Progress in Organic Coatings 55 (2006) 149153

Fast drying cobalt-free high solids alkyd paints

R.P. Klaasen , R.P.C. van der Leeuw
Akzo Nobel Decorative Coatings, Technology Center Deco, Rijksstraatweg 31, 2171AJ Sassenheim, The Netherlands Received 20 June 2005; received in revised form 1 September 2005; accepted 3 September 2005

Abstract The drying of trade sales alkyd paints at adverse conditions has always been critical. Several routes are available for improving the physical drying properties of alkyd paints at low temperatures. Unfortunately, these approaches will always result in an increase in the VOC of these paints, which is not desired for high solids alkyd paints. Therefore, a new curing mechanism has been developed within Akzo Nobel Decorative Coatings for the improvement of the drying of high solids alkyd paints at adverse conditions. This paper presents the development of a one pot fast drying alkyd system based on thiol-ene chemistry. This novel technology is based on a mixture of a polyfunctional thiol resin and an alkyd resin. By using visible light photoinitiators and/or cobalt-free metal catalysts fast drying high solids alkyd paints were obtained. 2005 Elsevier B.V. All rights reserved.
Keywords: Alkyds; High solids; Thiol-ene chemistry; Fast drying; Cobalt-free

1. Introduction Oxidatively drying alkyd paints are applied in a wide range of environmental conditions. Especially at adverse conditions (e.g. 510 C) the oxidative crosslinking is quite slow [1]. One way of accelerating the drying at lower temperatures is to improve the physical drying properties of the alkyd by increasing the Tg . This can be done by decreasing the oil length of the alkyd polymer or by blending with high Tg acrylics. However, these approaches will result in an increase of the VOC of the paint. Consequently, this approach is not desired for high solids alkyd paints, which have to be developed for compliance with the new European VOC limits. Due to the low molecular nature of the high solids binders the drying is predominantly depending on the chemical (oxidative) drying reaction. Therefore, for improving the drying properties of high solids alkyds research has been done on an additional crosslinking reaction, which can assist the oxidative drying mechanism of alkyd paints. It has been found that thiol-ene chemistry can be used for drying enhancement of alkyd paints at adverse conditions. Thiol-ene chemistry has gained a lot of interest the last decades. The mechanism is known to follow a step-growth

mechanism, in which a thiyl radical adds to an unsaturation, producing a carbon radical able to abstract a new hydrogen from a thiol and thus propagating the polymerization. A recent review article by C. Hoyle gives an overview on thiol-ene chemistry and the various thiol compounds and activated unsaturated compounds which can be used [2]. A unique property of the thiol-ene polymerization is that it does not suffer from oxygen inhibition, contrary to traditional acrylate-based systems. If oxygen adds to a propagating chain it will be terminated because the formed peroxy radical has a too low reactivity to add to a new unsaturated compound. In the case of the thiol polymerization, the peroxy radical will still be able to abstract a hydrogen from a thiol producing a new thiyl radical and thus propagating the polymerization. Within Akzo Nobel Decorative Coatings it has been found that the thiol-ene chemistry can also be used in combination with oxidatively drying alkyds which contain less activated unsaturated fatty acid moieties [3,4]. The fact that thiol-ene chemistry is rather uninhibited by the presence of oxygen makes it very useful in an oxidatively drying coating. 2. Experimental 2.1. Materials

Corresponding author. E-mail address: rob.klaasen@ssh.akzonobel.com (R.P. Klaasen).

BAPO: Irgacure 819, a bisacyl phosphine oxide photo initiator available from Ciba Specialty Chemicals.

0300-9440/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.porgcoat.2005.09.010

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Nuodex Combi APB: A drier comprising cobalt, zirconium and calcium, commercially available from Elementis Pigments. TiO2 : Kronos 2310 available from Kronos. Vanadium catalyst: CUR-RX E, a vanadyl neodecanoate catalyst available from OMG. Vanadyl acetylacetonate: In situ formation of complex by mixing 1 equivalent vanadyl neodecanoate with an excess of acetylacetone available from Aldrich (1% acetylacetone on formulation). Vanadyl bipyridyl: In situ formation of complex by mixing 1 equivalent vanadyl neodecanoate with 2 equivalents 2,2 bipirydyl from Dri-RX, a 2,2 -bipyridyl solution available from OMG. Manganese catalyst: Nuodex Mn 10, a drier comprising manganese ethyl hexanoate available from Elementis Pigments. Iron catalyst: Durham Iron 9LF, a drier comprising iron carboxylate available from Elementis Pigments. HS Alkyd A: A proprietary high solids alkyd based on sunower fatty acid, with an oil length of 74% and a solids content of 90%. LS Alkyd A: A proprietary low solids alkyd based on soy bean oil, with an oil length of 65% and a solids content of 70%. Thiol A: Pentaerythritol tetrakis (3-mercaptopropionate), a 4-functional thiol resin commercially available from Aldrich. Thiol B: A proprietary polyfunctional thiol resin prepared by condensation of di(trimethylolpropane), 2,2dimethylolpropionic acid and 3-mercaptopropionic acid. Thiol C: A proprietary 3-functional thiol resin prepared by condensation of dipentaerythritol, phtalic anhydride, sunower fatty acid and 3-mercaptopropionic acid. Thiol D: A proprietary 3-functional thiol resin prepared by condensation of dipentaerythritol, phtalic anhydride, sunower fatty acid and 2-mercaptopropionic acid. Thiol E: A proprietary 3-functional thiol resin prepared by condensation of dipentaerythritol, phtalic anhydride, sunower fatty acid and mercaptoacetic acid. 2.2. Drying tests Except for the analytical experiments with FTIR, all paint formulations had a pigment volume concentration of 15% (TiO2 ). For drying tests the coating composition was applied on a glass plate with a 90 m applicator. Curing took place at 10 C and 80% relative humidity in a climatized room under TL-055 light. The paint drying was tested with a BK Drying Recorder. The results obtained this way were judged as follows: Phase 1, the line traced by the pin closed up again (end of phase 1 is called open time). Phase 2, the pin traced a scratchy line (end of phase 2 is called dust free time). Phase 3, the pin traced a straight line in the paint which didnt close up (end of phase 3 is called tack-free time).

2.3. Analytical tests By using transmission FTIR spectroscopy (Biorad FTS 60) the concentration of thiol groups in a drying paint lm of 150 m on a silicon wafer has been monitored. After a ash off time of 5 min at room temperature the integrated SH absorption peak at 2570 cm1 has been measured in time. The paint consisted of 90 wt.% HS alkyd A and 10 wt.% Thiol C with vanadyl acetylacetonate as catalyst (0.03% V on resin solids) and contained no pigment. 2.4. Storage stability tests Storage stability was determined by viscosity changes in time and skin formation. Viscosity was measured with a Brookeld CAP 2000 viscometer at 10000 s1 and 23 C. A maximum viscosity increase of 20% in one year at room temperature is allowed. Determination of skin formation was done visually by storing half-lled and closed 125 mL tin cans with paint at room temperature. 3. Results and discussion 3.1. Thiol-ene curing with fatty acids The thiol-ene reaction follows a stepwise mechanism in which a thiyl radical formed by a radical source adds to an unsaturation, producing a carbon radical able to abstract a new hydrogen from a thiol and thus propagating the polymerization (Fig. 1) [5]. For the drying enhancement of high solids alkyds by use of thiol-ene chemistry the authors propose a mechanism existing of two polymerization steps. The rst step is the fast reaction of thiyl radicals with the fatty acid moieties from, e.g. linoleic fatty acid of the high solids alkyd. By using a poly functional thiol binder a fast initial molecular weight increase occurs as depicted in Fig. 2. The second step is the standard oxidative drying reaction of an alkyd by formation and decomposition of the hydroperoxides, which will give the nal network formation. For a good oxidative through drying performance it is important that the fatty acid groups are in excess to the thiol groups. Thiol-ene chemistry is not inhibited by oxygen [2]. Hydroperoxides formed in the rst stage of the polymerization (Fig. 1) can promote the second oxidative polymerization step. 3.2. Thiol-ene curing by visible light photoinitiator It has been found that photoinitiators are good initiators for the thiol-ene reaction in alkyd paints. The major problem with white pigmented paints is the fact that due to the TiO2 pigments light below 390 nm is blocked. By using a special UV-A/visible light photoinitiator such as Irgacure 819 a fast drying HS alkyd paint can be developed as shown in Fig. 3. At a photoinitiator level of 0.5 wt.% on total resin solids, increasing the amount of Thiol A resulted in a faster drying performance. Increasing the amount of thiol resin over 10 wt.% did not increase the drying performance any further. This is

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Fig. 1. Proposed mechanism of the thiol-ene reaction with an alkyd.

Fig. 2. Schematic depiction of the reaction of a four functional thiol resin with an alkyd resulting in a highly functional alkyd resin which can polymerize further by oxidative drying.

probably due to the fact that at higher levels of thiol-ene reaction the amount of remaining oxidatively reactive linoleic moieties needed for step 2 of the reaction mechanism is decreased. 3.3. Thiol-ene curing with metal driers During the oxidative drying of alkyd paints many radical species can be formed which could theoretically act as radical

source for the thiol-ene reaction [6]. A commonly used primary metal catalyst in oxidatively drying alkyd paints is cobalt ethylhexanoate. Unfortunately, it was found that the combination of cobalt ions and thiol groups resulted in immediate red coloring of the paint, probably by formation of cobalt thiol complexes. Furthermore, cobalt compounds have recently been reported to be possibly carcinogenic and genotoxic [7]. Therefore, several commercially available alternative catalysts based on manganese, iron and vanadium were tested. Vanadyl bipyridyl and vanadyl acetylacetonate complexes were found to be effective catalysts giving no discoloration with thiol groups. Using low amounts of these vanadyl complexes very fast drying paints, even at 10 C were developed. An example of the drying performance of a thiol-ene assisted drying of a high solids alkyd system is shown in Table 1. The vanadyl bipyridyl complex as such isnt a good catalyst for the oxidative curing of a high solids alkyd. However, in combination with a polyfunctional thiol binder it outperformed the drying of the reference system based on a standard cobalt based combination drier. 3.4. Analytical aspects

Fig. 3. BK-drying chart of HS alkyd A with 0.5 wt.% BAPO on total resin solids and different amounts of Thiol A.1) Reference formulation based on HS Alkyd A with Nuodex Combi APB drier.

By using FTIR spectroscopy the concentration of thiol groups in a drying paint lm of 150 m on a silicon wafer has been

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Table 1 Drying performance of a thiol-ene alkyd system initiated by vanadyl bipyridyl catalyst Composition 0 pbw Thiol B 100 pbw HS alkyd A 0.03 pbw vanadiuma 0.18 pbw 2,2 -bipyridylb 14 pbw Thiol B 86 pbw HS alkyd A 0.03 pbw vanadiuma 0.18 pbw 2,2 -bipyridylb Reference 0 pbw Thiol B 100 pbw HS alkyd A 7.5 pbw Combi APB
a b

Phase 1 (h) 9.0

Phase 2 (h) 14.0

Phase 3 (h) 20.0

0.5

0.5

1.0

2.6

3.5

4.7

Vanadium compound based on Cur RX-E. 2,2 -Bipyridyl compound based on Dri-RX.

Fig. 5. Depiction of an alkyd compatible three functional thiol resin.

monitored. The paint consisted of HS alkyd A and Thiol C with vanadyl acetylacetonate as catalyst. It can be seen from Fig. 4 that within 1 h the majority of the thiol groups had reacted with HS alkyd A. This fast reaction of the thiol groups is consistent with the proposed drying mechanism as earlier described and depicted in Figs. 1 and 2. 3.5. Paint formulation optimization During lm formulation of the rst metal catalyzed thiol-ene concepts based on the polar Thiol A resin and apolar high solids alkyds incompatibility problems were encountered. A compatible thiol-ene system could be made by using more apolar thiol resins, which were prepared by synthesizing polyesters with mixtures of 3-mercaptopropionic acid and fatty acids. An example of such a resin structure is shown in Fig. 5. Another advantage of this class of thiol resins is the reduced odor of the resin by the comparatively high molecular weight. Furthermore, for a low odor and good viscostability of this class of resins the process conditions, like indirect heating and type of condensation catalyst, are very important.

The reactivity of the thiol resins can be tuned by the choice of mercapto acid type [8]. A series of three functional polyesters based on three different mercapto acids (3-mercaptopropionic acid, 2-mercaptopropionic acid and mercaptoacetic acid) was synthesized. The 3-mercaptopropionic based polyesters showed the best drying performance as shown in Fig. 6. The storage stability of trade sales alkyd paints is an important issue. A storage stability of over 1 year is demanded. The vanadyl bipyridyl complex proved to be a very effective catalyst for the thiol-ene reaction, but the corresponding paint systems with 0.3 wt.% on formulation of the standard anti skinning/complexing agent methylethylketoxime were very sensitive for skin formation. Even formulations with 0.6 wt.% of methylethylketoxime on total formulation were critical in storage stability, in particular skin formation. Already after 1 week storage skin formation was observed. It was found that acetylaceton could be used both as complexing agent and anti skinning agent, giving storage stable fast drying paints as shown in Fig. 7. It was remarkable that acetylacetone could act both as drying accelerator and as stabilizer. Possibly the vanadyl acetylacetonate complex is not active, while during paint application, due to evaporation of the acetylacetone, an active vanadyl acetylacetonate thiol complex is formed.

Fig. 4. FTIR measurement on thiol decrease at 2570 cm1 of Thiol C in HS alkyd A. Vanadyl acetylacetonate was used as catalyst.

Fig. 6. Inuence of thiol building block on drying performance in thiol-ene assisted drying of HS alkyd A with, respectively Thiol C, Thiol D and Thiol E. Vanadyl acetylacetonate was used as a catalyst.

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4. Conclusions With this work we proved the applicability of thiol-ene chemistry for the drying enhancement of high solids alkyds at adverse conditions. A radical producing photoinitiator proved to be a good radical source for initiating the thiol-ene reaction in alkyd paints. Suitable metal catalysts for the thiol-ene reaction in alkyds are vanadyl bipyridyl and vanadyl acetylacetonate. Furthermore, by right choice of paint components storage stable and fast drying high solids alkyd paints can be formulated.
Fig. 7. Inuence of complexing agent of vanadyl catalyst on drying performance of thiol-ene assisted HS alkyd A with Thiol C.

Acknowledgements The authors wish to thank the staff of Akzo Nobels Technology Center Decorative Coatings for their evaluation of the described thiol-ene concepts and Akzo Nobels CoRA department for the synthesis of the thiol resins and their analytical support. References
[1] K.H. Zabel, Polym. Paint Col. J. 178 (1988) 526. [2] C.E. Hoyle, T.Y. Lee, T. Roper, J. Polym. Sci. Part A: Polym. Chem. 42 (21) (2004) 53015338. [3] F.J.A.D. Bakkeren, R.P. Klaasen, A.J.H. Lansbergen, WO 00/66672. [4] F.J.A.D. Bakkeren, R.P. Klaasen, WO 01/46294. [5] R. Stephen Davidson, RADnews 37 (2001) 1821. [6] W.J. Muizebelt, J.J. Donkerbroek, M.W.F. Nielen, J.B. Hussem, M.E.F. Biemond, R.P. Klaasen, K.H. Zabel, J. Coatings Technol. 70 (876) (1998) 8393. [7] D. Lison, M. de Boeck, V. Verougstraete, M. Kirsch-Volders, Update on the genotoxity and carcinogenity of cobalt compounds, J. Occup. Environ. Med. 58 (2001) 619625. [8] J. Samuelsson, M. Jonsson, T. Brinck, M. Johansson, J. Poly. Sci. Part A: Polym. Chem. 42 (24) (2004) 63466352.

Fig. 8. Inuence of thiol-ene curing assistance with Thiol C on the drying performance of a low solids alkyd paint (VOC 380 g/L) based on LS alkyd A and a high solids alkyd paint (VOC 280 g/L) based on HS alkyd A.

The thiol-ene curing could be used for a wide range of alkyd paint systems. As shown in Fig. 8 both low solids and high solids alkyd systems could be formulated showing an excellent drying performance at 10 C.