lundberg,
J. Am. Oil Chem. Assoc. 38 (1961) 22.
83 L. A. O’Neill, S. M. Rybicka, T. Robey, Chem. Ind.
(London) 1962, 1796 – 1797.
84 L. A. O’Neill, Paint Technol. 27 (1963) 44.
85 G. Link, Farbe þ Lack 92 (1986) 279.
86 C. Boelhouwer, J. Th. Knegtel, M. Tels, Fette, Seifen,
Anstrichm. 69 (1967) 432.
87 D. H. Wheeler, Off. Dig. Fed. Paint Varn. Prod. Clubs 23
(1951) no. 11, 661 – 668.
88 R. F. Paschke, D. H. Wheeler, J. Am. Oil Chem. Soc. 26
(1949) 278.
89 R. F. Paschke, D. H. Wheeler, J. Am. Oil Chem. Soc. 31
(1954) 208.
636 Drying Oils and Related Products
90 A. L. Clingman, D. E. A. Rivett, D. A. Sutton, J. Chem.
Soc. 1954, 1088 – 1090.
91 J. A. MacDonald, J. Am. Oil Chem. Soc. 33 (1956) 394.
92 G. H. Hutchinson, J. Oil. Colour Chem. Assoc. 41 (1958)
474.
93 S. B. Radlove, H. M. Teeter, W. H. Bond, J. C. Cowan, J.
P. Kass, Ind. Eng. Chem. 38 (1946) 997.
94 J. D. von Mikusch, Farbe þ Lack 57 (1951) 341 – 345.
95 J. D. von Mikusch, Farbe þ Lack 57 (1951) 393 – 399.
96 J. D. von Mikusch, Farben, Lacke, Anstrichst. 4 (1950)
149.
97 P. L. Nichols, S. F. Herb, R. W. Riemenschneider, J. Am.
Chem. Soc. 73 (1951) 247.
98 J. Baltes, F. Weghorst, O. Wechmann, Fette, Seifen,
Anstrichm. 63 (1961) 413.
99 BE 13 378, 1900 (A. Kronstein).
100 J. Scheiber, Farbe þ Lack 63 (1957) 443.
101 S. R. Vranish, R. M. Jackman, R. F. Helmreich, W. A.
Henson, Off. Dig. Fed. Paint Varn. Prod. Clubs 29
(1957) no. 1, 56 – 74.
102 H. P. Kaufmann, H. Gruber, Fette, Seifen, Anstrichm. 62
(1960) 607.
103 H. P. Kaufmann, H. Br€uning, Fette, Seifen, Anstrichm.
62 (1960) 1146.
104 F. R. Mayo, C. W. Gould, J. Am. Oil Chem. Soc. 41
(1964) 25.
105 K. Hamann, O. Mauz, Fette, Seifen, Anstrichm. 58
(1956) 528.
106 J. B. Crofts, J. Appl. Chem. 5 (1955) 88.
107 E. F. Redknap, J. Oil Colour Chem. Assoc. 43 (1960)
260.
108 M. Dyck, Farbe þ Lack 67 (1961) 148.
109 US 2 033 131, 1931 (Ellis-Foster).
110 US 2 033 132, 1931 (Ellis-Foster).
111 US 2 188 882, 1934 (E. T. Clocker).
112 Springer & M€oller, DE 635 926, 1935.
113 W. G. Bickford, E. F. DuPre, C. H. Mack, R. T.
O’Connor, J. Am. Oil Chem. Soc. 30 (1953) 376.
114 J. Sauer, R. Sustmann, Angew. Chem. 92 (1980) 779.
115 C. P. A. Kappelmeier, J. H. van der Neut, Kunststoffe 40
(1950) 81.
116 A. E. Rheineck, T. H. Khoe, Fette, Seifen, Anstrichm. 71
(1969) 644.
117 A. E. Rheineck, R. A. Heskin, J. Paint Technol. 40
(1968) 450.
118 Glasurit Werke, DE-AS 15 19 167, 1965 (G. Tr€oger, H.
Noak).
119 Am. Cyanamid, DE-OS 16 69 593, 1967 (J. N. Koral).
120 PPG, DE-OS 1938 191, 1969 (E. J. Kapalko, W. H.
English).
121 Ford Motor Co., DE-AS 15 46 944, 1962 (A. B.
Gilchrist).
Vol. 11
122 ICI, DE-OS 15 46 995, 1963 (N. McPherson, J. P.
Burden).
123 Herberts, DE-AS 2 737 174, 1977 (H.-P. Patzschke, D.
Saatweber).
124 G. Dantlo, Peintures, Pigments, Vernis 23 (1947) 171.
125 Koller & Co., EP 334 527, 1929; FP 676 456, 1929 (H.
H€onel, Beck).
126 V. H. Turkington, I. Allen, Ind. Eng. Chem. 33 (1941)
966.
127 H. Hultzsch, Kunstst. 37 (1947) 43.
128 K. Hajek, J. Stanek, J. Hires, Plaste Kautsch. 15 (1968)
679.
129 R. Sch€ollner, L. L€abisch, Fette Seifen Anstrichm. 69
(1967) 426.
130 N. A. Ghanem, F. F. Abd. El-Mohsen, J. Oil Colour
Chem. Assoc. 50 (1967) 441.
131 F. Mort, J. Oil Colour Chem. Assoc. 47 (1964) 919.
132 A. C. Jolly, J. Oil Colour Chem. Assoc. 47 (1964)
919.
133 K. Hajek, J. Kitzler, J. Stanek, E. Krejcar, Farbe þ Lack
77 (1971) 422.
134 Statistics from Verband der Lackindustrie e.V.,
Frankfurt, Germany 1999.
135 J. T. P. Derksen, B. G. Muuse, F. P. Cuperus in D. J.
Murphy (ed.): Designer Oil Crops, Breeding, Proces-
sing and Biotechnology, VCH, Weinheim, Germany
1993.
136 J. T. P. Derksen, F. P. Cuperus, Industrial Crops and
Products 3 (1995) 57.
137 B. G. Muuse, F. P. Cuperus, J. T. P. Derksen, Industrial
Crops and Products 3 (1992) 57.
138 H. G. Hauthal, ‘‘Bunsentage 1992, Nachwachsende
Rohstoffe, ’’ Nachr. Chem. Techn. Lab. 40 (1992) no.
9, 996.
139 E. M. S. Hammersveld, F. P. Cuperus, J. T. P. Derksen:
Modified and Novel Veg. Oils in a New Gen. of
Emulsion Paints, Agrotechnical Research Institute,
Wageningen, Netherlands 1994.
140 Project: VOICI (Vegetable Oils for Innovation in Chem.
Ind.) in ECLAIR (Europ. Collaborative Linkage of
Agriculture and Industry through Research), Br€usselsss
1993.
Further Reading
Z. W. Wicks Jr.: Drying Oils, ‘‘Kirk Othmer Encyclope-
dia of Chemical Technology’’, 5th edition, vol. 9, p.
142–155, John Wiley & Sons, Hoboken, NJ, 2005,
online DOI: 10.1002/0471238961.0418250923090311.
a01.pub2