80 Driers ‘Milton Nowak Bboy Chemical References, 80-3 Driers are metallic soaps (metal salts of various organic acids) used primarily for the catalysis of the drying of oils, oleoresinous compositions, alkyd resins, and polyesters “Metallic soaps have a long history prior to their use as driers. Evidence indicates that calcium greases in the form of combinations of lime and fats were used as axle greases as early as 1400 B.C. A combi of red lead with drying oil was patented in 1773 as a grease for reducing friction between iron or steel parts. As early as 1880, A. W, Pratt patented liquid paint driers based on lead and manganese linoleates dissolved in linseed oil, naphtha, and turpentine, Cobalt soaps appeared sometime around 1900. ‘The drying mechanism is complicated by various factors such as (a) the nature of the deying oil or resin, (b) the drier or drier combination that is used, and (c) the conditions under which dryingis achieved, Drying oils absorb oxygen from the atmosphere and evolve carbon dioxide and water during drying? ‘The presence of driers causes somewhat less oxygen to be absorbed, although the amount of carbon. dioxide evolved is the same.’ Many studies have been made to substantiate the various theories of oxidation and polymerization. Drying involves a number of steps, the frst of which is period of induction. This interval, during Which no deying occurs, is the result of the presence of natural inhibitors present in most deying oils (When the inhibitors are overcome, the second stage of drying is initiated by the absorption of oxygen.) ‘The presence of dryers rapidly neutralizes the inhibitors and accelerates the absorption of oxygen, Absorption of oxygen at the unsaturated sites of the oil molecule results in the formation of peroxides, Which often decompose to form free radicals. These act as catalysts to promote cross-linking of the oil or resin molecules at the unsaturated sites, resulting in a dried film, ‘The basic equations involved in the drying of paint films in the presence of a catalyst such as cobalt may be outlined as follows: tion RH +0, 5 ROOH ‘This represents the frst reaction, involving the methylene groups adjacent to the double bonds of the drying oil and oxygen to form hydroperoxides. Depending on the nature of the drying ol, resin, or alkyd, there is then a shift in double-bond p to form conjugated molecular structures. There is a subsequent decomposition of hydroperoxides to form free radicals tives ROOH + RO'+ 01H ‘These propagate further reactions: RO+RHR'ROH 80-180.2 Coatings Technology Handbook, Third Edition OH+RH OR +HO Free radicals terminate the process by interaction: RER ORR R+RO9R-O-R RO+RO5R-O-OR ‘The products of these interactions then react with radicals to form products of greater molecular Weight, the net result being the polymerization of the drying oil ‘There have been many detailed studies of the drying mechanism. ‘As many as 24 metals have been demonstrated to have some activity as driets” but only the soaps of cobalt, manganese, lead, iron, vanadium, and cerium are considered as primarily “active,” although. neodymium, aluminum, and lanthanum have also been added to this list. Soaps of zirconium, calcium, zine, potassium, and lithium, are used as auxiliary driers. These metals exert a definite effect on drying. fon film formation when used in conjunction with the primary metals driers, although they are inert when present by themselves Driers may be prepared by various types of chemical reactions. In the early 1900s, so-called “Japan” driers were used. These consisted mainly of cobalt acetate fused with rosin or other high-bodied ois. Similar lead compounds were also used. The amount of cobalt of lead present was generally unknown, or roughly indicated, and the solubility of the metal in the drying oil system was unknown, Production of driers of standard metal content and adequate solubility was achieved through three types of reactions 1. Fusion of metallic oxides with suitable organic acids — for example, lead oxide and 2-ethyl hexoic acid to yield lead 2-ethylhexoate 2. Double decomposition, as represented by the reaction of a solution of cobalt sulfate with sodium naphthenate in the presence of a solvent such as mineral spirit to yield a solvent solution of cobalt naphthenate (The aqueous solution of sodium sulfate that forms is separated from the solvent solution.) 3. Direct metal fusion,* where, for example, cobalt metal is reacted with an organic acid in the presence of air and water yielding cobalt soaps of high purity Many organic acids have been used at one time or another for the preparation of metallic soaps. To produce oil-soluble soaps, which are most suitable for use as driers in oil-based paints, acids such as, oleic acid, tall il fatty acids, 2-ethylexoic acid, iso octanoie acid, iso decanoie acid, nonanoic acid, and. naphthenic acid have been utilized, ‘The solubility of the metal soap depends on the particular metal and acid. For example, metal soaps of naphthenic acid are quite soluble in mineral spirits. The cobalt soap of 2-ethylhexoic acid is also soluble, but the copper soap of 2-ethylhexoic acid is only slightly soluble in mineral spits. The cobalt soap of oleic acid is moderately soluble in mineral spirits, but the zine soap is not. ‘One cannot, therelore, generalize as to the solubility of metal soaps of various acids ‘The most active and the most important “active” drier metal is cobalt, usualy prepared as a mineral spirits solution of a cobalt soap containing 1296 cobalt as metal. ‘Cobalt causes the surface of the film to dry rapidly, and itis used at very low levels — 0.02 to 0.04% based on the oil. Excessive amounts will cause wrinkling or cracking of the film, Cobalt is not a“through”” drier; that is, it will cause the surface to dry but will eave a wet film underneath. When used in polyester resins, cobalt will cause polymerization when used together with an organic peroxide, ‘The phenomenon, “loss of dry” aflects many highly pigmented paints. This is primarily because of the adsorption of the cobalt drier on the pigment surface, thus removing it from solution, Use of ©2009 Tyr Ar Gap.Driers 80.3 coordination compounds such as ortho phenanthroline or, di-pyridyl seems to reduce or eliminate such adsorption and prevent “loss of dey” This may also be accomplished by using highly basic cobalt compounds that slowly release cobalt into solution. By “basi,” we mean that the metal soap contains ‘more moles of metal than the equivalent moles of acid from which itis formed. ‘To accomplish complete drying of oil films, the cobalt drier is used with another that possesses the property of initiating complete dry. Lead soaps are the most effective in this regard, but their use has been limited because of toxicity. Calcium and zirconium are the metals used to replace lead. They are considered auxiliary driers. Calcium soaps at one time consisted of the napthenates, usually at 4% and 6% calcium concentration, ‘These were highly acidic and quite viscous. They have largely been replaced by calcium octoate, a highly basic material, low in viscosity and odor and available in solvent solutions in various concentrations. Zisconium 2-ethylhexanoate is also a basic soap, usually available in 12%, 1896, and 24% Zr concen trations. It seems to have a catalytic effect on cobalt and manganese driers, and is said to have a jon potential of namely 8, and a low redox potential. When electron-donating groups develop, jon polymerization occurs, asistng in the overall drying effec. Barium 2-ethylhexanoate has also been used asa replacement for lead driers, but also has found limited tse because ofits toxicity. Manganese is the other “active” drier that is widely used in oil paints and in baking finishes. Although active as an oxidant, it seems to promote polymerization to a greater extent than cobalt, Solutions of manganese 2-ethylhexanoate rapidly oxidize to a dark brown color on exposure to air. The use of manganese in white paints presents discoloration problems that must be handled by careful formulation, Manganese is often used alone in baking finishes. ‘A number of other metals have been used as auxiliary driers. Neodymium, lanthanum, and aluminum are reported to be useful as “through” driers” Vanadium is also effective but causes severe discoloration, [Bismuth soaps have been used as a replacement for lead soaps in drier systems. Iron is potent drier, similar to manganese in its effects. However iti highly staining and is used in systems where color is of no importance. Cerium may also be considered an oxidative drier, but itis of low activity compared with cobalt or manganese. ‘Waterborne coatings present another problem forthe formulator because the presence of large volumes of water changes the chemistry of coating resins." It was found that adequate drying required a larger percent of cobalt drier rather than various cobalt combinations utilizing the cobalt concentrations adequate for oil-based systems. ‘There is growing use of premixed blends of drier metal soaps according to the individual requirements of the paint manufacturer, Formulation of such combinations requites careful study to achieve stable blends, because the individual metal soaps may be normal, acid, oF basic. ‘Antiskinning agents are antioxidants used to prevent formation of oxidized surface films on the paint \while stored in containers. The type of antioxidant and the concentration in the paint have to be carefully considered. Phenolic compounds are most effective but will prolong the drying time of the film. The coximes can be used over a wider range of concentrations without seriously affecting drying time. The types most widely used are the oximes, such as acetone oxime, methyl ethylketoxime, butyraldoxime, and cyelohexanone oxime. Itis believed that these compounds function by forming weak complexes with, cobalt or manganese, thus inhibiting the oxidizing power of the metal, When the paint is exposed as a thin film, the oxime volatilizs fairly rapidly, leaving the metal in its active state ‘Various phenolic compounds are also used as antioxidants, These function by contributing protons that interrupt the peroxide free radical oxidation chain and do not volatilize from the film. Compounds such as hydroquinone, ortho isopropylphenol, eugenol, and guaiacol are used in paints formulated with highly reactive vehicles such as tung oil, oiticica oil, and dehydrated castor oil References 1. S.Cofley, J. Chem. Soc, 119, 1408-1415 (1921), 2. 1.S.Long, A. E Rheineck, and G. L. Ball, Ind. Eng. Chem, 25, 1086-1091 (1933). ©2009 Tyr Ar Gap.80-4 Coatings Technology Handbook, Thied Edition 3. A.C Elm, Ind. Eng. Chem, 26, 386-388 (1934), 4. P.O. Powers, Ind. Bug. Chem, 41, 304-309 (1949). 5. PS. Hess and G. A. O'Hare, Ind. Fug. Chem, 44, 2424-2428 (1952). 6. RLR. Myers and A.C. Zettlemoyer, Ind. Eng. Chem, 46, 2223-2225 (1954). 7. W.]. Steward, Offic. Dig. Federation Paint & Varnish Prod. Clubs, 26,413 (1954), 8. M. Nowak and A. Fischer, US. Patent 2584041 (January 29, 1952). 9. R.W, Hein, J. Coat, Technol, 71, 898 (1999), 10, R.W. Hein, J. Coat, Technol, 70, 886 (1998) ©2009 Tyr Ar Gap.