Biorenewable hydrocarbon compositions and uses thereof

Abstract

To provide compositions comprising dimeric decarboxylated rosins (DDCRs), methods for making them, and applications thereof.SOLUTION: DDCR of purity from 50-100 wt.% is obtained by decarboxylating a dimeric rosin acid or by dimerizing a decarboxylated rosin, in the presence of a catalyst, followed by one or more purification steps separation based on differences in boiling point. The isolated DDCR fractions display unexpectedly high Tg / Mn ratios, softening points and viscosities, and low polydispersities. The DDCR product comprises 50 to 100 wt.% of polycyclic hydrocarbon compounds having one or more aliphatic, unsaturated or aromatic groups, and 34-80 carbon atoms, with a molecular weight Mn of 250-900 Da, and an oxygen to carbon ratio of less than 5%. The DDCR product has at least 50%, and up to 100% as dimeric species, with the remainder being trimeric and larger polymeric species.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to bio-renewable rosin-derived hydrocarbon compositions and uses thereof. [Background technology]

[0002] Dimeric rosin acid (DRA) has been known in the art for over 80 years. See, for example, U.S. Pat. No. 2,124,675 to Rummelsburg. DRA and derivatives, such as their esters, are used as additives in a wide variety of applications, including hot melt and pressure-sensitive adhesives, modifiers for rubber and various plastics, emulsifiers for synthetic rubber, base materials for chewing gum, resins in coating compositions such as road paints and inks, fluxes, and sizing agents for papermaking.

[0003] Many of these additives are suitable for many applications but lack the properties that make them suitable for certain applications. They are relatively polar compounds that may be incompatible with less polar polymers, such as polyolefins. In contrast, fossil-derived hydrocarbon compounds exhibit this compatibility.

[0004] Thus, there continues to be a need for rosin-based hydrocarbon compositions that exhibit improved properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 2,124,675 Summary of the Invention [Problem to be solved by the invention]

[0006] (Summary of the Invention) Novel compositions comprising dimeric decarboxylated rosin (DDCR), methods for making same, and uses thereof are disclosed. [Means for solving the problem]

[0007] In one embodiment, the dimeric decarboxylated rosin (DDCR) composition comprises 50-100 wt. % polycyclic hydrocarbon compounds having one or more aliphatic, unsaturated, or aromatic groups and 34-80 carbon atoms. The composition has a molecular weight M of 250-900 Da, preferably 300-600 Da, more preferably 350-450 Da, and most preferably 380-420 Da, as measured using gel permeation chromatography and polystyrene calibration standards. n and an oxygen-to-carbon ratio of less than 5%, preferably less than 3%, more preferably less than 2%, and most preferably 0-1%. The compositions are formed by decarboxylating dimeric rosin acids or by dimerizing decarboxylated rosin. In embodiments, the DDCR has up to 100% dimeric species.

[0008] In embodiments, the DDCR composition has an acid number, measured using ASTM D465, of less than 80 mg KOH / g, preferably less than 25 mg KOH / g, more preferably less than 15 mg KOH / g, and most preferably less than 5 mg KOH / g; a flash point according to ASTM D92 of greater than 150°C; a ring and ball softening point according to ASTM E28-18 of 30-160°C, preferably 50-125°C, more preferably 60-120°C, and most preferably 75-110°C; a Gardner color (neat) according to ASTM D6166 of 0-18, preferably 1-14, more preferably 2-10, and most preferably less than 5; a Brookfield viscosity at 177°C, ASTM D2196, of 15-1000 mPa·s, preferably 25-500 mPa·s, and more preferably 35-250 mPa·s; Glass transition temperature (Tg) according to E1356: -20 to 110°C, preferably 0 to 90°C, more preferably 15 to 75°C, and most preferably 25 to 65°C; and 1.00 to 1.04, preferably 1.01 to 1.03, and more preferably 1.015 to 1.025 g / cm. 3 a density of 1.0 to 1.2, preferably 1.05 to 1.15; a polydispersity index of greater than 0.6, preferably 0.6 to 1.0, more preferably 0.65 to 0.9, most preferably 0.7 to 0.85;g / M n (K / Da) ratio; and a polyolefin cloud point of less than 70°C, preferably less than 60°C, more preferably less than 50°C, and most preferably less than 40°C.

[0009] In a second aspect, a method for producing a dimeric decarboxylated rosin (DDCR) composition is disclosed. The method includes: a) providing a feedstock containing dimeric rosin acid; b) heating the dimeric rosin acid feedstock with a catalyst in a decarboxylation reaction at a temperature of 200-400°C to form crude dimeric decarboxylated rosin (DDCR) in a mixture containing monomeric decarboxylated rosin, dimeric rosin acid, and remaining multimeric species; and c) subjecting the mixture containing crude dimeric decarboxylated rosin (DDCR) to separation based on the difference in boiling points of the monomeric decarboxylated rosin, dimeric rosin acid, dimeric decarboxylated rosin, and remaining multimeric species to produce the DDCR composition.

[0010] In an embodiment, preparing a dimeric rosin acid (DRA) feedstock includes heating a feedstock comprising rosin acid with a catalyst at a temperature of −80 to 200° C. in a dimerization reaction to form dimeric rosin acid (DRA).

[0011] In a third aspect, a method for producing a dimeric decarboxylated rosin (DDCR) composition is disclosed. The method includes providing a feedstock containing rosin acid; heating the feedstock containing rosin acid with a catalyst in a decarboxylation reaction at a temperature of 200 to 400°C to form decarboxylated rosin; heating the decarboxylated rosin with a catalyst in a dimerization reaction at a temperature of −80 to 200°C to form crude dimeric decarboxylated rosin (DDCR) in a mixture containing monomeric decarboxylated rosin, dimeric rosin acid, and remaining multimeric species; and subjecting the mixture containing crude dimeric decarboxylated rosin (DDCR) to separation based on the difference in boiling points of the monomeric decarboxylated rosin, dimeric rosin acid, dimeric decarboxylated rosin, and remaining multimeric species to provide the DDCR composition.

[0012] In a fourth aspect, a polymer composition and articles made therefrom are disclosed, comprising 1 to 80 wt. % of a DDCR composition, wherein the polymer comprises at least one polymer selected from styrenic block copolymers, engineering thermoplastics, polyolefins, plastomers, rubbers, and blends. DETAILED DESCRIPTION OF THE INVENTION

[0013] As used herein, the following terms have the following meanings:

[0014] GPC molecular weights are measured against polystyrene calibration standards using a triple detector array and mixed column set.

[0015] Acid number is measured according to ASTM D1240-14 (2018).

[0016] Ring and ball softening point is measured according to ASTM E28-18.

[0017] Density is measured according to ASTM D792-13.

[0018] Simulated distillation (SimDist) analysis according to EN 15199-2.

[0019] Glass transition temperature by differential scanning calorimetry according to ASTM E1356.

[0020] Dynamic Brookfield viscosity is measured at 177°C according to ASTM D2196.

[0021] The cloud point of a composition refers to the temperature below which a clear mixture becomes cloudy, the mixture being a 1:1 (by weight) blend of the composition and a commercially available metallocene-catalyzed polyolefin, such as Dow Chemical's AFFINITY™ GA 1950. The cloud point can be measured using a chemical-electronics instrumented turbidity detection system that records a cooling curve and correlates therefrom the cloud point temperature detected at 50% light transmittance.

[0022] Flash point is measured according to ASTM D92.

[0023] Weight percent refers to weight concentration.

[0024] The disclosure herein provides compositions comprising dimeric decarboxylated rosin (DDCR) and methods for forming DDCR by decarboxylating dimeric rosin acid (DRA) and isolating DDCR in purified form therefrom. An embodiment of the decarboxylation reaction for forming DDCR from DRA is shown schematically below.

[0025] [ka]

[0026] In embodiments, DRA is first prepared in situ from rosin acid starting material. The in situ formed DRA is then decarboxylated to generate crude DDCR for subsequent isolation / purification.

[0027] Starting Material—Dimeric Rosin Acid (DRA) Feedstock: In embodiments, the feedstock comprises, consists essentially of, or consists of dimeric rosin acid (DRA). DRA can be produced from rosin acid using at least one catalyst selected from: (i) a Lewis acid, such as BF, AlCl, or ZnCl; (ii) a Bronsted acid, such as (aqueous) HSO (sulfuric acid), HPO (phosphoric acid), fluoroboric acid, fluorosulfonic acid, monofluorophosphoric acid, and difluorophosphoric acid, optionally in the presence of a protic carboxylic acid, such as acetic acid, or in the presence of fluorobenzene as a solvent; or (iii) a protic carboxylic acid, such as formic acid, acetic acid, or (carboxylated) sulfonic acid, and a solid-phase deposition catalyst.

[0028] In embodiments, the starting DRA material has an acid number (AV) of 130-160 mg KOH / g, or greater than 100 mg KOH / g, or greater than 120 mg KOH / g, or less than 250 mg KOH / g. The starting DRA material has a softening point of 70-200°C, or 90-150°C, or less than 250°C, or greater than 50°C.

[0029] In embodiments, any DRA derivative understood by those skilled in the art may be used, e.g., a precursor or reaction product of DRA, e.g., modified compounds containing functional groups such as esters (e.g., aliphatic, aromatic, benzyl), amides, salts, acyl halides (e.g., as carboxylic acid chlorides), alcohols, anhydrides, and combinations thereof, e.g., alkyl-substituted, aryl-substituted, or combinations thereof.

[0030] Starting Material—Rosin Acid Feedstock: In embodiments, the feedstock comprises, consists essentially of, or consists of rosin acid. The rosin acid may be a tall oil-based feedstock, such as tall oil rosin. Gum-derived rosin acid and stump-derived rosin acid may also be used. Isomeric compounds present in tall oil rosin may also be used, including, but not limited to, abietic acid, neoabietic acid, palustric acid, levopimaric acid, dehydroabietic acid, sandaracopimaric acid, and any mixtures thereof. These types of compounds may also be used as part of a blend, including, but not limited to, crude tall oil (CTO). The rosin acid may contain varying amounts of diunsaturated conjugated isomers and dimeric rosin acids, which may affect the yield and blending of the DRA product composition. In embodiments, the rosin acid starting material has an acid number (AV) of 160-190 mg KOH / g, or greater than 100 mg KOH / g, or greater than 120 mg KOH / g, or less than 250 mg KOH / g. In embodiments, the rosin acid has a softening point of 55-75°C, or less than 100°C, or greater than 50°C.

[0031] In embodiments, DRA may be prepared from a mixture of abietic acids, pimarane acids, and isopimaranic acids. In embodiments, the abietic acids are present in an amount of 50-90% by weight, 55-80% by weight, or 60-70% by weight. Examples of abietic acids include palustric acid, abietic acid, neoabietic acid, dihydroabietic acid, levopimaric acid, and dehydroabietic acid. In embodiments, the amount of pimarane acids ranges from 2-10% by weight, 4-8% by weight, or 4-6% by weight. Examples of pimarane acids include pimaric acid, 7,15-pimaradienoic acid, and 8,15-pimaric acid. In embodiments, the amount of isopimaranic acid ranges from 5 to 30% by weight, or 8 to 25% by weight, or 10 to 20% by weight, and is selected from sandaracopimaric acid, isopimaric acid, 8,15-isopimaric acid, and mixtures thereof. In embodiments, the starting material is primarily an abietic acid, including a mixture of abietic acid, neoabietic acid, palustric acid, levopimaric acid, and dehydroabietic acid.

[0032] In embodiments, the feedstock further includes rosin acid derivatives that will be understood by those skilled in the art to be useful, e.g., precursors or reaction products of DRA, e.g., modified compounds containing functional groups such as esters (e.g., aliphatic, aromatic, benzyl), amides, salts, acyl halides (e.g., as carboxylic acid chlorides), alcohols, anhydrides, and combinations thereof, e.g., alkyl-substituted, aryl-substituted, or combinations thereof.

[0033] In embodiments, the feedstock (e.g., dimeric rosin acid or rosin acid) optionally includes one or more copolymerizable monomers, such as monomers capable of participating in a self-polymerization reaction. Examples include (i) aromatic compounds having olefinic groups, (ii) cyclodienes or dimers thereof, (iii) divinylarenes other than the diisoalkenylarenes of formula (I) or (II), and (iv) adducts of 1,3-cyclodienes and acylic dienes, or any combination of comonomers (i)-(iv). In embodiments, the copolymerizable monomers are selected from limonene, terpenes, α-pinene, β-coumarone, pinene, indene, styrene and their homologs, such as α-methylstyrene, 4-methylstyrene, p-tert-butylstyrene; vinyltoluene; dicyclopentadiene; C5 and C9 feedstocks; and the like.

[0034] The rosin acid derivative and / or any copolymerizable monomer may optionally be added in an amount of up to 10% by weight of the feedstock, or up to 20% by weight, or up to 40% by weight, or 5-50% by weight.

[0035] Methods for Formation: In embodiments, decarboxylation of DRA is accomplished by heating DRA in the presence of a catalyst to generate crude DDCR. In embodiments, the DRA starting material can be diluted in a suitable solvent before initiating the decarboxylation reaction. A solvent can be used to aid in introducing the DRA into the reactor, for example, by pumping. Examples of suitable solvents include toluene, xylene, dodecane, hexadecane, formic acid, acetic acid, or mixtures thereof. Alternatively, decarboxylation can be carried out in a solvent-free manner.

[0036] In a second embodiment, DRA is first prepared in situ from rosin acid. The in situ-formed DRA is then decarboxylated to generate crude DDCR. This in situ dimerization of rosin acid to form DRA and subsequent decarboxylation can be achieved by a process comprising heating rosin acid in the presence of a catalyst to generate crude DDCR. Optionally, prior to the decarboxylation step at elevated temperatures, e.g., above 200°C, a holding period may be applied to promote dimerization first, e.g., in bulk at temperatures of 150-200°C or 170-190°C; for a period of 0.5-8 hours or 1-4 hours. Lower temperatures ranging from the freezing point to the boiling point of the solvent may also be applied. A solvent may optionally be used in either or both of the dimerization and decarboxylation reactions, in an amount of at least 50% by weight of the reactants or 75-300% by weight of the total reactant weight.

[0037] In a third embodiment, rosin acids are first decarboxylated, and the resulting decarboxylated rosin is subsequently dimerized to produce crude DDCR. Decarboxylation of the rosin acids can be achieved by heating the rosin acids in the presence of a catalyst to produce crude DCR (as monomeric decarboxylated rosin, or MDCR). Subsequent dimerization of the crude DCR can be achieved by a process comprising heating the crude DCR in the presence of a catalyst to produce a crude DDCR material product.

[0038] In embodiments, the rosin acid starting material can be diluted in a suitable solvent before initiating the dimerization and / or decarboxylation reactions. A solvent can be used to aid in introducing the rosin acid into the reactor, for example, by pumping. Examples include toluene, xylene, dodecane, hexadecane, formic acid, acetic acid, or mixtures thereof. Alternatively, the dimerization and / or decarboxylation can be carried out in a solvent-free manner. The decarboxylation catalyst can be the same as or different from the dimerization catalyst.

[0039] The above step, i.e., decarboxylation or dimerization, may be carried out in a batch reactor, a semi-batch reactor, or a continuous reactor. The reaction may be carried out under vacuum or under a pressure of 1 to 60 bar, alternatively 5 to 50 bar, alternatively 10 to 40 bar, alternatively 20 to 30 bar, etc.; at a temperature of 100°C to 400°C, or 150 to 350°C, or 200 to 350°C, or 250 to 300°C, for a period of 0.25 to 48 hours, or 0.5 to 24 hours, or 1 to 14 hours.

[0040] The dimerization reaction is preferably carried out at a temperature below 200° C., for example, 100 to 150° C. or 125 to 175° C. The decarboxylation reaction is preferably carried out at a higher temperature, for example, above 200° C. or 235 to 300° C. or 250 to 350° C. or 300 to 375° C. In embodiments involving the use of a solvent in the dimerization reaction, the reaction temperature may be within the range from the freezing point to the boiling point of the solvent, for example, −80° C., −50 to 150° C., −20 to 120° C., −10 to 80° C., or 0 to 30° C.

[0041] Since decarboxylation results in weight loss due to the evolution of water, CO, CO2, and / or light, the above process steps can provide a crude DDCR material product with a yield of up to 85 wt. % based on the weight of the starting DRA.

[0042] The crude DDCR is subsequently purified in one or more steps, for example, by separation based on differences in boiling points, for example, by fractional distillation, evaporation such as scraped-film evaporation, or a combination thereof. If necessary, a washing step can first be carried out to remove residual catalyst. This can be done by methods known in the art, for example, by decantation and / or filtration. Washing can be carried out using water or aqueous solvents and suitable organic solvents, such as aromatic solvents, for example, toluene and xylene.

[0043] Subsequent one or more successive separation steps aid in separating the mixture containing different types of species in the crude DDCR, such as rosin acids, dimeric rosin acids, monomeric decarboxylated rosin (MDCR), DDCR, and remaining multimeric species. The different fractions typically contain multiple isomers of generally the same type of species. The DDCR product is isolated by purification to provide DDCR with a purity ranging from greater than 95% by weight, or 50-100% by weight, 60-95% by weight, or greater than 75% by weight, or greater than 85% by weight, or greater than 95% by weight, or even up to 100% by weight DDCR.

[0044] Collection of other relevant fractions, such as monomeric decarboxylated rosin (MDCR), can help maximize process throughput / output. High temperature GC-FID / MS analysis can be used to identify the DDCR content and individual components present. The crude product, product fractions obtained from the separation step, such as DDCR, and combinations thereof, may be hydrogenated to provide products that can be used as additives in a variety of polymer compositions.

[0045] Catalyst Material: The catalyst is selected depending on the feedstock, purity, and desired properties of the final DDCR product. With the use of rosin acid as the feedstock, the same or different catalysts can be used for the decarboxylation step and the dimerization step. In embodiments, certain catalysts are preferably (but not limited to) used as decarboxylation catalysts ("Category A"); certain catalysts are preferably (but not limited to) used as dimerization catalysts ("Category B"); and certain catalysts are preferably used for both the dimerization step and the decarboxylation step ("Category C").

[0046] The catalyst can be either a Bronsted acid type or a Lewis acid type. Alternatively, the catalyst may have both Bronsted acid type and Lewis acid type catalytic activity. In embodiments, the catalyst comprises a supported Bronsted acid, an unsupported Bronsted acid, a Lewis acid, precursors thereof, or combinations thereof. Various non-limiting classes of catalysts can be used, including organic acids, organic sulfonic acids, organic sulfonyl chlorides, inorganic acids, peroxides, clays, siliceous earths, zeolites, any Lewis acid based on metals from Groups 4, 5, 12, 13, 14, and 15 of the Periodic Table of the Elements, metal halides of elements from Groups 2 and 3 of the Periodic Table of the Elements, and mineral acids or anhydrides from Groups 4, 5, and 6 of the Periodic Table of the Elements, salts thereof, and mixtures thereof.

[0047] In embodiments, the catalyst is selected from the group of organic and inorganic phosphoric acid species, such as phosphoric anhydride, phosphoric acid, hypophosphorous acid, phosphorus pentoxide, triphenyl phosphate, calcium (3,5-di-tert-butyl-4-hydroxybenzyl monoethylphosphonate), and polyphosphoric acid, which are classified as catalyst type A.

[0048] In an embodiment, the catalyst is selected from the group of organic carboxylic acids, such as formic acid, acetic acid, propionic acid, carboxylic acid esters, such as methyl formate, ethyl acetate, acyl halides, such as acetyl chloride, benzoyl chloride, acetyl iodide, carboxylic acid anhydrides, such as formic anhydride, acetic anhydride, carboxylic acid halides, such as chloroformic acid, trifluoroacetic acid, which are classified as catalyst type B.

[0049] In an embodiment, the catalyst is selected from organic and inorganic sulfur species such as diphenyl sulfide, benzyl phenyl sulfide, ditoluyl sulfide, dinaphthyl sulfide, diheptyl sulfide, sodium sulfide, potassium sulfide, lithium sulfide, magnesium sulfide, calcium sulfide, iron sulfide, sulfuric acid, sulfur dioxide, 2,5-dichlorobenzenesulfonic acid, chlorosulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonyl chloride, benzenesulfonic acid, benzenesulfonyl chloride, 2,5-dichlorobenzenesulfonic acid, β-naphthol-3,6,8-trisulfonic acid, sulfosalicylic acid, p-toluidine-m-sulfonic acid, sulfur chloride, thionyl chloride, sulfuryl chloride, sulfonated solid acid derivatives such as sulfonated styrene-divinylbenzene, sulfonated silica, sulfonated fluoropolymers and polystyrene-supported sulfonic acid, and mixtures thereof. These are classified as catalyst type C.

[0050] In an embodiment, the catalyst is selected from the group of mineral acids, such as hydrochloric acid, nitric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, hydroiodic acid, and heteropolyacids, such as tungstophosphoric acid and tungstosilicic acid, which are classified as catalyst type C.

[0051] In an embodiment, the catalyst is a metal oxide selected from TiO2-based catalysts, ZrO2-based catalysts, bauxite, metal dusts, powders and shavings such as those based on zinc, iron, nickel and / or copper, MgSO4, NHI, Ba(SCN)2, ZnCO3, ZnBr2, PbCrO4, K2Cr2O7, BaS, CdS, Li2CO3, MgCl2, (NH4)2SO3, Ba(SCN)2, Pb(OAc)2, MgCO3, diphenyl hydrobromide, NaHSO3, BaO2, hydroiodic acid, magnesium oxide, ammonium iodide, calcium oxide, zinc oxide, zinc formate, zinc, boron, aluminum, gallium, indium, titanium, zirconium, tin, vanadium, arsenic, antimony and any Lewis acid based on a metal from Groups 4, 5, 12, 13, 14 and 15 of the Periodic Table of the Elements, including bismuth. Examples include AlCl, (alkyl)AlCl, (C2H5)2AlCl and (C2H5)3Al2Cl, BF3, SnCl, TiCl, ZnCl, SnCl, CuCl or combinations, which are classified as catalyst type B.

[0052] In an embodiment, the catalyst is based on a phyllosilicate, such as a natural or synthetic clay from the kaolin group, such as kaolinite, halloysite, dickite, or the smectite group, such as montmorillonite, nontronite, hectorite, or saponite, or the illite / mica group, such as glauconite, muscovite, or sodalite, or the chlorite group, such as chamosite, cookite, or nimite, calcined at temperatures between 200° C. and 1000° C., treated, washed, activated, or used with a mineral acid, such as sulfuric acid or hydrochloric acid, altered with salts of lithium, sodium, magnesium, iron, etc., and / or exchanged in a medium such as water, modified or pillared with aluminum, and is classified as catalyst type A.

[0053] In embodiments, the catalyst is a solid inorganic acid catalyst based on a metal oxide refractory material such as silicon, silica, aluminum, and / or alumina. In other embodiments, the catalyst is based on a natural or synthetic microporous aluminosilicate from the zeolite group, in proton or cationic form. In still other embodiments, the catalyst is based on a mesoporous material, in proton or cationic form, e.g., silica aluminophosphates such as SAPO-11, SAPO-34, or aluminosilicates such as MCM-41, MCM-48. Illustrative examples include amorphous silica alumina, zeolite catalysts such as USY, L, mordenite, ferrierite, ZSM-5, β; and silicates such as SBA-15, SBA-16, each having a silica content of 0.1 to 99.9%, a pore size of 0.1 ml / g to 5 ml / g, and / or a pore size of 100 to 1000 m. 2 / g surface area (BET), calcined at temperatures between 200°C and 1000°C, supported with metals such as Ni, Pt, Au, Fe, Co, treated, washed, activated or used with mineral acids such as sulfuric acid or hydrochloric acid, these are classified as catalyst type A.

[0054] The amount of catalyst used depends in part on the nature of the catalyst and the reaction type, e.g., decarboxylation or dimerization, and the feedstock. Generally, catalyst loading is greater than 0.01 wt. % based on the weight of the rosin acid or dimer rosin acid feed, and typically ranges from 0.05 to 10 wt. %, or 0.1 to 8 wt. %, or 0.2 to 5 wt. %, or 0.25 to 2.5 wt. %.

[0055] DDCR Product: In embodiments, the DDCR product comprises, in an amount of 50-100% by weight, one or more polycyclic compounds containing one or more aliphatic, unsaturated, or aromatic groups having 34-80 carbon atoms, or 34-60, or 34-40, or 36-38 carbon atoms. Examples of polycyclic compounds include, but are not limited to, dimers, trimers, and higher oligomers / polymers. In embodiments, the DDCR comprises polycyclic compounds having the exemplary structures shown in (I) and (II).

[0056] [ka]

[0057] The DDCR product comprises primarily dimeric species (50% by weight or more, or 75% by weight or more, or 90% by weight or more, or 99% by weight or more), with the remainder being trimer and higher polymeric groups in amounts of 50% by weight or less, or 10% by weight or less, or 15% by weight or less, or 5% by weight or more.

[0058] DDCR products have flash points above 150°C according to ASTM D92.

[0059] In embodiments, the DDCR product has a molar mass (vs. polystyrene calibration standards) in the range of 250-900 Da, or 300-600 Da, or 350-450 Da, or 380-420 Da, as measured using GPC with a triple detector array and mixed column set.

[0060] In embodiments, the DDCR product has an acid number according to ASTM D-465 of less than 80 mg KOH / g, or less than 25 mg KOH / g, or less than 15 mg KOH / g, or less than 5 mg KOH / g, or between 5 and 10 mg KOH / g.

[0061] In embodiments, the DDCR product has a ring and ball softening point of 30-160°C, or 50-125°C, or 60-120°C, or 70-115°C, or 75-110°C, as measured by ASTM E28-18.

[0062] In embodiments, the DDCR product has a Gardner color (neat) according to ASTM D6166 of 0 to 18, or 1 to 14, or 2 to 10. In embodiments with hydrogenated DDCR, the DDCR composition has a Gardner color of less than 12, or less than 8, or less than 5.

[0063] In embodiments, the DDCR product has a Brookfield viscosity, measured at 177°C according to ASTM D2196, of 15 to 1000 mPa·s, or 25 to 500 mPa·s, or 35 to 250 mPa·s.

[0064] In embodiments, the DDCR product has a glass transition temperature (T) according to ASTM E1356 of -20°C to 110°C, or 0 to 90°C, or 15 to 75°C, or 25 to 65°C. g )

[0065] In an embodiment, the DDCR product has a viscosity of 1.00 to 1.04, or 1.01 to 1.03, or 1.015 to 1.025 g / cm 3 It has a density of

[0066] In embodiments, the DDCR product has a T of greater than 0.6, or between 0.6 and 1.0, between 0.65 and 0.9, or between 0.7 and 0.85. g / M n The ratio (K / Da) is presented.

[0067] In embodiments, the DDCR product exhibits a polydispersity index (PDI) (GPC) of 1.0 to 1.2 or 1.05 to 1.15.

[0068] In embodiments, the DDCR product is characterized as having an oxygen content of less than 5%, or less than 3%, or less than 2%, or 0-1%. The oxygen content (in %) in the DDCR is calculated as the oxygen to carbon ratio, i.e., the total oxygen atoms present in the DDCR divided by the total carbon atoms present, where the number of oxygen and carbon atoms is obtained from atomic analysis.

[0069] The DDCR product is a high softening point solid containing primarily relatively low molecular weight dimeric species, and in embodiments, the DDCR product exhibits a low cloud point in polyolefins, indicating high compatibility with non-polar polymers. In embodiments, the DDCR product exhibits a cloud point in polyolefins below 70°C, below 60°C, below 50°C, below 40°C, above -30°C, or above -15°C, and the starting DRA material is not miscible over the temperature range of 0 to 200°C.

[0070] Uses of DDCR: DDCR products can be used in adhesives, such as hot melt adhesives, pressure-sensitive adhesives (PSAs), and flexographic printing applications, including, but not limited to, DDCR. DDCR can also be used as a polymer compatibilizer, tackifier, toughener, or extender in bitumen and asphalt applications, rubber compound and extrusion applications, tire applications, oil field and gas applications, adhesive applications such as carpet construction and road marking, metallic cold-cut paints, painting inks, and waxes. DDCR can also be used to modify hydrocarbon products to increase naphthenic and cyclic content, improve additive solubility, and increase dosage. Other applications include waterproofing, alkali, acid, and moisture resistance in sealants, bitumen binders in roofing and asphalt roads, and coatings.

[0071] In embodiments, DDCR is used as a resin additive, e.g., a tackifier, plasticizer, etc., in various polymer compositions to achieve unique viscoelastic properties and low cloud points due to its inherent compatibility with both aliphatic and aromatic groups in typical polymer compositions. The polymer "modified" by DDCR can generally be any polymer in the prior art, such as a thermoplastic polymer or a thermosetting polymer. Suitable thermoplastic polymers include styrene block copolymers, homopolymers, copolymers, polyolefin homopolymers, copolymers, and plastomers, as well as blends thereof.

[0072] Styrene block copolymers may be linear or radial. An example of a linear polymer is an ABA triblock, where A is an aromatic (hard) block and B is a polydiene (soft) block. Block copolymers may also be diblock, triblock, or multiblock copolymers. Multiblock and radical block copolymers can contain any combination of hard and soft segments. Commercially available thermoplastic rubber-type polymers are particularly useful. The most common structures are linear ABA block types, such as styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS). Other examples of suitable block copolymers include styrene-ethylene-butylene-styrene (S-EB-S) structures. AB-type diblock polymers, such as styrene-ethylene / propylene (S-EP) and styrene-ethylene / butylene (S-EB), styrene-butadiene (SB), and styrene-isoprene (SI), may also be used. Other hydrogenated styrene block copolymers such as S-EP-S (poly(styrene-ethylene / propylene-styrene)) and hydrogenated poly-isoprene / butadiene-styrene (SE / EP-S) polymers may also be used.

[0073] Suitable polyolefins include those made using Ziegler-Natta catalysts or metallocene catalysts. Non-limiting examples of suitable polyolefins made using metallocene or single-site catalysts include plastomers, polyolefin elastomers, metallocene-catalyzed EPDM polymers, low molecular weight polyethylene, polypropylene, and polybutylene.

[0074] The polymer composition may also include polar engineering thermoplastics such as polyamide (PA-6,6 or PA-6), polycarbonate, polymethyl methacrylate, and polyesters derived from aromatic acids such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and combinations thereof. Such engineering thermoplasts may optionally be blended with polyurethane resins and modified polycarbonates.

[0075] The polymer compositions include polybutadiene, natural rubber, synthetic polyisoprene, butadiene copolymers, isoprene copolymers and blends of such elastomers; butyl rubber, halogenated butyl rubber and EPDM (ethylene propylene diene monomer rubber) and blends thereof; natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), synthetic polyisoprene rubber, epoxylated natural rubber, polybutadiene rubber, nitrile-hydrogenated butadiene rubber HNBR, hydrogenated SBR, ethylene propylene diene monomer rubber, ethylene propylene rubber, maleic acid-modified ethylene propylene rubber, butyl rubber, isobutylene-aromatic vinyl or diene monomer copolymers, brominated NR, chlorinated NR, brominated isobutylene p-methylstyrene copolymer, chloroprene rubber. The rubber may include any of unsaturated diene elastomers selected from rubbers such as epichlorohydrin homopolymer rubbers, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubbers, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubbers, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubbers, dimethyl silicone rubbers, methyl phenyl vinyl silicone rubbers, polysulfide rubbers, vinylidene fluoride rubbers, tetrafluoroethylene-propylene rubbers, fluorinated silicone rubbers, fluorinated phosphagen rubbers, styrene elastomers, thermoplastic olefin elastomers, polyester elastomers, urethane elastomers, and polyamide elastomers.

[0076] Examples of the polymer composition include olefin block copolymers, polyvinyl chloride, polystyrene, (meth)acrylic polymers, polyethylene, polypropylene, ethylene-vinyl acetate polymers, fluoropolymers, chlorofluoropolymers, acrylonitrile-butadiene-styrene polymers, polylactic acid, polybenzimidazole, polyethersulfone, polyoxymethylene, polyetheretherketone, polyetherimide, polyphenylene oxide, polyphenylene sulfide, polysaccharides, polycaprolactone, polyhydroxyalkanoates, polyhydroxybutyrate, polyhydroxybutyrate-co-hydroxyvalerate, polyvinyl butyral, polyesteramides, polybutylene succinate, polybutylene adipate-co-terephthalate, and polyvinyl alcohol.

[0077] The polymer composition may include liquid polybutene, liquid polyisoprene copolymer, liquid styrene / isoprene copolymer or liquid hydrogenated styrene / conjugated diene copolymer; vegetable oils and their derivatives; or paraffin and microcrystalline wax. Paraffin oil may also be used.

[0078] As an additive to a polymer composition, the amount of DDCR typically ranges from 1 to 80 wt%, or 5 to 30 wt%, or less than 60 wt%, or more than 10 wt%.

[0079] In use as a polymer additive, DDCR reduces the cloud point of the polymer composition by at least 10°C or more than 20°C or more than 50°C or more than 100°C or more than 150°C when compared to a polymer composition having an equivalent amount of DRA as an additive. [Example]

[0080] The following illustrative examples are not limiting.

[0081] Comparative Example 1: Gum DRA (Eastman's Dymerex™ Polymerized Rosin) having the properties listed in Table 1.

[0082] Comparative Example 2 : Tall oil DRA with the properties listed in Table 1.

[0083] Comparative Example 3 : A commercially available metallocene-catalyzed plastomer (AFFINITY™ GA 1950 from DOW Chemical) with a cloud point of 35°C.

[0084] Comparative Example 4 : A 1:1 (by weight) blend of Gum DRA of Comparative Example 1 and a commercial metallocene-catalyzed plastomer of Comparative Example 3. The blend has a cloud point above 200°C.

[0085] Comparative Example 5 : A 1:1 (by weight) blend of tall oil DRA of Comparative Example 2 and a commercial metallocene-catalyzed plastomer of Comparative Example 3. The blend has a cloud point above 200°C.

[0086] Comparative Example 6 : A 1:1 (by weight) blend of a fossil-derived hydrocarbon resin (ESCOREZ™ 5400 from ExxonMobil Chemical) and the commercially available metallocene-catalyzed plastomer of Comparative Example 3. The blend has a cloud point of 24°C.

[0087] Comparative Example 7 : A 1:1 (by weight) blend of a fossil-derived hydrocarbon resin (ESCOREZ™ 5600 from ExxonMobil Chemical) and the commercially available metallocene-catalyzed plastomer of Comparative Example 3. The blend has a cloud point of 43°C.

[0088] Example 1Gum DRA (1200 g) from Comparative Example 1 was placed in a four-neck flask (2 liters) and heated to 180°C under a nitrogen flow. After the DRA was completely melted and mechanically stirred, a catalyst (10 wt. % IMERYS bentonite clay IKOMONT DMC Classic) was gradually added, and the temperature was gradually increased to a typical maximum of 280°C. The reaction was carried out at this temperature for 7 hours, followed by an extended reaction at 300°C for 3 hours. Volatile species formed during decarboxylation escaped as vapor, and the condensed liquid portion was collected in a round-bottom flask. The end point was determined by monitoring the acid value (titration with 0.5 M KOH and phenolphthalein as indicator). After cooling the mixture, a crude reaction product with an acid value of 7.8 mg KOH / g was obtained. Further separation into fractions based on boiling point differences was carried out using conventional distillation techniques, yielding DDCR as the bottom distillation fraction at a split ratio of 51.1 wt. % and a vacuum of 0.1 mbar. The overall yield was 39% by weight, and the resulting physical properties are listed in Table 1.

[0089] Example 2 Tall oil DRA (1200 g) from Comparative Example 2 was charged into a four-neck flask (2 liters) and heated to 180°C under a nitrogen flow. After the DRA was completely melted and mechanically stirred, the catalyst (trifluoromethanesulfonic acid, 0.1 wt%) was gradually added, and the temperature was gradually increased to a typical maximum of 280°C, at which temperature the reaction was carried out for 4 hours. Volatile species formed during decarboxylation escaped as vapor, and the condensed liquid portion was collected in a round-bottom flask. The end point was determined by monitoring the acid value (titration with 0.5 M KOH and phenolphthalein as indicator). After cooling the mixture, a crude reaction product with an acid value of 2.3 mg KOH / g was obtained. Further separation into fractions based on boiling point differences was carried out using conventional distillation techniques, yielding DDCR as the bottom distillate fraction at a split ratio of 40.7 wt% and a vacuum of 0.1 mbar. The overall yield was 33 wt%. The resulting physical properties are listed in Table 1.

[0090] Example 3Tall oil DRA (1200 g) from Comparative Example 2 was charged into a four-neck flask (2 liters) and heated to 180°C under a nitrogen flow. After the DRA was completely melted and mechanically stirred, the catalyst (methanesulfonic acid, 1 wt%) was gradually added, and the temperature was gradually increased to a typical maximum of 280°C, at which temperature the reaction was carried out for 6 hours. Volatile species formed during decarboxylation escaped as vapor, and the condensed liquid portion was collected in a round-bottom flask. The end point was determined by monitoring the acid value (titration with 0.5 M KOH and phenolphthalein as indicator). After cooling the mixture, a crude reaction product with an acid value of 3.2 mg KOH / g was obtained. Further separation into fractions based on boiling point differences was carried out using conventional distillation techniques, yielding DDCR as the bottom distillate fraction at a split ratio of 39.1 wt% and a vacuum of 0.1 mbar. The overall yield was 32 wt%. The resulting physical properties are listed in Table 1.

[0091] Example 4 A 1:1 (by weight) blend of Gum DRA (Comparative Example 1) (600 g) and Tall Oil DRA (Comparative Example 2) (600 g) was placed in a four-neck flask (2 liters) and heated to 180°C under a nitrogen flow. After the DRA blend was completely melted and mechanically stirred, a catalyst (methanesulfonic acid, 1 wt%) was gradually added, and the temperature was gradually increased to a typical maximum of 280°C, at which point the reaction was carried out for 6 hours. Volatile species formed during decarboxylation escaped as vapor, and the condensed liquid portion was collected in a round-bottom flask. The end point was determined by monitoring the acid number (titration with 0.5 M KOH and phenolphthalein as indicator). After cooling the mixture, a crude reaction product with an acid number of 6 mg KOH / g was obtained. Further separation into fractions based on boiling point differences was carried out using conventional distillation techniques, yielding DDCR as the bottom distillation fraction at a split ratio of 45.9 wt% and a vacuum of 0.1 mbar. The overall yield was 37% by weight, and the resulting physical properties are listed in Table 1.

[0092] Example 5 - Preparation of in situ DRAKraton Chemical tall oil rosin SYLVAROS™ HYR (2500 g) was charged to a four-neck flask (2 liters) and heated to 180°C under a nitrogen flow. After the rosin was completely melted and mechanically stirred, the catalyst (methanesulfonic acid, 1 wt%) was gradually added, and the temperature was increased at 5°C / h to 200°C (dimerization phase) and then at 20°C / h to a typical maximum temperature of 280°C, at which temperature the reaction was carried out for 12 hours (decarboxylation phase). Volatile species formed during decarboxylation escaped as vapor, and the condensed liquid portion was collected in a round-bottom flask. The end point was determined by monitoring the acid number (titration with 0.5 M KOH and phenolphthalein as indicator). After cooling the mixture, a crude reaction product with an acid number of 1.5 mg KOH / g was obtained. Further separation into fractions based on boiling point differences was carried out using conventional distillation techniques to obtain DDCR as the bottom distillation fraction at a split ratio of 41.4 wt% and a vacuum of 0.1 mbar. The overall yield was 34 wt%. The resulting physical properties are listed in Table 1.

[0093] Example 6 - Preparation of in situ DRAKraton Chemical tall oil rosin SYLVAROS™ HYR (2500 g) was charged to a four-neck flask (2 liters) and heated to 180°C under a nitrogen flow. After the rosin was completely melted and mechanically stirred, the catalyst (p-toluenesulfonic acid, 2 wt%) was gradually added, and the temperature was increased at 5°C / h to 200°C (dimerization phase) and then at 20°C / h to a typical maximum temperature of 280°C, at which temperature the reaction was carried out for 12 hours (decarboxylation phase). Volatile species formed during decarboxylation escaped as vapor, and the condensed liquid portion was collected in a round-bottom flask. The end point was determined by monitoring the acid number (titration with 0.5 M KOH and phenolphthalein as indicator). After cooling the mixture, a crude reaction product with an acid number of 15.1 mg KOH / g was obtained. Further separation into fractions based on boiling point differences was carried out using conventional distillation techniques to obtain DDCR as the bottom distillation fraction at a split ratio of 37.9 wt% and a vacuum of 0.1 mbar. The overall yield was 32 wt%. The resulting physical properties are listed in Table 1.

[0094] The resulting DDCR fraction and crude precursor are analyzed for, for example, dimer / polymer content, % oxygen content, acid number, M n , M w ,PDI,T. g , T g / M n The polymers were analyzed for softening point, Brookfield viscosity and density as summarized in Table 1. The % polymer in the table refers to trimers and higher.

[0095] [Table 1]

[0096] Example 7 : A 1:1 (by weight) blend of purified DDCR from Example 1 and metallocene-catalyzed plastomer from Comparative Example 3.

[0097] Example 8 : A 1:1 (by weight) blend of purified DDCR from Example 2 and metallocene-catalyzed plastomer from Comparative Example 3.

[0098] Example 9 : A 1:1 (by weight) blend of purified DDCR of Example 3 and metallocene-catalyzed plastomer of Comparative Example 3.

[0099] Example 10 : A 1:1 (by weight) blend of purified DDCR from Example 4 and metallocene-catalyzed plastomer from Comparative Example 3.

[0100] Example 11 : A 1:1 (by weight) blend of purified DDCR from Example 5 and metallocene-catalyzed plastomer from Comparative Example 3.

[0101] Example 12 : A 1:1 (by weight) blend of purified DDCR from Example 6 and metallocene-catalyzed plastomer from Comparative Example 3.

[0102] Determination of compatibility of polymer compositions containing DDCR by cloud point: The compatibility of the samples was evaluated by turbidity measurement. A turbidity measurement instrument (Chemotronic High-Visc Automatic Turbidimetry Analyzer) from Novomatics GmbH was applied. Each sample (30 g) was placed in a test tube (commercially available from Verrerie Soufflee Mecanique SA) with a height of 200 mm, an outer diameter of 21.25 mm, an inner diameter of 18.75 mm, and a total volume of 53 mL. The sample was heated to 230 °C by a chemo-electronic device and subsequently cooled to 20 °C using the instrument settings shown in Table 2.

[0103] [Table 2]

[0104] Turbidity detection systems in chemical and electronic equipment are based on light transmittance. In principle, turbidity is detected by absorption due to suspended particles in a liquid, which is related to the cloud point and can be qualitatively related to the degree of incompatibility. The degree of light transmission through molten hot melt adhesive samples versus temperature was measured over a temperature range of 20°C to 230°C. The resulting relationship is represented graphically. Light transmittance is given as % light transmitted, and temperature is presented as °C. A lower light transmission percentage correlates with a higher degree of turbidity, thereby serving as an indicator of a higher cloud point temperature, and thus a lower degree of compatibility of the measured material blend at a given temperature value or over a given temperature range. The temperature at 50% transmittance was recorded as the cloud point temperature.

[0105] Cloud point results over the relevant temperature range of 0°C to 140°C are set forth in Table 3. Blends (1:1 by weight) of the materials in Table 1 with commercially available metallocene-catalyzed polyolefin (mPO) AFFINITY™ GA 1950 were prepared. Comparative Examples 4 and 5 were not miscible over the entire temperature range. Unexpectedly, the blends of Examples 7-12 exhibited compatibility over a wide temperature range, including low temperatures, resulting in unexpectedly low recorded cloud points. This allows for the production of polymer compositions with unexpectedly unique viscoelastic properties.

[0106] [Table 3]

Claims

1. 1. A dimeric decarboxylated rosin (DDCR) composition comprising 50 to 100 wt. % of a polycyclic hydrocarbon compound having one or more aliphatic, unsaturated, or aromatic groups and 34 to 80 carbon atoms, The composition comprises: Molecular weight M of 250-900 Da, measured using gel permeation chromatography and polystyrene calibration standards ｎ ;and an oxygen to carbon atomic ratio (O / C atomic ratio) of less than 0.05 and having greater than 50% by weight of dimeric species, with the remainder being trimeric and higher order polymeric species; DDCR composition.

2. an acid number of less than 80 mg KOH / g, as measured using ASTM D465; Flash point above 150°C by ASTM D92; Ring and ball softening point of 30 to 160°C according to ASTM E28-18; Gardner color scale (neat) of 0-18 according to ASTM D6166; Brookfield viscosity at 177°C of 15 to 1000 mPa·s according to ASTM D2196; A glass transition temperature (Tg) of −20 to 110° C. according to ASTM E1356; and density of 1.00 to 1.04; a polydispersity index of 1.0 to 1.2; T over 0.6 ｇ / M ｎ (K / Da) ratio; and Cloud point in polyolefins below 70°C 2. The DDCR composition of claim 1, characterized in that it comprises one or more of:

3. 3. The DDCR composition of claim 1, wherein the composition is hydrogenated and the hydrogenated DDCR composition has a Gardner color number of less than 5.

4. 1 to 80% by weight of the DDCR composition of claim 1 or 2 and a styrene block copolymer, polyolefin, plastomer, polyolefin, polyamide, polyester, polycarbonate, polymethyl methacrylate, polyester, polypropylene terephthalate, natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), synthetic polyisoprene rubber, epoxidized natural rubber, polybutadiene rubber, nitrile-hydrogenated butadiene rubber (NHBR), hydrogenated styrene-butadiene rubber (HSBR), ethylene propylene diene monomer rubber, ethylene propylene rubber, maleic acid modified ethylene propylene rubber, butyl rubber, isobutylene-aromatic vinyl or diene monomer copolymer, brominated NR, chlorinated NR, brominated isobutylene p-methylstyrene copolymer , and a polymer selected from chloroprene rubber, epichlorohydrin homopolymer rubber, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubber, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid-modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber, fluorinated silicone rubber, fluorinated phosphagen rubber, styrene elastomer, thermoplastic olefin elastomer, polyester elastomer, urethane elastomer, and polyamide elastomer.

5. An article comprising the composition of claim 4.

6. 1. A method for forming a dimeric decarboxylated rosin (DDCR) composition, comprising: providing a feedstock comprising dimeric rosin acid (DRA); heating the feedstock containing the dimeric rosin acid (DRA) with a catalyst in a decarboxylation reaction at a temperature of 200-400°C to form crude dimeric decarboxylated rosin (DDCR) in a mixture containing monomeric decarboxylated rosin, dimeric rosin acid, dimeric decarboxylated rosin, and residual polymeric species; and subjecting the mixture containing the crude dimeric decarboxylated rosin (DDCR) to a separation based on the difference in boiling points of the monomeric decarboxylated rosin, the dimeric rosin acid, the dimeric decarboxylated rosin, and the remaining polymeric species to form a DDCR composition. Including, the DDCR composition comprises 50 to 100 weight percent of a polycyclic hydrocarbon compound having one or more aliphatic, unsaturated, or aromatic groups and 34 to 80 carbon atoms; The DDCR composition has an acid number of less than 80 mg KOH / g as measured using ASTM D465; a molecular weight M of 250 to 900 Da as measured using gel permeation chromatography and polystyrene calibration standards. ｎ and an oxygen to carbon atomic ratio (O / C atomic ratio) of less than 0.

05. method.

7. 7. The method of claim 6, wherein providing the dimer rosin acid (DRA) feedstock comprises heating a feedstock comprising rosin acid with a catalyst at a temperature of −80 to 200° C. in a dimerization reaction to form the dimer rosin acid (DRA).

8. 1. A method for forming a dimeric decarboxylated rosin (DDCR) composition, comprising: providing a feedstock comprising rosin acids; heating a feedstock containing rosin acids with a catalyst in a decarboxylation reaction at a temperature of 200-400°C to form decarboxylated rosin; heating the decarboxylated rosin with a catalyst in a dimerization reaction at a temperature of −80 to 200° C. to form crude dimeric decarboxylated rosin (DDCR) in a mixture containing monomeric decarboxylated rosin, dimeric rosin acid, dimeric decarboxylated rosin, and residual polymeric species; and subjecting the mixture containing the crude dimeric decarboxylated rosin (DDCR) to a separation based on the difference in boiling points of the monomeric decarboxylated rosin, the dimeric rosin acid, the dimeric decarboxylated rosin, and the remaining polymeric species to form a DDCR composition. Including, the DDCR composition comprises 50 to 100 weight percent of a polycyclic hydrocarbon compound having one or more aliphatic, unsaturated, or aromatic groups and 34 to 80 carbon atoms; The DDCR composition has an acid number of less than 80 mg KOH / g according to ASTM D465; a molecular weight M of 250 to 900 Da, as measured using gel permeation chromatography and polystyrene calibration standards. ｎ and an oxygen to carbon atomic ratio (O / C atomic ratio) of less than 0.

05. method.

9. 9. The method according to any one of claims 6 and 8, wherein the catalyst used in the decarboxylation reaction is selected from the group of organic and inorganic phosphoric acid species, phyllosilicates, solid inorganic acid catalysts based on metal oxide refractory materials, organic and inorganic sulfur species, and mineral acids.

10. 9. The method of claim 8, wherein the dimerization reaction is carried out in a solvent at a temperature between the freezing point and the boiling point of the solvent.

11. The catalyst used in the dimerization reaction is a metal oxide catalyst, TiO ２ catalyst, ZrO ２ System catalyst, bauxite, MgSO ４ , N.H. ４ I, Ba (SCN) ２ , ZnCO ３ , ZnBr ２ , PbCrO ４ , K. ２ Cr ２ O ７ , BaS, CdS, Li ２ CO ３ , MgCl ２ , (NH ４ ) ２ SO ３ , Ba(SCN) ２ , Pb(OAc) ２ , MgCO ３ , diphenyl hydrobromide, NaHSO ３ , BaO ２ 9. The method of claim 8, wherein the acid is selected from the group consisting of hydroiodic acid, magnesium oxide, ammonium iodide, calcium oxide, zinc oxide, zinc formate, Lewis acids based on metals of groups 4, 5, 12, 13, 14 and 15 of the periodic table of the elements, organic and inorganic sulfur species, mineral acids and mixtures thereof.

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