Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

• This disclosure relates to the synthesis of furan-2,5-dicarboxylate (FDCA ) and furan-2,5-dicarboxylic acid (FDCA) from CO2 and furan-2-carboxylic acid and/or furan-2- carboxylate.
• FDCA furan-2,5-dicarboxylate
• FDCA furan-2,5-dicarboxylic acid
• a method for synthesizing furan-2, 5- dicarboxylate is provided.
• Furan-2-carboxylate is provided with an inorganic base in the form of an inorganic base salt, wherein the furan-2-carboxylate and the inorganic base salt form a mixture.
• a CO2 gas is provided to the mixture.
• the mixture is heated to a temperature to at least partially melt the mixture, wherein the heating of the mixture causes the synthesizing of
• M X FDCA denotes a salt comprising furan-2, 5-dicarboxylate (FDCA ) and cation M + and/or M 2+ , where x is a number between 1 and 2, inclusive.
• the mixture containing furan-2-carboxylate is mechanically agitated, wherein the mechanically agitating breaks up the M X FDCA solid.
• Furan-2-carboxylate is provided with an inorganic base in the form of an inorganic base salt, wherein the furan-2-carboxylate and the inorganic base salt form a mixture.
• a CO2 gas is provided to the mixture.
• the mixture is heated to a temperature to at least partially melt the mixture, wherein the heating of the mixture causes the synthesizing of a M X FDCA solid, wherein M X FDCA denotes a salt comprising furan-2, 5-dicarboxylate (FDCA ) and cation M + and/or M 2+ , where x is a number between 1 and 2, inclusive.
• M X FDCA denotes a salt comprising furan-2, 5-dicarboxylate (FDCA ) and cation M + and/or M 2+ , where x is a number between 1 and 2, inclusive.
• the mixture is cooled to solidify the mixture to form a solid mixture. Particle sizes of the solid mixture are reduced.
• the mixture is reheated while providing a CO2 gas to partially melt the mixture.
• FIG. 1A is a chemical equation showing the reaction of cesium furan-2-carboxylate, cesium carbonate, and CO2 to form cesium furan-2,5-dicarboxylate.
• FIG. IB is a schematic depiction of the phase composition of the reaction in FIG. 1A as a function of conversion.
• FIG. 3A is a schematic of a reactor used to perform C-H carboxylation of furan-2- carboxylate.
• FIG. 3B is the temperature profile of the thermocouple for the reaction described in EXAMPLE 1.
• FIG. 3C is the crude 'll NMR of the product of the reaction in EXAMPLE 1.
• FIG. 4 is a schematic view of another reactor that may be used in another embodiment.
• FIG. 5 is a high-level block diagram showing a computer system, which may be used to provide a controller.
• Furan-2,5-dicarboxylic acid is a bio-based molecule that can be used to make performance-advantaged polymers and chemicals with wide ranging applications.
• polyesters made from FDCA have attracted substantial commercial interest because they have superior gas barrier, thermal, and mechanical properties compared to the commonly used polyester polyethylene terephthalate (PET) (Burgess, et al. Macromolecules , 47, 1383—
• FDCA FDCA from a monoaldehyde impurity that compromises its use in polymer applications.
• the use of food ingredients as feedstocks for a chemical with high- volume applications is undesirable from a sustainability perspective because of the environmental footprint of agriculture and the potential for incentivizing detrimental land use changes.
• FDCA can be produced from furfural and CO 2 by a process comprising: i) oxidation of furfural to furan-2- carboxylic acid/furan-2-carboxylate; ii) carbonate-promoted C-H carboxylation of furan-2- carboxylate to produce furan-2,5-dicarboxylate, described in U.S.
• Patent 10,160,740 entitled, “CARBONATE-PROMOTED CARBOXYLATION REACTIONS FOR THE SYNTHESIS OF VALUABLE ORGANIC COMPOUNDS”, by Kanan et al, which is incorporated by reference for all purposes, iii) protonation of furan-2,5-dicarboxylate to produce FDCA.
• This approach has a number of advantages including i) it requires only a single substrate oxidation (furfural to furan-2-carboxylic acid/furan-2-carboxylate); ii) it avoids the formation of the problematic monoaldehyde impurity; iii) it does not require the use of organic solvents; iv) the feedstock furfural has been produced industrially from lignocellulose (inedible biomass) on a large scale for many decades, as described in Lange et al. ChemSusChem 5, 150-166 (2012), which is incorporated b reference for all purposes.
• Furan-2-carboxylic acid has previously been converted into furan-2,5-dicarboxylate by reacting with two equivalents of lithium diisopropylamide (LDA) followed by CO 2 in an aprotic organic solvent, which is described inThiyagarajan et al. RSC Adv. 3, 15678-15686 (2013), which is incorporated by reference for all purposes.
• LDA lithium diisopropylamide
• Van Haveren et al. describe a method to produce a mixture of furan-2,5-dicarboxylate and furan-
• (CO 3 ) can deprotonate the very weakly acidic C-H bond of furan- 2-carboxylate, generating a carbon-centered nucleophile that reacts with CO 2 to form furan- 2,5-dicarboxylate.
• Carbonate-promoted C-H carboxylation of furan-2-carboxylate proceeds at elevated temperature and does not require a catalyst or solvent. Conditions have been previously described that produce high yields of the desired furan-2,5-dicarboxylate product in Banerjee et al. Nature 531215-219 (2016) and Dick et al. Green Chem. 19, 2966-2972 (2017) which are incorporated by reference for all purposes, but the reaction times are impractical for high- volume production or commercial applications. Various embodiments in this specification reduce the reaction time required to achieve high yields for carbonate-promoted C-H carboxylation of furan-2-carboxylate.
• MFA denotes a salt comprised of M + and FA-
• M + denotes an alkali cation or mixture of alkali cations and FA- is the furan-2-carboxylate anion
• M 2 C0 3 denotes a salt comprised of M + and CO 3 2 , which is the carbonate anion
• M 2 FDCA denotes a salt comprised of M and FDCA , where FDCA denotes the furan-2,5-dicarboxylate anion.
• the reaction can be carried out with excess M 2 CO 3 , but the stoichiometric relation above defines the minimum amount required for full conversion (i.e. JV ⁇ CC ⁇ MFA > 0.5 in terms of molar equivalents).
• the CO 2 may be provided as a static pressure or flowing gas. When a flow of CO 2 is provided, the H 2 O produced as a byproduct is stripped from the system.
• M + alkali cation
• additional components may be added, including additional salts such as alkali salts of other carboxylates (e.g. alkali formate or alkali acetate), or other salts containing non-alkali cations, including divalent and trivalent cations. Additional gases may also be provided along with CO 2 .
• M + is Cs + and no additional salts are used.
• FIG 1A shows the equation for the carboxylation of cesium furan-2-carboxylate with CS 2 CO 3 and CO 2 with the chemical structures drawn.
• FIG IB shows a schematic depiction of the evolution of the phase composition of this reaction as a function of conversion. The phase behavior is further described below. Both salts in the starting material (CsFA and CS 2 CO 3 ) are solid at room temperature, and the reaction will not proceed from this state. Heating a mixture of these two salts above its eutectic temperature (T e ) at 256 °C results in the formation of a molten eutectic that consists of
• CSFA/CS 2 CO 3 system is measured by differential scanning calorimetry, which carefully controls and accurately measures the sample temperature.) Most of the CS 2 CO 3 remains in its solid state at this initial stage. The reaction mixture thus initially consists of three phases: molten eutectic
• CS 2 FDCA production also results in the consumption of the solid CS 2 CO 3 phase.
• the CS 2 FDCA produced remains fully dissolved in the molten phase, such that the mixture continues to consist of three phases: molten eutectic (CsFA, CS 2 CO 3 , and CS 2 FDCA), solid (CS 2 CO 3 ), and gas (CO 2 and 3 ⁇ 40).
• CsFA, CS 2 CO 3 , and CS 2 FDCA molten eutectic
• solid CS 2 CO 3
• gas CO 2 and 3 ⁇ 40
• the mixture consists of four phases: molten eutectic (CsFA, CS 2 CO 3 , and CS 2 FDCA), solid CS 2 CO 3 , solid CS 2 FDCA, and gas (CO 2 and
• the solid CS 2 FDCA phase will make up an increasingly large fraction of the mixture. Without some form of agitation, domains of solid CS 2 FDCA will continuously increase in size, eventually encasing the diminishing molten domains and limiting mass transport in two key ways. Firstly, decreased contact between the molten domains and solid CS 2 CO 3 limits the transport of CS 2 CO 3 into the molten phase. Secondly, transport of CO 2 gas into the molten phase (and, conversely, transport of H 2 O out) is inhibited.
• agitation of the reaction mixture can be used to avoid the situation described above and achieve high-yielding carboxylation reactions in short time periods if the agitation serves to break up the solid product.
• Solid CS 2 FDCA will still accumulate as the reaction proceeds, but agitation that breaks up the solid CS 2 FDCA domains can ensure adequate contact between the molten phase where the reaction occurs and the solid and gas- phase reactants necessary for the reaction to proceed.
• the mode of agitation must be able to i) maintain a high degree of contact between the solid, molten, and gas-phase components of the reaction mixture, and ii) maintain this contact for a reaction mixture whose phase composition changes over time (i.e. becomes more solid and less molten as a function of conversion).
• M + other than Cs + impacts the phase behavior of the salt mixture.
• Cs + salts provide a viable temperature operating window where a molten phase can be accessed without rapid decomposition of the furan-2-carboxylate.
• eutectic melting and hence carboxylation
• potassium isobutyrate salt can be added to a mixture of potassium furoate and carbonate (i.e. KFA and K2CO3) to induce eutectic melting and enable carboxylation reactivity, whereas the KFA/K2CO3 mixture in the absence of isobutyrate does not exhibit eutectic melting and is hence unreactive.
• FIG. 2 is a high level flow chart of an embodiment. Various embodiments may have more or less steps and may perform steps in a different order or simultaneously.
• a salt comprising furan-2-carboxylate with cation M + and/or M 2+ is provided (step 204).
• the salt comprising furan-2-carboxylate may be provided as a solution and/or a solid.
• a salt comprising CO3 2 with cation M + or M 2+ is provided (step 208).
• the salt comprising CO3 may be provided as a solution or a solid.
• 2_ comprising CO3 may be provided before or simultaneously with providing the salt comprising
• furan-2-carboxylate If the salt comprising furan-2-carboxylate and/or the salt comprising CO 3 is provided as a solution, the solvent is removed to form a solid.
• a solution of furan-2- carboxylate may be mixed with a solution of CO3 and then the solvent is removed to form the mixture.
• a CO2 gas is provided to the mixture (step 212).
• the CO2 gas may be provided by exposing the mixture to the CO2 gas under pressure. The mixture is heated to a temperature to at least partially melt the mixture, wherein the heating of the mixture causes the synthesizing of a
• the reaction and mixture used for the synthesizing of M X FDCA are substantially free from catalysts.
• the reaction is substantially free from metal-based catalysts. More specifically, the reaction is substantially free from metal based catalysts commonly used for Henkel reactions (disproportionations) including zinc compounds, cadmium compounds, mercury compounds, and iron compounds in the form of, for example, halides, oxides, carbonates, carboxylates, or sulfates of these metals.
• An advantage of having a reaction using a mixture that is substantially free of such catalysts is that the resulting material does not need to be further processed to recycle and/or remove the catalyst.
• FIG. 3 A is a schematic view of a reactor 300 that may be used in an embodiment.
• the reactor 300 is a Parr reactor equipped with an anchor stirrer 304 attached to a wall scraper 308.
• the wall scraper 308 is adjacent to chamber walls 312 of the reactor 300.
• the anchor stirrer 304 passes through a reactor cover 316.
• inlet ports 320 and outlet ports 322 are formed in the reactor cover 316 to provide the CO2 gas.
• a thermocouple 324 is placed inside the reactor 300. 100 g of a salt mixture composed of CsFA and 0.55 equivalents of CS2CO3 is placed in the reactor 300 and the reactor was purged with CO2.
• a heater 328 heated the reactor until the thermocouple reached a temperature of 252 °C, while CO2 was simultaneously flowed at 5.5 standard liters per minute (slpm) at 275 psig and the anchor stirrer 304 equipped with the wall scraper 308 was rotated at 150 rpm.
• the line providing CO2 to the reactor was heated to 350 °C to ensure that the gas flow did not cool the reaction mixture.
• the heater 328 was turned off.
• the temperature profile of the thermocouple is shown in FIG. 3B. After cooling, the reactor was opened and solid contents were removed by dissolving in H2O.
• a carboxylate salt is a salt comprised of an anion that is an organic compound with a deprotonated carboxylic acid (also referred to as carboxylate) and a cation that is an alkali cation, alkaline earth cation, or other metal cation.
• inorganic base salts such as a salt comprising hydroxide (OH ) or oxide (O ) could be provided, which would upon exposure to CO 2 react with the CO 2 to form a salt comprising substantially CO 3 .
• inorganic base salts such as a salt comprising hydroxide (OH ) or oxide (O ) could be provided, which would upon exposure to CO 2 react with the CO 2 to form a salt comprising substantially CO 3 .
• OH hydroxide
• O oxide
• CO 3 2_ carboxylation reaction will also enable the use of other inorganic bases other than CO 3 , such as phosphate (PO 4 ) or borate (B(OH) 4 ), provided as salts with alkali, alkaline earth, or other cations.
• inorganic bases such as phosphate (PO 4 ) or borate (B(OH) 4 ), provided as salts with alkali, alkaline earth, or other cations.
• PO 4 phosphate
• B(OH) 4 borate
• the use of CO 3 2 is preferred because CO 3 2 salts tend to be less expensive and corrosive than other bases and because CO 3 salts are consumed in the carboxylation reaction, forming water as the only byproduct.
• a method for synthesizing furan-2, 5-dicarboxylate is provided.
• Furan-2-carboxylate is provided.
• furan-2- carboxylate is provided as a salt comprising furan-2-carboxylate.
• furan-2- carboxylic acid is combined with a salt comprising CO 3 or another base such as OH to form a mixture, which converts the furan-2-carboxylic acid to a salt comprising furan-2-carboxylate.
• the salt comprising furan-2-carboxylate is combined with a salt comprising CO 3 to form a mixture.
• the mixture is heated to a temperature to at least partially melt the mixture, wherein the heating of the mixture causes the synthesizing of a salt comprising furan-2, 5-dicarboxylate (FDCA ).
• the salt comprising FDCA is herein referred to as an FDCA salt.
• the FDCA 2- salt is M 2 FDCA, wherein M + is a monovalent cation.
• the FDCA salt is MFDCA, wherein M is a divalent cation.
• the FDCA 2- salt contains a mixture of M + and M 2+ cations.
• a solid comprising FDCA salt is formed.
• the reaction mixture containing furan-2-carboxylate is mechanically agitated, wherein the mechanical agitation serves to break up the solid comprising FDCA 2- salt.
• the furan-2-carboxylate is provided as part of a salt with M + cations.
• the CO 3 2- salt is also provided with M + cations.
• the M + cations are alkali cations.
• the M + cations are either Cs + or K + .
• the mechanical agitation of the mixture sufficient to break up the solid comprising FDCA salt may be provided by various apparatus.
• mechanical agitation is provided by an agitator, such as an impeller, one or more screws, a scraper, or a ball mill.
• an agitator such as an impeller, one or more screws, a scraper, or a ball mill.
• the torque applied to the impeller must be sufficient to break the solid comprising FDCA salt, given the geometry of the blades of the impeller and the speed of rotation.
• the reaction may be performed continuously in an extruder, wherein the screws are used to push the reaction mixture through the reactor and continuously break up the solid components.
• mechanical agitation is provided by sound waves, such as ultrasound, with sufficient energy to break the solid comprising FDCA salt.
• FIG. 4 is a schematic view of a reactor 400 that may be used in another embodiment.
• a reactor chamber 404 houses two screws 408.
• the furan-2-carboxylate and CO3 salt are provided from a single source 416.
• the use of a single source 416 allows for the furan-2-carboxylate and CO3 salt to be thoroughly mixed at the proper ratio before being added to the reactor chamber 404.
• the thorough mixing at the proper ratio may be performed by mixing an aqueous solution of furan-2-carboxylate with an aqueous solution of CO3 salt at the proper ratios and then drying the resulting solution to provide a solid.
• a motor 428 drives the two screws 408 so that the two screws 408 draw the mixture from the input side of the reactor chamber 404 through the reactor chamber 404 to an output side of the reactor chamber 404.
• the two screws 408 have a first region 432 and a second region 436 where the threads of the two screws 408 have a tighter pitch causing the mixture to move more slowly through the first region 432 and the second region 436.
• CO2 gas is provided from a CO2 gas source 440.
• a first heater 444 is provided to heat a first part of the reactor chamber 404.
• a second heater 448 is provided to heat a second part of the reactor chamber 404.
• the two screws 408 move the mixture from the input side of the reactor chamber 404 through the first region 432, where CO2 gas is provided, past the first heater 444 where the mixture is heated to provide molten mixture and a M X FDCA solid is synthesized, then past the second region 436, where more CO2 gas is provided, then past the second heater 448 that provides a lower temperature than the first heater 444, so that when the mixture is provided to the output side of the reactor chamber 404 the molten mixture has solidified.
• Solid furan-2, 5-dicarboxylate is then provided to a collector 452.
• the furan-2-carboxylate and CO3 salt can be continuously added to the reactor chamber 404 with CO2 gas, while the furan-2, 5-dicarboxylate is continuously extracted. 2
• a controller 460 may be connected to the furan-2-carboxylate and CO3 source 416, the motor 428, the CO2 gas source, the first heater 444, and the second heater 448.
• the controller 460 may have computer readable media with computer readable code for providing the mixture of furan-2-carboxylate and CO3 salt, driving the two screws 408, providing the CO2 gas, and heating the reactor chamber 404 with the first heater 444 and the second heater 448.
• the controller 460 may allow the continuous processing.
• the controller 460 may have computer readable code to provide the right pressure of CO2, the right temperatures of the first heater 444 and the second heater 448, and the right speed of the two screws 408.
• the range of ratios for CO3 to furan-2-carboxylate i.e.
• 2_ moles CO3 to moles furan-2-carboxylate is from 1:4 to 2:1, inclusive. All of the provided ranges are inclusive. More preferably, the range of ratios for CO3 to furan-2-carboxylate is from 1:2 to 1:1, inclusive.
• the range of CO2 pressures is from 0.1 bar to 60 bar. In other embodiments, the range of CO2 pressures is 1 bar to 60 bar. In other embodiments, the range of CO2 pressures is 5 bar to 60 bar.
• the temperature is in the range of 150 °C to 450 °C. In other embodiments, the temperature is in the range of 200 °C to 350 °C. In other embodiments, the temperature is in the range of 225 °C to 300 °C.
• FIG. 5 is a high-level block diagram showing a computer system 500, which may be used to provide the controller 460.
• the computer system may have many physical forms ranging from an integrated circuit, a printed circuit board, and a small handheld device up to a computer.
• the computer system 500 includes one or more processors 502, and further can include an electronic display device 504, a main memory 506 (e.g., random access memory (RAM)), data storage device 508 (e.g., hard disk drive), removable storage device 510 (e.g., optical disk drive), user interface devices 512 (e.g., keyboards, touch screens, keypads, mice or other pointing devices, etc.), and a communication interface 514 (e.g., wireless network interface).
• main memory 506 e.g., random access memory (RAM)
• data storage device 508 e.g., hard disk drive
• removable storage device 510 e.g., optical disk drive
• user interface devices 512 e.g., keyboards, touch screens,
• the communication interface 514 allows software and data to be transferred between the computer system 500 and external devices via a link.
• the system may also include a communications infrastructure 516 (e.g., a communications bus, cross-over bar, or network) to which the aforementioned devices/modules are connected.
• a communications infrastructure 516 e.g., a communications bus, cross-over bar, or network
• Information transferred via communications interface 514 may be in the form of signals such as electronic, electromagnetic, optical, or other signals capable of being received by communications interface 514, via a communication link that carries signals and may be implemented using wire, cable, fiber optics, a phone line, a cellular phone link, a radio frequency link, and/or other communication channels.
• the one or more processors 502 might receive information from a network, or might output information to the network in the course of performing the above-described method steps.
• method embodiments of the present invention may execute solely upon the processors or may execute over a network such as the Internet in conjunction with remote processors that share a portion of the processing.
• non-transient computer readable media is used generally to refer to media such as main memory, secondary memory, removable storage, and storage devices, such as hard disks, flash memory, disk drive memory, CD-ROM, and other forms of persistent memory and shall not be construed to cover transitory subject matter, such as carrier waves or signals.
• Examples of computer code include machine code, such as produced by a compiler, and files containing higher level code that are executed by a computer using an interpreter.
• Computer readable media may also be computer code transmitted by a computer data signal embodied in a carrier wave and representing a sequence of instructions that are executable by a processor.
• the mixture instead of providing mechanical agitation to break up the solid comprising FDCA salt while the mixture is partially molten, the mixture is cooled and formed into a solid. Then mechanical agitation is provided to break up particle sizes of the solid mixture. The mixture is then heated to at least partially melt the mixture. The heating, then cooling, and then mechanical agitation may be repeated for several cycles.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Furan Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (8)

Applications Claiming Priority (2)

Publications (1)

Family

ID=77200885

Family Applications (1)

Country Status (7)

Cited By (7)

Families Citing this family (2)

Citations (6)

• 2021
  • 2021-02-05 US US17/793,890 patent/US12358882B2/en active Active
  • 2021-02-05 JP JP2022547038A patent/JP7728768B2/ja active Active
  • 2021-02-05 WO PCT/US2021/016772 patent/WO2021158890A1/en not_active Ceased
  • 2021-02-05 EP EP25176474.2A patent/EP4578851A3/en active Pending
  • 2021-02-05 CA CA3165817A patent/CA3165817A1/en active Pending
  • 2021-02-05 EP EP21751291.2A patent/EP4100386B1/en active Active
  • 2021-02-05 MX MX2022009679A patent/MX2022009679A/es unknown
  • 2021-02-05 BR BR112022015381A patent/BR112022015381A2/pt unknown

Patent Citations (8)

Non-Patent Citations (10)

Also Published As

Similar Documents

Legal Events