Tall oil resin

Schlack [2] and Castan [3,4] are credited with the earliest U.S. patents describing epoxy resin technology. Greenlee [5] further emphasized the use of bisphenols and their reaction with epichlorohydrin to yield diepoxides capable of reaction with crude tall oil resin acids to yield resins useful for coatings. The use of diepoxide resins that are cured with amines was reported by Whittier and Lawn [6] in a U.S. patent in 1956. 

There is a large-scale industry involved in producing gum rosin. In 2005, for example, China produced 700,000 t of tall oil resin (TOR) derived from tapping oleoresin of pine trees [168]. Rosin is a highly valued derivative of pine oleoresin. 

HLB number of 3.8, i.e. it is suitable for a W/O emulsifier. However, in many cases, accurate estimation of the saponification number is difficult, e.g. ester of tall oil, resin, beeswax and linolin. For the simpler ethoxylate alcohol surfactants, HLB can be calculated simply from the weight per cent of oxyethylene E and poly-hydric alcohol P, i.e. 

Soaps of resin and fatty acid mixtures have very different surfactant properties compared to fatty acids and resin acids alone, especially in waters containing salts. In an early study, tall oil resin acids were found to be much less effective in lowering surface tension than TOFAs [13]. This was studied in more detail later, with sodium oleate and sodium abietate as model compounds [14]. Both sodium oleate (NaOl) and sodium abietate (NaAb) form small micelles at low concentrations with a clearly defined critical micelle concentration (CMC). As expected, the CMC decreases with increasing salt concentration (Table 3.2). 

Polyols. Several important polyhydric alcohols or polyols are made from formaldehyde. The principal ones include pentaerythritol, made from acetaldehyde and formaldehyde trimethylolpropane, made from -butyraldehyde and formaldehyde and neopentyl glycol, made from isobutyraldehyde and formaldehyde. These polyols find use in the alkyd resin (qv) and synthetic lubricants markets. Pentaerythritol [115-77-5] is also used to produce rosin/tall oil esters and explosives (pentaerythritol tetranitrate). Trimethylolpropane [77-99-6] is also used in urethane coatings, polyurethane foams, and multiftmctional monomers. Neopentyl glycol [126-30-7] finds use in plastics produced from unsaturated polyester resins and in coatings based on saturated polyesters. 

In the initial black Hquor concentration, saponified fatty and resin acid salts separate as tall oil soaps (see Tall oil). These soaps can be skimmed from the aqueous spent Hquor, acidified, and refined to give a cmde tall oil composed of resin acids, chiefly abietic and neoabietic fatty acids, chiefly oleic and Hnoleic and an unsaponifiable fraction made of phytosterols, alcohols, and hydrocarbons. Tall oil is fractionated primarily into fatty acids (see... 

Black Liquor Soap Recovery. Black Hquor soap consists of the sodium salts of the resin and fatty acids with small amounts of unsaponifiables. The soap is most easily separated from the black Hquor by skimming at an intermediate stage, when the black Hquor is evaporated to 25% soHds (7). At this soHds level, the soap rises in the skimmer at a rate of 0.76 m/h. At higher soHds concentrations, the tall oil soap is less soluble, but higher viscosity lowers the soap rise rate and increases the necessary residence times in the soap skimmer beyond 3—4 hours. The time required for soap recovery can be reduced by installing baffles, by the use of chemical flocculants (8,9), and by air injection into the suction side of the soap skimmer feed pump. Soap density is controUed by the rate of air injection. Optimum results (70% skimmer efficiency) are obtained at a soap density of 0.84 kg/L (7 lb/gal). This soap has a minimum residual black Hquor content of 15% (10—12). 

Black Liquor Soap Acidulation. Only two-thirds of a typical black Hquor soap consists of the sodium salts of fatty acids and resin acids (rosin). These acids are layered in a Hquid crystal fashion. In between these layers is black Hquor at the concentration of the soap skimmer, with various impurities, such as sodium carbonate, sodium sulfide, sodium sulfate, sodium hydroxide, sodium Hgnate, and calcium salts. This makes up the remaining one-third of the soap. Cmde tall oil is generated by acidifying the black Hquor soap with 30% sulfuric acid to a pH of 3. This is usually done in a vessel at 95°C with 20—30 minutes of vigorous agitation. Caution should be taken to scmb the hydrogen sulfide from the exhaust gas. 

The cmde tall oil fatty acids obtained from the rosin column usually contain about 5% rosin because the boiling points of the heavier fatty acids and the lighter resin acids overlap. By adding the intermediate fraction to the fatty acid, rosin does not have to be redistilled. 

Wood is the raw material of the naval stores iadustry (77). Naval stores, so named because of their importance to the wooden ships of past centuries, consist of rosin (diterpene resin acids), turpentine (monoterpene hydrocarbons), and associated chemicals derived from pine (see Terpenoids). These were obtained by wounding the tree to yield pine gum, but the high labor costs have substantially reduced this production in the United States. Another source of rosin and turpentine is through extraction of old pine stumps, but this is a nonrenewable resource and this iadustry is in decline. The most important source of naval stores is spent sulfate pulpiag Hquors from kraft pulpiag of pine. In 1995, U.S. production of rosin from all sources was estimated at under 300,000 metric tons and of turpentine at 70,000 metric tons. Distillation of tall oil provides, in addition to rosin, nearly 128,000 metric tons of tall oil fatty acids annually (78). 

Tall oil [8002-26-4] has been referred to as the largest and fastest growing source of extractives such as turpentine and resin. It can be refined to give tall oil fatty acids (see Carboxylic acids) and tall oil pitch as well as resins. These fatty acids compete with fatty acids from vegetable sources for many of the same industrial markets. 

A rather impressive Hst of materials and products are made from renewable resources. For example, per capita consumption of wood is twice that of all metals combined. The ceUulosic fibers, rayon and cellulose acetate, are among the oldest and stiU relatively popular textile fibers and plastics. Soy and other oilseeds, including the cereals, are refined into important commodities such as starch, protein, oil, and their derivatives. The naval stores, turpentine, pine oil, and resin, are stiU important although their sources are changing from the traditional gum and pine stumps to tall oil recovered from pulping. 

Cobalt in Driers for Paints, Inks, and Varnishes. The cobalt soaps, eg, the oleate, naphthenate, resinate, Hnoleate, ethyUiexanoate, synthetic tertiary neodecanoate, and tall oils, are used to accelerate the natural drying process of unsaturated oils such as linseed oil and soybean oil. These oils are esters of unsaturated fatty acids and contain acids such as oleic, linoleic, and eleostearic. On exposure to air for several days a film of the acids convert from Hquid to soHd form by oxidative polymeri2ation. The incorporation of oil-soluble cobalt salts effects this drying process in hours instead of days. Soaps of manganese, lead, cerium, and vanadium are also used as driers, but none are as effective as cobalt (see Drying). 

Paint and varnish manufacturing Resin manufacturing closed reaction vessel Varnish cooldng-open or closed vessels Solvent thinning Acrolein, other aldehydes and fatty acids (odors), phthalic anhydride (sublimed) Ketones, fatty acids, formic acids, acetic acid, glycerine, acrolein, other aldehydes, phenols and terpenes from tall oils, hydrogen sulfide, alkyl sulfide, butyl mercaptan, and thiofen (odors) Olefins, branched-chain aromatics and ketones (odors), solvents Exhaust systems with scrubbers and fume burners Exhaust system with scrubbers and fume burners close-fitting hoods required for open kettles Exhaust system with fume burners... 

Extraction of rosin. Rosin resins are produced from three types of rosin, i.e. gum, tall oil, and wood. Extensive details about rosin resins extraction and derivatization can be found on page 269 in the book edited by Zinkel and Russell [18]. 

Tall oil rosin is obtained from crude tall oil obtained from the Kraft (sulphate) pulping of various coniferous trees in the paper manufacturing industry. During the Kraft pulping process the fatty acids and the resin acids from the coniferous wood are saponified by the alkaline medium. On concentration of the resulting pulping liquor, the sodium soap of these mixed acids rises to the surface from where they are skimmed out. By acidification of this material with sulphuric acid, the crude tall oil is obtained. Fractional steam distillation of the crude tall oil allows the separation of the tall oil fatty acids and the tall oil rosins [21]. 

Chemistry of rosin. All three types of rosin consist primarily of C20 mono-carboxylic diterpene resin acids, the most common of which have the molecular formula C20H20O2. In addition, rosins contain small amounts of neutral and other acidic components (e.g. fatty acids in tall oil rosin). The neutral components of rosins are diterpene alcohols, hydrocarbons and aldehydes, and their contents generally vary between 5 and 15 wt%. 

The resin acids found in rosins are generally of the abietic- and pimaric-type. Rosins of various pine species differ in their content of abietic vs. pimaric-type acids. Rosins from species exhibiting high abietic-type acid compositions are preferred for production of rosin derivatives. However, the differences in properties of rosins are often associated with their non-resin acid content instead of their chemical compositions. On the other hand, the compositions of rosins from different sources greatly differ [22]. Table 8 shows a typical distribution of resin acids in rosins obtained from gum, tall oil and wood sources. 

Resin acid Tall oil rosin Wood rosin Gum rosin... 

Odour. This aspect is important in resins derived from natural sources. Rosins based on wood and gum rosin retain trace quantities of terpenes and have a piney odour. Tall oil rosins retain the typical sour odour of the rosin. Odour can be removed by steam sparging under vacuum before or during esterification of rosins. Addition of odour masks can also be done. 

Tackifiers. The tackifiers usually are hydrocarbon resins (aliphatic C5, aromatic C9) or natural resins (polyterpenes, rosin and rosin derivates, tall oil rosin ester). They improve hot tack, wetting characteristics and open time and enhance adhesion. The content on tackifiers in a hot melt can be in the region of 10-25%. 

Tall oil fatty acids consist of resin acids (25% to 30%) and of a mixture of linolic acid, conjugated Cig fatty acids (45% to 65%), oleic acid (25% to 45%), 5,9,12-octadecatrienic acid (5% to 12%), and saturated fatty acids (1% to 3%). Resin acids are abietinic acid, dehydroabietic acid, and others. Properties of fatty acids are shown in Table 6-1. 

In the process we are describing here , the esterification reaction was carried ont in the homogeneous phase and followed by distillation under vacuum of the resinic acids. Hydrogenation of Tall Oil methylesters obtained in this way gave the resnlts reported in Table 31.2. 

Recently, the development of environmentally friendly binders produced from renewable agricultural resources, e. g. linseed and tall oil fatty acids, has been described [36]. These new poly(HAMCL) resins were applied in high solid alkyd-like coatings and paints. 

Tall oil is made up mostly of resin acids with around 10% of neutral components. These resin acids are isomers or structurally close relatives of abietic acid (Figure 2.9) and are used as antislip agents, as a chemical feedstock and as paper-sizing agents (see Chapter 7). 

Sources 1 D.H. Bennett, C.M. Falter and A.F. Campbell, Prediction of Effluent Characteristics, Use of Lime Treatments and Toxicity of the Proposed Ponderay Mill , Appendix in engineer s report on Effluent Characteristics for Washington State Department of Ecology, 1987. 2 D.F. Zinkel, Tall Oil Precursors of Loblolly Pine , Tappi, 1975, 58, 2, pp. 118-121. 3 R.W. Hemingway, P.J. Nelson and W.E. Hillis, Rapid Oxidation of the Fats and Resins in Pinus Radiata Chips for Pitch Control , Tappi, 1971, 54, 1, pp. 95-98. 4 D.O. Foster, D.F. Zinkel and A.H. Conner, Tall Oil Precursors of Douglas Fir , Tappi, 1980, 63, 12, pp. 103-105. 

Fatty acid methyl ester (FAME), resin acid (RA) from esterified tall oil (FAME, RA and free fatty acid) NaX Petroleum naphtha [181]... 

---