ROSIN OIL FROM CRUDE TALL OIL

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 62/140,523, filed on March 31, 2015, and to U.S. Provisional Patent Application No. 62/140,518, filed on March 31, 2015, which are both incorporated by reference herein.

BACKGROUND

Field

[0002] Embodiments described generally relate to methods for making fatty acids and rosin oil from tall oil. More particularly, such embodiments relate to in situ methods for making fatty acid dimers and rosin oil from crude tall oil.

Description of the Related Art

[0003] Fatty acid dimers and rosin oil are both commercially important materials. Fatty acid dimers and oligomers are conventionally made through intermolecular reaction of olefinic bonds of unsaturated acids. Heating the reactants with a small amount of catalyst leads to various ene and Diels-Alder reaction products, which are typically then purified by distillation. Rosin oil arises from the decarboxylation of rosin acids such as abietic acid, dehydroabietic acid, pimaric acid, and palustric acid among others. In most cases, decarboxylation is accompanied by aromatization of at least one ring of the tricyclic, di-unsaturated system, as dehydrogenation occurs. Similar to dimerization, rosin oil is produced by heating, typically near 300°C, with a small amount of catalyst, such as sulfuric acid, phosphoric acid, Lewis acids, or clays.

[0004] Rosin oil and dimer acids have been produced from mixtures of tall oil fatty acids ("TOFA") and rosin acids, as described in U.S. Patent Nos. 2,441,198; 2,441,197; 2,396,471; and 2,280,247. These TOFA and rosin mixtures were typically heated at high temperature with phosphoric or sulfuric acid. In some instances, the reaction mixture was purified, usually by distillation, but also by extraction of neutrals. The amount of rosin oils produced by these methods is not satisfactory; however, as only small amounts of rosin oils are obtained. The rosin acids are used to react with the tall oil fatty acids to make a dimer of the two molecules. It is desirable to produce greater quantities of the rosin oil from these mixtures. If more rosin was retained as monomeric units, then more TOFA would be available to react and form TOFA dimer acids.

[0005] There is a need, therefore, for improved methods for making fatty acid dimers and rosin oil.

SUMMARY

[0006] A first catalyst and a mixture that includes fatty acids and rosin acids can be combined and heated to a first temperature to produce a first reaction mixture. In some examples, a second catalyst and the first reaction mixture can be mixed or otherwise combined and heated to a second temperature to produce a second reaction mixture. In other examples, the second catalyst can be omitted and the first reaction mixture without the second catalyst can be heated to the second temperature to produce the second reaction mixture. The second temperature can be greater than the first temperature. The second temperature can be at 250°C or greater, such as greater than 260°C, about 275°C, or about 300°C. The second reaction mixture can include oligomeric acids that can be produced from the fatty acids and rosin oils that can be produced from the rosin acids. The second reaction mixture can have a rosin oil yield of greater than 25%, such as about 30% to about 95%. The first reaction mixture can have an enriched dehydroabietic acid concentration compared to the mixture that includes fatty acids and rosin acids.

[0007] In another example, one or more iron sources, one or more iodine sources, and optionally, one or more nitrogen sources can be added in succession to a mixture that includes one or more fatty acids and one or more rosin acids to produce a first mixture. The first mixture can be heated to a temperature of about 150°C to about 260°C to produce the first reaction mixture. A catalyst and the first reaction mixture can be mixed and heated to a temperature of greater than 250°C to produce a second reaction mixture. The second catalyst can be or can include one or more Bransted or Lewis acids, such as methanesulfonic acid.

[0008] The resulting compositions contain varying amount of oligomeric acids, monomer acids including branched chain fatty acids such as iso-oleic acids, and rosin oils.

DETAILED DESCRIPTION [0009] An improved method for making fatty acid dimers and rosin oil from a mixture of fatty acids and rosin acids is provided. The improved method can be done in situ to produce fatty acid dimers and rosin oil from a single, cost effective feedstock. The mixture that includes fatty acids and rosin acids can derive from a single feedstock or source that contains a mixture of rosin acids, fatty acids, sterols, high-molecular weight alcohols, and other alkyl chain materials. Such single feedstock or source can derive from tall oil, crude tall oil ("CTO"), distilled tall oil ("DTO"), or any mixture thereof including a mixture thereof with any one or more, two or more, or three or more intermediates of the DTO.

[0010] As used herein, the term crude tall oil ("CTO") refers to the crude by-product, and only the crude by-product, recovered as soap skimmings from the black liquor of a Kraft pulping process. The term crude tall oil ("CTO"), as used herein, purposefully excludes any derivatives and intermediates produced from extraction or distillation.

[0011] The components of the CTO can depend on a variety of factors, such as the particular species of the wood being processed (wood type), the geographical location of the wood source, the age of the wood, the particular season that the wood is harvested, and other factors. Thus, depending on the particular source, the CTO can contain about 20 wt% to about 75 wt% of fatty acids {e.g., about 30 wt% to about 60 wt% of fatty acids), about 20 wt% to about 65 wt% of rosin acids {e.g., about 30 wt% to about 60 wt% of rosin acids), and the balance being neutral and non- saponifiable components. In some examples, the CTO can include at least 3 wt%, at least 5 wt%, at least 8 wt%, or at least 10 wt% of neutral materials or non-saponifiable components.

[0012] In certain embodiments, the CTO can be distilled to provide one or more intermediate streams that contain a mixture of fatty acids and rosin acids, such as a distilled tall oil ("DTO") or "DTO fraction". The CTO and the DTO can contain saturated and unsaturated fatty acids in the Ci ₆ -Ci ₈ range. The DTO can have a fatty acids and/or esters of fatty acids concentration of about 55 wt%, about 60 wt%, or about 65 wt% to about 85 wt%, about 90 wt%, or about 95 wt%. The DTO can have a rosin acids or rosins concentration of about 5 wt%, about 10 wt%, or about 15 wt% to about 30 wt%, about 35 wt%, or about 40 wt%. The DTO can have a neutrals concentration of about 0.1 wt%, about 1 wt%, or about 1.5 wt% to about 2 wt%, about 3.5 wt%, or about 5 wt%. The DTO can have an acid value of about 20, about 25, or about 30 to about 40, about 45, or about 50, as measured according to ASTM D465-15. The DTO can have a viscosity (centipoise at 85°C) of about 10 cP, about 20 cP, about 30 cP, or about 40 cP to about 100 cP, about 120 cP, about 135 cP, or about 150 cP. The DTO can have a density of about 840 g/L, about 860 g/L, or about 880 g/L to about 900 g/L, about 920 g/L, or about 935 g/L. The DTO can have a saponification number of about 180, about 185, or about 190 to about 200, about 205, or about 210. The DTO can have an iodine value of about 115, about 117, or about 120 to about 130, about 135, or about 140.

[0013] Regardless of the source, the mixture that includes fatty acids and rosin acids can contain or more different fatty acids and one or more different rosin acids. Illustrative fatty acids can be or can include, for example, oleic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, and palmitic acid. Illustrative rosin acids can be or can include, for example, abietic acid, pimaric acid, dehydroabietic acid, palustric acid, isopimaric acid, neoabietic acid, sandaroco- pimaric acid, levopimaric acid, isomers thereof, or any mixture thereof.

[0014] Commercially available tall oil products include XTOL ^® 100, XTOL ^® 300, XTOL ^® 304, XTOL ^® 520, and XTOL ^® 3030, all of which are commercially available from Georgia-Pacific Chemicals LLC, Atlanta, GA. XTOL ^® 100 can include about 1.6 wt% of palmitic acid, about

2.5 wt% of stearic acid, about 37.9 wt% of oleic acid, about 26.3 wt% of linoleic acid, about 0.3 wt% of linolenic acid, about 2.9 wt% of linoleic isomers, about 0.2 wt% of arachidic acid, about

3.6 wt% eicosatrienoic acid, about 1.4 wt% of pimaric acid, less than 0.16 wt% of sandarocopimaric, less than 0.16 wt% of isopimaric acid, less than 0.16 wt% of dehydroabietic acid, about 0.2 wt% of abietic acid, with the balance being neutrals and high molecular weight species. XTOL ^® 520 DTO includes about 0.2 wt% of palmitic acid, about 3.3 wt% of stearic acid, about 37.9 wt% of oleic acid, about 26.3 wt% of linoleic acid, about 0.3 wt% of linolenic acid, about 2.9 wt% of linoleic isomers, about 0.2 wt% of arachidic acid, about 3.6 wt% eicosatrienoic acid, about 1.4 wt% of pimaric acid, less than 0.16 wt% wt% of sandarocopimaric, less than 0.16 wt% of isopimaric acid, less than 0.16 wt% of dehydroabietic acid, about 0.2 wt% of abietic acid, with the balance being neutrals and high molecular weight species.

[0015] Additional commercially available tall oil products include LYTOR ^® 100, LYTOR ^® 105, LYTOR ^® 105K, LYTOR ^® 110, and LYTOR ^® 307, which are commercially available from Georgia-Pacific Chemicals LLC, Atlanta, GA. LYTOR ^® 100 includes less than 0.16 wt% of palmitic acid, less than 0.16 wt% of stearic acid, about 0.2 wt% of oleic acid, about 0.2 wt% of arachidic acid, about 0.2 wt% eicosatrienoic acid, about 2.2 wt% of pimaric acid, about 0.6 wt% of sandarocopimaric, about 8.5 wt% of palustric acid, about 1.6 wt% of levopimaric acid, about 2.8 wt% of isopimaric acid, about 15.3 wt% of dehydroabietic acid, about 51.4 wt% of abietic acid, about 2.4 wt% of neoabietic acid, with the balance being neutrals and high molecular weight species.

[0016] The mixture that includes fatty acids and rosin acids can further include fatty acids and/or rosin acids from one or more additional sources that are blended or otherwise added to the CTO or DTO. In certain embodiments, a CTO can be blended or otherwise mixed with a DTO. In certain embodiments, a CTO or DTO can be blended or mixed with additional sources of fatty acids that include, but are not limited to, oxidized tall oil, tall oil fatty acids (TOFA), crude tall oils (CTO), distilled tall oils (DTO), depitched tall oil, tall oil pitches, plant and/or vegetable oils, animal fats or oils, portions thereof, fractions thereof, or any mixture thereof. The tall oil fatty acids can also be referred to as monomer tall oil fatty acids.

[0017] Illustrative plant and/or vegetable oils can include, but are not limited to, safflower oil, grapeseed oil, sunflower oil, walnut oil, soybean oil, cottonseed oil, coconut oil, corn oil, olive oil, palm oil, palm olein, peanut oil, rapeseed oil, canola oil, sesame oil, hazelnut oil, almond oil, beech nut oil, cashew oil, macadamia oil, mongongo nut oil, pecan oil, pine nut oil, pistachio oil, grapefruit seed oil, lemon oil, orange oil, watermelon seed oil, bitter gourd oil, buffalo gourd oil, butternut squash seed oil, egusi seed oil, pumpkin seed oil, borage seed oil, blackcurrant seed oil, evening primrose oil, acai oil, black seed oil, flaxseed oil, carob pod oil, amaranth oil, apricot oil, apple seed oil, argan oil, avocado oil, babassu oil, ben oil, borneo tallow nut oil, cape chestnut, algaroba oil, cocoa butter, cocklebur oil, poppyseed oil, cohune oil, coriander seed oil, date seed oil, dika oil, false flax oil, hemp oil, kapok seed oil, kenaf seed oil, lallemantia oil, mafura oil, marula oil, meadowfoam seed oil, mustard oil, okra seed oil, papaya seed oil, perilla seed oil, persimmon seed oil, pequi oil, pili nut oil, pomegranate seed oil, prune kernel oil, quinoa oil, ramtil oil, rice bran oil, royle oil, shea nut oil, sacha inchi oil, sapote oil, seje oil, taramira oil, tea seed oil, thistle oil, tigernut oil, tobacco seed oil, tomato seed oil, wheat germ oil, castor oil, colza oil, flax oil, radish oil, salicornia oil, lung oil, honge oil, jatropha oil, jojoba oil, nahor oil, paradise oil, petroleum nut oil, dammar oil, linseed oil, stillingia oil, vernonia oil, amur cork tree fruit oil, artichoke oil, balanos oil, bladderpod oil, brucea javanica oil, burdock oil, candlenut oil, carrot seed oil, chaulmoogra oil, crambe oil, croton oil, cuphea oil, mango oil, neem oil, rose hip seed oil, rubber seed oil, sea buckthorn oil, sea rocket seed oil, snowball seed oil, tall oil, tamanu oil, tonka bean oil, ucuhuba seed oil, or any mixture thereof. Illustrative animal fats or oils that can be used as the fatty acids can include, but are not limited to, fatty acids from animal sources, such as cows, pigs, lambs, chickens, turkeys, ducks, geese, and other animals, as well as dairy products such as milk, butter, or cheese. Illustrative fatty acids from animal sources can include palmitic acid, stearic acid, myristic acid, oleic acid, palmitoleic acid, linoleic acid, or any mixture thereof.

[0018] Other illustrative fatty acid sources can be or include oleic acid, palmitic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, arachidic acid, behenic acid, salts thereof, isomers thereof, or any mixture thereof. Fatty acids can also derive from a fatty acid ester, a mixture of fatty acid esters, a fatty acid amide, a mixture of fatty acid amides, a mixture of one or more fatty acids and one or more fatty acid esters, a mixture of one or more fatty acids and one or more fatty acid amides, or a mixture of one or more fatty acids, one or more fatty acid esters, and one or more fatty acid amides. For example, fatty acids derived from tall oils, otherwise known as tall oil fatty acids, can include oleic acid, palmitic acid, linoleic acid, linolenic acid, eicosatrienoic acid, stearic acid, arachidic acid, behenic acid, isomers thereof, or any mixture thereof.

[0019] Additional sources of rosin oil can include, but are not limited to, derivatives of CTO including oxidized tall oil, tall oil rosin acids, dehydrated tall oil, bottoms products of tall oil, residuals from the tall oil fractionation process, as well as wood rosin and gum rosin. Additional sources of rosin oil can be rosin acid. Illustrative rosin acids can be or can include abietic acid, pimaric acid, dehydroabietic acid, palustric acid, isopimaric acid, neoabietic acid, sandaroco- pimaric acid, levopimaric acid, isomers thereof, or any mixture thereof.

[0020] In some examples, the rosin oil can include rosin acids in an amount of less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, or less than 1 wt%. For example, the rosin oil can include rosin acids in an amount of about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, about 0.01 wt% to less than 8 wt%, about 0.01 wt% to less than 6 wt%, about 0.01 wt% to less than 5 wt%, about 0.01 wt% to less than 4 wt%, about 0.1 wt% to less than 15 wt%, about 0.1 wt% to less than 10 wt%, about 0.1 wt% to less than 8 wt%, about 0.1 wt% to less than 6 wt%, about 0.1 wt% to less than 5 wt%, about 0.1 wt% to less than 4 wt%, about 1 wt% to less than 15 wt%, about 1 wt% to less than 10 wt%, about 1 wt% to less than 8 wt%, about 1 wt% to less than 6 wt%, about 1 wt% to less than 5 wt%, or about 1 wt% to less than 4 wt%. In some specific examples, the rosin oil can include rosin acids in an amount of about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, or about 0.01 wt% to less than 5 wt%.

[0021] In some examples, the rosin oil can have an acid value of about 1, about 10, about 20, about 30, or about 50 mg to about 60, about 80, about 100, about 110, about 120, about 130, about 140, or about 150 mg KOH/g of rosin oil. In other examples, the rosin oil can have an acid value of less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, less than 10, less than 5, less than 3, or about 1 mg KOH/g of rosin oil. In other examples, the rosin oil can have an acid value of about 1 to about 150, about 1 mg to about 130, about 1 mg to about 110, about 50 to about 150, about 50 to about 130, or about 50 to about 110 mg KOH/g of rosin oil. The acid value (mg KOH/g) of the oligomeric acid can be measured according to ASTM D465-15.

[0022] A first catalyst and the mixture that includes fatty acids and rosin acids can be combined and heated to a first temperature to produce a first reaction mixture. In some examples, a second catalyst and the first reaction mixture can be mixed or otherwise combined and heated to a second temperature to produce a second reaction mixture. In other examples, the second catalyst can be omitted and the first reaction mixture, without the second catalyst, can be heated to the second temperature to produce the second reaction mixture.

[0023] The first catalyst and the mixture that includes the fatty acids and the rosin acids can be mixed, blend, or otherwise combined to produce a first mixture. In some examples, when the first catalyst and the mixture that includes the fatty acids and the rosin acids are mixed, the iron source, the nitrogen source, and the iodine source can be added in succession to the mixture that includes fatty acids and rosin acids. The first catalyst can be or can include nickel, palladium, platinum, iron, copper, cobalt, manganese, tin, sulfur, iodine, selenium source or a combination thereof. The first catalyst also can be or can include one or more iron sources, one or more nitrogen sources, one or more iodine sources, one or more sulfur sources or any mixture thereof. The iron source can be or can include metallic iron, ferric compounds, and ferrous compounds, including, but not limited to iron halides, iron oxides, iron hydroxides, iron sulfides, organic-iron compounds, or any mixture thereof. Illustrative iron sources can include one or more of metallic iron, ferrous chloride, ferric chloride, ferrous iodide, ferric iodide, ferrous bromide, ferric bromide, ferrous oxide, ferric oxide, ferrous hydroxide, ferric hydroxide, ferrous sulfide, ferric sulfide, ferrous selenide, ferric selenide, hydrates thereof, or any mixture thereof. Nitrogen sources can include one or more ammonium compounds, one or more amine compounds, one or more urea compounds, or any mixture thereof. Illustrative nitrogen sources can include ammonium carbonate, a mixture of carbonate and carbamate, urea carbonate, urea, dimethylurea, tetramethylurea, ammonium chloride, ammonium bromide, ammonium iodide, ammonium hydroxide, alkanolamines, ethylenediamine, diethylenetriamine, or any mixture thereof. Illustrative iodine sources can include elemental iodine (I ₂ ), iodide salts of alkaline metals (e.g., lithium iodide, sodium iodide, potassium iodide, cesium iodide), iodide salts of rare earth metals (e.g., magnesium iodide or calcium iodide), transition metal iodides (e.g., ferrous or ferric iodide), or any mixture thereof. In some examples, the iron source can be or can include one or more iron halides, the nitrogen source can be or can include ammonium carbonate or ethylenediamine, and the iodine source can be or can include elemental iodine. If the iron source is an iron chloride, then the iron source can be or can include ferric chloride, ferrous chloride, hydrates thereof, or any mixture thereof. In some examples, the iron source and the iodine source can both be or include ferrous iodide or ferric iodide. Illustrative sulfur sources can include an alkylphenol sulfide, a phenol sulfide, 2-2'-thiobis(4-methyl-6-t-butylphenol), l-thio-2- naphthol, l, l '-di-(2-naphthol)-disulfide, l, l '-di(2-naphthol)-sulfide, 2,5-diphenyl dithiin, 1,3,4- thiadiazole polysulfides, 4,4'-thiobis(resorcinol), 2,2'-thiobis(4,6-dimethylphenol), or any combination thereof.

[0024] The first mixture can include the first catalyst in an amount of about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.05 wt%, about 0.07 wt%, about 0.1 wt%, about 0.15 wt%, or about 0.2 wt% to about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.45 wt%, about 0.5 wt%, about 0.55 wt%, about 0.6 wt%, about 0.65 wt%, about 0.7 wt%, about 0.75 wt%, about 0.8 wt%, about 0.85 wt%, about 0.9 wt%, about 1 wt%, about 1.2 wt%, about 1.4 wt%, about 1.6 wt%, about 1.8 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5 wt%, based on the total or combined weight of the fatty acids and the rosin acids. For example, the first mixture can include the first catalyst in an amount of about 0.01 wt% to about 2 wt%, about 0.03 wt% to about 2 wt%, about 0.05 wt% to about 2 wt%, about 0.1 wt% to about 1.5 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.6 wt%, about 0.1 wt% to about 0.5 wt%, about 0.2 wt% to about 1.5 wt%, about 0.2 wt% to about 1 wt%, about 0.2 wt% to about 0.6 wt%, about 0.2 wt% to about 0.5 wt%, about 0.4 wt% to about 1.5 wt%, about 0.4 wt% to about 1 wt%, about 0.4 wt% to about 0.8 wt%, about 0.4 wt% to about 0.6 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, or about 0.5 wt% to about 0.8 wt%, about 0.01 wt% to about 1 wt%, about 0.03 wt% to about 1 wt%, about 0.05 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, about 0.03 wt% to about 0.5 wt%, about 0.05 wt% to about 0.5 wt%, about 0.01 wt% to about 0.1 wt%, about 0.03 wt% to about 0.1 wt%, about 0.05 wt% to about 0.1 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0025] The first temperature can be about 50°C, about 80°C, about 100°C, about 120°C, about 150°C, or about 180°C to about 190°C, about 200°C, about 210°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about 245°C, about 250°C, about 255°C, about 260°C, about 265°C, or about 270°C, to produce the first reaction mixture. For example, the first mixture can be heated to about 50°C to about 270°C, about 50°C to about 260°C, about 50°C to about 250°C, about 100°C to about 250°C, about 150°C to about 250°C, about 180°C to about 250°C, about 200°C to about 250°C, about 220°C to about 250°C, about 230°C to about 250°C, about 100°C to about 230°C, about 150°C to about 230°C, about 180°C to about 230°C, about 200°C to about 230°C, or about 220°C to about 230°C. In other examples, the mixture that includes the first catalyst, the fatty acids, and the rosin acids can be heated to about 50°C to less than 270°C, about 50°C to less than 260°C, about 100°C to less than 260°C, about 150°C to less than 260°C, about 180°C to less than 260°C, about 200°C to less than 260°C, about 220°C to less than 260°C, about 50°C to less than 250°C, about 100°C to less than 250°C, about 150°C to less than 250°C, about 180°C to less than 250°C, about 200°C to less than 250°C, or about 220°C to less than 250°C. The first mixture can be heated to the first temperature for about 1 min, about 5 min, about 10 min, or about 15 min to about 20 min, about 30 min, about 1 hr, about 2 hr, about 3 hr, about 4 hr, about 6 hr, or longer to produce the first reaction mixture. For example, the first mixture can be heated for about 1 min to about 6 hr, about 1 min to about 4 hr, about 1 min to about 2 hr, about 1 min to about 1 hr, about 1 min to about 30 min, about 1 min to about 20 min, about 1 min to about 8 min, about 10 min to about 4 hr, about 10 min to about 5 hr, or about 10 min to about 1 hr. The first mixture can be heated to about 150°C or about 180°C to 250°C or less than 250°C for about 1 min to about 30 min or about 5 min to about 20 min to produce the first reaction mixture. In some examples, one or more acids, such as oxalic acid, can be added to first reaction mixture to quench the first catalyst, ceasing the disproportionation reaction, and bleaching the first reaction mixture.

[0026] In some examples, the mixture that includes fatty acids and rosin acids can have a first dehydroabietic acid concentration. The first reaction mixture can have a second dehydroabietic acid concentration. The second dehydroabietic acid concentration can be greater than the first dehydroabietic acid concentration. The first reaction mixture, therefore, can have an enriched dehydroabietic acid concentration relative to the mixture that includes fatty acids and rosin acids. The first reaction mixture has an enriched dehydroabietic acid concentration, at least in part, due to the disproportionation reaction that produces the first reaction mixture. The first dehydroabietic acid concentration can be about 0.5 wt%, about 1 wt%, about 2 wt%, or about 3 wt% to about 4 wt% about 5 wt%, about 7 wt%, about 9 wt%, about 10 wt%, or about 12 wt%, based on the combined weight of the fatty acids and the rosin acids. For example, the first dehydroabietic acid concentration can be about 1 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 5 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 8 wt%, or about 5 wt% to about 8 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0027] The first reaction mixture can have a second dehydroabietic acid concentration of about 1 wt%, about 2 wt%, about 3 wt%, or about 5 wt% to about 7 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 18 wt%, about 20 wt%, about 22 wt%, about 25 wt%, or about 30 wt%, based on the combined weight of the fatty acids and the rosin acids. For example, the second dehydroabietic acid concentration can be about 1 wt% to about 30 wt%, about 2 wt% to about 25 wt%, about 2 wt% to about 20 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, or about 5 wt% to about 12 wt%, based on the combined weight of the fatty acids and the rosin acids. The enriched dehydroabietic acid ratio, such as the second dehydroabietic acid concentration to the first dehydroabietic acid concentration, of the first reaction mixture can be greater than 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 4.5, about 5, about 6, about 7, about 8, about 9, about 10, about 12, about 15, or about 20.

[0028] In some examples, the second catalyst and the first reaction mixture can be mixed, blended, or otherwise combined to produce the second mixture. In other examples, the second catalyst can be omitted and the first reaction mixture can be further heated to produce the second reaction mixture. The second catalyst can be or can include one or more acids, such as, for example, one or more Bransted acids and/or one or more Lewis acids. Illustrative Bransted acids can be or can include methanesulfonic acid, p-toluenesulfonic acid (4- methylbenzenesulfonic acid), phosphoric acids, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, sulfuric acid, isomers thereof, salts thereof, esters thereof, or any mixture thereof. Illustrative Lewis acids can be or can include one or more clays, such as, for example, montmorillonite. The second catalyst can also be or include one or more metal-containing compounds, such as zinc compounds, aluminum compounds, iron compounds, tin compounds, or any mixture thereof. In some examples, metal-containing compounds can be or can include one or more metal halides, such as, but not limited to, zinc chloride, aluminum chloride, iron chlorides, tin chlorides, or any mixture thereof. The second catalyst can also be or include a clay, such as for example, hectorite, montmorillonite, attapulgite, halloysite, kaolinite, sepiolite, bentonite, calcium bentonite, Fuller's Earth, acid-treated clay, acid-treated bentonite, acid-treated montmorillonite, alkaline clay, alkaline earth metal halide, lithium hydroxide, lithium carbonate, or acidic ion exchange resins such as Amberlyst 15, zinc halides, zinc chloride, zinc, bromide, zinc halides in presence of hydrogen halides, magnesium silicates, magnesium silicates in the presence of nitrogenous compounds, stannic halides, stannic chloride, and/or stannic bromide.

[0029] The second mixture can include the second catalyst in an amount of about 0.05 wt%, about 0.07 wt%, about 0.1 wt%, about 0.15 wt%, or about 0.2 wt% to about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.45 wt%, about 0.5 wt%, about 0.55 wt%, about 0.6 wt%, about 0.65 wt%, about 0.7 wt%, about 0.75 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.2 wt%, about 1.4 wt%, about 1.6 wt%, about 1.8 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5 wt%, based on the combined weight of the fatty acids and the rosin acids in the first mixture. For example, the second mixture can include the second catalyst in an amount of about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2.5 wt%, about 0.05 wt% to about 2 wt%, about 0.1 wt% to about 1.5 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.6 wt%, about 0.1 wt% to about 0.5 wt%, about 0.2 wt% to about 1.5 wt%, about 0.2 wt% to about 1 wt%, about 0.2 wt% to about 0.8 wt%, about 0.2 wt% to about 0.6 wt%, about 0.2 wt% to about 0.5 wt%, about 0.4 wt% to about 1.5 wt%, about 0.4 wt% to about 1 wt%, about 0.4 wt% to about 0.8 wt%, about 0.4 wt% to about 0.6 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, about 0.5 wt% to about 0.8 wt%, or about 0.5 wt% to about 0.7 wt%, based on the combined weight of the fatty acids and the rosin acids in the first mixture.

[0030] One or more chelating agents can be combined with the second reaction mixture and can be used to chelate and deactivate iron in the second reaction mixture. The chelating agent can be or can include one or more amines. Illustrative amines can include one or more monoamines, one or more polyamines (e.g., diamine or triamine), one or more alkanolamines, or any mixture thereof. The amine can be or can include one or more C ₂ -C ₂ o-monoamines, one or more C ₂ -C ₂₀ - diamines, one or more C3-C ₂ o-triamines, salts thereof, or any mixture thereof. In some examples, the amine can be or can include one or more polyamines, such as one or more C ₂ -C5-diamines. Illustrative amines or other basic or alkaline compounds useful as the second catalyst can include ethylamine, ethylenediamine, diethylenetriamine, propylamine, propylenediamine, laurylamine, octadecylamine, isomers thereof, salts thereof, or any mixture thereof. In some examples, the second catalyst and the chelator can be included into the mixture separately or together and can be or can include methanesulfonic acid, ethylenediamine, or a mixture thereof.

[0031] The second reaction mixture can include the chelating agent in an amount of about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, or about 0.5 wt% to about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.2 wt%, about 1.4 wt%, about 1.6 wt%, about 1.8 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt%, based on the combined weight of the fatty acids and the rosin acids in the first reaction mixture. For example, the second reaction mixture can include the chelating agent in an amount of about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 8 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 1 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, or about 1 wt% to about 3 wt%, based on the combined weight of the fatty acids and the rosin acids in the first reaction mixture. [0032] The second temperature is greater than the first temperature. The second temperature can be about 250°C, about 252°C, about 255°C, or about 260°C to about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about 295°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 400°C, about 450°C, or about 500°C to produce the second reaction mixture. For example, the second mixture can be heated to a temperature greater than 250°C to about 500°C, greater than 250°C to about 400°C, greater than 250°C to about 350°C, greater than 250°C to about 330°C, greater than 250°C to about 320°C, greater than 250°C to about 310°C, greater than 250°C to about 300°C, or greater than 250°C to about 280°C. In other examples, the second mixture can be heated to about 280°C to about 350°C, about 280°C to about 330°C, about 280°C to about 320°C, or about 280°C to about 300°C.

[0033] The second mixture can be heated for about 0.5 hr, about 0.75 hr, about 1 hr, or about 1.25 hr to about 1.5 hr, about 2 hr, about 3 hr, about 4 hr, about 5 hr, about 6 hr, about 7 hr, about 8 hr, about 10 hr, about 12 hr, about 15 hr, about 18 hr, about 20 hr, about 24 hr, about 30 hr, about 40 hr, about 48 hr, or longer to produce the second reaction mixture. For example, the second mixture can be heated for about 0.5 hr to about 48 hr, about 1 hr to about 24 hr, about 2 hr to about 12 hr, about 2 hr to about 10 hr, about 2 hr to about 8 hr, about 2 hr to about 6 hr, about 2 hr to about 4 hr, about 3 hr to about 12 hr, about 3 hr to about 10 hr, about 3 hr to about 8 hr, about 3 hr to about 6 hr, about 3 hr to about 4 hr, about 4 hr to about 12 hr, about 4 hr to about 10 hr, about 4 hr to about 8 hr, or about 4 hr to about 6 hr. In one specific example, the second mixture can be heated to greater than 250°C to about 350°C or about 280°C to about 320°C for about 1 hr to about 24 hr or about 2 hr to about 12 hr to produce the second reaction mixture.

[0034] The second reaction mixture can include oligomeric acids produced from the fatty acids and/or rosin acids. The second reaction mixture also can include rosin oils produced from the rosin acids. The second reaction mixture can have a rosin oil yield of greater than 25%, greater than 30%), greater than 32%, greater than 35%, greater than 37%, greater than 40%, or greater than 42%. For example, the second reaction mixture can have a rosin oil yield of about 25% to about 95%, about 25% to about 85%, about 27% to about 77%, about 32% to about 67%, about 30 wt% to about 95 wt%, about 35 wt% to about 60 wt%, about 40 wt% to about 70 wt%, about 45 wt% to about 75 wt%, or about 50 wt% to about 90 wt%. [0035] The rosin oil yield can be calculated by taking the weight percent of rosin oil produced in the second reaction mixture over the weight percent of rosin acid in the starting mixture that includes fatty acids and rosin acids (e.g., CTO or DTO). The second reaction mixture can have a rosin oil yield of greater than 25%, about 26%>, about 28%, about 30%>, or about 35% to about 36%, about 38%, about 40%, about 42%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 97%, about 98%), or about 99%. The second reaction mixture can have a rosin oil yield of greater than 25% to about 95%, about 30% to about 95%, about 30% to about 85%, about 35% to about 80%, about 40%) to about 95%, or about 40% to about 85%. In some examples, the second reaction mixture can have a rosin oil yield of about 30% to about 95% or about 35% to about 80%.

[0036] The second reaction mixture can be cooled to ambient temperature (about 23°C). The second reaction mixture can include oligomeric acids and rosin oil. The oligomeric acids can include one or more dimer acids, one or more trimer acids, one or more higher acids (e.g., acids containing 4, 5, or more monomer acid units), or any mixture thereof. The oligomeric acid can be or can include one or more homomeric acids and/or one or more heteromeric acids. The oligomeric acid can be produced from one or more monomer fatty acids that can include oleic acid, palmitic acid, linoleic acid, stearic acid, arachidic acid, behenic acid, isomers thereof, or any mixture thereof. The oligomeric acid can include one or more dimer acids and/or trimer acids. The oligomeric acid can have an acid value of about 100, about 150, or about 160 to about 170, about 200, about 250, or about 300 mg KOH/g of oligomeric acid. The oligomeric acid can have an acid value of about 150 to about 400, about 150 to about 300, about 160 to about 250, or about 170 to about 200 mg KOH/g of oligomeric acid.

[0037] The rosin oil can include rosin acids in an amount of less than 60 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, or less than 1 wt%. For example, the rosin oil can include rosin acids in an amount of about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, about 0.01 wt% to less than 5 wt%, or about 1 wt% to less than 15 wt%. The second reaction mixture can include rosin acids in an amount of less than 60 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, or less than 1 wt%. For example, the second reaction mixture can include rosin acids in an amount of about 0.01 wt% to less than 15 wt%, about 0.01 wt% to less than 10 wt%, about 0.01 wt% to less than 5 wt%, or about 1 wt% to less than 15 wt%.

[0038] The rosin oil can have an acid value of about 1, about 20, about 30, or about 50 to about 60, about 80, about 100, about 120, about 140, or about 150 mg KOH/g of rosin oil. The rosin oil can have an acid value of less than 150, less than 130, less than 110, less than 100, less than 80, less than 60, less than 50, less than 40, less than 20, less than 10, less than 5, or about 1 mg KOH/g of rosin oil. The rosin oil can have an acid value of about 1 to about 150, about 1 to about 130, or about 50 to about 130 mg KOH/g of rosin oil.

Examples

[0039] In order to provide a better understanding of the foregoing discussion, the following non- limiting examples are offered. Although the examples can be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect.

[0040] Reaction products of various mixtures of fatty acids and rosin acids derived from various sources were prepared in accordance with the examples below. Tables 1-6 report the components and concentrations of the mixtures and their resulting rosin acid conversions. In Tables 2, 4, and 6, the values under Rosin Acids and Rosin Oils are listed in wt%; the values under Rosin Total were calculated as the wt% of Rosin Acids + the wt% of Rosin Oils; Rosin Oil Conversion was calculated as 1 - (wt% of Rosin Acids / wt% of Rosin Acids of CTO 1, CT02, or FA/RA mix); Rosin Retention was calculated as (wt% of Rosin Acids + wt% of Rosin Oils) / (wt% of Rosin Acids of CTO 1, CT02, or FA/RA mix); Rosin Oil Yield was calculated as (wt% of Rosin Oil / wt% of Rosin Acids of CTO 1, CT02, or FA/RA mix). The Rosin Oil standard listed in the Samples column in Tables 1-4 was made by heating rosin acid (commercially available as LYTOR ^® 100 tall oil rosin acid, from Georgia-Pacific Chemicals LLC) at 320°C for 20 hr.

[0041] As shown in the Tables below, the selectivity for rosin oils surprising and unexpectedly increased approximately 2.5 times from 20% to 50%. Moreover, many of the mono- and polyunsaturated fatty acids were retained in monomeric form after disproportionation in the second stage of reaction to make more oligomeric and branched-chain fatty acids, as compared to the comparative examples. [0042] Comparative Example 1 (CEx. 1): About 100 g of crude tall oil (CTO 1) was added to a 250 mL 4-neck round-bottom flask equipped with a thermocouple, Barrett trap and condenser, nitrogen gas-inlet, and mechanical stirring shaft. Methanesulfonic acid (70 wt%, about 0.714 g) was added to produce a mixture and the reactor was purged for about 10 min under nitrogen. The mixture was heated to a temperature of about 200°C and held for about 15 min. The temperature of the mixture was increased to about 300°C and held for about 5 hr with a light stream of nitrogen passing overhead to produce a reaction product. The reaction product was cooled to about 23 °C under nitrogen.

[0043] Comparative Example 2 (CEx. 2): About 100 g of CTO 1 was added to a 250 mL 4-neck round-bottom flask equipped with a thermocouple, Barrett trap and condenser, nitrogen gas-inlet, and mechanical stirring shaft. Phosphoric acid (0.588 g) was added to produce a mixture and the reactor was purged for about 10 min under nitrogen. The mixture was heated to a temperature of about 200°C and held for about 15 min. The temperature of the mixture was increased to about 300°C and held for about 4 hr with a light stream of nitrogen passing overhead to produce a reaction product. The reaction product was cooled to about 23 °C under nitrogen.

[0044] Comparative Example 3 (CEx. 3): About 100 g of CTO 1 was added to a 250 mL 4-neck round-bottom flask equipped with a thermocouple, Barrett trap and condenser, nitrogen gas-inlet, and mechanical stirring shaft. Phosphoric acid (0.588 g) was added to produce a mixture and the reactor was purged for about 10 min under nitrogen. The mixture was heated to a temperature of about 200°C and held for about 15 min. The temperature of the mixture was increased to about 300°C and held for about 7 hr with a light stream of nitrogen passing overhead to produce a reaction product. The reaction product was cooled to about 23 °C under nitrogen.

[0045] Example 4 (Ex. 4): About 30 g of CTO 1 was added to a 50 mL 3-neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The reactor was purged for about 10 min with nitrogen. The CTOl was heated to a temperature of about 200°C. FeCl ₃ (about 7.2 mg), ( H ₄ ) ₂ C0 ₃ (about 36 mg), and I ₂ (about 90 mg) were added to the flask in succession with the flask under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. About 32 mg of ethylenediamine was added and a reaction product was cooled to about 23 °C under nitrogen. [0046] Example 5 (Ex. 5): About 30 g of CTO 1 was added to a 50 mL 3-neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The reactor was purged for about 10 min with nitrogen. The CTOl was heated to a temperature of about 200°C. FeCl ₃ (7.2 mg), ( H ₄ ) ₂ C0 ₃ (about 36 mg), and I ₂ (about 90 mg) were added to the flask in succession with the flask under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. About 32 mg of ethylenediamine and about 0.214 g of methanesulfonic acid (70 wt%) were added and the temperature of the mixture was increased to about 300°C. Heating continued for about 4 hr at which point a reaction product was cooled to about 23 °C under nitrogen.

CEx. 3 6.0 4.5 10.5 79 36 16

Ex. 4 25.6 D 25.6 12 88 ND

Ex. 5 9.3 9.9 19.2 68 66 34

[0047] Example 6 (Ex. 6): About 30 g of crude tall oil (CTO 2) was added to a 50 mL 3-neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The reactor was purged for about 10 min with nitrogen. The CT02 was heated to a temperature of about 200°C. FeCl ₃ (about 12 mg), (NH ₄ ) ₂ C0 ₃ (about 36 mg), and I ₂ (about 90 mg) were added to the flask in succession with the flask under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. About 30 mg of ethylenediamine was added and the reaction mixture was rapidly cooled to about 23 °C with an ice-bath under nitrogen.

[0048] Example 7 (Ex. 7): About 30 g of CTO 2 was added to a 50 mL 3-neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The reactor was purged for about 10 min with nitrogen. The CT02 was heated to a temperature of about 200°C. FeCl ₃ (about 12 mg), (NH ₄ ) ₂ C0 ₃ (about 36 mg), and I ₂ (about 90 mg) were added to the flask in succession with the flask under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. About 30 mg of ethylenediamine and about 0.214 g of methanesulfonic acid (70 wt%) were added to the flask and the reaction mixture was rapidly cooled to about 23 °C with an external ice-bath under nitrogen. The temperature of the mixture was increased to about 300°C. Heating continued for about 4 hr at which point a reaction product was cooled to about 23 °C under nitrogen.

[0049] Example 8 (Ex. 8): About 30 g of CTO 2 was added to a 50 mL 3-neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The reactor was purged for about 10 min with nitrogen. The CT02 was heated to a temperature of about 200°C. FeCl ₃ (about 12 mg), (NH ₄ ) ₂ C0 ₃ (about 36 mg), and I ₂ (about 90 mg) were added to the flask in succession with the flask under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. About 30 mg of ethylenediamine and about 0.214 g of methanesulfonic acid (70 wt%) were added to the flask and the reaction mixture was rapidly cooled to about 23 °C with an external ice-bath under nitrogen. The temperature of the mixture was increased to about 300°C. Heating continued for 8 hr at which point a reaction product was cooled to about 23 °C under nitrogen. Table 3: Fatty Acids and Rosin Acids Amounts

Fatty Acids: (wt%)

Sample Oleic Linoleic Linolenic Eicosatrienoic Palmitic Total

CT0 2 19.3 21.8 0.2 1.7 3.5 47.6

Rosin

1.4 - - - - 1.4

Oil

Ex. 6 22.2 11.5 0.2 - 3.7 38.8

Ex. 7 18.5 0.2 - - 3.1 23.1

Ex. 8 12.8 0.2 0.2 - 2.5 16.6

Rosin Acids: (wt%)

Sample Abietic Dehydroabietic Palustric Pimaric Total

CT0 2 11.5 3.6 5.8 3.2 29.8

Rosin

- 2.5 - - 2.5

Oil

Ex. 6 2.2 16.7 - - 18.8

Ex. 7 - 3.0 - - 3.0

Ex. 8 - 1.2 - - 1.2

[0050] Example 9 (Ex. 9): A fatty acids mixture (about 20 g, commercially available as XTOL ^® 100 tall oil fatty acids, from Georgia-Pacific Chemicals LLC) and a rosin acids mixture (about 10 g, commercially available as LYTOR ^® 100 tall oil rosin acid, from Georgia-Pacific Chemicals LLC) were added to a 50 mL 3 -neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The reactor was purged for about 10 min with nitrogen. The mixture of fatty and rosin acids was heated to a temperature of about 200°C. FeCl ₃ (10 mg), ( H ₄ ) ₂ C0 ₃ (about 36 mg), and I ₂ (about 90 mg) were added to the flask in succession with the flask under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. Ethylenediamine (about 30 mg) and methanesulfonic acid (70 wt%, about 0.214 g) were added and a reaction product was cooled to about 23°C under nitrogen. [0051] Example 10 (Ex. 10): A fatty acids mixture (about 20 g, commercially available as XTOL ^® 100 tall oil fatty acids, from Georgia-Pacific Chemicals LLC) and a rosin acids mixture (about 10 g, commercially available as LYTOR ^® 100 tall oil rosin acid, from Georgia-Pacific Chemicals LLC) were added to a 50 mL 3 -neck round-bottom flask equipped with a thermocouple, condenser, nitrogen gas-inlet, and magnetic stir bar. The reactor was purged for about 10 min with nitrogen. The mixture of fatty and rosin acids was heated to a temperature of about 200°C. FeCl ₃ (about 10 mg), ( H ₄ ) ₂ C0 ₃ (about 36 mg), and I ₂ (about 90 mg) were added to the flask in succession with the flask under positive nitrogen pressure. The mixture was heated to a temperature of about 230°C and held for about 15 min. Ethylenediamine (about 30 mg) and methanesulfonic acid (70 wt%, about 0.214 g) were added to the flask and the reaction mixture was rapidly cooled to about 23 °C with an external ice-bath under nitrogen. The temperature of the mixture was increased to about 300°C. Heating continued for about 4 hr at which point a reaction product was cooled to about 23 °C under nitrogen.

[0052] Embodiments of the present disclosure further relate to any one or more of the following paragraphs: [0053] 1. A method for making a fatty acid dimer composition, comprising: combining a first catalyst and a mixture comprising fatty acids and rosin acids to produce a first mixture, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration; heating the first mixture to a first temperature that is less than 250°C to produce a first reaction mixture having a second dehydroabietic acid concentration greater than the first dehydroabietic acid concentration; and heating the first reaction mixture to a second temperature that is at 250°C or greater to produce a second reaction mixture, wherein the second reaction mixture comprises rosin oil, oligomeric acids and monomer acids, and has a rosin oil yield of greater than 25%.

[0054] 2. A method for making a fatty acid dimer composition, comprising: combining a first catalyst and a mixture comprising fatty acids and rosin acids to produce a first mixture, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration; heating the first mixture to a first temperature that is less than 250°C to produce a first reaction mixture having a second dehydroabietic acid concentration greater than the first dehydroabietic acid concentration; combining a second catalyst and the first reaction mixture to produce a second mixture; and heating the second mixture to a second temperature that is at 250°C or greater to produce a second reaction mixture, wherein the second reaction mixture comprises rosin oil, oligomeric acids and monomer acids, and has a rosin oil yield of greater than 25%.

[0055] 3. A method for making a fatty acid dimer composition, comprising: adding a first catalyst comprising at least one iron source and at least one iodine source to a mixture comprising fatty acids and rosin acids to produce a first mixture, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration; heating the first mixture to a first temperature of about 150°C to about 260°C to produce a first reaction mixture, wherein the first reaction mixture has a second dehydroabietic acid concentration that is greater than the first dehydroabietic acid concentration; and heating the first reaction mixture in the presence of a second catalyst to a temperature greater than the first temperature to produce a second reaction mixture comprising oligomeric acids and rosin oils, wherein the second catalyst comprises methanesulfonic acid, ethylenediamine, or a mixture thereof, the rosin oils are produced from the rosin acids, and the second reaction mixture has a rosin oil yield of greater than 25%. [0056] 4. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids comprises crude tall oil, and the second reaction mixture has a rosin oil yield of about 30% to about 95%.

[0057] 5. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids comprises crude tall oil, and the second reaction mixture has a rosin oil yield of about 35% to about 60%.

[0058] 6. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids comprises crude tall oil, and the second reaction mixture has a rosin oil yield of about 40% to about 70%.

[0059] 7. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids comprises crude tall oil, and the second reaction mixture has a rosin oil yield of about 45% to about 75%.

[0060] 8. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids comprises crude tall oil, and the second reaction mixture has a rosin oil yield of about 50% to about 90%.

[0061] 9. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids is derived entirely from crude tall oil, and the second reaction mixture has a rosin oil yield of about 30% to about 95%.

[0062] 10. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids is derived entirely from crude tall oil, and the second reaction mixture has a rosin oil yield of about 35% to about 60%.

[0063] 11. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids is derived entirely from crude tall oil, and the second reaction mixture has a rosin oil yield of about 40% to about 70%.

[0064] 12. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids is derived entirely from crude tall oil, and the second reaction mixture has a rosin oil yield of about 45% to about 75%. [0065] 13. The method according to any one of paragraphs 1 to 3, wherein the mixture comprising fatty acids and rosin acids is derived entirely from crude tall oil, and the second reaction mixture has a rosin oil yield of about 50% to about 90%.

[0066] 14. The method according to any one of paragraphs 1 to 13, wherein the first catalyst comprises an iron source and an iodine source, or a mixture thereof, and added in succession to the mixture comprising fatty acids and rosin acids.

[0067] 15. The method according to paragraph 14, wherein the iron source comprises an iron halide and the iodine source comprises elemental iodine (I ₂ ).

[0068] 16. The method according to any one of paragraphs 1 to 15, wherein the first catalyst comprises nickel, palladium, platinum, iron, copper, cobalt, manganese, tin, sulfur, iodine, selenium, or any combination thereof.

[0069] 17. The method according to any one of paragraphs 1 to 16, wherein the first catalyst comprises a sulfur source comprising an alkylphenol sulfide, a phenol sulfide, 2-2'-thiobis(4- methyl-6-t-butylphenol), 1 -thio-2-naphthol, 1 , 1 '-di-(2-naphthol)-disulfide, 1 , 1 '-di(2-naphthol)- sulfide, 2,5-diphenyl dithiin, 1,3,4-thiadiazole polysulfides, 4,4'-thiobis(resorcinol), 2,2'- thiobis(4,6-dimethylphenol), or any combination thereof.

[0070] 18. The method according to any one of paragraphs 1 to 17, wherein the first catalyst comprises an iron source, a nitrogen source and an iodine source that are added in succession to the mixture comprising fatty acids and rosin acids, and wherein the iron source comprises an iron halide, the nitrogen source comprises an ammonium compound, an amine compound, a urea compound, or a mixture thereof, and the iodine source comprises elemental iodine (I ₂ ).

[0071] 19. The method according to any one of paragraphs 1 to 18, wherein the first catalyst is combined with the mixture comprising fatty acids and rosin acids in an amount of about 0.01 wt% to about 2 wt%, based on the total weight of the fatty acids and the rosin acids.

[0072] 20. The method according to any one of paragraphs 1 to 19, wherein the first temperature is about 180°C to less than 250°C and the mixture comprising the first catalyst, the fatty acids, and the rosin acids is heated at the first temperature for about 1 min to about 30 min to produce the first reaction mixture. [0073] 21. The method according to any one of paragraphs 1 to 3 or 14 to 20, wherein the mixture comprising fatty acids and rosin acids is derived from crude tall oil, distilled tall oil, or a blend thereof.

[0074] 22. The method according to any one of paragraphs 2 to 21, wherein the second catalyst comprises a Bransted acid or a Lewis acid, and wherein the second catalyst is added to the first reaction mixture.

[0075] 23. The method according to any one of paragraphs 2 to 22, wherein the second catalyst comprises methanesulfonic acid, p-toluenesulfonic acid, phosphoric acids, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, sulfuric acid, isomers thereof, salts thereof, esters thereof, or any mixture thereof.

[0076] 24. The method according to any one of paragraphs 2 to 23, wherein the second catalyst is combined with the first reaction mixture in an amount of about 0.05 wt% to about 3 wt%, based on the total weight of the fatty acids and the rosin acids.

[0077] 25. The method according to any one of paragraphs 2 to 24, wherein the mixture comprising the second catalyst and the first reaction mixture is heated to about 280°C to about 320°C for about 2 hr to about 12 hr to produce the second reaction mixture.

[0078] 26. The method according to any one of paragraphs 1 to 25, wherein the mixture comprising fatty acids and rosin acids has a first dehydroabietic acid concentration, the first reaction mixture has a second dehydroabietic acid concentration, and wherein the second dehydroabietic acid concentration is greater than the first dehydroabietic acid concentration.

[0079] 27. The method according to any one of paragraphs 2 to 26, wherein the second catalyst comprises clay.

[0080] 28. The method according to paragraph 27, wherein the clay comprises hectorite, montmorillonite, attapulgite, halloysite, kaolinite, sepiolite, bentonite, calcium bentonite, Fuller's Earth, acid-treated clay, acid-treated bentonite, acid-treated montmorillonite, alkaline clay, or any mixture thereof.

[0081] 29. The method according to any one of paragraphs 2 to 28, wherein the second catalyst comprises an alkaline earth metal halide, lithium hydroxide, lithium carbonate, or an acidic ion exchange resin. [0082] 30. The method according to any one of paragraphs 2 to 29, wherein the second catalyst comprises a zinc halide, a zinc halide in presence of a hydrogen halide, a magnesium silicate, a magnesium silicate in the presence of a nitrogenous compound, a stannic halide, or any mixture thereof.

[0083] 31. The method according to any one of paragraphs 1 to 30, wherein the first dehydroabietic acid concentration is about 0.5 wt% to about 12 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0084] 32. The method according to any one of paragraphs 1 to 31, wherein the first dehydroabietic acid concentration is about 0.5 wt% to about 10 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0085] 33. The method according to any one of paragraphs 1 to 32, wherein the first dehydroabietic acid concentration is about 0.5 wt% to about 8 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0086] 34. The method according to any one of paragraphs 1 to 33, wherein the first dehydroabietic acid concentration is about 1 wt% to about 6 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0087] 35. The method according to any one of paragraphs 1 to 34, wherein the second dehydroabietic acid concentration is about 1 wt% to about 30 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0088] 36. The method according to any one of paragraphs 1 to 35, wherein the second dehydroabietic acid concentration is about 2 wt% to about 25 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0089] 37. The method according to any one of paragraphs 1 to 36, wherein the second dehydroabietic acid concentration is about 3 wt% to about 10 wt%, based on the combined weight of the fatty acids and the rosin acids.

[0090] 38. The method according to any one of paragraphs 1 to 37, wherein the second dehydroabietic acid concentration is about 5 wt% to about 25 wt%, based on the combined weight of the fatty acids and the rosin acids. [0091] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0092] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. And if applicable, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0093] While the foregoing is directed to certain illustrative embodiments, other and further embodiments of the invention can be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.