9

Paints, Varnishes, and Related Products
K. F. Lin

1. RELATIONSHIP OF FATS AND OILS TO THE PAINT-COATING INDUSTRY Historically, drying oils have been the major film formers of coatings, including paints, varnishes, and inks. Although it is not certain whether linseed oil was used in paints in ancient Egypt, flax was grown and flax seeds were collected at that time. The early Renaissance was probably the real beginning of paints as we know them today in the West. The Van Eyck brothers (1388–1441) are said to be the first to use linseed oil as a binder (1). Whereas in China, tung oil has been used for centuries as waterproofing caulking or as coating for wood objects including boats, houses, and furniture. The first American paint factory was opened in Boston in 1737 by Thomas Childs (2). The pigment and oil were placed on a granite trough, and a granite ball, known as the Boston Stone, was then rolled over the mixture to make the paint. The ball is now preserved and serves as the symbol for the Federation of Societies for Paint Technology. The drying oils owe their value as raw materials for decorative and protective coatings to their ability to polymerize and cross-link, or ‘‘dry,’’ after they have been applied to a surface, to form tough, adherent, impervious, and abrasion-resistant

Bailey’s Industrial Oil and Fat Products, Sixth Edition, Six Volume Set. Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.

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films. Their film-forming properties are closely related to their degree of unsaturation, since it is through the unsaturated centers or double bonds that polymerization and cross-linking take place. With one exception (to be noted later) the oils used in paints varnishes and similar products are relatively high in iodine value. In any given product, there is an optimum degree of reactivity in the oil; the speed with which the oil dries must be balanced against such factors as elasticity and durability in the paint film. In general, however, unsaturation is at a premium in paint and varnish oils, and the oils in greatest demand are those in which drying takes place most readily. The form in which drying oils are used in coating applications has gone through an evolutionary change over time. The simplest and most primitive way is to use them directly as the film former of a coating. It was discovered that drying oils may be made more useful by altering their natural state. By aging in vats, by heating, or by blowing air through, the viscosity and drying characteristics of the drying oil may be changed enough to improve its general properties for coating applications. In the case of fast-drying oils with conjugated double bonds, such as tung, oiticica, and dehydrated castor oil, heat treatment is necessary to ‘‘gas-proof’’ them, so that the oils do not dry into undesirable wrinked and/or frosted films. The oils are not necessarily used in their original form of triglycerides for coating applications. It has become a common practice to hydrolyze them first, and the free fatty acids are then used to synthesize coating resins with certain advantages. Therefore, the term fats and oils includes fatty acids for the purpose of the discussions in this Chapter, unless otherwise specified. Through progress, people found that sometimes mixtures of different oils could be used to greater advantage and that natural gums could be added; thus oleoresinous varnishes were born. Thereafter, human creativity started to make rapid and diversed progress in the development of new coating materials, many of which have departed completely away from the drying oil base. When the drying characteristics of oils were relied on as the sole (or major) cause for a varnish-based coating film to dry, those oils belonging to the linolenic or conjugated acid groups, such as linseed, perilla, tung, oiticica, and highly unsaturated winterized fish oils were of the prime interest to coating formulators. Since about the 1950s, with the advent of synthetic resins, particularly, alkyd resins, it has become possible to make considerable use of oils with poorer drying characteristics. Semidrying oils such as soybean oil, safflower oil, and sunflower seed oil have become viable as raw materials for making ‘‘drying’’ paints. Nondrying oils, such as coconut oil, are also used in coating materials. However, their function is primarily that of a plasticizer rather than of an active component for air drying. In addition, castor oil, a nondrying oil, has been converted chemically by dehydration to give excellent drying property. There is no denying that the once prominent position of fats and oils as the most important raw material for coatings has been greatly eroded by other materials. The total U.S. consumption of drying and semidrying oils in coating and allied applications peaked around 1950 at about 1.2 billion lb. It went down steadily thereafter. According to SRI International (3), the direct use of drying oils accounted for only

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about 4% of the total film formers consumed in the United States in 1990, at about 98 million lb, whereas the consumption of alkyds, urethane alkyds, and epoxy esters was estimated at 645, 40, and 12 million lb, respectively (4–6). Very little drying oil is used in paints at present. Drying oils and oxidizing alkyds have been studied as binders for organic inorganic coatings (4). Urethane coatings are the fastest growing sector. Use in 2003 was 1:6 Â 106 t (5). Epoxy resins are among the most widely used (6).

2. A BRIEF OVERVIEW OF THE COATINGS TECHNOLOGY Modern requirements in protective coatings are extremely diverse and exacting. They go far beyond the mere necessity of protecting the finished surface from weather or from ordinary wear or abrasion. Some coatings (e.g., those employed as electrical insulation) must possess extreme resistance to high temperatures or to penetration by moisture. Others (e.g., marine varnishes and the enamels for coating the interior of cans) must withstand prolonged contact with water or aqueous solutions. Modern assembly-line methods of manufacture produce many particular requirements and have created a special demand for quick-drying finishes. The wide distribution of illustrated journals, the proliferation of advertising matter, and the development of high speed printing processes have greatly elaborated the requirements of users of printing inks. Tung and other conjugated oils are particularly suitable for manufacture of fast-drying finishes, and for a time, the consumption of these oils increased significantly in response to more exacting requirements for specialized finishes. New systems based on epoxy resins, urethane polymers, silicones, and other synthetic intermediates have greatly decreased dependency on tung oil, and use has shrunk significantly. The complex and diversified requirements of modern industry have to a large extent removed the manufacture of paints and varnishes from the category of an art to that of a science. In most plants, the manufacturing processes are now carried out under careful laboratory control and are freely modified or revised, whenever revision is indicated, in accordance with known scientific principles. As a result, the industry has been able to offer a succession of constantly improved products through periods of fluctuation in the availability of many important raw materials, pressures for solvent replacement to meet emerging air quality standards, and extensive pigment reformulation to replace mercury and lead to conform to new federal regulations on toxicity. A most important development in the modern paint and varnish industry has been the introduction of synthetic resins as replacements for natural resins in the manufacture of varnishes and enamels. By using synthetic resins it has been possible to produce a variety of coatings that, in many cases, have important points of superiority over any of those compounded from natural resins. The synthetic vehicles are particularly distinguished by their hardness and durability and their high degree of resistance to the action of water, alkalies, and other chemical agents.

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New methods for application of paint films and new procedures for curing have placed challenging demands on the resourcefulness of the resin chemist. For years brushing was virtually the only method of application; later, spraying, was used. Now a host of new application and curing techniques are commonplace. These include roller coating, dipping, coil coating, powder coating, electrodeposition, hot spray, fluid bed coating, electrostatic spray, two-component spray, ultraviolet cure, and electron beam cure. The two foremost reasons for the decline of the direct use of oils, including oleoresinous varnishes, for coating applications are performance and environment. Drying oils by themselves, or even in the form of oleoresinous varnishes, do not give the drying speed and, sometimes, film properties that would satisfy the modern needs. The ease in the application and cleaning of latex paints caused oil-based paint to lose most, if not all, of the trade-sales market. The implementation of Rule 66 in California was the opening salvo for protecting the environment against solvent-based coatings of which practically all oil-based coatings belong. Thus the emphasis has switched to the development and commercialization of other coating materials or systems that are more environment friendly than oil-based materials. Indeed, it is quite remarkable that in the face of such severe odds, oil-based materials have been able to hold ground as well as they have. There is an extraordinary body of terms used to define various features of protective coatings. Before discussing paints and varnishes and the particular function of fats and oils in coatings, it is desirable to review and define some of the language of the industry. Protective coatings protect (or decorate) surfaces. Greases, mineral oils, plastic web coats, and mastic compositions may be used for protection, particularly of metal surfaces; but in the usual sense, protective coatings are materials that form durable films adhered to the surface to provide protection. A varnish is a solvent-thinned combination of a drying oil and a hard resin. Also, a varnish is the clear film obtained using a varnish as a coating vehicle. By extension, vehicles used for clear films are called varnishes although the vehicle may be a true varnish, an alkyd resin solution, a urethane-modified oil, or even a lacquer. A paint is a pigmented system applied to hide and protect a surface. Paints contain a wide range of ingredients as follows: The vehicle is the carrier for pigment, consisting of combinations of oils, resins, polymers, and solvents; the nonvolatile portion is commonly called the binder. Prime pigments are used for their ability to hide or cover the surface. The term hiding power is used to describe the relative ability of fixed amounts of different pigments to cover a surface and depends on the difference in refractive indices between the pigment and the binder; thus primary pigments usually have high values in refractive index. Extender pigments give relatively little hiding, but their cost is lower than that of prime pigments; they provide control of such properties as flow consistency, durability, and adhesion.

a paste prepared from all of the pigment and a portion of the vehicle is subjected to the appropriate grinding technique until the desired fineness of grind is attained. Antisag agents minimize sagging or ‘‘curtaining’’ of wet films during application. and increases when allowed to stand). Actually the term grinding is somewhat inaccurate. Solvents or thinners control paint consistency and application properties. as in barn paints or house paints. it is rarely used now. as under the shear of brushing. that accelerate the conversion of the liquid film to a solid. in ball mills or pebble mills. manganese. Puffing agents. in which steel balls or pebbles rotating and rubbing against each other in a closed cylinder to produce the shear for dispersing the pigment. or in sand mills. Griding is usually carried out in roller mills. Paints are made by grinding pigments in the vehicle. Antisetting agents minimize separation of pigment into a firm or hard mass in the bottom of the can. For products in which a fine grind (fine pigment dispersion) is not required. zirconium. The grinding operation is designed to break up the aggregates of pigment particles and to disperse them in the vehicle so that each particle is wetted. Antiskin agents minimize skin formation on the top of the can during use or storage. which is a shallow wedge cut from polished metal. in which agitation of sand causes pigment separation and dispersion.A BRIEF OVERVIEW OF THE COATINGS TECHNOLOGY 311 Driers are metal salts. or thixotropic agents. and the resultant paste is ‘‘let down’’ (diluted) with the remaining portion of vehicle and solvent. increase the paint consistency and minimize sagging by giving a thixotropic consistency to paint (a type of behavior in which the viscosity of the system decreases when agitated. and iron. lead was commonly used as a primary drier. high speed rotors may be used to grind the paint. Fineness of grind is commonly expressed numerically using a grind gauge. especially of cobalt. The pigments are received from the manufacturer are already as fine in particle size as they will be in the finished paint. which evaporate rapidly. deficiencies characterized by separation of colored pigments during drying. Slow solvents evaporate slowly and leave the film ‘‘open’’ (workable) for longer periods than fast solvents. in water-thinned paints. in which shear between steel rollers disperses pigments. Mildewcides protect the applied film from fungus growth. but due to its toxicity. water is the thinner and there is no control over rate of evaporation. In typical paint manufacture. A variety of other materials may be added for special effects. calcium. Paint is filled into the wedge . Antiflood and antifloat agents minimize flooding and floating. Wetting agents or griding aids promote wetting of pigment particles by the vehicle.

thus resulting in low gloss. there will be more pigment particles or aggregates at or near the film surface to cause a scattering of light.312 PAINTS. AND RELATED PRODUCTS and a bar is drawn across the surface. which gives the gloss measurement. the paint fills the wedge even to the shallowest part. depends on the smoothness of the surface. which measures light reflectance at a low angle from the horizontal (20 gloss) or high angle (60 gloss). Paints and enamels are classified by type of finish as follows: Flat paints or enamels dry to a velvety nonglossy or matte surface. The amount of pigment in the paint is measured by the pigment volume concentration (PVC). the general consensus is as follows: Type of Paint Flat Eggshell Semigloss Low gloss High or full gloss 60 Reflectance 4 or 5 maximum 5–20 20–60 (up to 80) 80 to 90þ 90 to 98þ Since the ability of a surface to reflect light.e.. the volume percent of pigments in the dried paint film. with a high pigment content. the paint is pulled away from the shallow edge of the wedge of the deeper end. and although ranges of values are not sharply divided. The degree of gloss is measured by a glossmeter. products of low PVC (up to 20–25%) are glossy. The line of demarcation ranging from 0 (very coarse grind) to 8 (ultrafine grind) designated the quality of the pigment dispersion. With coarse grinds. VARNISHES. There are many variations in the nomenclature. With fine grinds. thus high in gloss. one can readily visualize that a coating with a greater surplus of binder over its pigment content will have a greater ability to produce a smooth surface. and films that are called gloss films by one observer might be classified as a semigloss by the individual who demands mirrorlike surfaces. Gloss paints or enamels dry to a highly reflecting surface. products in the middle range . Other designations might be used also such as eggshell (between flat and semigloss) or full gloss to differentiate mirror gloss from normal gloss. Semigloss paints or enamels dry to an intermediate gloss range between flat and glossy. i. The 60 reflectance is most common. An enamel is a paint based on a vehicle that dries to a considerably harder film than paints derived from unmodified drying oils. In solvent-based systems. Conversely.

viscosity. Implement. usually by brush or roller. Industrial finishes are applied to objects by the manufacturer. including color and color retention of films. or other high speed production application methods. thermoplasticity.’’ a film defect in which variation in penetration causes gloss differences and visual color differences in the final coat. Protection against corrosion is an especially important characteristic of metal primers. water resistance. durability. etc. automotive. stain resistance. and similar user-applied finishes. gloss. mar resistance. rate of cure of films. dipping. architectural enamels. Hiding is a secondary function. appliance. especially as an enamel undercoat. . gloss retention. and they are usually force dried by baking. air knife. wetting action in grinding with pigments. solvent resistance. and products in the high range (45–70) have a flat or matte surface. A primer is used to coat the original surface. no single product can be optimum in all of these characteristics. depending on the point of application. particularly in emulsion systems. usually by spraying. Sanding sealers are most important in furniture finishes and industrial finishes such as automotive systems. abrasion resistance. wall paints. varnishes. Included are barn paints. Coating systems are divided into two general classifications. The specification of products for coating applications involves a large number of factors. Gloss in water-thinned systems does not correspond to the above. Obviously. porch and deck enamels. performance in the varnish kettle. reactivity with driers.A BRIEF OVERVIEW OF THE COATINGS TECHNOLOGY 313 (25–50%) have a semigloss finish. A sealer is a primer whose major function is covering a porous surface such as plaster. Solvent-thinned paints containing certain ‘‘flatting agents’’ such as extremely fine silica do not conform to the normal pattern. compatibility with other film-forming agents. and in each use a compromise must be made to provide the best performance in the intended usage. An undercoat is another name for primer or sealer. viscosity stability in the package as clear products or in pigmented systems. A typical ghosting effect is obtained in painting wallpaper in which the pattern can show through multiple coats because of the variability in porosity of the substrate. hardness of films. Good sealing prevents ‘‘ghosting. Finishes are also described by the function of the paint. rate of setup. gypsum board. Trade sales finishes are purchased by the user in a paint store or hardware store (or today even in a drugstore or a supermarket) and are applied by the purchaser. which serves to supply a uniform base for an enamel so that there will not be a wide variation in gloss. Its major functional property is good adhesion. A sanding sealer is designed for easy sanding after short dry so that smoother top coats can be attained. The top coat or finish coat is the outside layer of paint applied over the primer or sealer. reactivity with pigments. Undercoats may be applied over sealers. alkali resistance. flexibility and retention of flexibility on aging. trim paints. and furniture finishes are typical industrials. roller coating. house paints. adhesion. because the pigment particles are not wetted uniformly by the binder. bakability. or paperboard with a surface coating that exhibits a minimum penetration into the surface.

according to the authors. more or less. it does not provide a ‘‘rule’’ for classifying oils with conjugated unsaturation.2 is a drying oil. Polymerization and scission reactions begin and yield high molecular weight cross-linked products and low molecular weight carbonyl and hydroxy compounds. discrete interaction of oxygen and olefins takes place followed by the formation of hydroperoxides. oils are conventionally classified. An oil with an fn value of greater than 2. which has been summarized as follows (8): 1. the iodine values determined are usually low due to incomplete halogen absorption. and <125. A period of induction at the beginning of the reaction during which no visible change in physical or chemical properties in the oil is noticed. Such a classification can only be used for a rough guidance. FILM DRYING PROCESS OF OIL-BASED COATING MATERIALS 3. . the CH2 groups allylic to two CÀ C groups.314 PAINTS. based on their iodine values into three groups: drying. AND RELATED PRODUCTS 3. Wicks and Jones (7) suggested that the methylene groups between two double À bonds. These numbers are. >140. the reaction becomes autocatalytic. VARNISHES. 5. Thus the average number of such groups fn in an oil molecule serves as a better indicator for the drying characteristics of the oil.2 are semidrying..e. 2. The reaction becomes perceptible and oxygen uptake is considerable. and there is no sharp dividing composition between semidrying and nondrying oils. carbon dioxide and water are also formed and are present in the volatile products of film formation. The hydroperoxides start to decompose to form a high free-radical concentration. The rate depends on the reaction conditions such as temperature. are much more reactive than À those being allylic to only one CÀ C group and are mostly responsible for the drying of the nonconjugated oil. natural antioxidant compounds are consumed during this period. The generally accepted demarcations are. takes place.1. 140–125. light. it is through the unsaturated centers or double bonds of the fatty acids in drying oils that polymerization and cross-linking. i. and traces of heavy metals or inhibitors in the oil or coating (9). While such a classification system does have merits over the conventional way (based on iodine value). semidrying. Drying of a Nonconjugated System As mentioned earlier. 4.. Hence. arbitrarily assigned. i. 3. It is now generally believed that the induction is slow at first but is autocatalytic and the rate increases steadily. respectively. When the oil contains conjugated double bonds. drying. and nondrying. The chemical mechanism of drying has been established as an oxidative radical chain reaction process. those with fn values somewhat less than 2.e. Conjugation of double bonds occurs accompanied by isomerization of cis to trans unsaturation.

two of which are conjugated CH CH CH OOH CH CH CH CH CH CH OOH The initial step is believed to be the dehydrogenation from the a-methylene group to form a radical.FILM DRYING PROCESS OF OIL-BASED COATING MATERIALS 315 The active sites are the allylic carbon a to a double bond.12-octadecadienoic (linoleic) acid and proceeds through the following mechanism: CH CH CH2 CH CH −H Abstraction of a hydrogen atom CH CH CH CH CH CH CH CH CH O2 CH CH CH CH CH CH Resonance hybrid free radicals CH CH CH OO CH CH CH CH CH CH OO H CH CH Three possible peroxy radicals CH CH OO CH CH Addition of hydrogen atom abstracted from another linoleate molecule CH CH CH CH OOH CH CH Three possible hydroperoxides. resonance hybrid free radicals are formed resulting in shifting the double bonds to a conjugated position. Thus a radical. abstracts a hydrogen from a molecule of linoleate. A Á. RH. to form the radical R Á. RH þ AÁ ! R Á þAH Since the radical is allylic to the double bonds on either side of it. Since such a hydrogen extraction would require a considerable amount of energy. This is then followed by: R Á þ O2 ! RO2 Á . especially those a to two double bonds with one on each side. a number of investigators proposed that the hydrogen is removed through reaction with a free radical. such as carbon number 11 in a 9.

12). Originally. using cobalt as an . although some (16) proposed a limited attack at the double bond to produce radicals in sufficient amount to initiate the chain reaction through the a-methylenic carbon. trans and trans.cis unsaturation of linoleate is converted to cis. initiation of the reaction by light can produce quantum yields much greater than unity and easily oxidized substances that consume free radicals. Infrared spectra of the 99% purity p-phenylphenacyl linoleate hydroperoxide correspond to a trans. it was proposed that hydroperoxides are the initial products of autoxidation (14. Ethyl or methyl linoleate hydroperoxides are relatively low melting and as a result purification by crystallization is difficult.316 PAINTS. The autoxidation of linoleate described above shows the characteristic features of a chain reaction involving free radicals. Primarily because of the high energy requirement for rupture of the a-methylenic carbon–hydrogen bond several authors (16–19) almost simultaneously concluded that the initial point of oxidative attack was the double bond and not the a-methylene group. but do not themselves undergo significant autoxidation. which breaks down to yield the hydroperoxide. Bailey and Barlow (13) prepared high melting p-phenylphenacyl linoleate. AND RELATED PRODUCTS and RO2 Á þ RH ! ROOH þ RÁ The net reaction is hydroperoxide formation: RH þ O2 ! ROOH During the oxidation to form hydroperoxides. there is much less unanimity of opinion on the primary reaction to produce the radicals (indicated as A Á above) responsible for the initiation of the chain reaction. The theory of oxidation has received little support. 22). trans isomers. oxidized the ester in benzene solution. Privett and co-workers (10) concluded that at least 90% of linoleate hydroperoxide preparations are conjugated. and it has been considered that trace metal contaminants catalyze the initiation of autoxidation by producing free radicals through electron transfer. Alternative pathways are as follows. can markedly inhibit the chain reaction. the natural cis. trans isomers. and isolated virtually pure hydroperoxide by crystallization. It has been contended that the direct attack of oxygen on the double bond has low thermodynamic probability (21. trans unsaturation (11. VARNISHES. Kahn (20) questioned the formation of a diradical and proposed direct addition of oxygen to a double bond to form a cyclic transition state. Materials that decompose to form free radicals catalyze the reaction even when present in very low concentrations to produce high yields of hydroperoxides. because it does not explain the inhibitory effect of free-radical acceptors in the initial stages of autoxidation. Although there is quite general agreement on the mechanism of the chain propagation reaction. but room temperature oxidation produces a large amount of trans. trans conjugated isomer. 15). When the oxidation is conducted at 0 C the hydroperoxides are predominately cis.

Co3þ þ RH ! Co2þ þ Hþ þ RÁ According to Uri (21) the kinetic and thermodynamic probabilities for formation of free radicals by the metal-catalyzed initiation reaction are considerably more favorable than the Bolland and Gee (16) proposal of diradicals by direct oxidation of a double bond. they can play a profound role in the autocatalysis. Co2þ þ OÀ ! Co3þ Á O2 2 Co3þ Á O2 þ XH ! Co3þ þ XÀ þ HO2 Á 4. Monomolecular decomposition yields two free radicals: ROOH RO + HO A bimolecular reaction. such as coupling or disproportionation. 3. Reduction activation of trace hydroperoxides in the system yields free radicals. 2 which can initiate the chain reaction of oxidation. is more probable: ROO + HOOR H [ROO H HOOR] HOH + RO + RO 2 Either the monomolecular or the dimolecular decomposition serves to feed new radicals into the reaction to initiate the chain reaction of autoxidation. perhaps proceeding through intermediate hydrogen bonding. Once hydroperoxides are formed. . Direct reaction of a metal ion with oxygen: Co2þ þ O2 ! Co3þ þ OÀ Á 2 The OÀ Á radical ion reacts readily with a proton to form the HO2 Á radical. They may follow a radical chain mechanism or other well-known radical reactions. Complex reaction of metal compounds with oxygen and subsequent formation of an HO2 Á radical. These radicals may further react through different paths. Co2þ þ ROOH ! Co3þ þ OHÀ þ ROÁ 2. even in trace amounts.FILM DRYING PROCESS OF OIL-BASED COATING MATERIALS 317 example of a metal that can facilely shift valence states in oxidation–reduction reactions: 1. Oxidation by electron transfer of the a-methylenic group by the metal ion.

6-peroxide in addition and suggested that the autoxidation does not proceed via hydroperoxide groups but rather via cyclic peroxides. whereas CÀ bonds are predominantly ÀOÀ ÀC formed under baking conditions. coating systems were advanced from oil-only vehicles to oleoresinous varnishes for improved performances. Faulkner (26) identified 1. 3. These are basically oils that have been . drying). infusible film (i. mostly CÀ ÀC bonds are produced. and less energy is required to eliminate the proton as illustrated below (24).11.4-addition to the diene system to yield noncyclic peroxides. forming polymers via CÀ or CÀ ÀC bonds (29). ÀC ÀOÀ 4. such as water. dries to a coherent film with absorption of only 5% by weight of oxygen. Apparently. aldehydes.e. Drying of a Conjugated System Tung oil. VARNISHES. whose dominant feature is the conjugated cis. The peroxides then react with allylic methylene groups or thermally dissociate to give radicals. trans. trans-9. ketones.318 PAINTS. Chemically. a-eleostearic acid.2. the dominant reaction path depends on the temperature. the air-drying of a nonconjugated oil such as linseed is characterized by the adsorption of 12–16% by weight of oxygen. The main reaction is believed to consist of a direct À attack by oxygen on the CÀ C double bonds to form cyclic peroxides and dienes. resulting in an insoluble. Low molecular weight by-products. initiating a radical chain reaction mechanism.or 1. 28). OLEORESINOUS VARNISHES As noted. which cause the odor and taste of the oils. Privett (25) suggested oxidation through 1. It has also been found that the triene content decreased and the diene content increased in proportion to the absorption of oxygen (27. and alcohols may be formed. AND RELATED PRODUCTS The reactions may lead to the formation of dimers or polymers or may achieve cross-linking.13-octadecatrienoic acid. The free radicals may also undergo chain cleavage reactions. Activation Energy (kJ/mol) 415 335 289 168 Relative Rate of Oxidation 0 1 120 330 Triglycerides Stearate Oleate Linoleate Linolenate a Mesomers a 2 5 11 Saturated molecules. The reactivity of drying oils is based on the mesomeric stabilization of the radical intermediate: the unpaired electron is delocalized over several carbon atoms.. The strong odor of rancid soybean oil was shown to be caused by 2-pentylfuran found in oxidized oil in storage (23). At room temperature. carbon dioxide.2.

medium. which is defined as the number of gallons of oil used per 100 lb of the resins in the varnish. Varnishes are categorized according to their oil length as short. greater film hardness. Thus thermoplastic polyesters typified by polyethylene terephthalate (PET) used in synthetic fibers. The oils and resins are combined.(5–15 gal). natural or synthetic. polyesters. until a homogeneous mixture is formed. While one might say that this was only an evolutionary change. In some cases. usually long-chain fatty acids. The degree of property change depends on the type and the amount of the resin incorporated in the oil. It behooves us to take a more comprehensive look at the various aspects of alkyd resins. such as that between the methylol groups of a ‘‘heat-reactive’’ phenolic resin and the double bonds of a drying oil in forming a chroman ring structure as shown below (30): R′ OH HOH2C CH2OH + R R′ CH CH R′′ R Chroman ring structure O HOH2C CH CH C H R′′ The major improvements obtained by incorporating resins into drying oils are faster drying. it is simply a case of dissolving the resin or resins in the oil. and greater durability. In most cases. ALKYD RESINS Alkyd resins have been the workhorse for the coatings industry over the last half century. chemical reaction may have taken place between the resin and the oil.ALKYD RESINS 319 ‘‘hardened’’ or modified by treatment with one or more suitable resins. and long-oil (30 þ gal) varnishes. .(16–30 gal). it nevertheless did open a new horizon for coating technologists and has been responsible for the longevity of oil-based coating materials. The term alkyd was coined to define the reaction product of polyhydric alcohols and polybasic acids. Varnish makers express the oil to resin ratio in terms of oil length. These demarcations are somewhat arbitrary and not universally agreed. usually by heating together at temperatures of 250 C or above. and plastics and unsaturated polyesters typified by the condensation product of glycols and unsaturated dibasic acids (which are widely used in conjunction with vinylic monomers in making sheet molding compounds or other thermosetting molded plastics) are not considered as part of the alkyd family and are beyond the scope of the present discussion. higher gloss. its definition has been narrowed to include only those polyesters containing monobasic acids. From oleoresinous varnishes. in other words. better water and chemical resistance. films. However. the coatings industry progressed into alkyd resins. 5.

a polyol molecule or radical. there is usually some amount of residual acidity along with free hydroxyl groups left in the resin molecules.’’ The proliferation of literature on alkyd resins peaked in the 1940s through the 1960s. but still appeared as ‘‘see resinous products. Schematic representation of an alkyd resin molecule. In spite of the challenges from many new coating resins developed over the decades. alkyds are extremely versatile. Basic Reactions and Resin Structure The main reactions involved in alkyd resin synthesis are polycondensation by esterification and ester interchange. have maintained a prominent position even until today. For almost any given coating application.’’ It was not until 1936 that alkyd resins was listed in its alphabetical place. alkyd resins. Classification of Alkyd Resins Alkyd resins are usually referred to by a shorthand description based on a certain way of classification or a combined classification. Most of the raw materials are fairly low cost commodity items. First.320 PAINTS. . 5. Research activities on alkyds in the United States. AND RELATED PRODUCTS The first appearance of the term alkyd resin in the subject index of Chemical Abstracts was in 1929. as indicated by the number of publications. from which the general properties Figure 1. as their availability or cost may sometimes so dictate. An alkyd technologist can choose from a large variety of reaction ingredients and at widely different ratios to tailor the structure and properties of the resin or to obtain similar resin properties from different ingredients. O XÀ ÀX. If one uses the following symbols to represent the basic components of an alkyd resin: O R O .1. As Figure 1 implies. The structure-property relationship and the principles commonly followed to design the resin structure will be discussed below. VARNISHES. Readers who are alkyd history buffs can find more detailed historical reviews (31–34). cule or radical. There are two major reasons for such sustained popularity. from baking enamels for appliances to flat house paints to clear wood finishes.2. has apparently tapered off in the last two decades. as a family. one can design an alkyd resin to meet the property requirements. under ‘‘resins. and XÀ a mono-basic acid moleÀAÀ ÀF. a schematic representation of the resin molecule can be given (Figure 1). and major capital investment and high processing cost are not needed to produce the resins. 5. The second reason is that alkyd resins can be made at relatively low cost. a polybasic acid molecule or radical.

Such descriptions as an isophthalic. the resin represented in Figure 1. the polybasic acid is phthalic anhydride. Drying versus Nondrying. or are cross-linked through their hydroxyl functional groups to become part of the film former. More frequently. as the weight percent of fatty acids in the finished resin. The formula weight of the resin would be 1674 and the triglyceride equivalent of the fatty acids would be 878. and a coconut alkyd. the above resin would be described as one having 50.g. the resin would belong to the drying type and is usually used as the film former of coatings or inks. the boundaries are usually not clear-cut.ALKYD RESINS 321 of the resin become immediately apparent. such as coconut oil. and any unusual ingredients. e. such as in nitrocellulose lacquers. More frequently. not polyethylene) alkyd or a short oil lauric-benzoic alkyd would immediately project the general properties of the resin. alkyd resins are described by a combined classification in terms of their oil length. the resin would be a nondrying alkyd. Alkyd resins can be broadly classified into the drying type and the nondrying type. Probably inherited from oleoresinous varnish practice but with a different way of expression. The structure indicates that the molar ratio of these three ingredients is 4 : 4 : 3. Assume that the polyol is glycerol. On the other hand. depending on the ability of their film to dry by air oxidation. such as linseed oil. The commonly used bases for classification are as follows. the oil length is defined as the weight percent of oil or triglyceride equivalent. Alternatively. and the Specific Source of Fatty Acids. very long tall oil alkyd or a medium oil dehydrated castor-PE (the PE refers to pentaerythritol. They are used either as plasticizers for other film-formers.4%.. a linseed alkyd. if the fatty acids come from nondrying oils. Furthermore. thus the oil length would be 52. or alternatively. the type of fatty acids. Since the overwhelming majority of alkyd resins are based on phthalic anhydride. and the fatty acids came from soybean oil with an average molecular weight of 280. a tung oil-modified soy alkyd. for example. By this approach. are the sources of the fatty acids for the alkyd. it is also customary to describe an alkyd in terms of its phthalic anhydride content in percents based on the finished resin. Classified by Oil Length or Fatty Acid Content. alkyd resins are classified into four classes: Percent Fatty Acids >68 53–68 43–52 <42 Percent Phthalic Anhydride <20 20–30 30–35 >35 Resin Class Very long oil Long oil Medium oil Short oil Percent Oil >70 56–70 46–55 <45 It should be noted that these demarcations are arbitrary and may vary from author to author.2% fatty acids. . an alkyd resin is classified by the source of the fatty acids. This drying ability is derived from the polyunsaturated fatty acids in the resin composition. For an alkyd resin. alkyd resins are also classified by their oil length. If drying oils.

Alkyd resin molecules have a comblike structure. one could design and make alkyd resins at almost any oil length. set-to-touch. as the oil length decreases and the phthalic content increases. characteristics of the resin. their through-dry in air is usually slower. VARNISHES. Theoretically. Effect on Solubility. therefore. for any given set of starting ingredients. short oil alkyds develop a surface dryness relatively quickly due to a faster solvent release. considering how the structure of resin molecules would change with oil length. A few of these effects are discussed below. whereas the side chain fraction dries in a manner similar to the oil from which the fatty acids came. the oil length of an alkyd resin has profound effects on the properties of the resin. the aliphatic hydrocarbon chains of the fatty acids constitute the major portion of the mass of the resin molecules. similar to a lacquer material. However. AND RELATED PRODUCTS 5. as the oil length goes up. Each of these two fractions contributes to the drying. Through-dry Film hardness Gloss Gloss retention Color retention Exterior durability a Long Medium Short ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ! ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ! ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ! ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ À À À À ÀÀ ÀÀ ÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀ ÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀ À À À ÀÀ ÀÀ À ÀÀÀÀÀ À ÀÀÀÀ ! À ÀÀÀÀÀ À ÀÀÀ À À À À ÀÀ À À ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ! ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ! ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ! ÀÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ÀÀÀÀÀÀÀÀÀÀÀÀÀÀ ! À ÀÀÀÀÀ À ÀÀÀÀ ! À ÀÀÀÀÀ À ÀÀÀ À À À À ÀÀ À À Primarily referring to drying-type alkyds. long oil alkyds are relatively slow in reaching the ‘‘set-to-touch’’ stage of surface drying. Oil Length Requirement of aromatic. . it will reach a point TABLE 1 Trends of Property Changes with Oil Length of Alkyd Resinsa. and the aromaticity and/or the polarity of the solvent will also need to be increased to dissolve the resin effectively. Therefore. Other trends of changing properties (Table 1) would become obvious. polar solvents Compatibility with other film formers Viscosity Ease of brushing Air dry time.3. On the other hand. Oil Length–Resin Property Relationship Obviously. However.322 PAINTS. but the greater abundance of fatty acid side chains and the relative openness of the film surface would facilitate the film to reach through-dry. the aromaticity of the resin molecules increases. because the fatty acid side chains are fewer in numbers and more scattered in space to cross-link with each other through the action of oxygen. Effect on Drying Characteristics. with a thermoplastic polyester backbone and dangling fatty acid side chains. which is often further facilitated by the fact that the solvents used have high volatility. and the dry surface would impede the transportation of air oxygen to reach down into the film. or film-forming. Conversely. At long oil lengths. the resin would be soluble in nonpolar aliphatic solvents. The backbone fraction dries by solvent release.

The selection of each one of these ingredients will affect the properties of the resin. the resin would have an oil length of 60. Therefore. the choice of ingredients may even affect the choice of manufacturing processes.ALKYD RESINS 323 where the maximum extent of fatty acid modification of the polyester molecules has been achieved. for every 1 mole of phthalic anhydride and pentaerythritol. On the other hand. 5. If the C18 soy fatty acids in the above example is replaced with C12 lauric acid.5%. the ‘‘very long oil’’ types of alkyd resins would almost certainly be resin–oil blends. Thus theoretically. the selection of the proper ingredients is a major decision. Obviously. and any additional amounts of fatty acids or oil remain as separate entities. Major Ingredients Each of the three principal components of alkyd resins—the polybasic acids.9% of fatty acids. Molecular Weight 148 166 98 116 146 160 174 371 192 Equivalent Weight 74 83 49 58 73 80 87 185. replaces glycerol. Polybasic Acids and Anhydrides.6% oil.9%. such as pentaerythritol. if a tetra-hydroxyl polyol. the excess amount of oil would only be retained in the resin as a blend. because of its low cost and the excellent overall properties it imparts to the . the polyols.5 64 Type Phthalic anhydride Isophthalic acid Maleic anhydride Fumaric acid Adipic acid Azelaic acid Sebacic acid Chlorendic anhydride Trimellitic anhydride Phthalic anhydride is by far the most important dibasic acid used in alkyd preparation.5%. with those three ingredients. the maximum amount of soy fatty acids that may be chemically combined in the resin structure would be 70. phthalic anhydride. equivalent to a 74. and soy acids and the reaction was carried to completion. if the oil length exceeds 60.1% oil length. Refer again to the resin structure in Figure 1. blended with the polyester molecules. the transition would be reached at 52. There is no more room in the resin structure to accommodate any additional amount of fatty acid. As will be shown later. If the molar ratio is 1 : 1 : 1 among glycerol.4. and the monobasic acids—has a large variety to be chosen from. or 57. The maximum oil length of an alkyd resin (before it becomes a resin–oil blend) depends on the molecular weight of the ingredients as well as the functionality of the polyol. the stoichiometry would allow 2 moles of fatty acids. To both the resin manufacturers and the users. The major types of polybasic acids used in alkyd preparation are as follows.

the resin cooking process needs to be monitored and controlled with greater care. or other vinyl monomers. and the average molecular weight would tend to be low. care must be taken to prevent its loss. thereby avoiding the danger of excessive foaming in the reactor. AND RELATED PRODUCTS resin. Therefore. up to 10% on molar base of the total dibasic acids. However.2 g-cal/g. However. and are often. Since the two carboxyl groups are adequately separated. adhesion. additional care and equipment are needed for the higher processing temperature required for isophthalic acid. Consequently. However. Isophthalic acid is the meta isomer of phthalic acid. may be used in an equivalent manner. in the resin formulation would accelerate the viscosity increase during the resin manufacturing process. heat of vaporization: 87. which allows the resin to be grafted with styrene. Its melting point (350 C) is much higher than that of phthalic anhydride (131 C). it has all the disadvantages of isophthalic acid and is more expensive. The resins usually dry more rapidly and give harder films with improved color. VARNISHES. The diacid does not readily form half-esters at relatively low reaction temperature as would the anhydride. since the two carboxyl groups of phthalic anhydride are in the ortho position to each other on the benzene ring. The adducts are tribasic acids. particularly when it is near the desired end point. isophthalic acid has not gained the same popularity as phthalic anhydride in alkyds. the development of chain length of the polymer would be restricted. acrylic esters. cyclic structure may and does occur in the resin molecules. Maleic anhydride is sometimes used for partial substitution of phthalic anhydride in making alkyds. which causes the reactants to stay as a two-phase solid–liquid system and does not become clear until the reaction is near complete (36. the trans isomer of maleic acid. the chances of forming a cyclic structure in the resin molecules are greatly diminished. Fumaric acid. Maleic and fumaric acid can also be. . Another major advantage of isophthalic acid is that the resultant alkyd resins show much higher thermal stability than the phthalic type (35). This is the major motivation for resin manufacturers to use isophthalic acid for the preparation of long oil alkyds. They provide one of the means to impart pendant carboxyl groups in the resin molecules. The para isomer terephthalic acid may also be used for making alkyds.) Therefore. Usually. It imparts vinylic unsaturation functionalities in the backbone chain of the resin molecules. Phthalic anhydride has a tendency to sublime. and exterior durability. (Heat of sublimation: 143 g-cal/g. because the resin making process is much more complicated and difficult than that with phthalic anhydride. water resistance. The presence of a small amount of maleic anhydride. 37). isophthalic alkyds usually attain higher molecular weight and show much higher viscosity than their phthalic counterparts at the same oil length. and it has a low solubility in the initial alkyd reactants. In spite of these advantages. It is rarely used in making alkyd resins. and twice as much water will be formed and needs to be removed from esterification. Its anhydride structure allows a fast esterification to form half-esters at relatively low reaction temperatures without liberating water. alkali resistance. to prevent gelation.324 PAINTS. The resultant resins showed even better thermal stability than isophthalic alkyds (35). incorporated in alkyd resins in the form of the Diels-Alder adduct of rosin.

such as succinic. is the basis for its many interesting attributes. azelaic. in turn. Molecular Weight 136 92 134 120 62 104 Equivalent Weight 34 31a 44. gloss retention. Premature cross-linking of alkyd resins formulated with a high content of TMA would occur at high acid numbers when large amounts of trimellitic acid are present (40). Pentaerythritol (PE) is one of the most important polyols used in alkyd resins.7 40 31 52 Type Pentaerythritol Glycerol Trimethylolpropane Trimethylolethane Ethylene glycol Neopentyl glycol a Since glycerol is usually supplied at 99% purity (1% moisture). Chlorendic anhydride is the Diels-Alder adduct of maleic anhydride and hexachlorocyclopentadiene. It has been reported to give a greater reaction rate than phthalic anhydride. Alkyds containing maleic–rosin adducts often have poorer color retention. would also impart flame retardancy to its alkyds. The major types of polyol used in alkyd synthesis are as follows. It is also known as hexachloro-endo-tetrahydrophthalic (HET) anhydride. its equivalent weight is commonly assumed to be 31 in recipe calculations. Their linear and flexible chain structure lends higher flexibility and lower viscosity to the resin than the rigid aromatic rings of phthalic acids.2. A partial substitution of the phthalic anhydride with TMA gives a measured quantity of pendent carboxyl groups for water solubilization with ammonia or other suitable base. Aliphatic dibasic acids. and sebacic acids have also been used to make alkyd resins. water-soluble characteristics to the resin. it is appreciably less soluble in the usual processing solvents than is phthalic anhydride and is reported to be of appreciably lower chemical reactivity (39). Its molecular structure. However. the resins are prone to develop darker color. such that at 204– 210 C (400–410 F) the reaction rate approximates that of phthalic anhydride at a temperature of 238 C (460 F) (38).4-benzenetricarboxylic acid anhydride. has gained greater prominence in recent years due to the greater interest in watersoluble alkyds. The four equal and highly . adipic. The anhydride hydrolyzes to the acid form simply by allowing it to stand in open containers.ALKYD RESINS 325 which can then be saponified to give ionic and. 1. Polyhydric Alcohols. made by conventional chlorination of phthalic anhydride. particularly at high processing temperature. toughness. and exterior durability. Trimellitic anhydride (TMA). The major interest of the alkyd industry in this material is that the resultant resins contribute to the flame retardancy of the coatings. However. four methylol groups (CH2OH) surrounding a center carbon atom. Tetrachlorophthalic anhydride.

AND RELATED PRODUCTS reactive primary hydroxyl groups make it versatile for designing resin structures. thermal stability.and tri-PE that were not completely removed in the manufacturing process. which has lower reactivity than primary hydroxyl groups. The high functionality of these materials makes them impractical to be considered as the sole or major polyol of an alkyd resin. Therefore. color and color retention. propylene glycol. Besides the difference in functionality. the major difference between glycerol and PE is that one of the hydroxyl groups in glycerol is secondary. Among the triols.326 PAINTS. for the above three glycols) require that special precautionary measures be taken during the resin manufacturing process. and moisture. light. Trimethylolethane has been reported to give alkyds that are faster drying and higher in film hardness than trimethylolpropane (41). flexible chains between hydroxyl groups (such as 1. resulting in darkening of the resin. respectively. Glycerol alkyds are more prone to thermally decompose to give color bodies. glycerol will automatically be a part of the polyols of the resin. and the equivalent weights of these polyols are higher than that of PE. Technical grades of PE usually contain small or trace quantities of di. whereas such reaction is not possible with PE.4-butanediol. the proton on the secondary carbon in glycerol may undergo a dehydration reaction with one of the primary hydroxyl groups on the adjacent carbon atom to give water and acrolein.o-dibasic acids (such as adipic and sebacic). they have the neopentyl structure and equivalent primary hydroxyl functional groups. Like PE. and impact resistance than trimethylolethane (42). 188. color and color stability. Their relatively low boiling points. and alkali than glycerol. Trimethylolethane and trimethylolpropane are synthetic triols.6-hexanediol. light. humidity resistance. glycerol is undoubtedly the most important one in alkyd technology. They have one less hydroxyl group than PE. film hardness. Diols such as ethylene glycol. Dipentaerythritol and tripentaerythritol are linear dimer and trimer of PE. Therefore. and neopentyl glycol are sometimes used as part of the polyols in alkyd formulations primarily for the purpose of regulating the functionality of the reaction system. (197. . and 207 C). and the neopentyl core structure lends stability against heat. polyols with long. This often manifests itself as if glycerol had a de facto functionality of less than 3. which would result in poorer resin properties as a coating material. a larger excess of glycerol would be required in the resin formulas. drying properties. gloss retention. respectively. They are hexa. 1.and octafunctional polyols. Analogous to the use of linear a. At high temperatures. alkyds based on PE usually are superior to their counterparts based on glycerol in viscosity. whereas trimethylolpropane was claimed to give alkyds with better water and alkaline resistance. As a result. whenever oils are used directly as the source of fatty acids in an alkyd resin. they also yield alkyds with better resistance to heat. VARNISHES. Consequently. moisture. and diethylene glycol) may also be used to impart greater flexibility in the resin. Natural fats and oils are triglycerides. its high functionality demands that the resin composition be more carefully designed and the synthesizing process be more carefully monitored and controlled to reduce or eliminate the tendency of gelation. and exterior durability. On the other hand.

which is caused by the dimerization of the fatty acid chains through a Diels-Alder addition between the conjugated diene structure on one molecule and a double bond on another molecule. The fatty acid composition of various types of fats and oils that are commonly used in alkyd resins are given in Table 2. Rheineck and co-workers (44) have found that linolenic acid is responsible for the high yellowing tendency of alkyds based on linseed oil fatty acids. its supply and price are more stable than agricultural products like soy fatty acids. tall oil fatty acids (TOFA) have become available in good quality and large quantities. Even so. Refined grades of TOFA have degrees of unsaturation rivaling that of soy acids. A number of monobasic acids that are not derived from fats and oils have been used in alkyd resins. Since it is a year-round by-product from the paper industry. such as those from tung and oiticica oils. soy fatty acids. However. greater care must be exercised during the manufacturing process to avoid gelation. Since the mid-1950s. in alkyd resins. It should be pointed out that alkyds based on conjugated unsaturated fatty acids. coconut fatty acids. etherification between the hydroxyl groups of two polyol molecules may condense them into a new polyol with a functionality of n þ n0 À 2. They may be used in the form of oil or free fatty acids. viz. the surface layer will dry long before the underlayer. Free fatty acids are usually available and classified by their origin. where n and n0 are the numbers of hydroxyl groups of the two original molecules. except in the rare cases of making the so-called . They are frequently the choice for white industrial baking enamels and lacquers.ALKYD RESINS 327 It should be pointed out that under high temperatures. Monobasic Acids. dry so fast that if not properly moderated. alkyds intended for making white or light color enamels should avoid high linolenic content fatty acids by choosing soy oil. such as those in linoleic and linolenic acids. It should be noted that nonconjugated diene groups. It is used extensively in medium. safflower oil. which leads to gelation. Therefore. or dehydrated castor oil (DCO). Alkyds made with nondrying oils or their fatty acids have excellent color and gloss stability. ene-reaction could also occur between two unsaturated fatty acid chains. tung oil and oiticica oil are primarily used to furnish a minor portion of the fatty acids to improve drying properties. such as those used for alkyd resin synthesis. virtually as equivalent to soy fatty acids. its lack of linolenic acid may be more than enough to give as good or even better color retention than soy fatty acids. The introduction of such high functionality polyols plus the net reduction of total available hydroxyl groups can lead to an increased danger of gelation during the poly-condensation process..to long-oil alkyds. etc. The drying property of alkyd resins reflects directly that of the oil or fatty acids in the resin structure. linseed fatty acids. resulting in a wrinkled surface due to the stresses created in the dried surface layer. may undergo isomerization to become conjugated. Furthermore. Although the minor quantities of rosin acids in TOFA may impart some yellowing tendency. discussed earlier. The overwhelming majority of monobasic acids used in alkyd resins are long-chain fatty acids of natural occurrence. and in the presence of high acidity. The typical properties of refined grades of commercial TOFA are given in Table 3. Therefore.

iodine values for conjugated acid oils by the usual methods (Wijs.0 13.8 6.2 Highly unsaturated C20H2(20 À x)O2.2 132.4.8 23. The true value of fresh tung oil.0 15.0 5. 0. behenic 3.8. 0.9 19. 87 Cottonseed Linseed Menhaden 105.5 3.0. capric.3 12. etc. 48.0 2. as determined by special method.8 — — 8.) are both low and variable.1 Behenic. Owing to incomplete halogen absorption. 0.8 191 193 188 192 6.5 6.2 54.3 13.7 1.0 and myristic.1 5.11-conjugated. 17.9.5 34.8.0 — 15. 0.4 8.7: lignoceric. erucle.3 24.0 22.4 7. principally palmitic and stearic.1 51.3 102.0 5.6 About 33% of the linoleic is 9.0 — Other Ricinoleic. 2.0 — — 32.1 — — 47.6 Palmitoleic — — — Oleic 7.0 30.4 Lignoceric.4 2. and C22H2(22 À x)O2.5 — — Aliphatic monocarboxylic acids. lauric. Hanus. eicosenole. dihydroxystearic.5 Arachidic. 19. 0. x ¼ 4 À 10. 1. Caprylic.8 24.5 Tetradecenoic.7 Safflower Soybean Sunflower Tung a b 136.b Licanic.1: lignoceric. 2. 0.3 — 26. 7.2.1 86 2. 82.6 Linolenic — 3.1 — 1.5 Saturated C20-C24.8.1 Lignoceric.4 Eleostearic.0 61.8 125–135 8. dehydrated Coconut Iodine Value 85.0 1 8.TABLE 2.0 180 148–185 196 191 191 27. 47.2 9. Fatty Acid Composition (Percent by Weight) Oil Castor Castor. 4. .7 Linoleic 3. is 248–252: that of oiticica oil is 205–220 (43). Fatty Acid Compositions of Fats and Oils Commonly Used in Alkyd Resins. C12 to C20. of the saturated.0 — 1.3 192 190 175 11. 12.4 76. docosendienole.0 47. 87.4 — Oiticica Peanut Rapeseed 93.7 Saponification Value 195 191 257 Saturateda 2.2 57. 1.6 130. 7.

Presumably. since rosin does not participate in the oxidative drying mechanism that applies to polyunsaturated fatty acids. However. the fused ring structure of rosin contributes to the film hardness. c Same as Pamolyn 200.0 — 1.5 1.0 39.0 40. Grade Designation Pamak 1 193 125 96. However. The Concept of Functionality and Gelation The concept of functionality and its relationship to polymer formation was first advanced by Carothers (45) in 1929. are the most common type of such acids.0 39.5 6 6 195 162 97 <1 22.0 6.8 3 5 Pamak 2 192 128 95. similar to rosin. conjugated Linolenic Rosin acids.5 3 À28 Characteristic Acid number Iodine number Total fatty acids. Synthetic saturated carboxylic acids (such as pelargonic acid.1 — — — — — 3.). % Color. Rosin acids. they are used in conjunction with fatty acids to modify resin properties. % of free fatty acids Oleic Linoleic. also give higher film hardness and faster apparent drying rate.0 51. Del. only linear polymer molecules . The drying rate of alkyds usually appears to be improved with rosin modification. the true drying rate of the alkyd resin would be reduced due to a reduction of the fatty acid unsaturation.8 2. and water resistance of the alkyd. assuming there is no possibility of other side reactions to complicate the issue.0 68.0 — 1.4 4 5 188 131 91.3 3 5 Pamak Pamak Pamolyn Pamolyn 4A 4 200b 300a 191 130 94. nonconjugated Linoleic.5 4. and exterior durability will be adversely affected if the rosin content goes much above 5–6%. The aromatic acids. initial gloss. % Saturated acids.9 — — — — — 1. gloss retention. Enriched polyunsaturated fatty acids from highly refined TOFA. Inc. color and color retention. 2-ethylhexanoic acid. oil-free alkyds for special purposes. Thus if a dibasic acid and a diol are reacted to form a polyester.0 41.0 6.8 2.0 — 1. They may be used in neat form or be brought in as a part of TOFA.4 1.0 10.ALKYD RESINS 329 TABLE 3. % Unsaponifiables.5 3þ À28 196 156 97 <1 21. with further treatment to isomerize the nonconjugated linoleic acid. and isoctanoic acid) and aromatic monobasic acids (such as benzoic acid and p-alkyl-benzoic acids) can improve color retention. Flory (46) greatly expanded the theoretical consideration and mathematical treatment of polycondensation systems.5 1.0 4. 5.5. and exterior durability even better than those based on castor or coconut fatty acids. (Wilmington. primarily in the form of abietic acid. Gardner Titer.  C a b Data from Hercules.0 51.0 — 4.5 2. Typical Properties of Refined Tall Oil Fatty Acidsa.

. when there are reactants with three or more functionalities participating in the polymerization. Thus in the above equimolar reaction system: f ¼ ð1 Â 2 þ 1 Â 2Þ=ð1 þ 1Þ ¼ 2 However. the average degree of polymerization n follows the equation: x n ¼ 1=ð1 À pÞ x ð1Þ where p is the extent of reaction. the polymerization system should have an average functionality of no more than 2. divided by the total number of moles of the reactants present in the system. Thus when the reaction is driven to completion.330 PAINTS. Thus.0) Adipic (1. The experimental results of several such reaction systems reported by different investigators are collected in Table 4. it is considered and defined as a gel. gelation occurs before the completion of esterification. branching and the formation of intermolecular linkages (i. This can be accomplished by adding low functionality reactants and/or adding an excess amount of one of the reactants. equivalents. to avoid premature gelation.. AND RELATED PRODUCTS will be formed. and this would be the only time that difunctional ‘‘monomers’’ could be polymerized to gelation.765 0. p ¼ 2=f . Although the material should theoretically be still soluble and fusible.0)a glycerol (1.0) a b Polyol (OH) di-EG (1. theoretically.707) þ tricarballylic (0. Carothers (47) showed that at the gel point. Polybasic Acid (COOH) Adipic (0.0)b f 2. The latter has the net effect of reducing the functionality of the reactant.293) Dibasic (1. Then the system would lose its fluidity and transform from a moderately viscous liquid to a gelled material with infinite viscosity. For example. The data in Table 4 show that when the reactants are present in stoichiometric proportions. in fractions. If extensive cross-linking occurs in a polymer system to form network structures.578 Diethylene glycol.0) PE (1. if a 20% excess of glycerol over the stoichiometric TABLE 4. i. the mobility of the polymer chains is greatly restricted.e. and the extent of reaction p reached at the gel point depends on the functionality of the system. cross-linking of the polymer chains) become definite possibilities.400 2.103 2. .e. usually the one with high functionality constituents. Pentaerythritol. VARNISHES.911 0. The functionality of the system f is the sum of all of the functional groups. the molecular weight would approach infinity and the whole mass would form one giant polymer molecule. Gel Points of Polyesterification Reaction Systems with Stoichiometric Reactants (46). When the reactants are present in stoichiometric amounts.667 Percent Esterification at Gel Point 0.

2.. Microgel Formation and Molecular Weight Distribution Bobalek and co-workers (49) observed that the behavior of alkyd resin reaction often deviates from that predicted by the theory of Flory. surface activity develops to form micelles. . and particle diameters as large as 2m have been reported. Furthermore. the oil-free systems showed no sign of microgel formation under electron microscope. ‘‘when the highest molecular weight fraction representing about 20% of the total was removed through fractionation. more microgel particles would be formed.e.’’ They showed that the drying capability of an alkyd resin comes primarily from the microgel fraction and.ALKYD RESINS 331 amount required to esterify all of the carboxyl groups present in the formula is added. Functional groups such as OH groups in the microgel particles are believed to be buried in the structure and not available for reactions. mo is the total number of moles of all reactants at the beginning. they observed that the size of microgels increased with reaction time.5. and f is the effective average functionality of the formulation. The microgel particles would be dispersed and stabilized by smaller molecules in the remaining reaction mixture. The microgel particles would then coalesce or flocculate. From electronmicroscopy evidence. at all stages of the reaction up until the physical gelation of the reaction mixture.’’ Solomon and co-workers (50. the excess reactants are discounted in the manner discussed above). or 2. the hydroxyl values corresponded with the calculated values. which would lead to the eventual formation of microgels. and the reaction mixture would undergo a sudden change from a soluble polymer to a gelled mass. They proposed that when some of the molecules have grown to reach certain fatty acid: polyester ratios. Frequently. the glycerol would have an effective functionality of 3/1. As polyesterification proceeds. the residual linoleic alkyd lost all ability to air dry to a hard film. 5. until finally a point is reached at which they could no longer be kept separated. and the entire reaction mass would be ‘‘gelled. Patton (48) showed that for alkyd resins. They proposed a mechanism of microgel formation by some of the alkyd molecules at a relatively early stage of the reaction. both of these measures are taken to safeguard against premature gelation.6. The reaction temperature for alkyd preparation in both of the above references was kept at no more than 200 C. This indicates that polymerization between unsaturated fatty acids of the resin molecules is not necessary for the formation of microgels. the extent of the reaction at gel point was pc ¼ 2=f ¼ 2mo =eo where eo is the total effective equivalents of all of the reactants present at the beginning of the reaction (i. The polyesterification reactivity at the surface of the micelles would be preferentially greater. well short of what would normally be required for the bodying of unsaturated oils in the absence of an oxidizing reagent. 51) further elaborated on the microgel theory by proposing the formation of micelles as precursors of microgels. Whereas in polyesterification reactions without fatty acids. phase inversion would occur.

7. environmental endurance. Basic Principles for the Designing of Alkyd Resins The process of alkyd resin designing should begin with the following question: what would be the intended application(s) of the resin? The application would dictate property requirements. film flexibility. Acid value and hydroxyl value each went through a minimum in the middle fractions (molecular weight about 103–104). and several approaches have been proposed for such purpose (56–59). 5. with or without unsaturated fatty acids in the alkyd formulation. and potential hazard to health. The list may be further narrowed by limitations imposed by the production equipment or other considerations. safety. chemical resistance. Higher reaction temperature led to higher molecular weight and broader molecular weight distribution. The film integrity is largely derived after the resin molecules have been cross-linked. a selection on oil length. Once the oil length and ingredients are chosen. the etherification of polyols. It would be highly desirable that one could rely on a simple equation or formula to obtain the optimum formulation of the alkyd resin with the chosen ingredients. the first draft of a detail formulation for the resin can then be made. either through the unsaturation functionalities on their fatty . whereas the polyester: monoacid ratio increased with the molecular weight of the fraction. AND RELATED PRODUCTS Kumanotani and co-workers (52–55) further confirmed the formation of microgels by characterizing fractions of alkyd resins from preparative GPC columns. Cured films from alkyds with greater amount of colloidal fractions gave better thermomechanical properties. impact on processing cost. which would increase the chance of gelation. the cross-linking between unsaturation groups. which would increase the chance of gelation by forming higher functionality materials and reducing the number of hydroxyl groups available for esterification. acid value. availability.332 PAINTS. For commercial production. VARNISHES. alkyd resins do not remain as a thermoplastic material in their ultimate application. the high molecular weight colloidal fractions were preferentially adsorbed by pigment particles and would thus stabilize the pigment dispersion in the coating formulation. the raw material list is screened based on considerations in material cost. especially the conjugated double bonds. the unsaturated fatty acids made a significant contribution to the formation of the colloidal particles. However. viscosity. Their results showed that the presence of microgel can be detected even in low molecular weight fractions. Except when nondrying alkyds are used strictly as plasticizers for other thermoplastic polymers. film hardness. etc. Colloidal gel particles up to 10þ mm in diameter were observed in the high molecular weight (>105) fractions. water resistance. compatibility. and the phenomenon of microgel formation. However. such as solubility. the complexity of the alkyd reaction system has rendered these equations to be of no more value than providing a first approximation of a starting formula. yield. and the environment. drying characteristics. which would reduce the chance of gelation. Finally. and a preliminary list of alternative choices of ingredients can then be made. The causes of the complexities include the formation of intramolecular cyclic structures. With these targets in mind.

The procedure of this method for formulating alkyd resins will be illustrated with examples. From Table 5. Most of the published data show that the average molecular weight of alkyds is less than 10. In fact. such requirements may be better rationalized. The first example demonstrates the formulations of a 50% soy oil alkyd for baking enamels. adjust accordingly. 58). the excess OH recommended at 50% oil length is 25%. The basis for calculation is 1 mole of PA. With the new understanding that some of the hydroxyl groups would be buried in microgel structures (49–55). phthalic anhydride (PA). If the average equivalent weight of the monobasic acids is significantly different. Thus a simple molecular approach is favored by some of the alkyd chemists for deriving the starting formulation.ALKYD RESINS 333 acid side chains or through the reactions of their residual hydroxyl or carboxyl functionalities with such cross-linking agents as amino resins or polyisocyanate materials. The preliminary selection of ingredients would be alkaline refined soy oil. would be EPE ¼ 1 Â 2 Â ð1 þ 0:25Þ ¼ 2:5 eq: ¼ 0:625 moles TABLE 5. within the practical limits. Percent Fatty Acida 62 or more 59–62 57–59 53–57 48–53 38–48 29–38 Percent Excess OH Based on Diacid Equivalents 0 5 10 18 25 30 32 Percent Excess OH in Finished Resin 0 0–5 5–10 10–15 15–20 20–25 25–30 a Based on C18 fatty acids with average equivalent weight of 280. . as one would for thermoplastic polymers. In a sense. alkyds are usually made and applied as B-stage resins. The values were developed based on experimental experience (57. too high a molecular weight would lead to poor solubility and high solution viscosity and would be undesirable for practical applications. and pentaerythritol. it is still preferred to have a linear backbone structure and high molecular weight to give the best film-forming and film properties.000. the probability for gelation to occur would be small. Oil Length. Therefore. Alkyd formulations with an equimolar ratio of dibasic acids: polyols tend to have the best chance of achieving a linear molecular structure and high molecular weight. it is not necessary to build the molecules of alkyd resins to huge molecular weights. the quantity of PE required. Therefore. in equivalents. Nevertheless. Table 5 lists the empirical requirements of excess hydroxyl groups based on the oil (fatty acid) length of the alkyd. Excess Hydroxyl Content Required in Alkyd Formulations. The basic premise of this approach is that when the total number of moles of polyols is equal to or slightly larger than that of the dibasic acids and the hydroxyl groups are present in an empirically prescribed excess amount.

720 — — 2. The next example shows the formulation of a 50% TOFA alkyd for baking enamels.3 440. and the 50% oil length requirement gives the following: 880Z=ð148 þ 141:6X þ 93Y þ 880Z À 18Þ ¼ 0:5 where 880. Since the total polyols is to be equimolar to dibasic acids.221 — — Weight (g) 148.720 1. X þ Yþ Z ¼ 1. Y ¼ 0:539. Let MPE ¼ X.6.221 2. The 25% excess OH requirement defines 4X þ 3Y ¼ ð2 Â 1:25Þ ¼ 2:5. Assume that PA. and water. and 18 are the molecular weights of the oil.0 0. The oil content must reduced.0 — COOH 2. i.000 1. equimolar PA and polyols. From the given constraints. PA.617 0.500 3. VARNISHES. free glycerol is added to make up the loss. PE.884 3. 25% excess OH.2 50.0) 548. 93. and Z ¼ 0:240. and 50% oil.125 2.e. respectively.240 0.125 — 3.625 2.6 (18.625 — — Weight (g) 148.6 The above formulation meets all of the requirements of the resin design. 148.0 0.000 0. the .334 PAINTS.0 88. PE.5 The above formulation does not meet the test of 50% oil length. the glycerol from the soy oil will. The ingredients can be listed as follows: Ingredient PA Soy oil Tech-PE Total Water Resin M 1.000 1. glycerol.125 — — OH 1. MGly ¼ Y. and Moil ¼ Z. ethylene glycol (EG). be ð1 À 0:625Þ ¼ 0:375 moles.720 — — OH — 0. When solve the simultaneous equations to find X ¼ 0:221. A reduction in oil would cause a corresponding reduction in glycerol.375 0.5 566. which gives ð3 Â 0:375Þ ¼ 1:125 moles of soy fatty acids. and refined TOFA with 4% rosin acids are the chosen ingredients.1 31.0 330.0 — COOH 2.000 1.539 0.0) 422.0 211. 141.. AND RELATED PRODUCTS Since the total polyol is to be equimolar to PA. therefore. Thus the ‘‘final’’ formulation is listed as follows: Ingredient PA Soy oil Glycerol Tech-PE Total Water Resin M 1.6 (18. consequently.

000 — — 0.776 1. It has been shown that the esterification of phthalic anhydride was slower and showed higher temperature dependence. If the molar ratio between the polyols and the dibasic acids is r. They should be fine-tuned based on small-scale laboratory experiments before being used in plant production. to find X ¼ 0:362. The ‘‘final’’ formulations derived in the above examples are meant to be only the starting formulations.638 0.276 — — Weight (g) 148. MPE ¼ Y. one may assume that the residual acidity belongs to unreacted dibasic acids. Generally. an additional safety margin against premature gelation is provided by having a slight molar excess of polyols over dibasic acids in the alkyd formulation.05.4 228.. XþY ¼1 2X þ 4Y ¼ 2  ð1 þ 0:25Þ þ Z 295Z Ä ½148 þ 141:8Y þ 62X þ 295Z À 18  ð1 þ Zފ ¼ 0:5 Solve the equations. and MTOFA ¼ Z.776 2. to a finite acid number to guard against premature gelation.e.6 The percent excess OH ¼ ð3:276 À 2:776Þ=2 ¼ 25%. i. . higher activation energy.6 (32. Since the molecular chain length or the degree of polymerization is a function of the extent of the reaction as shown in equation 1.776 — COOH 2.0 90. Therefore.. Let MEG ¼ X. the value of r is chosen between x 1 and 1.724 — 3. and the oil length ¼ 228:9=457:6 ¼ 50% TOFA. the ‘‘final’’ formulation can be listed as follows: Ingredient PA Tech-PE EG TOFA-4 Total Water Resin M 1.000 0. Y ¼ 0:638.552 0. In real practice. i.e. which contributes to the limiting of chain growth. and Z ¼ 0:776.776 — — OH — 2. the alkyd reaction is usually carried to a point short of completion.ALKYD RESINS 335 following simultaneous equations can be established.776 2.3 22. Therefore.9 489. equation (1) may be rewritten as: n ¼ ð1 þ 1=rÞ=½ð2=rÞð1 À pÞ þ 1 À 1=rŠ x ð2Þ which indicates that a fractional increment in r and/or a fractional reduction in p would give a substantial reduction in n . than that of fatty acids (60–62).362 0.0) 457.

Alcoholysis Process. and soy oil and monopentaerythritol have been reported as follows (63): Component Glycerol Monoester Diester Triester Free glycerol PE Monoester Diester Triester Tetraester Free PE Mole Percent ————————————— Oil-Glycerol Oil-Mono-PE 42 21 3 33 20. or soaps such as naphthanates. Ideally.0 16.8 5. The reaction is alcoholysis.8. It is usually catalyzed by basic compounds such as metal oxides.2 2. poor water resistance.008 to 0. sodium hydroxide. is essentially inert and would not participate in the polyesterification reaction. The two phases thus would be incompatible with each other. The composition of the alcoholysis product at equilibrium from soy oil and glycerol (1 : 2 mole ratio). They may cause poor color. the triglycerides must first react with additional polyol to redistribute the fatty acids among all of the polyols. In reality. The choice is usually dictated by the choice of the starting ingredients.6 6.3 . or haziness in the final resin. VARNISHES. Since oil. In recent years.1 Negligible 6.06% metal based on the weight of the oil for lead and 0. heating the oil with the polyol and the dibasic acid would result in the formation of seedy polycondensates between the polyol and the polybasic acids leaving the oil unreacted.336 PAINTS. It was found that on a molar basis lead compounds were the most efficient among the 36 that were included in the study (58). thereby liberating free hydroxyl groups from the oil for further reaction with the dibasic acids. The dosage of these catalysts usually ranges from 0. litharge was the most popular choice as the catalyst. or calcium oxide have been commonly used. in the form of triglycerides. be used as raw material for alkyd synthesis. hydroxides. including glycerol and the added polyol.01 to 0. In the past. The amount of catalyst added should be kept at the minimum required for completing the reaction in an acceptable batch time. AND RELATED PRODUCTS 5. would coexist in the reaction mixture. salts. Therefore. Chemical Procedures for Alkyd Resin Synthesis Different chemical procedures may be used for the synthesis of alkyd resins.02% for lithium or calcium. due to the concern of lead poisoning from the resultant coatings. whereby some amount of diesters and triesters and neat polyol. Cost and availability often dictate that oil. lithium hydroxide.0 29. the reaction would reach an equilibrium. rather than free fatty acids.0 14. 2 moles of polyol would react with 1 mole of triglyceride to form 3 moles of monoester.

or there are high acidity residues left in the reactor from the previous batch. After the acid value of the reactant has reached a desired low level. When oil represents only a minor portion (33% or less) of the total furnish of fatty acids in an alkyd formulation. oil. When a volume of the alcoholysate can tolerate three or more volumes of methanol without becoming turbid. When free fatty acids are used instead of oil as the starting component. Acidic contaminants are poisonous to the alcoholysis catalysts and must be avoided. the alcoholysis step is avoided. under agitation and inert blanket. the alcoholysis process is considered complete. and higher viscosity than the corresponding ones with identical formulation but prepared by the conventional process. the alcoholysis step may be avoided. Apparently. This is because triglycerides are not soluble in methanol. therefore. A longer batch time or additional amount of the catalyst would then be required. Fatty Acid–Oil Process. The reactants are heated together. and free fatty acids may be charged together into the reactor and proceed as in the fatty acid process. The resins prepared by this technique have more linear backbone chain structure. be charged into the reactor to start a batch. the oil is first heated to 230–250 C under an inert gas blanket and agitation. In general practice. A modified form of the fatty acid process. the reaction can be severely retarded. All of the ingredients can. polyol. dubbed ‘‘high polymer alkyd technique’’ was reported (65). The progress of the reaction is monitored by periodical sampling from the reactor and checking miscibility with anhydrous methanol. The catalyst. the polybasic acid(s) and the balance of polyol. the oil is incorporated into the resin by ester interchange at the reaction . the remaining portion of fatty acids is then added to complete the process. thus severely limiting their utility in the structure design of the resin molecules. Both are undesirable. If the oil has a high acid number. higher molecular weight. usually a combination of the acid value and viscosity of the resin. Fatty Acid Process. dibasic acid. and the polyol.ALKYD RESINS 337 Diols. Chen and Kumanotani (64) reported that alkyds prepared by the fatty acid process have narrower molecular weight distribution and give films with better dynamicmechanical properties. All of the ingredients. are added. usually at 2 times the molar quantity of the oil present in the reactor. usually in the 230–250 C range. such as sublimed phthalic anhydride condensed under the dome of the reactor. until the desired end point is reached. usually predispersed in a small quantity of the oil. are usually not added during the alcoholysis step. whereas monoglyceride is. The batch is reheated to and maintained at the desired temperature. are added. When the alcoholysis step is complete. The batch is reheated to and maintained at about 250 C to carry out the polycondensation step to the desired endpoint. indicating the completion of the poly-condensation. if any. A portion of the fatty acids is withheld in the first stage of the process to allow the polycondensation between the dibasic acid and the polyol to have a better chance of extending the polyester chain without being terminated by the monoacids. such as ethylene glycol. This is because their monoesters have only one remaining hydroxyl group and would function as chain stoppers.

due to their high melting point and low solubility in the reaction mixture. the reactant temperature is dropped to about 230 . the polyol is charged and heated back up to the desired temperature to bring the esterification step to the desired end point. The dibasic acid is heated together with the oil in the resin formulation under agitation and inert gas blanket to about 280 C. which will contaminate or even become catalyst poisons to the subsequent batches. faster surface drying. The resultant resins give higher viscosity (4). Alkyd Resin Production Processes. After acidolysis. The completeness of the acidolysis reaction is determined by a tedious extraction of the oil phase and analysis of its free fatty acid content by titration. based on experience. A carboxyl group of the dibasic acid displaces that of a fatty acid on the oil molecule and splits off the fatty acid. Rapid test methods. an ester interchange occurs. In this reaction. comparable to the methanol miscibility test for alcoholysis. Parallel to the above chemical procedures. would result in a partial gelation to form ‘‘seeds. holding for about 40 min. inert gas is continuously sparged from the bottom of the reactor to carry away water vapor from the reaction mixture. AND RELATED PRODUCTS temperature. However. filtered. not enough of it may be incorporated in time. The material loss causes an increase in the cost of the resin. Reactants as well as the product may adhere to the reactor walls above the surface level of the charge. and slower through-dry (3). The reactor usually needs to be cleaned by charging a small volume of solvent into the vessel and heated to reflux for an appropriate time period. If the oil content is too high. Fusion Process. After the reaction is completed. such as glycols and phthalic anhydride. Therefore. also frequently referred to as fusion cook. For these reasons. it has several significant disadvantages. which is frequently a small vessel with water atomizing nozzles. would be lost during the reaction causing the product composition and its properties to deviate from the design. Low boiling and/or subliming ingredients. . More frequently. And the resin produced from a fusion cook is more prone to develop dark colors. the processing method may also be varied with different mechanical arrangements to remove by-product water. unless it is dictated by the existing equipment. isophthalic and terephthalic acids are difficult to process in ordinary alkyd preparation methods. then it. that could be used for process control of the acidolysis reaction have yet to be developed. The analysis takes several hours to complete. or pumped to a storage tank. the vessel is further cleaned by digesting with caustic soda solution.’’ Acidolysis Process.338 PAINTS. filtered. The acidolysis process is not suitable for phthalic anhydride or other dibasic acids with a high tendency to sublime. The fusion process has the advantage of simplicity in mechanical arrangement. the finished resin may be discharged. An acidolysis process was developed for this purpose (6). As mentioned previously. and packaged. which is self-catalyzed by the acidity of the reaction mixture. most of the manufacturers have discontinued the practice of fusion cook. The exhaust is then either vented away or sent to a fume scrubber. it is cooled to a safe temperature. to drive the esterification reaction toward completion. If deemed necessary. then dissolved with the desired type and amount of solvent in a thinning tank. VARNISHES. and packaged without solvent. the process is normally controlled by reaction time and temperature. In the fusion process.

). The reactor temperature is . The condensed water and solvent have low solubility in each other. or solvent cook. the water formed from the reaction is removed from the reactor as an azeotropic mixture with an added solvent. (Wilminton. Del. typically xylene. The mixed vapor passes through a condenser. usually to a measuring vessel. Courtesy of Hercules Inc. Solvent Process. The solvent is continuously returned to the reactor to be recycled. Usually between 3 to 10 weight percent. The amount of water collected can be monitored as one of the indicators of the extent of the reaction. Equipment for solvent processing of alkyd resins. are added at the beginning of the esterification step. and phase separation is allowed to occur in an automatic decanter.ALKYD RESINS 339 Figure 2. based on the total charge of the solvent. In the solvent process. The water is removed. A typical equipment for this process is shown in Figure 2.

few would consider building a new alkyd plant without solvent process capability.9.340 PAINTS. If the fractionation is poor and water vapor is also condensed and returned. the reactor requires no more than a solvent wash to be clean enough for the next batch. which is installed between the reactor and the overhead total condenser (Figure 3). which improves the effectiveness of the agitation. Therefore. As the reaction proceeds toward completion. a special provision in the form of a partial condenser will be needed to return them back into the reactor. When low boiling ingredients such as ethylene glycol are used. Ordinarily. water evolution slows down. VARNISHES. and the viscosity of the reaction mixture is lower. 5. and most of the glycol will have been combined into the resin structure. AND RELATED PRODUCTS modulated by the amount and type of refluxing solvent. Typical conditions are as follows. The product usually has better color and is more uniform than those made by the fusion process. These advantages far outweigh the higher cost of the production facility. The frequency of sampling is commonly every half hour. Solvent Xylene Xylene Xylene High flash naphtha Weight Percent 3 4 7 10 Temperature ( C) 251–260 246–251 204–210 204–210 The solvent vapor also serves as a blanket in the reactor. which is to be condensed and returned to the reactor. The general practice is to plot the determined values separately against time on semilogarithmic coordinants (Figure 4). Process Control The progress of the alkyd reaction is usually monitored by periodical determinations of the acid number and the viscosity (solution in a suitable solvent and at an appropriate concentration) of samples taken from the reactor. not only would the balance of the reactants be upset and the raw material cost of the resin be increased. The temperature in the partial condenser may then be raised to facilitate the removal of water vapor. . Otherwise. a vertical reflux condenser or a packed column is used as the partial condenser. The reaction temperature is better controlled by the constant refluxing. they would also become part of the pollutant in the waste water and incur additional water treatment costs. The temperature in the partial condenser is monitored and maintained at a level to effect a fractionation between water. the reaction will be retarded and result in a loss of productivity. Usually. which is to pass through the reactor. and brings back the reactants that had escaped out of the reaction mixture. The processing solvent is usually left in the product as part of the dilution solvent. and the glycol or other materials. The refluxing solvent provides a constant wash to the reactor.

ALKYD RESINS 341 Figure 3. After the onset of gelation.). Gelation in the reactor is always a threat. Toward the end of the reaction. due either to what the formulation would theoretically allow by the completion of the polyesterification or to the occurrence of some of the side reactions. it is routine to . Courtesy of Hercules Inc. Del. (Wilmington. the resin viscosity tends to increase exponentially. it would progress extremely rapidly and would be almost impossible to arrest. Solvent-processing equipment using a partial condenser. Therefore.

disperses the gel. VARNISHES. it would cause not only the loss of product but also significant down time for cleaning the reactor. A technique of injecting water or steam during the condensation process to reverse or retard gelation has been reported in the patent literature (66). . Alkyd reaction control plots.342 PAINTS. extrapolate the plots in Figure 4 when predicting the point at which to terminate the reaction in time to prevent gelation. If gelation should occur in the reactor. Some alkyd practitioners have found that a rapid addition of a large quantity of raw oil quenches the runaway gelation. and significantly eases the cleanup operation. AND RELATED PRODUCTS Figure 4.

gloves. With the ever increasing awareness of the need for environmental protection. and many of the vinyl (especially acrylic) monomers are known irritants. on the one hand. some of them such as phthalic anhydride. This good compatibility comes from the relatively low molecular weight of the alkyds and the fact that the resin structure contains. Since large quantities of highly flammable solvents are routinely handled in an alkyd plant. and all equipment should be properly grounded. maleic anhydride. solvents. The areas for the reactors and storage tanks should be separated by fire walls and must be adequately ventilated. While most of them are relatively mild with low toxicity. on the other hand.or mediumoil alkyds to improve flexibility and adhesion. A slight positive pressure of inert gas should be maintained in the reactor or storage tanks during discharge of the resin or resin solution to prevent air from being sucked into the vessel to form an explosive mixture with the solvent vapor.MODIFICATION OF ALKYD RESINS BY BLENDING WITH OTHER POLYMERS 343 6. Amino resins or urethane resins with residual isocyanate functional groups may be added to cross-link the coating film for improved . Electrical equipment and power circuitry in the plant should conform to all applicable codes. one of the important attributes of alkyds is their good compatibility with a wide variety of other coating polymers. and are poisonous to humans. or it may be the major film former and the other polymer may serve as the modifier for the alkyd to enhance certain properties. The following describes some of these compatible blends. The alkyd resin involved in a blend with another coating polymer may serve as a modifier for the other film former. the emission of solvent vapors and organic fumes into the atmosphere should be prevented by passing the exhaust through a proper scrubber. clothing. or skin sensitizers. The most commonly used are short-oil nondrying alkyds. The storage tanks should be blanketed by inert gas. Aqueous effluent should be properly treated before discharge. The use of personal safety equipment such as protective goggles. Nitrocellulose-based lacquers often contain a fair amount of short. many aliphatic side chains with low polarity. and respiratory devices should be diligently observed. Persons involved should be thoroughly familiar with the hazard potential of each and every one of the chemicals by consulting the material safety data sheets provided by the suppliers and practicing the recommended safety precautions in handling the materials. a relatively polar and aromatic backbone and. SAFETY AND ENVIRONMENTAL PRECAUTIONS The manufacturing of alkyd resins involves a wide variety of organic ingredients. fire safety should be the utmost in everyone’s mind. 7. MODIFICATION OF ALKYD RESINS BY BLENDING WITH OTHER POLYMERS As mentioned earlier. The solvent used for cleaning the reactor is usually consumed as part of the thinning solvent.

top lacquer for printed paper. and marine coatings.g. such as those for appliances. and adhesion from the alkyd as well as fast solvent release. Some of the so-called catalyzed lacquers for finishing wood substrate require low bake or no bake at all.or short-oil alkyds as blends in air-dried or baked coatings to improve heat and weather resistance. The major applications are highway traffic paint. Vinylated alkyds are alkyd resins that have been incorporated with a significant amount (20–60% by weight) of vinyl monomers (such as styrene. AND RELATED PRODUCTS solvent and chemical resistance. The reaction sites on alkyd resin molecules are primarily the allylic carbons on unsaturated fatty acid chains .1. Chlorinated rubber is often used in combination with medium-oil drying type alkyds. and durability to the coating. and the chlorinated rubber contributes to faster dry and better resistance to water and chemicals. Vinyl resins of the type that are the copolymers of vinyl chloride and vinyl acetate and that contain a fair amount of hydroxyl groups (from the partial hydrolysis of vinyl acetate) and/or carboxyl groups (e. The major applications are furniture coatings. mar resistance. Synthetic latex house paints sometimes contain emulsified long-oil or very long oil drying alkyds to improve adhesion to chalky painted surfaces. flexibility. adhesion. heat-resistant paints. from copolymerized maleic anhydride) may be formulated with alkyd resins to improve application properties and adhesion. and methyl methacrylate) by grafting the monomers through a free-radical mechanism onto unsaturated reaction sites in the resin molecules. and weather resistance from the vinyl modification. Chemically Modified Alkyd Resins While blending with other coating resins provides a variety of ways to improve the performance of alkyds. chemical resistance. The common objective of such a modification is for achieving a drying rate comparable to that of lacquer materials.. coil coatings.or melamine–formaldehyde resins are compatible with alkyds. Color and color retention requirements often dominate the choice of the alkyd. The blends are primarily used in making marine topcoat paints. Butylated urea. hardness. whereas the alkyd component contributes to adhesion and flexibility. and automotive refinishing primers. good wetting. and durability. Amino resins are probably the most important modifiers for alkyd resins. and swimming pool paints. are based on alkyd-amino resin blends. chemically combining the desired modifier into the alkyd structure would eliminate the compatibility problem and give a more uniform product. and are described below. The modified resin embodies the good attributes of ease of application. Shortor medium-oil alkyds of both drying and nondrying types are frequently used. and automotive finishes (especially refinishing enamels). VARNISHES. or vice versa. Major applications include insulation varnishes. vinyl toluene. 7. They react with the free hydroxyl groups of the alkyd to effect cross-linking and to impart hardness. The alkyd gives better toughness.344 PAINTS. concrete floor. Many industrial baking enamels. Several such chemical modifications of the alkyd resins have gained commercial importance. Silicone resins with high phenyl contents may be used with medium.

The presence of a large amount and high molecular weight homopolymer of the vinyl monomer would lead to incompatibility and result in a hazy product. generated from the thermolysis of such free-radical initiators as benzoyl peroxide. the initiating species would attack the active sites on the resin molecules and all of the added monomers would be evenly distributed in grafted side chains. Usually. and would result in poor film properties. a base alkyd resin is brought to the desired end point. It has been reported that the optimum amount of maleic anhydride in the alkyd is an amount having a maleic group in one-third of the resin molecules (17). with the added advantage of incorporating the stable À ÀOÀ À structure into the alkyd moleÀSiÀ ÀCÀ cules. care must be exercised. Next. if any. choosing monomers that would have a more favorable tendency to copolymerize with the active species on the alkyd resin. Occasionally. It should be emphasized that the presence of a large amount of either conjugated fatty acids or maleic anhydride in the alkyd formulation gives rise to a high degree of probability of premature gelation during the alkyd reaction. If an additional transferring agent is used. The residual monomer. A common procedure for the preparation of vinylated alkyds is as follows: first. 68). The property improvements and applications are similar to those of the alkyd-silicone blends. and packaged. and di-t-butyl peroxide are usually required to kick off the reaction. and the monomer are effective chain-transfer agents. Alternatively. The preferred silicone oligomers are those with high phenyl contents. a premix of the monomer and the initiator is added at a controlled rate over most of the reaction. An allowance must be made in the alkyd formulation. the solvent.MODIFICATION OF ALKYD RESINS BY BLENDING WITH OTHER POLYMERS 345 and the double bond of a. or too much of it could cause the formation of a large amount of very low molecular weight homopolymers. Then the reaction is brought to monomer reflux. followed by an appropriate amount of a free-radical initiator. the desired monomer is added. choosing initiators such as peroxides or hydroperoxides that tend more to extract allylic protons than to add to double bonds. In reality. filtered. and some of the resin molecules would remain unmodified. Silicone alkyds are etherification products of alkoxy-polysiloxane oligomers and the free hydroxyl groups of alkyd resins (67. and properly maintaining the reaction temperature. usually at about 20–60% based on the final product. avoiding initiators that would decompose at very low temperatures. and the polyesterification is frequently terminated at a relatively high acid number (about 15). vinylation is first performed on the fatty acids or the oil before the alkyd reactions. the fatty acid chain. The resin is then cooled to about 160 C and often diluted with aromatic thinner. is stripped away before the product is diluted in a solvent. to avoid gelation. until the residual monomer content has dropped below a specified level. dicumyl peroxide. Chain transferring is the preferred mechanism for terminating chain growth from the addition polymerization of the monomer. and . Free radicals. it is inevitable that part of the monomers would engage in homopolymerization. Methods that have been used to minimize homopolymerization include using fatty acids having conjugated diene structure. using maleic anhydride as part of the dibasic acids for the alkyd. Ideally.b-unsaturated dibasic acids. adding the monomer gradually along with an appropriate amount of the initiator.

Pigment settling during storage of the paint is also . VARNISHES. The À ÀNCOÀ group para to the methyl group has about 8 times greater reactivity than the one on the ortho position. such as dibutyltin dilaurate. Presumably. It is commercially supplied as an 80 : 20 mixture of 2. which aids greatly the control of the reaction. Polyamide modified alkyds show a special rheological behavior—they are thixotropic (69.6-isomers. reacts with ÀN À À the hydroxyl group of a polyol. Etherification between the methylol group and free hydroxyl of the alkyd resin. would be another possible reaction. TDI is highly toxic and is usually handled in a closed system under a dry inert gas blanket. metal primers. and water and chemical resistance in oleoresinous varnishes. are used as reaction catalysts. such as ethylene diamine. similar to what is believed to have occurred in the varnish. Since the NCO group is reactive with labile protons. This allows the preparation of ‘‘no-drip’’ paints. dimerized unsaturated fatty acids. The etherification reaction may be carried out on an alkyd resin designed for the purpose or on the polyol before it is used in alkyd preparation. i. the methylol group would react with the unsaturation functionality on the fatty acid chain to form the chroman structure. to form a urethane linkage. and chemical resistance to the unmodified alkyds. durability. and aliphatic diamines. The esterification reaction of the base alkyd must be brought to the desired end point with the by-product water removed. and the temperature lowered to about 100 C to prevent any continuation of the esterification before the introduction of the NCO reactant.and 2. and calcium naphthanate. and great care must be exercised to bring the reaction under proper control. at low temperature. The reaction products from the polyamide and the alkyd are gel-like materials that undergo a time-dependent shear thinning and recover to the gel-like state after the shearing action is stopped.4.346 PAINTS. Metallic soaps. Phenolic resins are well known for their contribution in improving hardness. À ÀNHC(O)OÀ without spitting out water as a by-product. marine coatings. Toluene diisocyanate À. The reaction is vigorous and exothermic. 70). hardness. are alkyds with a part or even all of the dibasic acids replaced by diisocyanates. one can use isophthalic alkyds rather than the phthalic type. catalyzed by the residual acidity in the resin. AND RELATED PRODUCTS the alkyds at long. Those based on p-alkyl-substituted phenols and with heat-reactive methylol groups have also been incorporated into alkyd resins. These would react to form polyamide resins with low acid and amine values.or long-oil drying alkyd. gloss. and maintenance paints. The silicone content of the modified alkyd lies usually between 20 and 60% of the total product. Urethane alkyds. Uralkyds have superior adhesion. the reaction temperature is maintained under 135 C. water must be excluded from the reaction system. The reaction has not been well studied. The alkyd resin would be a medium.or medium-oil length based on polyols with primary hydroxyls.e. stannous octoate. Typically. (TDI) is commonly used for such modification. The isocyanate group.. abrasion resistance. or uralkyds. the polyamide resin would be of the type based on dimer acids. which are easy to brush and can be applied at high film thickness from a single coat with little or no danger of sagging. Therefore. To improve the thermal stability effect imparted by the silicone modification further. They find major applications in wood floor finishes. À À CÀ O.

the molecular weight of the resin must be reduced. High Solids Alkyds There has been a strong trend in recent years to increase the solids level of all coating materials. For air drying applications. and there is no unreacted polyamide left in the system. Most of the high solids alkyd systems are used in industrial baking finishes. film integrity must be developed through further chain extension and/or cross-linking of the resin molecules during the ‘‘drying’’ step. Therefore. the reaction must be precisely controlled to give the desired degree of thixotropy. The major applications are flat oil-based architectural paints and maintenance paints. polyether polyols.5% in the product. The stiffness of the structure decreases with the increasing amount of the compatibilizer. Therefore. Generally. If the reaction is allowed to continue. and cause it to be prone to cracking.MODIFICATION OF ALKYD RESINS BY BLENDING WITH OTHER POLYMERS 347 minimized. Thus long-chain diols. The modified alkyd serves as a compatibilizer for the mutually insoluble unreacted polyamide and alkyd to form a gellike structure. The hydroxyl functionality of the formulation should be controlled by a careful selection of polyols to avoid an overpresence of free hydroxyl groups in the product. Consequently. the molar ratio between polyols and dibasic acids should be greater than 1. In addition to the manipulation of resin molecular structure for increasing coating solids. oxygenated solvents also serves to reduce the viscosity of resin solutions. Therefore. Aromatic solvents such as xylene tend to destroy the thixotropic structure. higher doses of driers are usually needed to achieve acceptable drying rate (71). To raise the solids level and still maintain a manageable viscosity. they must be reduced to less than 0. to reduce solvent vapor emission. An adequate amount of excess hydroxyl groups must be designed into the alkyd structure to provide reaction sites for these modifiers. To limit the molecular weight of the alkyd resin. Chain extension and cross-linking of high solids alkyd resins are typically achieved by the use of polyisocyanato oligomers or amino resins. the use of more active.o-dibasic acids would not only build in more flexibility but also reduce the viscosity for high solids alkyds. though more expensive. . adequate flexibility should be designed into the resin structure.2. and fragments of the polyamide resin become chemically bonded to the alkyd. 7. This means that the distance between the hydroxyl groups of the polyol and the carboxyl groups of the dibasic acid would need to be lengthened by linear linkages. A high cross-linking density necessitated by the lower molecular weight of the resin would build a high level of stress in the film. Polyamide modified alkyd resins are available commercially to be used as additives for making thixotropic alkyd paints. due to the greater spacing of polar ester groups and the reduction of aromaticity in the resin structure. Ester interchange reaction takes place. up to 10% of the polyamide based on the weight of the alkyd is added to the alkyd and heated at normal alkyd reaction temperature under agitation. which would adversely affect water resistance and other properties of the coating film. and linear a. little or no thixotropy will be exhibited. including alkyds.

VARNISHES.3. such as benzyl alcohol. and the remaining two carboxyl groups would essentially remain unreacted. ECONOMIC ASPECTS Alkyd resins as a family have remained the workhorse of the coatings industry for decades. At such a temperature. the temperature is lowered to 180 C.348 PAINTS.e. to improve the solubilization of the resin in aqueous media and the handling of the resin. The remaining TMA is then added in the same manner as described to ‘‘end cap’’ the resin and to provide pendent carboxyl groups for water solubilization. the total consumption of alkyds increased from about 200. The recommended procedure (37) for the preparation of water-soluble alkyds is to hold off the TMA in the initial stage of the alkyd reaction so that the high functionality of TMA would not be a cause of gelation. molecular chains would be extended. AND RELATED PRODUCTS 7. The latter will be the subject for further discussion.000 t in the mid-1960s. the solvent would be enriched in the coating film as water evaporates preferentially. the TMA is then added and maintained at that temperature until a desired acid number.. Nonfugitive base materials. The most common approach for imparting water solubility in an alkyd resin is to leave enough pendent carboxyl groups in the resin and to neutralize them with a fugitive base. 8. such as caustic soda. only the anhydride group of the TMA would react to form half esters. Therefore. usually about 50–60. Alkyd resins may be rendered water-reducible by either converting the resin into an emulsion form or by incorporating ‘‘water-soluble’’ groups in the molecules. The resin molecules would become better solubilized.. Water and the base are premixed and added to the resin solution when needed.and corrosion-resistance. If one desires to have the TMA participating in the backbone structure of the resin.e. to build ionic characteristics into the resin. Trimellitic anhydride (TMA) is the most frequent choice of ingredient to provide the pendent carboxyl groups. such as glycol ethers. During the drying process. polyols with primary hydroxyl groups are preferred for the preparation of water-soluble alkyds. The coupling solvents usually have higher boiling points than water. a part of the TMA is charged in the beginning of the alkyd reaction. Water-Reducible Alkyds Replacing solvent-borne coatings with water-borne coatings would not only reduce solvent vapor emission but also improve safety against the fire and health hazards of organic solvents. such as ammonia or low molecular weight amines. the building of the polymer chain is completed. would leave the salt in the coating film and damage its water. It peaked in .000 t in the mid-1950s to more than 300. often with the presence of an appropriate amount of a monohydric alcohol. The finished resins are usually dissolved in oxygenated coupling solvents. is reached. When the reaction has progressed to a desired low acid number. In the United States. i. to balance the functionality of the system. and result in better formation and integrity of the film. i. It was reported that glycerol gives resins with poor hydrolytic stability (72).

In 1980. P. At present. 9. Deffar and M. its market share among all coating resins was reduced to 26% in 1987 and 25% in 1989. Other uses for alkyds are in general industrial coatings such as machinery and metal furniture. Pappas. However. Aug.000 t/year. 55–60% of the alkyd resins consumed in the United States are used for architectural coatings. E. 1992. Paint Technol. 73 (919). Jr.. but has stabilized because high performance alternatives have already replaced the coatings in question. 7. 1992. W. 2004. . New York.000 t of all resins consumed for coatings. There is one more good reason to remain optimistic about alkyds for the future—a significant portion of their raw material. Alkyd resin-chlorinated rubber based coatings are used in traffic paints. Jones. J. although the consumption maintained at about 300. Z. 1. SRI Consulting. Coat. D. An Overview of the Paint and Coatings Industry. Some alkyds are still used in refinish paints for automobiles. Soucek. 9. Alkyd producers are already developing new water-borne products (73). eds.REFERENCES 349 1973 at about 345. John Wiley & Sons. fatty acids. Technol. A decline in consumption is expected because of regulations involving VOCs (volatile organic emissions). alkyds still accounted for 30% of the 1. Inc. Pittsburgh Plate Glass Co. REFERENCES 1... Urethane Surface Coatings. Chapt. 35–54 Apr. 1951. The industry was hard hit in 2003–2004 with higher prices for raw materials such as linseed and soybean oil. SRI Consulting. The overall demand in Europe is expected to decrease at the rate of 3%/yr over the next five years. Wicks. 4. Organic Coatings Science & Technology. California and the Northeastern United States are expected to adopt regulations that will severely restrict the use of solvent-borne coatings (73). is renewable. Japan’s consumption has declined. and F. their versatility and low cost will undoubtedly continue to keep alkyds as major players in the coatings arena. SRI International. J. 5. Oct. but use is declining because of VOC concerns. F. 95 (2001). Uralkyds are used as a vehicle for urethane varnishes for the do-it-yourself market. Vol. Jones in Z. W. Environmental regulations are expected by 2007. 44(566). Alkyds are much more amenable to move toward higher solids than most other coating resins. 2. Wicks. A. 2004. From 1987 to 1989. D. 3. Epoxy Surface Coatings. Great strides in the development of water-borne types have also been made in recent years. N.090. there has been a clear trend of gradual decline in the market share of alkyd resins. Rheineck. 1972. constituting about 33% of all synthetic coating resins. FUTURE PROSPECTS Stemming from the drive by the coatings industry to reduce solvent emission. N. 6. and S. A History of Paint and Color. Oct.000 t.

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