Progress in Organic Coatings 53 (2005) 99105

The combination of reducing agents/iron as environmentally friendlier

alternatives for Co-based driers in the drying of alkyd paints
Fabrizio Miccich`e a, b , Eef Oostveen a , Jacco van Haveren a, 1 , Robert van der Linde b,
a

Agrotechnology and Food Innovations B.V., Department of Polymers, Composites and Additives, P.O. Box 17,
6700 AA Wageningen, The Netherlands
b Laboratory of Coatings Technology, Department of Chemical Engineering and Chemistry,
Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
Received 29 July 2004; accepted 15 December 2004

Abstract
In answer to the increased demand for Co-free driers for alkyd based paints, a biomimetic approach has been used to find suitable and
environmentally friendly alternatives for Co-based driers for alkyd paints. This approach was chosen due to the resemblance between the
mechanisms by which alkyd paints dry and lipids are oxidized in biological systems. As a consequence, the combination of iron with reducing
agents was tested as drier for alkyd paints.
Ascorbic acid and several ascorbic acid derivatives, in combination with iron salts, have been tested in alkyd emulsions, alkyd resins (or
varnishes), and in a high gloss white paint formulation. We have found that the combination of iron salts with reducing agents forms an excellent
drier, in terms of film hardness and particularly total drying time, compared to a commercial Co drier and a new Mn-based alternative. The
effect of two nitrogen donor ligands, N,N-bis(2-ethyl-5-methyl-imidazol-4-ylmethyl)aminopropane (BIAP) and 2-ethyl-4-methylimidazole
(Im), to the mixture reducing agent/iron was also studied in a high gloss white paint formulation. Outstanding total drying time of just 2.2 h
was observed for the combination of ascorbic acid 6-palmitate, iron and imidazole.
2005 Elsevier B.V. All rights reserved.
Keywords: Cobalt salts; Paint driers; Alkyd paints; Iron salts; Reducing agents; Ascorbic acid

1. Introduction
Air drying alkyd paints contain besides the main constituents, such as pigments, alkyd resins (binders), and solvents, also small amounts of driers.
Driers are inorganic compounds typically consisting of
transition metal salts that accelerate the transformation of
paint films from the liquid to the solid state after application
on a surface. Typical driers for alkyd systems are metal salts of
long chain fatty acids according to the formula (Men+ )(X )n ,
in which Men+ is a transition metal ion, such as Co, Pb, Fe,
Mn, and X is a C6 C18 aliphatic carboxylate.

Corresponding author. Tel.: +31 40 247 3077; fax: +31 40 244 5619.
E-mail addresses: jacco.vanhaveren@wur.nl (J.v. Haveren),
r.van.der.linde@tue.nl (R.v.d. Linde).
1 Tel.: +31 317 47 52 33; fax: +31 317 47 53 47.
0300-9440/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2004.12.008

The drying of alkyd paints is a consequence of: (1) the

physical drying that is due to the evaporation of volatile components from the paint film after its application on a surface
and (2) the chemical drying. Basically, the chemical drying
is a metal-catalyzed lipid oxidation process that takes place
at the fatty acid chains (such as linoleic and linolenic acid)
of binder molecules [1].
For decades cobalt, as cobalt 2-ethylhexanoate, has been
widely used as the main active drier for alkyd paints because
of its good performance at ambient temperature. However,
Co-based driers are not free of disadvantages; first, the drying properties of Co-based driers diminish upon standing (especially in water-borne alkyd paints) [2,3]; and secondly, as
the result of a recent study with cobalt sulphate heptahydrate, cobalt compounds are suspected of being carcinogenic
in aerosols [4]. Although it is still unclear whether these toxicity data are relevant for Co-based driers, they have risen

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F. Miccich`e et al. / Progress in Organic Coatings 53 (2005) 99105

health and environmental issues. Therefore finding substitutes for cobalt-based catalysts is of high importance to the
alkyd producing and using industry.
Various transition metals have been reported as having
good drying properties. Among them manganese and iron are
included. Research has been done on developing alternatives
based on manganese [5], but iron has not been considered yet
as a valid alternative for Co-driers. This is due to the fact that it
is generally assumed that iron is not effective in the oxidative
drying of coatings [6] at ambient temperature, becoming only
catalytically active at baking temperatures above 130 C, and
due to the dark color of paint films induced by iron.
Although conventional solvent-borne alkyd paints still
dominate the paint market, the demand for water-borne
(alkyd) paints has increased in the past years, due to restrictions on the use of volatile organic compounds (VOC) [2].
In order to find replacements for Co-based driers, suitable
for both solvent and water-borne alkyd paints, a biomimetic
approach has been used in our laboratories. The biomimetic
approach is the result of the similarities between the mechanism by which alkyd paints dry, and the mechanism by which
lipids are oxidized in biological systems. In the present paper, we report on the combination of iron salts with reducing
agents as environmentally friendly alternatives for Co-based
driers in the drying of water-borne and solvent-borne alkyd
paints [7].

2. Experimental
2.1. Materials
2.1.1. Alkyd systems
1. DSM WB paint based on URADIL AZ 554 Z-50 (alkyd
emulsion; solid material content is approx. 50 wt.%; oil
length: approx. 40%; type of fatty acid: special processed
soybean).
2. Alkyd emulsion URADIL AZ 516 Z-60 (solid material
content is approx. 50 wt.%; oil length: approx. 63%; type
of fatty acid: tallow oil, supplied by DSM Coating Resins).
3. Uralac AD142 W-50 (50 wt.% in white spirit; oil length:
approx. 53%; type of oil: linseed, supplied by DSM Coating Resins)
4. Setal 16 LV WS-70: a white solvent-borne paint (70 wt.%
in white spirit; type of oil: linseed, white paint formulation
prepared and supplied by Sasol Servo BV, Delden, The
Netherlands). The paint also comprises TiO2 and a number
of additives.
2.1.2. Driers
To evaluate the efficiency of the mixture reducing
agent/iron, a commercial Co drier (NUODEX WEB Co 6
DP (Co-octanoate), and a newly developed Mn-based drier
NUODEX CF 578 DP were employed as reference. Both driers were supplied by Sasol Servo BV, Delden, The Netherlands. As source of iron a commercial product was used

(NUODEX Fe 10 (Fe-octanoate), Sasol Servo BV, Delden,

The Netherlands).
No secondary driers were used in our tests.
2.1.3. Reducing agents
Ascorbic acid 6-palmitate (AsA6p, 95% pure, purchased
from Aldrich) was mainly used throughout our experiments.
In order to evaluate the effect of the chain length attached
to the ascorbic acid, several ascorbic acid derivatives were
synthesized according to literature [8].
Ascorbic acid (AsA), 99+%, was obtained from Acros.
2.1.4. Ligands
The 2-ethyl-4-methylimidazole (Im) was purchased from
Aldrich.
The N,N-bis(2-ethyl-5-methyl-imidazol-4-ylmethyl)aminopropane ligand (BIAP) was synthesized following a literature method [9].
2.1.5. Antiskinning
To prevent skin formation during storage for the Cocontaining formulations, Exkin 2 (butanone oxime supplied
by Sasol Servo BV, Delden, The Netherlands) was used at
0.25 wt.% to the solid binder content.
2.2. Methods
2.2.1. Drying time
The drying performance of different catalysts was determined according to ASTM D5895-96 using a Braive, and a
BK drying recorder. The instrument is a straight-line recorder
equipped with hemispherical ended needles that travel the
length of the test strip within a chosen range of time (typically
24 h). A test strip (BK recorder: 30.5 cm 2.5 cm, Braive
recorder: 70 cm 2.5 cm) made of plain glass is prepared by
casting a film upon it of approx. 60 m in thickness (wet film).
Instruments accommodate several test strips (BK recorder: 6,
Braive recorder: 10). The trace left on the film during the drying can be used to define the different stages of the drying
process as described, e.g. by Bieleman [5]. Stages considered
in this work could be summarized as follow:
Stage a: the paint flows together, the wet-edge time.
Stage b: a line is visible, the paint begins to polymerize,
dust-free time.
Stage c: this is the so-called surface drying or tack-free.
Stage d: no lines are visible on the film. This stage is called
total dry or through dry.
In some cases the drying was also established by hand, or
thumb-test, according to ASTM D1640.
2.2.2. Film hardness
Film hardness was measured by using a pendulumdamping test according to DIN53157. The method is based on
registering the time (the number of pendulum swings) it takes
before the amplitude of the pendulum is damped to a certain

F. Miccich`e et al. / Progress in Organic Coatings 53 (2005) 99105

extent. The more swings observed, the harder is the film. Typically, a plain glass test plate measuring 20 cm 9 cm was
coated with a 60 m film (wet thickness) and film hardness
was measured after different periods of drying time. Values
were expressed in s/K (Konig hardness).
2.2.3. Whiteness index
The whiteness index was determined using a Color
Reader CR-10 of Minolta by comparing the whiteness of
the paint film with that of a standard white sheet.
2.2.4. Varnish samples preparation
Typical experiments consist of mixing appropriate
amounts of drier, and when necessary amounts of a solution of AsA6p (0.8 g in 20 ml of 2-butoxyethanol), with the
resin/paint to reach the 0.07 wt.% (or otherwise specified) of
metal to the solid binder content of the alkyd resin/paint, and
the intended molar ratio AsA6p/Fe. The catalyst was mixed
in the varnish/paint by using a Siemens, Speed Mixer DAC
150 FVZ, and stored for 2 weeks before testing.
2.2.5. Alkyd emulsion samples preparation
Experiments were carried out by mixing appropriate
amounts of NUODEX WEB Co 6 DP or ferrous sulfate
(Fe(II)SO4 7H2 O) and a solution of AsA in water, with the
alkyd emulsion to the 0.07 wt.% of metal to the solid binder
content of the alkyd emulsion, and the intended molar ratio
AsA/Fe. Tests were carried out after 24 h of storing.

3. Results and discussions

3.1. Ascorbic acid and its lipophilic derivatives
It is well known that one of the most pronounced effects of reducing agents on the lipid oxidation process in
biological systems is the reduction of metal ions, iron in particular, resulting in an increase in the lipid oxidation rate
by the so-called proxidant effect [10,11]. The proxidant effect of reducing agents, such as ascorbic acid, in most of

101

the cases is controlled by the concentration of the reducing agent itself in the reaction media. In fact, high concentrations of ascorbic acid in the media can result in slowing
down or even inhibiting the oxidation process (antioxidant effect). In the present work, both ascorbic acid, for water-borne
alkyd systems, and lipophilic derivatives of it, for solventborne alkyd systems, were used. In addition to AsA6p, several other ascorbic acid derivatives were used in our tests
(Fig. 1).
3.2. The ascorbic acid (AsA)/Fe combination in
water-borne alkyd paints
3.2.1. Alkyd emulsion: URADIL AZ 554 Z-50 (based on
special processed soybean fatty acid)
Drying tests were carried out on a water-borne alkyd emulsion based on URADIL AZ 554 Z-50 using different molar
ratios AsA/Fe. In Tables 1 and 2 total drying times and film
hardness values are compared.
Clearly the combination AsA/Fe results in good drying
capabilities at both ambient temperature and at 10 C when
compared to the Co drier, and the drying properties of the
iron-based catalyst depends on the molar ratio AsA/Fe used.
Actually, low molar ratios (2/1 and 4/1) give shorter drying times than the commercial Co drier. On the contrary,
similar or longer drying times than Co were obtained at
higher molar ratios (5/1 and 6/1) especially at 10 C. Despite the good drying times, the iron catalyst did not result in the same film hardness as Co. In fact, film hardness increases during the first 8 h of drying, but no significant changes were measured afterwards (Table 2). This
fact may be associated with the limited solubility of both
the ascorbic acid and the ferrous sulfate in the paint system after water has completely evaporated from the film inhibiting its catalytic properties. In order to avoid potential
solubility limiting effects, it was decided to use lipophilic
derivatives of the ascorbic acid and Fe-2-ethylhexanoate
(NUODEX Fe 10) for solvent-borne systems. Tests of
lipophilic derivatives will also be attempted in water-borne
systems.

Fig. 1. Schematic representation of the ascorbic acid and its lipophilic derivatives used in combination with iron as drier.

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F. Miccich`e et al. / Progress in Organic Coatings 53 (2005) 99105

Table 1
Drying of a commercial coating composition based on URADIL AZ 554 Z-50 by the combination AsA/Fe and Co at different temperatures
Catalyst

Molar ratio AsA/Fe

Braive recorder at 23 C
and 50% RH (h)
Stage a

Stage b

Stage c

Surface dry

Through dry

WEB Co 6
AsAa /Feb
AsAa /Feb
AsAa /Feb
AsAa /Feb
No catalyst

2/1
4/1
5/1
6/1

0.04
0.07
0.08
0.07
0.10
0.14

0.47
0.50
0.52
0.42

5
3.40
3.50
4.25
>5
>5

1.00
0.30
0.30
0.30
0.30
1.30

4.00
4.00
4.00
4.00
4.00
>8.00

By hand at 23 C and 50% RH (h)

BK recorder at 10 C and
25% RH (total dry, h)
6.30
3.15
3.00
n.d.
n.d.
>12.00

Fe and Co were dosed as 0.07 wt.% to the resin solid content.

a AsA: ascorbic acid.
b Fe: iron(II) sulfate.

3.2.2. Alkyd emulsion: URADIL AZ 516 Z-60 (based on

tallow oil)
When a tallow oil based alkyd emulsion was used a drop
in performance of the AsA/Fe combination, compared to the
special processed soybean based alkyd emulsion, was observed. Table 3 shows that the activity of the drier is related
with the molar ratio AsA/Fe pointing the ratio 4/1 is equivalent to the Co-based drier.
Comparable film hardness value for both the Co- and the
Fe-based catalyst were measured after 20 h of drying.
3.3. The ascorbic acid-6 palmitate (AsA6p)/Fe
combination in solvent-borne systems
3.3.1. Varnish: URALAC AD 142 W-50 (based on
linseed oil)
Table 4 shows the results of the drying experiments carried
out on URALAC AD 142 W-50 for different molar ratios
Table 2
Konig hardness development during drying of a commercial coating composition based on URADIL AZ 554 Z-50 by the combination AsA/Fe and
Co
Catalyst

WEB Co 6
AsA/Fe 2/1
AsA/Fe 4/1
AsA/Fe 5/1
AsA/Fe 6/1
No catalyst

Konig hardness at 23 C and 50% RH (s)

8h

1 day

3 days

1 week

24
21
20
17
17
10

31
24
22
21
20
10

38
28
27
27
25
14

45
29
29
26
28
17

AsA6p/Fe. Data were obtained after storing the samples in a

can for approx. 2 weeks.
A storage time was required for the catalyst to become
active. We observed that the storage time was accompanied
by a change in color of the alkyd solution. Although a scientific explanation has not been formulated yet and studies
are ongoing to understand what it is happening in the can
during these 2 weeks, we speculate that time is required for
the formation of the active drier as a complex between the
iron and an oxidation product of the reducing agent.
Table 4 clearly shows that in this system the AsA6p/Fe
catalyst has superior drying properties compared to Nuodex
Web Co 6 DP, and that the performance of the Fe-based catalyst is related to the ratio AsA6p/Fe used. The maximal activity is reached for a ratio AsA6p/Fe equal to three. Although
the molar ratio 1/1 is the least active drier among the four
ratios reported in this paper, the resulting film hardness after
5 days of drying did not differ significantly from the other
combinations. Film hardness obtained from the iron catalyst
did not vary as much as the total drying time when compared
to cobalt, which makes the iron-based catalyst as good as the
Co-based drier in terms of film hardness and even better in
terms of drying time.
3.3.2. The inuence of other ascorbic acid derivatives
on the drying of a solvent-borne alkyd resin
Several ascorbic derivatives have been synthesized
throughout our research. Derivatives were synthesized using
fatty acids having different chain length (C8 C18 ) aiming
at elucidating how the chain length might affect the drying
properties of the combination reducing agent/Fe. Results are
summarized in Table 5.

Fe and Co were dosed as 0.07 wt.% to the resin solid content.

Table 3
Drying tests on a commercial alkyd emulsion based on URADIL AZ 516 Z-60 by the combination of AsA/Fe and Co
Catalyst

Molar ratio AsA/Fe

BK recorder at 23 C (total dry; h)

Konig hardness at 23 C (s) (after 20 h)

WEB Co 6
AsA/Fe
Fe/AsA
Fe/AsA
No catalyst

2/1
4/1
6/1

5.4
8.8
6.0
9.2
>24

9.8
8.4
9.8
8.4

Fe and Co were dosed as 0.07 wt.% to the resin solid content.

F. Miccich`e et al. / Progress in Organic Coatings 53 (2005) 99105

103

Table 4
Drying tests of a commercial solvent-borne alkyd resin (URALAC AD 142 W-50) by the combination of AsA6p/Fe and Co
Catalyst
Reducing agent

Metal

AsA6p
AsA6p
AsA6p
AsA6p

Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
WEB Co 6/Exkin 2

Molar ratio reducing agent/metal

Braive recorder at 23 C (total dry, h)

Konig hardness at 23 C for 120 h (s)

1/1
2/1
3/1
4/1

8.5
4
3.4
4.6
14

90
96
75
107
89

Fe and Co were dosed as 0.07 wt.% to the resin solid content.

Table 5
Drying tests of a commercial solvent-borne alkyd resin (URALAC AD 142 W-50) by the combination of several AsA-derivatives/Fe and Co
Braive recorder at 23 C (total dry, h)

Catalyst
Reducing agent

Metal

AsA-stearate (C18 )
AsA-palmitate (C16 )
AsA-laurate (C12 )
AsA-octanoate (C8 )

Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
WEB Co 6/Exkin 2*

4.5
5
5
10
>24
11.2

Konig hardness at 23 C (s)

21 h

45 h

164 h

14
14
14
13

35

68
61
63
55

65

123
116
120
110
78
96

The molar ratio AsA-derivative/Fe was kept constant at 0.4/1; Fe and Co were dosed as 0.07 wt.% to the resin solid content.

It appears that the only difference, in terms of drying

time and film hardness, is noticeable when ascorbic acid 6octanoate is used in combination with iron. Actually a longer
drying time and slightly lower hardness were measured. No
appreciable differences were observed among AsA-stearate,
AsA-palmitate and AsA-laureate. This inferior performance
of the AsA-octanoate most probably can be associated with
a solubility limiting effect of the derivatives as a function of
the number of carbons of the fatty acid used for their synthesis. In fact less solubility may lead to poor activity of the
catalyst in the media. From our investigation it seems that a
minimal chain length between C8 and C12 is needed for the
combination AsA6-derivative/Fe to give good catalytic prop-

erties. Moreover, the fact of not observing improvements in

the drying time and film hardness by increasing the chain
length from C12 to C18 supports the solubility issue.
3.3.3. High gloss white paint: Setal 16 LV WS-70
In order to further establish the drying properties of the
AsA6p/Fe system tests have been carried out on a high gloss
fully pigmented white paint based on a linseed oil resin. In
Table 6 results are compared.
As already observed for the varnish, also in the white paint
the performance of the Fe-based catalyst, in terms of total
drying time, is superior compared to the commercial Co- and
Mn-based drier, irrespectively of the ratio AsA6p/Fe studied.

Table 6
Drying tests of a commercial high gloss white paint formulation based on Setal 16 LV WS-70 by the combination of AsA6p/Fe with and without the addition
of ligands and Co
Catalyst
Reducing agent

Metal

Ligand

AsA6p
AsA6p
AsA6p
AsA6p
AsA6p
AsA6p
AsA6p
AsA6p
AsA6p
AsA6p
AsA6p
AsA6p

Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex Fe 10
Nuodex CF 578 DP (a)
Nuodex CF 578 DP (b)
WEB Co 6 + Exkin 2*

Im
Im
Im
Im
BIAP
BIAP
BIAP
BIAP

Molar ratio reducing

agent/metal/ligand

Braive recorder at
23 C (total dry, h)

Konig hardness at
23 C for 120 h (s)

Whiteness
index

1/1/0
2/1/0
3/1/0
4/1/0
1/1/4
2/1/4
3/1/4
4/1/4
1/1/2
2/1/2
3/1/2
4/1/2

8.8
10
7.0
6.6
4.5
2.2
5.8
6.6
6.7
7.5
8.5
6.8
9.9
12.5
14

76
69
74
68
74
81
85
80
57
63
72
49
51.3
52
73

80.2
80.3
80.1
80.0
80.6
80.8
81.5
81.2
81.4
81.1
80.8
81.3
82.1
83
82.8

Fe and Co were dosed as 0.07 wt.% to the resin solid content. The Mn catalyst was used as the 0.07 wt.% (a) and the 0.04 wt.% (b) to the paint solid content,
respectively; Im: 2-ethyl-4-methyl-imidazole; BIAP: N,N-bis(2-ethyl-5-methyl-imidazol-4-ylmethyl)aminopropane.

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F. Miccich`e et al. / Progress in Organic Coatings 53 (2005) 99105

It is noticeable that the ratios 3/1 and 4/1 give better total
drying time than ratios 2/1 and 1/1. In addition, iron-based
catalysts give a film hardness value comparable to cobalt, but
better than the manganese-based drier.
The whiteness index of films was also considered. Although the iron catalyst gives very good drying times and
film hardness, the film color, when compared to cobalt and
manganese, still needs some improvements (even though the
difference was just of two units) (Table 6). The whiteness
index for the manganese drier was improved by dropping the
concentration of the metal from 0.07 to 0.04 wt.%, but it was
followed by a drop in drying performance. We believe that
the same effect on the whiteness index may be achieved by
diminishing the amount of iron in the paint but without causing a dramatic increase in the drying time as a consequence of
the high drying properties of the iron-based catalyst. Studies
are ongoing.
3.3.4. The effect of two N-donor ligands
It is well known that ligands, by coordination, can strongly
modify the chemistry, electrochemistry and catalytic properties of metal ions [12]. To evaluate the effect that ligands might have on the drying properties of the combination AsA6p/Fe, two nitrogen donor ligands were used in this
work. Ligands were used as monodentate (Im), and tridentate (BIAP) [9] aiming at elucidating the effect of the ligand
coordination number on drying properties of the iron-based
catalyst. Although many ligands of different nature, (N, O, or
N,O-donor) and complexity could be used in this work, our
choice went for simple ligands, of easy synthesis and usually
present in nature in iron-containing biomolecules, such as in
the active sites of enzymes (e.g. lipoxygenase). Although the
list of naturally occurring ligands is quite long, among them
imidazole rings are quite common.

The overall effect that both ligands had was quite remarkable, especially for low molar ratios AsA6p/Fe (1/1 and 2/1).
Table 6 shows that the most outstanding effect was obtained when Im was used. In fact, whereas the BIAP decreases
the drying time, for the ratio AsA6p/Fe 1/1 and 2/1, with approx. 2 h when compared to the data obtained without ligands,
the Im decreases it with approx. 4 h for the ratio AsA6p/Fe
1/1, and with more than 7 h for the ratio AsA6p/Fe 2/1. In
this latter case, the drying time was approx. 12 h shorter than
the total drying time measured for the Co drier. The addition of ligands makes the Fe-based catalyst even more active
compared to the Mn drier. Investigations to elucidate the coordination environment of the iron as well trying to identify

one or more of the active catalytic species involved in the

reaction are still ongoing.
Film hardness was also positively influenced by the addition of ligands. Actually, higher or similar film hardness
values compared to cobalt and manganese were measured. In
particularly, when compared to manganese higher hardness
values were always measured except for AsA6p/Fe/BIAP ratio 4/1/2.
The addition of ligands also improved the whiteness index
of paint films, even though values were still not completely
comparable to cobalt and manganese.

4. Conclusions
Our study shows that a new promising environmentally
friendly iron-based drier, as replacement for Co-driers in
alkyd paints, has been developed. This investigation also
proves the quality of the iron as drier for alkyd paints at
ambient temperature.
The simple combination of AsA/Fe sulfate was found to be
a good and better drier than Co in alkyd emulsion. However,
probably due to the limited solubility of both the reducing
agent and iron sulfate in the paint system after water evaporation, inferior film hardness was obtained. To overcome the
solubility limiting issue, lipophilic derivatives of the ascorbic acid and Fe-2-ethylhexanoate (NUODEX Fe 10) were
further used in the varnish and a white paint formulation. It
was found that the performance of the Fe-based catalyst was
dependent on the molar ratio reducing agent/Fe, and shorter
dying times and comparable film hardness value (after 5 days
of drying) were obtained compared to the Co-based drier
(NUODEX WEB Co 6 DP), and an alternative drier based on
Mn (NUODEX CF 578 DP).
The drying properties of different ascorbic acid derivatives
in combination with Fe were also tested. It was found that a
minimum chain length comprised between C8 and C12 was
required to obtain good total drying times and film hardness.
Despite the better whiteness index of the newly designed
Mn-based drier, the reducing agent/Fe combination remains
superior as drier and crosslinker. The addition of two N-donor
ligands to the mixture AsA6p/Fe in the high gloss white paint
leads to a general positive effect in the total drying time and
film hardness of the Fe-catalyst. Remarkably, the addition
of Im to the combination AsA6p/Fe 2/1 gave a total drying time of just 2.2 h. Additionally, an improvement in the
whiteness index of paint films was observed by the addition
of ligands.

Acknowledgements
Authors would like to thank Sasol Servo BV, for supplying cobalt, iron and antiskinning chemicals, and DSM for
supplying the alkyd resins. Thanks go to Vincent H. Wijkel,
from the Hogeschool of Utrecht, The Netherlands, for syn-

F. Miccich`e et al. / Progress in Organic Coatings 53 (2005) 99105

thesizing and testing the ascorbic acid derivatives used in this

work.
Authors are also thankful to SENTER/Innovation Oriented Research Programme (IOP) on Heavy Metals (IOP
Zware Metalen No. IZW99241a) sponsored by the Netherlands Ministry of Economic Affairs, for the financial support.

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