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WO2019053541A1 - Acrylates par couplage oléfine/dioxyde de carbone - Google Patents

Acrylates par couplage oléfine/dioxyde de carbone Download PDF

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Publication number
WO2019053541A1
WO2019053541A1 PCT/IB2018/056605 IB2018056605W WO2019053541A1 WO 2019053541 A1 WO2019053541 A1 WO 2019053541A1 IB 2018056605 W IB2018056605 W IB 2018056605W WO 2019053541 A1 WO2019053541 A1 WO 2019053541A1
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inorganic base
mpa
protic solvent
carboxylic acid
unsaturated carboxylic
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Dirk BEETSTRA
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids

Definitions

  • the invention generally concerns methods of producing ⁇ , ⁇ -unsaturated carboxylic acid salts through coupling of an alkene and carbon dioxide.
  • the invention concerns reacting an alkene and carbon dioxide with a composition that includes an inorganic base and a carboxylation catalyst to produce an ⁇ , ⁇ -unsaturated carboxylic acid salt.
  • ⁇ , ⁇ -Unsaturated carboxylic acids e.g., acrylic acid or methacrylic acid
  • salts thereof are commercially produced through a two-step oxidation of propylene process (shown below in Reaction Scheme (1):
  • This process requires two reactors and two separate catalysts to oxidize the propylene to acrylic acid, which can be capital intensive and inefficient.
  • the catalyst is represented by M-Ln where M is the catalytically active metal and Ln is one or more ligands.
  • a base is then employed to decompose the metallolactone intermediate into an ⁇ , ⁇ -unsaturated carboxylic acid or carboxylate (inorganic base salt of the ⁇ , ⁇ -unsaturated carboxylic acid) and regenerate the catalyst.
  • International Patent Application Publication No. WO 2015/173295 to Limbach et al. describes a silica supported transition metal complex for conversion of ethylene to an ⁇ , ⁇ - unsaturated carboxylic acid.
  • International Patent Application No. WO 2016180775 to Schaub et al. describes reacting ethylene with CO2 in the presence of transition metal catalyst and sodium tert-butoxide or sodium isopropoxide base to decompose the metallocene, with the alkoxide being consumed during the reaction.
  • the solution is premised on the use of an inorganic base in combination with a protic solvent to provide a population of deprotonated solvent molecules.
  • the inorganic base can deprotonate the protic solvent.
  • the deprotonated solvent can then decompose metallolactone intermediates formed from a C02/alkene/ligand-supported metal catalyst reaction. This leads to the production of an ⁇ , ⁇ -unsaturated carboxylate product, and regeneration of both the protonated solvent molecule and the ligand-supported metal catalyst.
  • the liberated ligand-supported metal catalyst is then free to re-enter the C02-ethylene coupling step of the catalytic cycle.
  • the protonated solvent is believed to act as a co-catalyst by virtue of its deprotonation, participation in the catalytic cycle, and subsequent protonation/regeneration.
  • the regenerated protonated solvent can be subsequently deprotonated and participate in ensuing metallolactone decomposition steps.
  • the inorganic base is present in the reaction mixture, and can also deprotonate and decompose the metallolactone intermediate. In the cases where the inorganic base is partially soluble or insoluble in the protic solvent, it is believed that the deprotonated solvent is primarily responsible for metallolactone deprotonati on/ decompositi on .
  • the process of the present invention provides an elegant and cost-effect process for making ⁇ , ⁇ -unsaturated carboxylic acid salts (e.g., acrylates). Further, the process can be performed in a "one pot” manner, thereby avoiding the need to isolate and regenerate the inorganic base.
  • carboxylic acid salts e.g., acrylates
  • a method can include reacting an alkene and carbon dioxide with a composition that can include a carboxylation catalyst and an inorganic base in a protic solvent under reaction conditions suitable to produce an inorganic base salt of an ⁇ , ⁇ -unsaturated carboxylic acid.
  • the alkene, carbon dioxide, and the metal from the carboxylation catalyst can form a metallolactone.
  • the metallolactone cam be an intermediate metallolactone and undergoes a subsequent reaction.
  • the alkene can be ethylene and the inorganic base salt of the ⁇ , ⁇ - unsaturated carboxylic acid can be an alkali metal or an alkaline earth metal acrylate, preferably sodium or lithium acrylate.
  • an inorganic base salt of the protic solvent can be formed in situ from the inorganic base, and the inorganic base salt of the protic solvent reacts with the metallolactone to form the inorganic base salt of an ⁇ , ⁇ - unsaturated carboxylic acid, the protic solvent, and the carboxylation catalyst.
  • Reaction conditions can include: (a) maintaining the composition at a temperature of 120 °C to 200 °C, preferably 120 °C to 160 °C; (b) an alkene pressure of 0.1 MPa to 5 MPa, preferably 0.5 MPa to 1.5 MPa, or about 1.0 MPa; and (c) a carbon dioxide pressure of 0.1 MPa to 5.0 MPa, preferably 0.1 MPa to 1.0 MPa, or 0.1 MPa to 0.5 MPa.
  • the composition can include 0.0001 wt.% to 1 wt.% of the catalyst and 0.1 wt.% to 200 wt.% of the inorganic base.
  • the protic solvent can be an alcohol comprising 4 to 35 carbon atoms.
  • the alcohol can be one that has a melting point of up to 120 °C.
  • Non-limiting examples of alcohols that can be used in the context of the present invention include Ci to Cio alcohols (e.g., Ci, C 2 , C 3 , C 4 , Cs, C 6 , d, Cs, C9, C10 substituted alcohols.
  • Non-limiting examples of Ci to Cio alcohols include methanol, ethanol, «-propanol, isopropanol, «-butanol, isobutanol, tert-butanol, cyclohexanol, 2-methyl-2-butanol, 2- pentanol or mixtures thereof.
  • the protic solvents can be 2-methyl-2- butanol, 2-pentanol, or mixtures thereof.
  • a method for producing an ⁇ , ⁇ -unsaturated carboxylic acid salt further includes the steps of separating the inorganic base salt of an ⁇ , ⁇ -unsaturated carboxylic acid from the protic solvent and the carboxylation catalyst, and optionally providing an additional alkene, carbon dioxide, and/or inorganic base to the protic solvent to produce additional ⁇ , ⁇ -unsaturated carboxylic acid salt.
  • the alkene is ethylene
  • the protic solvent is 1-butanol
  • the produced inorganic base salt of the ⁇ , ⁇ - unsaturated carboxylic acid is an alkali metal or an alkaline earth metal acrylate, preferably sodium or lithium acrylate.
  • Non-limiting example of inorganic bases can include an alkali metal or an alkaline earth metal containing base, preferably, an alkali metal or alkaline earth metal carbonate, phosphate, nitrate, or halide, or mixtures thereof.
  • Alkali metal or alkaline earth metal carbonates can include sodium hydroxide, sodium carbonate, sodium bicarbonate, lithium hydroxide, lithium carbonate, lithium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, cesium hydroxide, cesium carbonate, cesium bicarbonate, magnesium carbonate, calcium carbonate, or mixtures thereof.
  • the carboxylation catalyst and the inorganic base can each be solubilized in the protic solvent.
  • the inorganic base is at least partially soluble in the protic solvent.
  • the carboxylation catalyst is not solubilized in the protic solvent and the inorganic base is solubilized in the protic solvent.
  • the carboxylation catalyst is solubilized in the protic solvent and the inorganic base is not solubilized in the protic solvent.
  • the protic solvent can require heating above room temperature in order to solubilize the catalyst and/or the inorganic base.
  • the inorganic base can be an aqueous inorganic base solution.
  • the composition is absent the aprotic solvent.
  • the method does not include the aprotic solvent.
  • the aqueous inorganic base solution can be immiscible in the composition.
  • the aqueous inorganic base solution can be dispersed in the composition such that a plurality of droplets of the inorganic base solution are present in the composition.
  • the composition does not include a Lewis acid.
  • the carboxylation catalyst can include at least one transition metal of Columns 4- 10 of the Periodic Table. Non-limiting examples of transition metals include nickel (Ni) or palladium (Pd). In some instances, the carboxylation catalyst includes at least one coordinating ligand.
  • the coordinating ligand can include at least two coordinating atoms selected from phosphorus (P), nitrogen (N), oxygen (O), sulfur (S), and carbene that coordinate with the transition metal.
  • the carboxylation catalyst is or (Ph3P)2Ni(C 2 H 4 ), where Cy is cyclohexane.
  • Embodiment 1 is a method of producing an ⁇ , ⁇ -unsaturated carboxylic acid salt, the method comprising reacting an alkene and carbon dioxide with a composition comprising a carboxylation catalyst and an inorganic base in a protic solvent under reaction conditions suitable to produce an inorganic base salt of an ⁇ , ⁇ -unsaturated carboxylic acid.
  • Embodiment 2 is the method of embodiment 1, wherein the alkene, carbon dioxide, and the metal from the carboxylation catalyst form a metallolactone.
  • Embodiment 3 is the method of embodiment 2, wherein an inorganic base salt of the protic solvent is formed in situ from the inorganic base, and wherein the inorganic base salt of the protic solvent reacts with the metallolactone to form the inorganic base salt of an ⁇ , ⁇ -unsaturated carboxylic acid, the protic solvent, and the carboxylation catalyst.
  • Embodiment 4 is the method of embodiment 3, further comprising: separating the inorganic base salt of an ⁇ , ⁇ -unsaturated carboxylic acid from the protic solvent and the carboxylation catalyst; and optionally providing an additional alkene, carbon dioxide, and/or inorganic base to the protic solvent to produce additional ⁇ , ⁇ -unsaturated carboxylic acid salt.
  • Embodiment 5 is the method of any one of embodiment 1 to 4, wherein the protic solvent is an alcohol.
  • Embodiment 6 is the method of embodiment 5, wherein the alcohol comprises 4 to 35 carbons.
  • Embodiment 7 is the method of any one of embodiments 5 and 6, wherein the alcohol has a melting point of up to 120 °C.
  • Embodiment 8 is the method of embodiment 7, wherein the alcohol is a butanol, a pentanol, a hexanol, or mixtures thereof.
  • Embodiment 9 is the method of embodiment 8, wherein the alcohol is 2-methyl-2- butanol, 2-pentanol or mixtures thereof.
  • Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the inorganic base is at least partially soluble in the protic solvent.
  • Embodiment 11 is the method of any one of embodiments 1 to 10, wherein the inorganic base comprises a carbonate, preferably a alkaline metal carbonate, an alkaline earth metal carbonate, or both.
  • Embodiment 12 is the method of embodiment 11, wherein the alkaline metal carbonate is sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, or mixtures thereof.
  • Embodiment 13 is the method of any one of embodiments 1 to 12, wherein the carboxylation catalyst comprises at least one transition metal of Columns 4, 5, 6, 7, 8, 9, or 10 of the Periodic Table.
  • Embodiment 14 is the method of embodiment 13, wherein the carboxylation catalyst comprises at least one transition metal, preferably, nickel (Ni) or palladium (Pd).
  • Embodiment 15 is the method of embodiment 14, wherein the carboxylation catalyst comprises at least one coordinating ligand, preferably a coordinating ligand comprising at least two coordinating atoms selected from nitrogen (N), oxygen (O), sulfur (S), and carbene that coordinate with the transition metal.
  • Embodiment 16 is the method of embodiment 15, wherein the carboxylation catalyst is (Cy 2 PCH2CH2PCy2)Ni(C2H4C0 2 ) or (Cy 2 PCH2CH2CH2PCy2)Ni(C2H 4 ).
  • Embodiment 17 is the method of any one of embodiments 1 to 16, wherein the alkene is ethylene and the produced inorganic base salt of an ⁇ , ⁇ -unsaturated carboxylic acid is an alkali metal or an alkaline earth metal acrylate, preferably sodium or lithium acrylate.
  • Embodiment 18 is the method of any one of embodiments 1 to 17, wherein the composition is absent an aprotic solvent.
  • Embodiment 19 is the method of any one of embodiments 1 to 18, wherein the reaction conditions include: (a) maintaining the composition at a temperature of 120 °C to 200 °C, preferably 120 °C to 160 °C; (b) an alkene pressure of 0.1 MPa to 5 MPa, preferably 0.5 MPa to 1.5 MPa, or about 1.0 MPa; and/or (c) a carbon dioxide pressure of 0.1 MPa to 5 MPa, preferably 0.1 MPa to 1 MPa, or 0.1 MPa to 0.5 MPa.
  • the reaction conditions include: (a) maintaining the composition at a temperature of 120 °C to 200 °C, preferably 120 °C to 160 °C; (b) an alkene pressure of 0.1 MPa to 5 MPa, preferably 0.5 MPa to 1.5 MPa, or about 1.0 MPa; and/or (c) a carbon dioxide pressure of 0.1 MPa to 5 MPa, preferably 0.1 MPa to 1 MPa, or 0.1 MPa to 0.5 MPa
  • Embodiment 20 is the method of any one of embodiments 1 to 19, wherein the alkene is ethylene, the protic solvent is 1- butanol, and the produced inorganic base salt of the ⁇ , ⁇ -unsaturated carboxylic acid is an alkali metal or an alkaline earth metal acrylate, preferably sodium or lithium acrylate
  • An "aliphatic group” is an acyclic or cyclic, saturated or unsaturated carbon group, excluding aromatic compounds.
  • An aliphatic group can include 1 to 50, 2 to 25, or 3 to 10 carbon atoms.
  • a linear aliphatic group does not include tertiary or quaternary carbons.
  • a branched aliphatic group includes at least one tertiary and/or quaternary carbon.
  • a cyclic aliphatic group includes at least one ring in its structure.
  • Polycyclic aliphatic groups can include fused, e.g., decalin, and/or spiro, e.g., spiro[5.5]undecane, polycyclic groups.
  • Non- limiting examples of linear, branched or cyclic, aliphatic group substituents include alkyl, halogen (e.g., fluoride, chloride, bromide, iodide), haloalkyl, haloalkoxy hydroxyl (— OH), alkyoxy (—OR 1 ), ether (R-O-R), carboxylic acid (RCO2H), ester (RCO2OR), amine (NH or NR), ammonium (N(R)3 + , NH(R)2 + , NH 2 (R)i + , NH 3 + ), amide, nitro, nitrile (CN), acyl (RCO), thiol (— SH), sulfoxides, sulfonates,, phosphine (— PRR"), phosphonium (P(R + , PH(R + , PH 2 (R)2 + , PH 3 (R)i + , PH 4 + ),
  • alkyl group is a linear or branched, substituted or unsubstituted, saturated hydrocarbon.
  • an alkyl group has 1 to 50, 2 to 30, 3 to 25, or 4 to 20 carbon atoms.
  • Alkyl groups in the context of the present invention include all isomers and all substitution types unless otherwise stated.
  • butyl includes n- butyl, isobutyl, and tert-butyl; pentyl includes n-pentyl, 1-methylbutyl, 2-methylbutyl, 3- methylbutyl, 1-ethylpropyl, and neopentyl.
  • Non-limiting examples of alkyl group substituents include halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether.
  • alkene or "alkenyl” is a linear or branched, unsubstituted or substituted, unsaturated hydrocarbon.
  • an alkenyl group has 1 to 50, 2 to 30, 3 to 25, 4 to 20, 2 to 8, or 2 to 4 carbon atoms.
  • alkyl groups include all isomers and all substitution types unless otherwise stated.
  • Non-limiting examples of an alkene group substituents include alkyl, halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether.
  • alkenes are shown in Structure LIV and include ethylene, propene, butylene, and styrene.
  • An "alkynyl” group refers to a linear or branched monovalent hydrocarbon radical of at least 2 carbon atoms with at least one triple bond. In the context of this invention, the alkenyl group has 1 to 50, 2 to 30, 3 to 25, 4 to 20, or 2 to 4 carbon atoms.
  • the alkynyl radical can be optionally substituted independently with one or more substituents described herein.
  • Non-limiting examples include ethynyl (-C ⁇ CH), propynyl (propargyl, -CH2C ⁇ CH), -C ⁇ C-CH 3 , and the like.
  • alkylene refers to a saturated divalent hydrocarbon group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms.
  • an alkenyl group has 1 to 50, 2 to 30, 3 to 25, 4 to 20, or 1 to 4 carbon atoms.
  • alkylene groups include methylene (-CH2- ), ethylene (-CH2CH2-), isopropylene (-CH(CH 3 )CH 2 -), and the like.
  • aryl group or an “aromatic group” is a substituted or unsubstituted, mono- or polycyclic hydrocarbon with alternating single and double bonds within each ring structure.
  • aryl group substituents include alkyl, halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether.
  • heteroatom refers to unsubstituted or substituted atom that is not carbon unless otherwise specified.
  • Non-limiting examples of heteroatoms are oxygen (O), nitrogen (N), phosphorus (P), or sulfur (S).
  • Non-limiting examples of heteroatoms substituents include hydrogen, aliphatic, alkyl, alkynyl, and alkenyl.
  • a “heteroaryl group” or “hetero-aromatic group” is a mono-or polycyclic hydrocarbon with alternating single and double bonds within each ring structure, and at least one atom (heteroatom) within at least one ring is not carbon.
  • Non-limiting examples of heteroaryl group substituents include alkyl, halogen, hydroxyl, alkyoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether.
  • heterocyclic group is a mono-or polycyclic saturated or unsaturated hydrocarbon with at least one atom (heteroatom) within at least one ring is not carbon.
  • heterocyclic rings include, but are not limited to, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, dihydropyranyl, tetrahydrothiopyranyl, piperidino, morpholino, thiomorpholino, thioxanyl, piperazinyl, homo-piperazinyl, azetidinyl, oxetanyl, thietanyl, homopiperidinyl, oxepanyl, thiepanyl, oxazepinyl, diazepinyl, thiazepinyl, 2-pyrrolinyl, 3-pyrrolinyl, indolin
  • a "haloalkyl” or “haloalkoxy” refers to an alkyl or alkoxy substituted with one or more halogen atoms.
  • the terms “catecholate” or “catecholate ligand” refer to ligands that include a phenyl ring. In non-limiting example, two oxygen atoms or nitrogen atoms connected to the phenyl ring at the ring's 1 and 2 positions. The ligand connects to the metal center of the catalyst through the two oxygen atoms: , where R'" and R"" are each independently alkyl, aryl, or form a fused ring with the phenyl ring.
  • wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or total moles of a material, that includes the component.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • the methods of the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the methods of the present invention are their abilities to efficiently produce ⁇ , ⁇ -unsaturated carboxylic acids salts from an alkene and carbon dioxide.
  • Methods of producing ⁇ , ⁇ -unsaturated carboxylic salts of the present invention can include reacting an alkene and carbon dioxide with a composition that includes a carboxylation catalyst, and an inorganic base in a protic solvent under reaction conditions suitable to produce an inorganic base salt of an ⁇ , ⁇ -unsaturated carboxylic acid.
  • the inorganic base can be soluble, partially soluble, or insoluble in the protic solvent.
  • the inorganic base can be dispersed in the protic solvent thereby creating a bi-phasic system.
  • a single-phase system can be formed.
  • the protic solvent temperature can be increased to increase solubility of the inorganic base.
  • the reaction temperature can be maintained from 30 °C to 200 °C, 50 °C to 70 °C, or 30 °C, 35 °C 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 1 10 °C, 1 15 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 190 °C, or any value or range there between.
  • An alkene pressure can range from 0.1 MPa to 5 MPa, 0.5 MPa to 1.5 MPa, or about 1.0 MPa or about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 MPa, or any value or range there between.
  • a carbon dioxide pressure can range from 0.1 MPa to 5 MPa, 0.1 MPa to 1 MPa, or 0.1 MPa to 0.5 MPa, or about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 MPa, or any value or range there between.
  • the reaction temperature and pressures can be adjusted to maintain the reaction conditions at temperatures that do not affect the catalyst stability.
  • Reaction Scheme 3 depicts a catalytic cycle for producing ⁇ , ⁇ -unsaturated carboxylic salts of the present invention.
  • R alkyl
  • the inorganic base sodium carbonate can be present in the alcohol solvent (e.g., butanol), and at least a portion of the butanol solvent can be deprotonated by the sodium carbonate base.
  • the catalyst M-Ln can couple ethylene to CO2 to give the metallolactone intermediate.
  • the deprotonated solvent can react with the metallolactone intermediate to generate the sodium acrylate product, regenerate the butanol solvent, and regenerate the metal catalyst.
  • the regenerated catalyst can participate in a subsequent ethylene/CCh coupling step.
  • the protonated/regenerated solvent can become available for a subsequent deprotonation and reentry into the catalytic cycle.
  • the composition can include a carboxylation catalyst, an inorganic base, and a protic solvent.
  • the carboxylation catalyst, inorganic base, or both can be solubilized, or substantially solubilized in the protic solvent.
  • the protic solvent temperature can be increased to increase inorganic base solubility and degree of solvent deprotonation.
  • a metallic co-reagent like metallic zinc, aluminum, iron, manganese (reducing metals) or an organic reducing agent can be included in the composition.
  • Organic reducing agents can include a benzene compound or substituted benzene groups that include at least one hydroxyl group.
  • Non-limiting examples of organic reducing agents include alkyl or aryl esters of 3,4-dihydroxybenzoic acid, 3,4-dihydroxy-benzaldehyde, 3,4-dihydroxy-benzamide, an alkyl or aryl (3,4-dihydroxyphenyl) ketone, 1,4-dihydroxybenzene (hydroquinone) or a substituted hydroquinone, hindered phenols, pyrogallol, methyl gallate, leuco dyes, or mixtures thereof can be added to facilitate regeneration of the metal of the carboxylation catalyst.
  • Bases 1,4-dihydroxybenzene (hydroquinone) or a substituted hydroquinone, hindered phenols, pyrogallol, methyl gallate, leuco dyes, or mixtures thereof can be added to facilitate regeneration of the metal of the carboxylation catalyst.
  • the inorganic base can be an alkali metal or an alkaline earth metal containing base, or mixtures thereof.
  • Alkali alkali metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and/or cesium (Cs).
  • Alkaline earth metals include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and/or barium (Ba).
  • metal carbonates or bicarbonates include Li 2 CCb, LiHC0 3 , Na 2 C0 3 , NaHC0 3 , Mg(HC0 3 ) 2 , MgC0 3 , Ca(HC0 3 ) 2 , CaC0 3 , Ba(HC0 3 ) 2 , BaC0 3 , and the like.
  • Non-limiting examples of metal phosphates include NaH 2 P0 4 , Na 2 HP0 4 , Na 3 P0 4 , KH 2 P0 4 , K 2 HP0 4 , K 3 P0 4 , CsH 2 P0 4 , Cs 2 HP0 4 , Cs 3 P0 4 , Mg 3 P0 4 , Ca 3 P0 4 , Ba 3 P0 4 , and the like.
  • Non-limiting examples of metal halides include Lil, Nal, KI, Csl, LiCl, LiBr, LiF, ZnCl 2 , CaCl 2 , MgCl 2 , AlCh, FeCh, FeCh, VCh, or the like. In some embodiments, metal halides (e.g., Lewis acids) are not used.
  • phase transfer compounds can be used to improve the solubility of the inorganic base in the protic solvent.
  • phase transfer agents include NaBF 4 , NaPFe, NaSbFe, Na(B(C 6 F 5 ) 4 ), Na(B(C 6 H 3 (CF 3 ) 2 ) 4 ) (here listed for sodium), quaternary ammonium salts, crown ethers and the like.
  • the protic solvent can be an alcohol comprising 4 to 35 carbon atoms.
  • Alcohols can be obtained from commercial sources such as Sigma-Aldrich® (U.S.A.).
  • Non-limiting examples of alcohols include a butanol, tert-butyl alcohol, 2-methyl- 2-butanol, a pentanol, 2-pentanol, a hexanol, 2,5-dimethyl-2,5-hexanediol, a heptanol, triacontanol, or mixtures thereof.
  • the alcohol is a secondary or tertiary alcohol.
  • the alcohol can be one that has a melting point of up to 120 °C, or from -89 °C to 120 °C, -50 °C to 100 °C, 0 °C to 80 °C, 25 °C to 50 °C or any value or range there between.
  • the carboxylation catalyst can be any carboxylation catalyst that promotes the reaction between an alkene and carbon dioxide and can be solubilized in the organic base or solvent of the composition. a. Metals
  • the metal carboxylation catalyst can include one or more transition metals from Columns 4 through 12 of the Periodic Table coordinating to one or more ligands.
  • transition metals include nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), cobalt (Co), iridium (Ir), and rhodium (Rh).
  • the metals used to prepare the catalyst of the present invention can be provided in various oxidation states (e.g., 0, +1, +2, +3, etc.).
  • the metal carboxylation catalyst can include a ligand L that can be displaced by the alkene.
  • a metal carboxylation catalyst/coordination ligand/alkene complex can be obtained initially by reacting a transition metal source with a coordinating ligand and an alkene to give metal carboxylation catalyst/coordination ligand/alkene complex.
  • the metal carboxylation catalyst can be one or more ligands selected from halides, amines, amides, oxides, phosphides, carboxylates, acetyl acetonate, aryl- or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, aromatics and heteroaromatics, ethers, PF 3 , phospholes, phosphabenzenes, and mono-, di- and polydentate phosphinite, phosphonite, phosphoramidite and phosphite ligands.
  • ligands selected from halides, amines, amides, oxides, phosphides, carboxylates, acetyl acetonate, aryl- or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins,
  • Non-limiting examples of stabilizing ligands include cycloocta-1,3- diene (COD), bis(cyclooctatetraene), bis(cycloocta-l,3,7-triene), bis(o-tolylphosphito) metal (ethylene), tetrakis (triphenylphosphite) bis(ethylene), 4-butyl-naphthalene-l,2-bisolate, 1- methyl-naphthalene-l,2-bisolate, 4-ethyl catecholate, 3,5-di(butyl)-4-(bromo)catecholate, 4- (propyl)catecholate, halides (e.g., bromides and chlorides).
  • COD cycloocta-1,3- diene
  • bis(cyclooctatetraene) bis(cycloocta-l,3,7-triene)
  • bis(o-tolylphosphito) metal ethylene
  • the metal carboxylation catalyst can be prepared by known methods or purchased from a commercial supplier.
  • Useful transition metal sources include commercial standard complexes, for example [M(p- cymene)Cl 2 ] 2 , [M(benzene)Cl 2 ]n, [M(COD)2], [M(CDT)], [M(C 2 H 4 ) 3 ], [MC1 2 x H2O], [MC1 3 x H2O], [M(acetylacetonate) 3 ], [M(DMS0)4MC1 2 ], where M is the transition metal.
  • nickel(bis(cycloocta-l,5-diene) or bis(triphenylphosphine)(ethylene)nickel can be used as the metal carboxylation catalyst.
  • a non-limiting example of a commercial source of the above mentioned metals or metal complexes is Sigma Aldrich® (U.S. A).
  • the coordinating ligand can be polydentate, for example, a bidentate ligand.
  • the bidentate ligand coordinates once to the metal center of the metal carboxylation catalyst.
  • the coordination ligand can include 2, 3, 4, 5, 6 or more coordination atoms or carbenes.
  • the coordinating atoms can be different or the same. Non-limiting examples of combinations of at least two different coordinating atoms are (P, P), (P, N), (P, O), (P, S), (P, carbene), (O, S), (N, S), (N, O), (N, carbene), (O, carbene), or (S, carbene).
  • the ligand includes at least two of the same coordinating atoms (e.g., (P, P), (N, N), (O, O), (S, S), or (carbene, carbene).
  • the bidentate ligand can include two or more heteroatoms (e.g., N, O, and S) or a heteroatom and a carbene (C:) that together coordinate with the metal in the metal carboxylation catalyst.
  • the ligand can be acyclic or cyclic.
  • the coordinating ligand can include a phosphorus atom in a non- coordinating position of the ligand. In other embodiments, the coordination ligand does not include a phosphorus atom.
  • An amount of coordinating ligand used with the metal coordination catalyst can be determined by the number of coordinating atoms. In a non- limiting example, a 1 : 1 molar ratio of coordinating ligand to metal carboxylation catalyst can be used for a bidentate ligand. i. ( ⁇ , ⁇ ) Ligands
  • the coordinating ligand can include two nitrogen atoms (N,N).
  • N,N nitrogen atoms
  • Non-limiting examples of ligands that include nitrogen atoms include di-, tri- and polyamines, imines, diimines, pyridine, substituted pyridines, bipyridines, imidazoles, substituted imidazoles, pyrroles, substituted pyrroles, pyrazoles and substituted pyrazoles, or combinations thereof. These compounds can be used together (e.g., two pyridines in one ligand or a diimine) to form a ligand having 2 nitrogen compounds.
  • a bidentate ligand can have a 1,4-diaza- 1,3 -butadiene structure:
  • Ri, R2, R3, and R 4 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a substituted heteroatom, a halogen, a heterocyclic or a heteroaryl group, or where Ri and R2, R2 and R3, and/or R3 and R 4 come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocycle ring.
  • Ri and R 4 can each independently an alkyl, a branched alkyl, a cycloalkyl, an aryl, or a substituted aryl group.
  • R2 and R3 can come together with other atoms to form a cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocycle ring.
  • Ri and R2 can come together to form a heteroaryl or heterocycle ring in combination with R3, and R 4 can be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heteroaryl group or coming together to with other atoms to form a heteroaryl or heterocyclic ring.
  • Ri through R 4 can include from 1 to 50 carbon atoms.
  • Non-limiting examples of Ri through R 4 groups include hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl, octacosyl, nonacosyl, triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclodecyl, phenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,4,6- trimethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 3- propylphenyl, 4-propylphenyl, 2,
  • R 6 , R7, Rs, R9, Rio, R11, R12, R13, and R14 are independently H, alkyl, branched alkyl, aryl, substituted aryl, or substituted heteroatom groups.
  • the alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3.
  • R5, R 6 , R7, Rs, R9, Rio, R11, R12, R13, and R14 can be selected from methyl, ethyl, and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.
  • R5, R9, Rio, and R14 can each independently be methyl (CH 3 ) or isopropyl ((CH 3 )2CH) groups, or combinations thereof.
  • R2 and R 3 are methyl and the coordinating ligand can have the following specific structures with their corresponding names:
  • Non-limiting examples of Ri and R2 joined together with other atoms includes cyclic or aromatic rings that include 4 to 10 atoms, or 5 to 6 atoms (e.g., carbon, oxygen, or sulfur).
  • Ri and R2 can form a pyridine ring (Structure VII) where R3 and R 4 are as defined above.
  • R3 and R 4 form a pyridine or substituted pyridine ring.
  • Suitable coordinating ligands can have the following specific structures with their corresponding names:
  • Ri and R2 and R3 and R 4 can form a bi-pyridyl (e.g., 2,2'- bipyridyl, (Structure VIII)), or substituted bipyridyl type structures.
  • Ri, R2, R3, and R 4 can join together with other carbon atoms to form phenanthroline (e.g., Structure IX) or substituted phenanthroline type structures.
  • Suitable (N,N) ligands can include an amine and an imine connected through a carbon bridge as depicted in the general structure (XVIII).
  • Ri, R2, R3, and R 4 area defined as above and R15 and Ri6 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heteroatom (e.g., O), a substituted heteroatom (e.g., OR), a halogen, a heterocyclic, or a heteroaryl group, or R 4 and R15 together with other atoms can form a heterocyclic or heteroaryl ring, or R 4 and Ri6 together with other atoms can form a heterocyclic or heteroaryl ring, or Ri6 is a chemical bond and R3 and R2 come together with other atoms to form a cyclic or heterocyclic ring.
  • R15 and Ri6 can have 1 to 50 atoms (e.g., carbon atoms, or a mixture of carbon atoms and heteroatoms), 2 to 20 atoms or 3 to atoms.
  • the bidentate nitrogen ligand can have the following structures:
  • R3, R 4 , R15, and Ri6 are as defined above, and R17, Ris, R19, and R20 can each independently be H, alkyl, or branched alkyl groups, or R17 and Ris, Ris and R19, or R19 and R20 can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or Ri7, Ris, Ri9, and/or R20 come together with other atoms can form a fused cyclic, aryl, heterocyclic, or heteroaryl ring system, or Ri6 is a chemical bond and R3 and R17 come together with other atoms to form a cyclic or heterocyclic ring.
  • alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3.
  • Ri6 is a chemical bond and R3 and R17 come together to form a substituted quinoline ring system as shown in structure (XX).
  • R 4 , R15, Ris, R19, and R20 are as previously defined.
  • Other suitable ligands include pyrazole or substituted pyrazole compounds as shown in structure (XXI).
  • R21, R22, R23, R24, R25, R26, R27, and R28 can each independently be H, alkyl, aryl, or branched alkyl groups, or R21 and R22, R21 and R23, and/or R23 and R24 can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R21, R22, R23, and/or R24 can come together with other atoms to form a fused ring system.
  • R23 can be an electron pair, when R24 is part of an aromatic ring.
  • the alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3.
  • R40, R41, R42, R43, R44, and R45 can be each independently H, alkyl, or branched alkyl groups or R40 and R 41 , R41 and R42, R42 and R43, R43 and R44, or R44 and R45 can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R40, R41, R42, R43, R44, and/or R45 can come together with other atoms to form a fused ring system.
  • the alkyl or branched alkyl groups can have a carbon number from 1 to 10, preferably 1 to 5, more preferably 1 to 3. ii. (N, O) and (N, S) Ligands
  • the coordinating atoms can be different.
  • the ligand includes at least two different coordinating atoms (e.g., (O, S), (N, S), (N, O), (N, carbene), (O, carbene), (S, carbene).
  • a ( ⁇ , ⁇ ) or (N,S) bidentate ligand can have the following generic structure: (XXIII) where Ri, R2, R3, R15, and Ri6 are as previously defined for structure (XIII) and X is oxygen or sulfur.
  • Non-limiting examples of coordinating ligands having these structures are: where Rn, Ris, Ri9, R20, R21, R22, R23, R25, R26, and R27 are as previously defined and R25, R26, and R27 can be H, alkyl, aryl, or branched alkyl groups. It should be understood that while not shown as substituted, the ring structures in (XXVI) can be substituted as defined for structures (XXIV). In some instances, the (N, O) ligand (XXVII), where Ri is a hydrogen and R2 is 2, 4, 6-trimethylbenzene having the structure of: (XXVIII). iii. (O, S), (O, O) and (S,S) Ligands
  • Suitable (O, S), (O, O) and (S,S) bidentate ligand can have the following generic structure:
  • R50 and R55 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a halogen, a heterocyclic, a heteroaryl group, or an electron pair
  • R51, R52, R53, and R54 can each independently be a hydrogen, an alkyl, a branched alkyl, a cycloalkyl, an aryl, a substituted aryl, a heteroatom (e.g., O), a substituted heteroatom (e.g., OR), a halogen, a heterocyclic, or a heteroaryl group, or R50 and R51 together with other atoms can form a heterocyclic or heteroaryl ring, or R51 and R53 together with other atoms can form a heterocyclic or heteroaryl ring, or R51 is chemical bond or are each independently chemical bonds and
  • R50, R51, R52, R53, R54, and R55 can have 1 to 50 atoms (e.g., carbon atoms, or a mixture of carbon atoms and heteroatoms), 2 to 20 atoms or 3 to atoms.
  • atoms e.g., carbon atoms, or a mixture of carbon atoms and heteroatoms
  • Non-limiting examples of specific structures include:
  • ring structures (XXX) and (XXXI) can be substituted as defined for structures (XXV) and (XXVII).
  • R53 in ligand (XXXI) is hydrogen and structures (XXXI) are as follows:
  • Suitable (N, carbene) bidentate coordinating ligands can include carbenes in a nitrogen heterocyclic ring (N, ⁇ , ⁇ -carbene) and/or sulfur heterocyclic ring(N, N,S-carbene).
  • a (N, ⁇ , ⁇ -carbene carbene) bidentate coordinating ligand can have the following general structure:
  • R 6 o, Rei, R 6 2, R 63 , R 6 4, R 65 , R 6 6, R 6 7, and R 68 can each independently be H, alkyl, branched alkyl groups, substituted alkyl, aryl, substituted aryl, alkoxy, heterocyclic, or heteroaryl, and X is N or S, or R 6 o and Rei, R 6 2 and R 6 4, R 6 4 and R 6 7, R 6 6 and R 68 , or R 6 7 and R 68 , or any combination thereof can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R 6 o, Rei, R 6 4, R 6 7, and/or R 68 can come together to form a fused ring system, or R 68 is an electron pair and R 6 7 together with other atoms can form a heterocyclic or heteroaryl ring system, or R 68 is an electron pair and R 6 o, Rei, R 6 4 and/or R 6 7
  • R 6 o, Rei, R 62 , R 63 , and R 6 4, are as defined above and R 66 , R 6 7, R 68 , and R 6 9, can each independently be H, alkyl, branched alkyl, substituted alkyl, aryl, substituted aryl, alkoxy, heterocyclic, or heteroaryl groups, or R 63 and R 6 9, R 6 6 and R 6 7, R 6 7 and R 68 , or R 68 and R 6 9, can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R 6 o, Rei, R 63 , and/or R 6 9 can come together to form a fused ring system.
  • structure (XLII) has the specific structure:
  • a bidentate carbene ligand is used.
  • a bidentate carbene can have the following generic structure:
  • R 6 o, Rei, R 62 , R 63 , R 6 4, R 66 , R 6 7, are as defined above for structure (XL), and R70, R71, R72, R73, R74, R75, and R76 can each independently be H, alkyl, branched alkyl groups, substituted alkyl, aryl, substituted aryl, alkoxy, heterocyclic, or heteroaryl, or R 6 o and Rei, R 6 2 and R 6 4, R70 and R71, R72 and R74, R74 and R73, or any combination thereof, can come together with other atoms to form cyclic, aryl, heterocyclic, heteroaryl rings, or R 6 o, Rei, R 6 4, R77, and/or R73 can come together to form a fused ring system.
  • the alkyl or branched alkyl groups can have a carbon number
  • Monodentate ligands can include one coordinating heteroatom. Two monodentate ligands are typically used to coordinate with metal of the metal carboxylation catalyst as each ligand coordinates once to the metal center. Suitable monodentate ligands have the generic structure:
  • XR 80 R 8 iR 82 (XLVI) where X is a nitrogen (N), sulfur (S), or oxygen (O) atoms, and R 8 oR 8 iR 8 2 can each be independently hydrogen, alkyl, cycloalkyl or aryl. vi. (P,P) Ligands
  • Suitable (P,P) bidentate coordinating ligands can include phosphorus.
  • Non- limiting examples of (P,P) ligands for the catalyst can include bis(dicyclohexylphosphino)ethane (dcpe, structure XLVII), 1,3- bis(dicyclohexlphosphino)propane (dcpp, structure XL VIII), 1,2- bis(diphenylphosphino)ethane (dppe, structure XLIX), l,3-bis(diphenylphosphino)propane (dppp, structure L), l,4-bis(diphenylphosphino)butane(dppb, structure LI), which are commercially available various suppliers such as Sigma-Aldrich® (U.S.A.).
  • ligands and metals described above can be reacted with alkenes and carbon dioxide to form a metallocycle catalyst intermediate.
  • a nickel metal precursor, ligand XL VII can react with the alkene and CO2 to form metallocycle structure LII ((dcpe)Ni(CH 2 CH 2 COO)):
  • a nickel metal precursor, ligand XL VIII can react with an olefin to form olefin complexed material shown as structure LIII ((dcpp)Ni(CH 2 CH 2 )), which then can react with C0 2 to form a metallocycle similar in structure to structure LII.
  • Alkenes used in the context of the present invention can be obtained from various commercial or natural sources or be a by-product of a hydrocarbon process (e.g., hydrocracking, etc.). Suitable alkenes are those of the following structure:
  • K a , R*, R c , and K d are each independently hydrogen, Ci-12-alkyl, C2-i2-alkenyl, or K a and R* together with the other atoms to which they are bonded are a mono- or di- ethylenically unsaturated, 5- to 8-membered carbocycle, with the proviso that at least one R a , R*, R c , and K d is hydrogen.
  • alkenes include ethene, propene, isobutene, butadiene, piperylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, 1-decene, styrene, substituted styrene, or combinations thereof.
  • the alkene to be used in the carboxylation can be in a gaseous or liquid phase under the reaction conditions.
  • the alkene is ethylene (ethene).
  • Carbon dioxide used in the present invention can be obtained from various sources.
  • the carbon dioxide can be obtained from a waste or recycle gas stream (e.g., from a plant on the same site, like for example from ammonia synthesis) or after recovering the carbon dioxide from a gas stream.
  • a benefit of recycling carbon dioxide by using it as a starting material in the process of the invention is that it can reduce the amount of carbon dioxide emitted to the atmosphere (e.g., from a chemical production site).
  • the CO2 stream can be include other gases, preferably inert gases such as helium (He), argon (Ar), or nitrogen (N2), and other inert gases that do not negatively affect the reaction.
  • the carbon dioxide stream can include the alkene.
  • the amount of CO2 in the reactant stream can range from 2 vol.%, 3 vol.%, 4 vol.%, 5 vol.%, 10 vol.%, 15 vol.%, 20 vol.%, 25 vol.%, 30 vol.%, 35 vol.%, 40 vol.%, 45 vol.%, 50 vol.%, 55 vol.%, 60 vol.%, 65 vol.%, 70 vol.%, 75 vol.%, 80 vol.%, 85 vol.%, 90 vol.%, 95 vol.%, 98 vol.% or any range or value there between.
  • the amount of alkene in the reactant stream can range from 2 vol.%, 3 vol.%, 4 vol.%, 5 vol.%, 10 vol.%, 15 vol.%, 20 vol.%, 25 vol.%, 30 vol.%, 35 vol.%, 40 vol.%, 45 vol.%, 50 vol.%, 55 vol.%, 60 vol.%, 65 vol.%, 70 vol.%, 75 vol.%, 80 vol.%, 85 vol.%), 90 vol.%), 95 vol.%), 98 vol.% or any range or value there between.
  • a volume ratio of CO2 to alkene can range from 0.02: 1 to 40: 1. 0.02.
  • the reactant feed stream can include 2.5 vol.% CO2 and 95.5 vol.% alkene, 25% vol.% CO2 and 75 vol.% alkene, 50 vol.% CO2 and 50 vol.% alkene, 75 vol.% CO2 and 25 vol.% alkene or 97.5 vol.% CO2 and 2.5 vol.% alkene.
  • 4 vol.% CO2 and 96 vol.% ethylene, 50 vol.%) CO2 and 50 vol.% ethylene, or 75 vol.%> CO2 and 25 vol.%> ethylene can be used.

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Abstract

L'invention concerne des procédés de production de sels d'acide carboxylique α,β-insaturé. Le procédé selon la présente invention peut consister à faire réagir un alcène et du dioxyde de carbone avec une composition qui comprend un catalyseur de carboxylation et une base inorganique dans un solvant protique dans des conditions de réaction appropriées pour produire un sel de base inorganique d'un acide carboxylique α,β-insaturé.
PCT/IB2018/056605 2017-09-14 2018-08-29 Acrylates par couplage oléfine/dioxyde de carbone Ceased WO2019053541A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3143603A1 (fr) 2022-12-20 2024-06-21 IFP Energies Nouvelles Conversion d’une charge hydrocarbonée issue de la biomasse en sels d’acrylate

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WO2015173295A1 (fr) 2014-05-16 2015-11-19 Basf Se Préparation d'un sel d'acide carboxylique insaturé à partir d'un alcène et de dioxyde de carbone à l'aide d'un complexe de métal de transition immobilisé de manière covalente
WO2016180775A1 (fr) 2015-05-13 2016-11-17 Basf Se Procédé de préparation d'un sel d'acide carboxylique insaturé

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WO2015173295A1 (fr) 2014-05-16 2015-11-19 Basf Se Préparation d'un sel d'acide carboxylique insaturé à partir d'un alcène et de dioxyde de carbone à l'aide d'un complexe de métal de transition immobilisé de manière covalente
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3143603A1 (fr) 2022-12-20 2024-06-21 IFP Energies Nouvelles Conversion d’une charge hydrocarbonée issue de la biomasse en sels d’acrylate
WO2024132696A1 (fr) 2022-12-20 2024-06-27 IFP Energies Nouvelles Conversion d'une charge hydrocarbonee issue de la biomasse en sels d'acrylate

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