Patent Application
20250091970
The disclosure relates to a hydrogenated decarboxylated rosin acid (HDCR) composition, methods of preparation, and applications thereof.
Rosin acid is a valuable resource for various compounds widely used in numerous applications. One modification of rosin acid involves decarboxylation, a process where carboxyl groups are removed, resulting in decarboxylated rosin acid (DCR). This modification is particularly useful for applications where the presence of acidic groups is undesirable.
However, DCR contains unsaturated structures, such as double bonds, which limit its usability in applications that demand high oxidative stability, such as cosmetics, thermal fluids, and medical products. These double bonds make DCR susceptible to oxidation, thereby reducing its stability and effectiveness in these applications.
In the prior art, to enhance the oxidative stability and reduce the color of DCR, the unsaturated structures are converted to saturated ones through hydrogenation. Common hydrogenation processes for DCR typically require severe conditions, including high pressure and high temperature, and the use of specific catalysts. Despite these challenging conditions, there remains some unsaturation in the product, affecting its properties.
There is still a need for a hydrogenated decarboxylated rosin acid (HDCR) composition with improved oxidative stability, increased hydrogenation level, and reduced color, for use to replace fossil-based alternatives, e.g., hydrotreated naphthenic oils, in many applications.
In one aspect, the disclosure relates to a hydrogenated decarboxylated rosin acid (HDCR) composition comprising, consisting essentially of, or consists of: a plurality of hydrogenated decarboxylated rosin acid (HDCR) components. Based on total weight of the composition, the HDCR composition contains: (a) 45 to 100 wt. % of the HDCR components have 19 carbon atoms (C19) and a molecular weight of 262 g/mol; (b) up to 50 wt. % of the HDCR components have 19 carbon atoms (C19) and a molecular weight of 256 g/mol; (c) up to 20 wt. % of the HDCR components have 19 carbon atoms (C19) and a molecular weight of 252 g/mol, or 19 carbon atoms (C19) and a molecular weight of 260 g/mol; and (d) up to 25 wt. % of the HDCR components have 13 carbon atoms (C13) and a molecular weight of 180 g/mol. The HDCR composition has an oxygen content of <0.5%.
In a second aspect, each HDCR component in the composition has a double bond equivalent (DBE). The HDCR composition has an average DBE of 0.1 to 2, the average DBE is computed as sum of weight percent of each HDCR component multiplied by its DBE.
In a third aspect, the HDCR composition comprises a plurality of hydrogenated decarboxylated rosin acid components having 18 to 20 carbon atoms (C18 to C20). Each HDCR component in the composition has a double bond equivalent (DBE) and the HDCR composition has: an average DBE of <2; an oxygen content of <0.5%; and a Gardner color of <1. The average DBE is computed as sum of weight percent of each HDCR component multiplied by its DBE.
In a fourth aspect, a method of preparation of a HDCR composition comprises: (m) providing a DCR feedstock; (n) contacting the DCR feedstock with a catalyst, optionally in the presence of a solvent, to obtain a reaction mixture; (o) supplying hydrogen gas with a pressure of 500 to 6000 kPa and heating the reaction mixture at a temperature of 150° C. to 350° C.; and (p) removing the catalyst and recovering the HDCR composition.
The following terms will be used throughout the specification.
“Consisting essentially of” means that the claimed composition primarily contains the specified materials, with allowances for additional components that do not materially affect novel characteristics or function of the claimed invention, with the additional components, if present, in an amount of <30%, or <20%, or <10%.
“At least one of [a group such as A, B, and C]” or “any of [a group such as A, B, and C],” or “selected from [A, B, and C], and combinations thereof” means a single member from the group, more than one member from the group, or a combination of members from the group. For example, at least one of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C; or A, B, and C, or any other all combinations of A, B, and C. In another example, at least one of A and B means A only, B only, as well as A and B.
A list of embodiments presented as “A, B, or C” is to be interpreted as including the embodiments, A only, B only, C only, “A or B,” “A or C,” “B or C,” or “A, B, or C.”
“Any of A, B, or C” refers to one option from A, B, or C.
“Any of A, B, and C” refers to one or more options from A, B, and C.
“Decarboxylated rosin acid” or DCR refers to a compound/material obtained by decarboxylation of rosin acid by removal (or loss) of a carboxyl group (—COOH). The decarboxylation process is typically carried out through heating or other methods, which results in loss of the carboxyl group. This chemical transformation changes the properties of the compound, including its solubility and reactivity.
“Hydrogenation of DCR” refers to a reaction involving the addition of hydrogen (H2) to DCR, resulting in the saturation of carbon-carbon double bonds to obtain a hydrogenated decarboxylated rosin acid (HDCR) composition. The hydrogenation of DCR aims to modify its chemical structure to enhance certain properties or achieve specific characteristics, e.g., stability, color, etc.
“Average Double Bond Equivalent” or “Average DBE” or “Ave. DBE” refers to the degree of unsaturation or the number of double/triple bonds present in a compound, and can be measured by GC-MS. The Ave. DBE is computed based on the DBE of the components in the compound:
“Hydrogenation percentage (%)” refers to the percentage of double bonds hydrogenated in a compound/molecule relative to the presence of double bonds in the compound/molecule prior to the hydrogenation. Hydrogenation of one double bond corresponds to 100% hydrogenation.
Hydrogenation % of rosin acid is based on the Ave. DBE of rosin acid before and after hydrogenation:
Hydrogenation % of HDCR composition is based on the Ave. DBE of the DCR feedstock before and the HDCR composition after hydrogenation:
“Oxidative stability” of a compound/material refers to its ability to resist degradation when exposed to oxygen or oxidative conditions at elevated temperatures. Materials with high oxidative stability maintain their chemical integrity and functional properties over time, despite the potential for oxidation. Oxidative stability can be assessed using differential scanning calorimetry (DSC), which measures parameters like the onset of oxidation (T onset) and the maximum rate of oxidative degradation (T max).
Molecular weight (MW) of compounds, components, or species in a compound can be determined by MS (mass spectroscopy), preferably in combination with a chromatographic separation method like GC (gas chromatography) or HPLC (high performance liquid chromatography). In embodiments, the MW is determined by GC-MS, using a column with a highly-substituted cyanopropyl phase (e.g. Supelco SP-2330, Restek Rtx-2330, or Agilent HP-88) of the size 30 m×0.25 mm×0.20 μm, with the following operating parameters: a temperature profile of 100° C. for 5.0 min, heating with 5° C./min to 250° C. and holding this temperature for 10.00 min; forming a solution with 10 mg of compound in 1 ml of a suitable solvent such as toluene, cyclohexane, etc.; injecting 1 μl of the solution with a split ratio of 1:40 at 250° C.; maintaining the flow at 1 ml/min throughout the analysis. Identification of the individual components is performed by QMS (quadrupole mass spectrometry) detector, with an ion source temperature of 200° C. and a mass range of 35-500 amu.
The disclosure relates to a hydrogenated decarboxylated rosin acid (HDCR) composition containing a plurality of HDCR components. The HDCR composition demonstrates enhanced oxidative stability and Gardner color, and finds utility across various applications, e.g., fertilizer coatings, cleaning agents, defoamers, cosmetics, lubricants, etc.
(Hydrogenated Decarboxylated Rosin Acid (HDCR) Composition): The HDCR composition is obtained by hydrogenation of a decarboxylated rosin acid (DCR) feedstock in the presence of a catalyst and at a suitable temperature and pressure. Hydrogenation of the DCR feedstock results in a reduction of C═C double bonds to obtain hydrogenated components.
The DCR feedstock is obtained by decarboxylation of a rosin acid, or by dimerizing and decarboxylation of the rosin acid followed by separation/removal of the dimerized species. The DCR feedstock comprises a plurality of DCR components, e.g., compound-A, compound-B, compound-C, compound-D, etc. In embodiments, the DCR feedstock comprises, based on total weight of the DCR feedstock: (ia)<30, or 1-25, or 3-20 wt. % compound-A having 19 carbon atoms (C19) and a MW of 262 g/mol; (ib)>40, or 40-60, or 43-55 wt. % compound-B having 19 carbon atoms (C19) and a MW of 256 g/mol; (ic)>20, or 10-40, or 12-35 wt. % of compound-C having 19 carbon atoms (C19) and any of a MW of 260 and 252 g/mol; and (id)<10, or <5, or 0-10 wt. % of compound-D having 13 carbon atoms (C13) and a MW of 180 g/mol.
After hydrogenation of the DCR feedstock, the HDCR composition is obtained, comprising a plurality of HDCR components, e.g., compound-I, compound-II, compound-IIIa, compound-IIIb, compound-IV, etc.
In embodiments, compound-I is C19H34; compound-II is C19H28; compound-IIIa is C19H24; compound-IIIb is C19H32; and compound-IV is C13H24.
In embodiments, the HDCR composition comprises, based on total weight of the HDCR composition: (a) 45-100 wt. % of the compound-I having 19 carbon atoms (C19) and a MW of 262 g/mol; (b) 0-50 wt. % of the compound-II having 19 carbon atoms (C19) and a MW of 256 g/mol; (c) 0 to 20 wt. % of the compound-IIIa having 19 carbon atoms (C19) and a MW of 252 g/mol or the compound-IIIb having 19 carbon atoms (C19) and a MW of 260 g/mol; and (d) 0 to 25 wt. % of the compound-IV having 13 carbon atoms (C13) and a MW of 180 g/mol.
In embodiments, the HDCR composition comprises: 50-85 wt. % of the compound-I; 0-40, or 15-40 wt. % of the compound-II; 0-15 wt. % of the compound-IIIa or IIIb; and 5-15 wt. % of the compound-IV.
The molecular weights of the HDCR components in the HDCR composition can be measured using any of MS, MS/GC/HPLC, and GC-MS. In an embodiment using the GC-MS method and column described above, the HDCR components and their associated MWs can be identified by the following retention profile (with ranges in minutes):
From the GC-MS retention profile above, the various HDCR components can be identified, e.g., compound-IV with a MW of 180 g/mol can be identified with a GC-MS peak in the range of 2.5-4.0 min., compound II with a MW of 256 g/mol can be identified in the range of 16.5-25.0 min., etc.
In the event of overlapping or identical retention time ranges for different HDCR components, the mass spectrum of each peak (as provided by the GC-MS) can be used to identify the molecular weight of the component, e.g., by comparing the mass spectra of the component with the mass spectra in reference databases like NIST or via library matching.
The species with the same molecular weights (isomers) are clustered and the total amount per isomer is reported.
In embodiments, the HDCR composition comprises several isomers of the compound-I in amounts of >3, or >5, or >10, or >20, or >50, or >100, or <300.
In embodiments, the HDCR composition comprises C═C double bonds in amounts of <40%, or <30%, or <20%, or <15%, or <10%, or <5%, or >1%, or 1-40%, or 1-20%, or 1-10%.
In embodiments, the HDCR composition has an average Double Bond Equivalent (DBE) of 0.1-2, or 0.2-1.5, or 0.5-1.4, or 0.5-2, or 0.01-1, or 0.05-0.9, or 0.08-0.8, or 0.1-0.5, or <2, or <1.8, or <1.5, or <1.2, or <1, or <0.8, or <0.5, or >0.01, or >0.1.
In embodiments, the HDCR composition has a hydrogenation % of >50%, or >60%, or >70%, or >80%, or >100%, or >120%, or >140%, or >160%, or >180%, or >200%, or >240%, or <400%.
In embodiments, the HDCR composition comprises tricyclic compounds having 18-20 carbon atoms in amounts of 70-100, or 75-95, or 75-100, or 80-100, or 80-95, or 80-90 wt. %, based on total weight of the HDCR composition.
In embodiments, sum of tricyclic compounds as aromatic and cycloaliphatic in the HDCR composition is at least 70, or >75, or >80, or >85, or >90, or >95, or <99, or 75-98, or 80-95, or 80-98 wt. %, based on total weight of the HDCR composition.
In embodiments, the HDCR composition comprises tricyclic cycloaliphatic compounds in amounts of >55, or >60, or >65, or >70, or 55-90, or 60-85, or 60-95 wt. %, based on total weight of the HDCR composition.
In embodiments, the HDCR composition comprises components having <18 carbon atoms in amounts of 0-30, or 1-20, or 0-15, or 1-15 wt. %, based on total weight of the HDCR composition.
In embodiments, the HDCR composition comprises C19H20 to C19H34 species in amounts of 70-100, or 75-95, or 75-100, or 80-100, or 80-95 wt. %, based on total weight of the HDCR composition.
It should be noted that the feedstock to the hydrogenation process, or the HDCR composition can be prepared from a starting material other than a purified decarboxylated rosin acid stream. In embodiments, the starting material is any of TOR (tall oil rosin) or gum rosin sources, wherein heat (e.g., between 200° C. and 300° C.) is applied to induce decarboxylation and remove the carboxyl group (—COOH) from the rosin acids, converting them into neutral compounds for a decarboxylated product, e.g., dehydroabietic acid or abietane-type compounds, for the next step of hydrogenation to make the HDCR composition.
(Methods of Preparation of HDCR Composition): As opposed to the prior art severe hydrogenation conditions with high pressure and high temperature and the use of specific catalysts, the HDCR composition in this disclosure is obtained by hydrogenating the DCR to a large extent under relatively mild conditions. In embodiment, the HDCR composition is prepared by hydrogenating the DCR feedstock in the presence of a catalyst, optionally in the presence of a solvent, at a hydrogen gas pressure of <3000, or <2500, or 500-2000, or 700-1800, or 1000-1600, or 800-1600, or 700-1900 kPa; and a temperature of <350° C., or 150-330° C., or 160-320° C., or 180-300° C., or 250-310° C., or 210-290° C., or >180° C., or >200° C. In embodiments, the reaction is continued for >1 hr., or >2 hrs., or <10 hrs., or 5-15 hrs., or 5-8 hrs., followed by cooling the reaction mixture at an ambient temperature (e.g., 25° C.). At high temperatures, e.g., >300° C., the hydrogenation can be completed in <1 hr. After completion of the hydrogenation reaction, catalyst and solvent are removed to recover the HDCR composition.
Examples of solvents (if present) include acids, such as, acetic, propionic, butyric, isobutyric, valeric, etc.; alcohols, such as, methyl, ethyl, propyl, isopropyl, n-butyl, -secondary butyl, amyl, cyclohexyl alcohol etc.; ethers, such as, dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, diisopropyl ether, ethyl propyl ether, etc.; esters, such as, methyl acetate, ethyl acetate, ethyl propionate, isopropyl acetate, methyl propionate, isopropyl propionate, etc.; hydrocarbons, such as, 2,2,3,3 tetramethyl butane, neo-pentane, 2,2,3,3,4,4 hexamethyl pentane, 2,3 dimethyl butane, etc.
In embodiments, the catalyst is selected from the group consisting of palladium, rhodium, ruthenium, platinum, osmium, nickel, molybdenum, cobalt, iron, and oxides and mixtures thereof. The catalyst can be supported on a support, e.g., diatomaceous earth, carbon, alumina, silica, titania, etc. The amount of catalyst used depends on the hydrogenation rate, the reaction time, the specifications of the reaction vessel, etc. In embodiments, the catalyst is used in amounts of 0.001-20, or 0.01-15, or 0.05-10, or 0.01-10, or 0.01-5 wt. %, based on total weight of all reactants.
In embodiments, the hydrogen pressure is increased mid-way in the hydrogenation process to speed up the hydrogenation reaction, and/or increasing the hydrogenation rate, e.g., up to 6000, or >2000, or >2500, or >3000, or >4000, or >4500 kPa.
In embodiments, further hydrogenation of the HDCR composition is conducted in the same reaction conditions as described above and using the same or different catalyst to further reduce remaining C═C double bonds, for an average DBE of <1, or <0.5, or <0.25, or 0.05-0.75.
(Properties of HDCR Composition): The HDCR composition is substantially free of non-aromatic unsaturation or C═C double bonds. With the reduction of unsaturation, the HDCR composition is characterized as having improved oxidative stability, light colored (e.g., water white), and with a low sulfur content.
In embodiments, the HDCR composition has an oxygen content of <0.5%, or <0.4%, or <0.3%, or <0.2%, or <0.1%, or 0-0.5%, or 0-0.3%, or 0-0.1%. The oxygent content can be calculated as the oxygen to carbon ratio, or the sum of oxygen atoms present divided by sum of carbon atoms present in the HDCR composition. The number of oxygen and carbon atoms can be obtained from elemental analyses.
In embodiments, the HDCR composition has an acid value of <10, or <8, or <5, or <2, or <1, or <0.8, or <0.5, or <0.2, or 0.01-10, or 0.1-5, or 0.01-2 mg KOH/g, measured according to ASTM D1240 or ASTM D465.
In embodiments, the HDCR composition has a viscosity at 40° C. of 5-50, or 10-45, or 15-40, or 10-30 cSt, measured according to ASTM D-445.
In embodiments, the HDCR composition has an aniline point of 3-80° C., or 5-70° C., or 5-60° C., or 5-50° C., or <80° C., or <70° C., or <60° C., measured according to ASTM D611.
In embodiments, the HDCR composition has a pour point of −40 to ˜10° C., or −35 to −20° C., or −35 to −25° C., measured according to ASTM D97.
In embodiments, the HDCR composition has a flash point of 95-140° C., or 100-135° C., or 95-135° C., or >95° C., or >100° C., or <140° C. measured according to ASTM D92.
In embodiments, the HDCR composition has a Gardner Color of <1, or <0.8, or <0.5, or <0.2, or 0-0.5, or 0.1-1, or 0.15-0.8, or 0.1-0.5, measured according to ASTM D6166.
In embodiments, the HDCR composition has a sulfur content of <10 ppm, or <8 ppm, or <5 ppm, or >0.001 ppm, measured according to ASTM D5453.
In embodiments, the HDCR composition has a T onset of >168° C., or >170° C., or >175° C., or >180° C., or >185° C., or >190° C., or >192° C., or <200° C., or <210° C., or 168-210° C.
In embodiments, the HDCR composition has a T max of >183° C., or >185° C., or >190° C., or >195° C., or >200° C., or >205° C., or >210° C., or <220° C., or 183-220° C.
(Applications of HDCR Compositions): The HDCR composition can be used in applications including adhesives, flexographic printing, polymer compatibilizer, tackifier, plasticizer, reinforcing agent, extender in bitumen and asphalt, tires, oilfield and gas industries, carpet construction, road marking, fertilizer coating, cleaning solvent, defoamer, metal working fluid, cosmetics, heat transfer fluid, waterproofing, alkali-, acid- and moisture resistance of sealants, emulsifier for emulsion polymerization, etc.
In embodiments, the HDCR composition is used to modify hydrocarbon products to increase naphthenic and cyclic contents, to improve additive solubility and increase dosage.
(Examples): The following illustrative examples are non-limiting.
The components used in examples include:
DCR-1 is a decarboxylated rosin acid having an acid value of 2.5 mg KOH/g, sulfur content of 81 ppm, Gardner color of 2.3, and oxygen content of 0.1%.
DCR-2 is a decarboxylated rosin acid having an acid value of 0.7 mg KOH/g, sulfur content of <5 ppm, Gardner color of 2.9, and oxygen content of 0%.
Rosin acid-1 (RA-1) has an acid value of 160 mg KOH/g, sulfur content of 29 ppm, Gardner color of 8.3, and oxygen content of 8.7%.
Rosin acid-2 (RA-2) has an acid value of 183 mg KOH/g, sulfur content of 322 ppm, Gardner color of 4.4, and oxygen content of 10%.
Rosin acid-3 (RA-3) has an acid value of 159 mg KOH/g, sulfur content of <10 ppm, Gardner color of 11.7, and oxygen content of 8.3%.
(Example 1): 1200 gm of DCR-1 feedstock was charged in a reactor and added 12 gm of Ni catalyst. Reaction content was mixed and purged with nitrogen gas three times at 350 kPa pressure, and then flushed with hydrogen gas three times at 1000 kPa pressure. At this stage, 1000 kPa of hydrogen gas was added to the reactor and reaction content was heated to 270° C. followed by increasing the pressure of hydrogen gas to 4000 kPa. Reaction was continued for 10 hours followed by cooling at an ambient temperature (e.g., 25° C.). Reaction content was filtered to remove the catalyst and HDCR-1 composition was recovered. A similar procedure was used to hydrogenate aged DCR-1 feedstock (1 year aging) and obtained HDCR-la composition.
(Example 2): Procedure of example 1 was repeated to use DCR-2 feedstock in place of DCR-1 feedstock.
(Examples 3-5): Procedure of example 1 was repeated to use rosin acid feedstocks (e.g., RA-1, RA-2, RA-3, etc.) in place of DCR-1 feedstock.
(Example 6): Procedure of example 1 was repeated to use HDCR-la composition in place of DCR-1 feedstock and palladium catalyst was used to further hydrogenate HDCR-1b composition.
Table 1 presents details of DCR and RA feedstocks used in hydrogenation reaction and their corresponding hydrogenated compositions. Table 2 shows properties of DCR and RA feedstocks, and their corresponding hydrogenated compositions. Table 3 presents oxidative stability of DCR-1 feedstock and corresponding hydrogenated compositions.
As used herein, the term “comprising” means including elements or steps that are identified following that term, but any such elements or steps are not exhaustive, and an embodiment can include other elements or steps. Although the terms “comprising” and “including” have been used herein to describe various aspects, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific aspects of the disclosure and are also disclosed.
For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained. It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural references unless expressly and unequivocally limited to one referent. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.
Unless otherwise specified, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed disclosure belongs. The recitation of a genus of elements, materials, or other components, from which an individual component or mixture of components can be selected, is intended to include all possible sub-generic combinations of the listed components and mixtures thereof.
The patentable scope is defined by the claims, and can include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. To an extent not inconsistent herewith, all citations referred to herein are hereby incorporated by reference.
This application claims benefit to U.S. provisional application No. 63/583,329, filed on Sep. 18, 2023, incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63583329 | Sep 2023 | US |
