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WO2020190047A1 - Catalyseur d'hydrogénation hétérogène, son procédé de préparation, et procédé d'hydrogénation de dioxyde de carbone à l'aide du catalyseur - Google Patents

Catalyseur d'hydrogénation hétérogène, son procédé de préparation, et procédé d'hydrogénation de dioxyde de carbone à l'aide du catalyseur Download PDF

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WO2020190047A1
WO2020190047A1 PCT/KR2020/003745 KR2020003745W WO2020190047A1 WO 2020190047 A1 WO2020190047 A1 WO 2020190047A1 KR 2020003745 W KR2020003745 W KR 2020003745W WO 2020190047 A1 WO2020190047 A1 WO 2020190047A1
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formula
ligand
hydrogenation catalyst
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aromatic
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Korean (ko)
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윤성호
하리야나담 구나세카르구니야
박광호
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Kookmin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group

Definitions

  • the present invention relates to a hydrogenation catalyst and a method for producing the same, and more particularly, to a heterogeneous hydrogenation catalyst by the Friedel Craft reaction.
  • the hydrogenation reaction is a reaction in which hydrogen is added to an unsaturated bond of an organic compound. One pi bond of the unsaturated bond is broken and two sigma bonds are formed. In this case, if the metal catalyst is added, the hydrogenation reaction may proceed rapidly, and thus a hydrogenation catalyst exhibiting excellent catalytic activity may be applied to the hydrogenation reaction of the unsaturated compound.
  • a hydrogenation catalyst can be applied to all unsaturated organic compounds in which the hydrogenation reaction can proceed.
  • an unsaturated organic compound it may include an olefin, ketone, aldehyde, or amine compound, and in particular, may be carbon dioxide.
  • the hydrogenation of carbon dioxide may produce formic acid, methanol, methane, and dimethylformamide.
  • the generation of formic acid through hydrogenation of carbon dioxide can be represented as shown in Tables 1 (a) and (b) below.
  • Catalysts can be classified into homogeneous catalysts and heterogeneous catalysts depending on whether they exist in the same phase as the reactants. When the reactant and the catalyst are in the same phase, it is called a homogeneous catalyst, and when they are different, it is called a heterogeneous catalyst. Heterogeneous catalysts are mainly solids, which are not mixed with reactants and products in a chemical reaction, so they can be easily recovered after reaction, and have the advantage of securing economical efficiency.
  • a first technical problem to be achieved by the present invention is to provide a heterogeneous hydrogenation catalyst having high activity in a hydrogenation reaction and excellent utility in a continuous process.
  • a second technical problem is to provide a method for producing a heterogeneous hydrogenation catalyst in which the catalyst synthesis process is easy.
  • the heterogeneous hydrogenation catalyst includes a porous organic polymer and a transition metal compound represented by M (L B ) x coordinated to the porous organic polymer, and the unit of the porous organic polymer includes an aromatic ring.
  • the unit of the porous organic polymer may be a heterogeneous hydrogenation catalyst represented by Formula 1 below.
  • FL is the frame ligand
  • M(L B ) x is the transition metal compound
  • Y is the linking group
  • CM is a supercrosslinked polymer unit having a crosslinkable functional group
  • m is an integer of 0 or 1. I can.
  • the frame ligand (FL) to which the transition metal compound is coordinated may be a heterogeneous hydrogenation catalyst represented by the following Chemical Formula 7, the following Chemical Formula 8, or the following Chemical Formula 9.
  • the organic ligand (L A ) may include one or more heteroaromatic rings, and may be a monodentate ligand having one coordination bond atom or a multidentate ligand having several coordination bond atoms.
  • the method of preparing the heterogeneous hydrogenation catalyst includes forming a porous organic polymer by performing a Friedel Craft reaction with a frame ligand precursor and a linker precursor including an aromatic ring to form a porous organic polymer, and M (L B ) in the porous organic polymer.
  • a metal fixing step of coordinating the transition metal compound represented by x wherein the linking group precursor is separated from a linking group connected by a Friedel Craft reaction with the aromatic ring included in the frame ligand precursor, and exists in an anionic state.
  • L B may be an anionic ligand or a neutral ligand.
  • anionic ligands Cl -, Br -, I -, SO 4 -, CF 3 SO 3 -.
  • the neutral ligand may include H 2 O, CO (carbon monoxide), phosphine series, carbon series, or nitrogen series, but is not limited thereto.
  • phosphine-based neutral ligand PPh 3 , PMe 3 , PH 3 , P(i-Pr) 3 , PF 3 or P(OMe) 3 may be used.
  • a carbon-based neutral ligand it may be Cymene, cyclopentadiene, or a derivative thereof.
  • the neutral ligand may be NH 3 (ammonia), NHMe 2 (dimethylamine), or NH 2 Me (methylamine).
  • x may be an integer from 1 to 5.
  • the method of preparing the heterogeneous hydrogenation catalyst comprises the steps of coordinating a frame ligand precursor containing an aromatic ring and a transition metal compound represented by M(L B ) x , and a frame ligand precursor and a linker precursor in which the transition metal compound is coordinated.
  • a step of forming a porous organic polymer by performing a Friedel Craft reaction wherein the linking group precursor is separated from a linking group connected by a Friedel Craft reaction with the aromatic ring included in the frame ligand precursor, It includes a leaving group present in the state, and M is 1 selected from the group consisting of Ir, Pt, Pd, Ru, Rh, Ni, Fe, Cu, V, Co, Cr, Au, Re, W, Zr and Mo It is an element selected from more than one species, and L B may be an anionic ligand or a neutral ligand. As an example of the anionic ligands, Cl -, Br -, I -, SO 4 -, CF 3 SO 3 -.
  • the neutral ligand may include H 2 O, CO (carbon monoxide), phosphine series, carbon series, or nitrogen series, but is not limited thereto.
  • phosphine-based neutral ligand PPh 3 , PMe 3 , PH 3 , P(i-Pr) 3 , PF 3 or P(OMe) 3 may be used.
  • a carbon-based neutral ligand it may be Cymene, cyclopentadiene, or a derivative thereof.
  • the neutral ligand may be NH 3 (ammonia), NHMe 2 (dimethylamine), or NH 2 Me (methylamine).
  • x may be an integer from 1 to 5.
  • the frame ligand precursor may be a method of preparing a heterogeneous hydrogenation catalyst represented by the following Chemical Formula 10 or the following Chemical Formula 11.
  • the leaving group is selected from the group consisting of -Cl (chloride), -Br (bromide), -I (iodide), -OTs (tosylate), -SO 3 H (sulfonate) and -OMs (mesylate). It may be a method of preparing a hydrogenation catalyst.
  • the linking group precursor may be a method of preparing a heterogeneous hydrogenation catalyst represented by the following Chemical Formulas 12 to 16.
  • a heterogeneous hydrogenation catalyst using a porous organic polymer as a support has a simple manufacturing method and can be more useful than a conventionally prepared homogeneous hydrogenation catalyst.
  • Example 1 is a scanning electron microscope (SEM) photograph of a [Phen-POP] hydrogenation catalyst synthesized according to Example 1-1 of the present invention.
  • Example 2 is a graph showing the results of EDS analysis for the [Phen-POP] hydrogenation catalyst synthesized according to Example 1-1 of the present invention.
  • FIG 3 is a graph showing a nitrogen adsorption isotherm of a hydrogenation catalyst synthesized according to an embodiment of the present invention.
  • the heterogeneous hydrogenation catalyst according to the present invention comprises a porous organic polymer (POP) and a transition metal compound represented by M (L B ) x coordinated to the porous organic polymer, and a unit of the porous organic polymer Is a frame ligand containing an aromatic ring, an aromatic ring included in the frame ligand and a linking group connected by a Friedel Craft reaction, wherein M is Ir, Pt, Pd, Ru, Rh, Ni, It may be one or more selected elements selected from the group consisting of Fe, Cu, V, Co, Cr, Au, Re, W, Zr and Mo.
  • L B can be an anionic ligand or a neutral ligand.
  • anionic ligands Cl -, Br -, I -, SO 4 -, CF 3 SO 3 -. NO 3 -, PF 6 -, carboxylate, oxalate, carbonate, acetylacetonate, OH - (hydroxide), H - (hydride), NO 2- (nitrite), ClO 2 - (chlorite) , SO 3 2- (sulfite), CH 3 O - (methoxide), CN - (cyanide), or SCN - may be (h between arylthio carbonate), and the like.
  • the neutral ligand may include H 2 O, CO (carbon monoxide), phosphine series, carbon series, or nitrogen series, but is not limited thereto.
  • a phosphine-based neutral ligand PPh 3 , PMe 3 , PH 3 , P(i-Pr) 3 , PF 3 or P(OMe) 3 may be used.
  • a carbon-based neutral ligand it may be Cymene, cyclopentadiene, or a derivative thereof.
  • the neutral ligand may be NH 3 (ammonia), NHMe 2 (dimethylamine), or NH 2 Me (methylamine).
  • x may be an integer from 1 to 5.
  • the unit of the porous organic polymer coordinating the transition metal compound may be represented by Formula 1 below.
  • FL is a frame ligand
  • M is a transition metal
  • L B is an anionic or neutral ligand
  • Y is a linking group
  • CM is a supercrosslinked polymer unit having a functional group capable of crosslinking.
  • m is an integer of 0 or 1
  • x is an integer of 1 to 5.
  • the frame ligand FL constitutes the main skeleton of a polymer and may include an organic ligand. It may contain an aromatic ring.
  • the transition metal compound (M(L B ) x ) may be coordination bonded to the frame ligand FL to receive electrons from the frame ligand FL.
  • M, L B , and x are as described above, respectively.
  • the linking group (Y) is connected by a Friedel Craft reaction with the aromatic ring contained in the frame ligand (FL), and may include sp 2 carbon or sp 3 carbon, and a more detailed description of the linking group (Y) is given below.
  • FL frame ligand
  • the linking group (Y) may be represented by the following Chemical Formulas 2 to 5, and in this case, it may be to connect compounds through sp 3 carbon.
  • R 3 is an alkyl group having 1 to 10 carbon atoms.
  • Each of the above alkyl groups may be linear or branched. In addition, it may be substituted or unsubstituted.
  • R 4 and R 5 are alkyl groups having 1 to 5 carbon atoms that are the same as or different from each other.
  • Each of the above alkyl groups may be linear or branched. In addition, it may be substituted or unsubstituted.
  • a 3 is one containing 1 to 10 aromatic rings.
  • the aromatic rings may be linearly connected or form a fused ring.
  • a 3 may be a central atom (carbon, silicon, nitrogen, phosphorus, etc.) or the aromatic ring or aromatic rings connected to a group having the same.
  • R 4 and R 5 are the same as in Formula 3.
  • R 4 , R 5 and A 3 are the same as in Formula 3.
  • linking group (Y) may be represented by Formula 6 below, and in this case, compounds may be connected through sp 2 carbon.
  • l is an integer of 2 or more and 6 or less
  • a 4 is an aromatic compound, which may include 1 to 20 aromatic rings.
  • the A 4 may be a homocyclic aromatic compound consisting only of carbon and hydrogen.
  • the homoaromatic ring may be monocyclic or polycyclic having two or more rings.
  • the homoaromatic ring may be substituted or unsubstituted.
  • a 4 may be a heteroaromatic compound in which a part of carbon atoms in the homoaromatic compound is substituted with a hetero atom other than carbon.
  • the heteroaromatic ring may be monocyclic or polycyclic having two or more rings.
  • the heteroaromatic ring may be substituted or unsubstituted.
  • the heterogeneous hydrogenation catalyst according to the present invention may be a porous organic polymer serving as a support for a transition metal compound.
  • the shape is not standardized and thus can be formed by bonding into various structures, and can have excellent bonding strength.
  • the organic polymer may be a porous organic polymer having microporosity. Accordingly, the organic polymer support in which the cavity is formed can secure a large space in which the transition metal compound can be easily coordinated, and thus can exhibit high catalytic activity.
  • the surface area in the support is large, the reaction material can rapidly diffuse in the catalyst.
  • the catalyst is a heterogeneous catalyst and has a phase different from that of a reactant and a product, it can be easily separated therefrom and thus the catalyst can be easily recovered.
  • the super-crosslinked polymer unit (CM) may be further included in the unit of the porous organic polymer, which may be to perform crosslinking.
  • a supercrosslinked polymer unit (CM) is an aromatic compound containing 1 to 20 aromatic rings, and is a homocyclic aromatic compound consisting only of carbon and hydrogen, or in a homoaromatic compound, some of the carbon atoms are heterogeneous other than carbon. It may be a heteroaromatic compound substituted with an atom (hetercyclic aromatic compound). In addition, it may be monocyclic or a homoaromatic polycyclic having two or more rings, and may be substituted or unsubstituted.
  • CM supercrosslinked polymer unit
  • the supercrosslinked polymer unit (CM) may be omitted.
  • the porous organic polymer When the porous organic polymer includes a supercrosslinked polymer, it may have an excellent degree of crosslinking compared to otherwise. Accordingly, the interchain bonding strength of the porous organic polymer is increased, and the porous organic polymer can have high mechanical strength and thermal and chemical stability in continuous impact, and thus can be advantageously utilized in a continuous process. In addition, the reaction surface area of the catalyst including the same increases, increasing the rate at which the reactant diffuses into the catalyst, and thus, excellent catalytic activity efficiency may be exhibited.
  • a frame ligand (FL) to which a transition metal compound is coordinated according to an embodiment of the present invention may be represented by the following Chemical Formula 7.
  • a 1 and A 2 are the same or different aromatic compounds and include 1 to 10 aromatic rings, L A is an organic ligand, and M(L B ) x is the same as in Chemical Formula 1.
  • a 1 or A 2 may be a homocyclic aromatic compound consisting only of carbon and hydrogen.
  • the homoaromatic compound may be a homoaromatic monocyclic or a homoaromatic polycyclic having two or more rings.
  • the homoaromatic ring may be substituted or unsubstituted.
  • a 1 or A 2 may be a heteroaromatic compound in which a part of carbon atoms in the homoaromatic compound is substituted with a hetero atom other than carbon.
  • the heteroaromatic compound may be a heteroaromatic monocyclic or heteroaromatic polycyclic having two or more rings.
  • the heteroaromatic ring may be substituted or unsubstituted.
  • the following compounds (1) to (7) are examples of an aromatic compound (A 1 or A 2 ), but are not limited thereto.
  • the organic ligand (L A ) includes at least one coordination bond atom that is coordinating with the transition metal compound, and may have a coordination bond atom or a group containing a coordination bond atom.
  • the coordinating bond atom may be one or more selected from the group consisting of carbon (C), nitrogen (N), oxygen (O), phosphorus (P), and sulfur (S) atoms.
  • the organic ligand (L A ) may be a monodentate ligand containing one coordination bond atom. In addition, it may be a polydentate ligand including a plurality of coordination bond atoms. In this case, when a plurality of coordination bond atoms are included, the coordination bond atoms may be the same or different from each other.
  • the organic ligand (L A ) may include one or more heteroaromatic rings.
  • the heteroaromatic ring may be a single ring, and in particular may be a macrocyclic ring.
  • the heteroaromatic ring may be substituted, and may be fused with other homoaromatic rings and/or heteroaromatic rings to form a fused bicyclic ring.
  • one or more nitrogen (N), oxygen (O), phosphorus (P) and/or sulfur (S) atoms constituting the heteroaromatic ring, or non-shared electron pairs of atoms are coordinating with the transition metal (M).
  • M transition metal
  • the organic ligand (L A ) is thiophene, pyridine, pyrrole, phosphinine, porphyrin, phenanthroline, bipyridine, Biphosphinine, bipyrrole, phenyl pyridine, bipyrimidine, biimidazole, bithiophene, or a derivative thereof, but is not limited thereto.
  • the organic ligand (L A ) may be phenanthroline.
  • the aromatic heterocycle is bonded between two aromatic compounds (A 1 and A 2 ), and an organic ligand (L A ) is linear with aromatic compounds water (A 1 and A 2 ) by covalent bonding. It may be connected by structure.
  • organic ligand (L A ) may be represented by Formula 8 below.
  • L′ and L′′ are coordination bond atoms selected from the group consisting of nitrogen (N), oxygen (O), phosphorus (P) and sulfur (S) atoms that are the same or different from each other.
  • R 1 or R 2 may be the same or different hydrogen, an alkyl group or a phenyl group having 1 to 3 carbon atoms
  • L′ or L′′ is In the case of oxygen (O) or sulfur (S), R 1 and R 2 may be unshared electron pairs.
  • r is an alkyl group having 1 to 10 carbon atoms
  • n is an integer of 0 or 1.
  • Each of the above alkyl groups may be linear or branched.
  • the frame ligand (FL) satisfying the organic ligand (L A ) triphenyl amine (triphenyl amine), triphenylphosphine (triphenylphosphine), methyl diphenylphosphine (methyl diphenylphosphine) or a derivative thereof I can.
  • a frame ligand (FL) to which a transition metal compound is coordinated may be represented by Formula 9 below.
  • the frame ligand (FL) is composed of an organic ligand (L A ), and in Chemical Formula 9, M(L B ) x is the same as in Chemical Formula 7.
  • L A is an organic ligand, and may be an aromatic compound including 1 to 20 aromatic rings.
  • the aromatic compound may be a homocyclic aromatic compound, which is an aromatic ring consisting only of carbon and hydrogen.
  • the homoaromatic ring may be a substituted or unsubstituted ring, and may be monocyclic or polycyclic having two or more rings. This means that carbon (C) constituting the homoaromatic compound is a coordination bond atom, and in detail, the pi bond may be a coordination bond with the transition metal compound.
  • the aromatic compound may be a heteroaromatic compound in which a part of carbon atoms in the homoaromatic compound is substituted with a hetero atom other than carbon.
  • the heteroaromatic compound may be a heteroaromatic monocyclic or heteroaromatic polycyclic having two or more rings. The heteroaromatic ring may be substituted or unsubstituted.
  • Unsaturated organic compounds or carbon dioxide can be hydrogenated using the above-described heterogeneous hydrogenation catalyst.
  • the unsaturated organic compound may be an olefin, a ketone, an aldehyde, an ester, a carboxylic acid, or a nitro compound.
  • a heterogeneous hydrogenation catalyst formic acid and / or formate - may generate (formate, HCOO).
  • the hydrogenation of carbon dioxide using the heterogeneous hydrogenation catalyst may be performed by reacting carbon dioxide and hydrogen in the presence of the catalyst. Specifically, the heterogeneous hydrogenation catalyst, a solvent, and a tertiary amine are injected and mixed into the reactor, carbon dioxide and hydrogen gas are injected into the reactor, heated, and then the heterogeneous hydrogenation catalyst is removed to remove formic acid and/or formic acid. it is possible to obtain a-mate (formate, HCOO).
  • the tertiary amine acts as a base in the carbon dioxide hydrogenation reaction and is not limited to any tertiary amine, and as an example, the tertiary amine may be trimethylamine, triethylamine, and/or tripropylamine.
  • the solvent is used to effectively disperse the carbon dioxide hydrogenation catalyst of the present invention, and may be a polar solvent as an example.
  • the polar solvent may be at least one selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, or water.
  • the reaction temperature is not limited, but as an example, the reaction temperature in the reactor may be carried out at 80°C to 200°C.
  • carbon dioxide and hydrogen gas injected into the reactor may be injected at a volume ratio of 1:9 to 9:1, and in one example, the total pressure of carbon dioxide and hydrogen gas may be 20 to 300 bar.
  • Removing and recovering the heterogeneous hydrogenation catalyst from the product is an example of solid-liquid separation, and may be performed through gravity sedimentation, centrifugation, or filtration.
  • the recovered catalyst can be reused for other hydrogenation reactions.
  • a method of preparing a heterogeneous hydrogenation catalyst according to an embodiment of the present invention includes forming a porous organic polymer by performing a Friedel Craft reaction with a frame ligand precursor and a linker precursor including an aromatic ring. I can.
  • Friedel Craft reaction is a kind of electrophilic aromatic substitution reaction (EAS).
  • EAS electrophilic aromatic substitution reaction
  • an aromatic ring acts as a nucleophile, reacts with an electrophile, and recovers the aromaticity to restore an aromatic having an alkyl group or an acyl group It may be to obtain a ring.
  • the frame ligand precursor may be represented by the following Chemical Formula 10 or 11, wherein hydrogen is attached to the linking (*) site of the frame ligand (FL) represented by Chemical Formula 7 or 9, and details of the frame ligand (FL) Is as described in the above heterogeneous hydrogenation catalyst.
  • a 1 and A 2 are the same as or different from each other and include 1 to 10 aromatic rings, and L A is an organic ligand.
  • a 1 or A 2 may be a homocyclic aromatic compound consisting only of carbon and hydrogen.
  • the homoaromatic compound may be a homoaromatic monocyclic or a homoaromatic polycyclic having two or more rings.
  • the homoaromatic ring may be substituted or unsubstituted.
  • a 1 or A 2 may be a heteroaromatic compound in which a part of carbon atoms in the homoaromatic compound is substituted with a hetero atom other than carbon.
  • the heteroaromatic compound may be a heteroaromatic monocyclic or heteroaromatic polycyclic having two or more rings.
  • the heteroaromatic ring may be substituted or unsubstituted.
  • the organic ligand (L A ) includes at least one coordination bond atom for coordination with the transition metal compound, and may have a coordination bond atom or a group including a coordination bond atom.
  • the coordinating bond atom may be one or more selected from the group consisting of carbon (C), nitrogen (N), oxygen (O), phosphorus (P), and sulfur (S) atoms.
  • the organic ligand (L A ) may be a monodentate ligand containing one coordination bond atom. In addition, it may be a polydentate ligand including a plurality of coordination bond atoms. In this case, when a plurality of coordination bond atoms are included, the coordination bond atoms may be the same or different from each other.
  • the organic ligand (L A ) may include one or more heteroaromatic rings.
  • the heteroaromatic ring may be a single ring, and in particular may be a macrocyclic ring.
  • the heteroaromatic ring may be substituted, and may be fused with other homoaromatic rings and/or heteroaromatic rings to form a fused bicyclic ring.
  • one or more nitrogen (N), oxygen (O), phosphorus (P) and/or sulfur (S) atoms constituting the heteroaromatic ring, or non-shared electron pairs of atoms are coordinating with the transition metal (M).
  • M transition metal
  • the organic ligand (L A ) is thiophene, pyridine, pyrrole, phosphinine, porphyrin, phenanthroline, bipyridine, Biphosphinine, bipyrrole, phenyl pyridine, bipyrimidine, biimidazole, bithiophene, or a derivative thereof, but is not limited thereto.
  • the organic ligand (L A ) may be phenanthroline.
  • the aromatic heterocycle is bonded between two aromatic compounds (A 1 and A 2 ), and an organic ligand (L A ) is linear with aromatic compounds water (A 1 and A 2 ) by covalent bonding. It may be connected by structure.
  • L A is an organic ligand, and may be an aromatic compound including 1 to 20 aromatic rings.
  • the aromatic compound may be a homocyclic aromatic compound, which is an aromatic ring consisting only of carbon and hydrogen.
  • the homoaromatic ring may be a substituted or unsubstituted ring, and may be monocyclic or polycyclic having two or more rings. This means that carbon (C) constituting the homoaromatic compound is a coordination bond atom, and in detail, the pi bond may be a coordination bond with the transition metal compound.
  • the aromatic compound may be a heteroaromatic compound in which a part of carbon atoms in the homoaromatic compound is substituted with a hetero atom other than carbon.
  • the heteroaromatic compound may be a heteroaromatic monocyclic or heteroaromatic polycyclic having two or more rings. The heteroaromatic ring may be substituted or unsubstituted.
  • the aromatic ring included in the frame ligand precursor may undergo a Friedel Craft reaction.
  • a reaction similar to the Friedel Craft reaction can also be performed from the viewpoint of the reaction mechanism.
  • the role of the nucleophile of the reaction may be performed by the frame ligand precursor. Accordingly, even when the aromatic ring constituting the frame ligand precursor has a substituent, the aromatic ring may have at least one carbon that performs the Friedel Craft reaction. As a result, it cannot be assumed that the Friedel Craft reaction cannot be performed due to reasons such as substitution of all hydrogens constituting the aromatic ring or the presence of an inert group.
  • the number of linkable bonds between compounds may increase.
  • the polymer thus obtained will have an excellent degree of crosslinking, and will have excellent inter-molecular bonding strength.
  • the catalyst can exhibit high mechanical strength in continuous impact and excellent thermal and chemical stability.
  • the porosity of a polymer formed by polymerizing it may be controlled through the length or structure of an aromatic ring capable of performing the Friedel Craft reaction.
  • the linking group precursor is a form including a leaving group to perform the Friedel Craft reaction, and may provide a linking group (Y).
  • the linking group precursor serves as an electrophile and may be subjected to nucleophilic attack from an aromatic ring. Therefore, as the aromatic ring nucleophilically attacks the sp 2 carbon or sp 3 carbon of the linking group (Y), and the leaving group included in the linking group precursor is removed, a new bond between the aromatic ring and the linking group (Y) may be formed.
  • the linking group Y may serve to connect adjacent frame ligands FL, and may connect the frame ligand FL and the super-crosslinked polymer unit CM.
  • linking group precursor it may be represented by the following Chemical Formula 12.
  • the linking group (Y) may be to connect each compound through sp 3 carbon.
  • R 3 is an alkyl group having 1 to 10 carbon atoms, and each of the alkyl groups may be linear or branched. In addition, it may be substituted or unsubstituted.
  • X 1 and X 2 are the same or different leaving groups.
  • the leaving group may be separated from the linking group precursor and exist in an anionic state, and the more stable ones having less reactivity when the anions are. Therefore, it is preferred that the anion is weakly basic.
  • a leaving group it may be -Cl (chloride), -Br (bromide), -I (iodide), -OTs (tosylate), -SO 3 H (sulfonate), -OMs (mesylate), and the reaction It is not limited thereto as long as it is a group that can function as a leaving group in general.
  • the linking group precursor may be the following compound (a).
  • linking group precursor it may be represented by the following formula (13).
  • R 4 and R 5 are alkyl groups having 1 to 5 carbon atoms that are the same or different from each other, and the alkyl groups may be linear or branched, respectively. In addition, it may be substituted or unsubstituted.
  • X 1 and X 2 are the same as in Chemical Formula 12.
  • a 3 is one containing 1 to 10 aromatic rings. When A 3 includes multiple rings, aromatic rings may be linearly linked or form a fused ring.
  • the linking group precursor may be the following compound (b).
  • a 3 may be a central atom (carbon, silicon, nitrogen, phosphorus, etc.) or a group having the aromatic ring or aromatic rings connected to the group having the same, and as a specific example, the linking group precursor may be the following compound (c).
  • the linking group (Y) includes an aromatic ring
  • a post-synthetic modification such as additional Friedel Craft reaction and the like may be performed.
  • an additional functional group may be introduced into the aromatic ring included in the linking group (Y).
  • the functional group include a sulfonated group, a hydroxy group, a nitro group, and an alkyl group, but are not limited thereto.
  • the porous polymer catalyst having the same can be controlled so as to have properties that are in contrast to the non-porous polymer catalyst. Accordingly, in carrying out a chemical reaction, there is an advantage that the catalyst can be induced to have a chemical property that can be activated.
  • linking group precursor it may be represented by the following Chemical Formula 14.
  • X 1 , X 2 and X 3 are the same or different leaving groups, and R 4 and R 5 are the same as in Formula 13.
  • the linking group precursor may be the following compound (d).
  • linking group precursor it may be represented by the following Chemical Formula 15.
  • X 1 , X 2 , X 3 , R 4 and R 5 are the same as in Formula 14, and A 3 is the same as in Formula 13.
  • the linking group precursor may be the following compound (e).
  • linking group precursor it may be represented by the following Chemical Formula 16.
  • the linking group (Y) may be to connect each compound through sp 2 carbon.
  • l is an integer of 2 or more and 6 or less
  • X l is a leaving group, and the leaving group may have a total of l (X 1 , X l-1 ,... X l ).
  • A4 may be an aromatic compound containing 1 to 20 aromatic rings.
  • A4 of the above may be a homocyclic aromatic compound consisting of only carbon and hydrogen (homocyclic aromatic compound).
  • the homoaromatic ring may be monocyclic or polycyclic having two or more rings.
  • the homoaromatic compound may be substituted or unsubstituted.
  • A4 may be a heteroaromatic compound in which a part of carbon atoms in the homoaromatic compound is substituted with a hetero atom other than carbon.
  • the heteroaromatic ring may be monocyclic or polycyclic having two or more rings.
  • the heteroaromatic ring may be substituted or unsubstituted.
  • X1 and X2 are the same as in Chemical Formula 12.
  • the linking group precursor may include three or more leaving groups, and the linking group (Y) serves to form a new bond between compounds, and the site at which the bond is formed has a leaving group. It could be a carbon site. Therefore, as the number of leaving groups increases, the number of times that compounds can be bonded may increase, so by controlling the number of leaving groups included in the linker precursor, the polymer according to an embodiment of the present invention can be controlled to have an excellent degree of crosslinking. I can. In addition, as the binding force of the polymer increases, it is possible to have high mechanical strength and excellent thermal and chemical stability under continuous impact.
  • the following compounds (a)-(g) are examples of a linking group precursor, but are not limited thereto.
  • the length or structure of the linking group (Y) may vary.
  • the number of carbons constituting the linking group (Y) is 1, the pore size of the polymer including the same is small, and thus it may not be easy as a carrier for the transition metal.
  • the number of carbons constituting the linking group (Y) is large or has a three-dimensional structure, the pore size of the polymer including the same is large, and may have excellent properties as a carrier for a transition metal. Accordingly, the polymer according to an embodiment of the present invention has an advantage of controlling the structure of the connector (Y), thereby controlling the surface area, the size, shape, and porosity of the pores, which are physical properties of the porous structure.
  • a catalyst may be added to increase the reaction rate of the Friedel Craft reaction.
  • the catalyst is Lewis acid, which can increase the electrophilicity of the electrophile.
  • a transition metal compound may be coordinated with a frame ligand (FL) constituting a porous organic polymer.
  • the transition metal compound (M(L B ) x ) may be coordinated with the frame ligand FL to receive electrons from the frame ligand FL.
  • M is one or more metals selected from groups 3 to 12 of the periodic table, in particular, Ir, Pt, Pd, Ru, Rh, Ni, Fe, Cu, V, Co, Cr, Au, Re, W, Zr and Mo. It may be one or more selected elements selected from the group consisting of.
  • L B can be an anionic ligand or a neutral ligand. As an example of the anionic ligands, Cl -, Br -, I -, SO 4 -, CF 3 SO 3 -.
  • the neutral ligand may include H 2 O, CO (carbon monoxide), phosphine series, carbon series, or nitrogen series, but is not limited thereto.
  • phosphine-based neutral ligand PPh 3 , PMe 3 , PH 3 , P(i-Pr) 3 , PF 3 or P(OMe) 3 may be used.
  • a carbon-based neutral ligand it may be Cymene, cyclopentadiene, or a derivative thereof.
  • the neutral ligand may be NH 3 (ammonia), NHMe 2 (dimethylamine), or NH 2 Me (methylamine).
  • x is an integer from 1 to 5.
  • the supercrosslinked polymer unit precursor may further include performing a Friedel Craft reaction with the linker precursor.
  • the supercrosslinked polymeric unit (CM) contains an aromatic ring and may be one that plays a role of a nucleophile in the Friedel Craft reaction.
  • a supercrosslinked polymer unit (CM) is an aromatic compound containing 1 to 20 aromatic rings, and is a homocyclic aromatic compound consisting only of carbon and hydrogen, or in a homoaromatic compound, some of the carbon atoms are heterogeneous other than carbon. It may be a heteroaromatic compound substituted with an atom (hetercyclic aromatic compound).
  • CM super-crosslinked polymer unit
  • benzene biphenyl, terphenyl, 1,3,5-triphenylbenzene, naphthalene, anthracene , Phenanthrene, pyrene, fluorene, tetraphenylmethane, or derivatives thereof, but are not limited thereto.
  • CM super-crosslinked polymer unit
  • a post-synthetic modification is performed through an additional Friedel Craft reaction, etc., in addition to the Friedel Craft reaction to form a porous organic polymer. can do.
  • an additional functional group may be introduced into the aromatic ring included in the linking group (Y).
  • the functional group include a sulfonated group, a hydroxy group, a nitro group, and an alkyl group, but are not limited thereto.
  • the porous polymer catalyst having the same can be controlled so as to have properties that are in contrast to the non-porous polymer catalyst. Accordingly, in carrying out a chemical reaction, there is an advantage that the catalyst can be induced to have a chemical property that can be activated.
  • the method for preparing a heterogeneous hydrogenation catalyst according to another embodiment of the present invention includes the steps of coordinating a frame ligand precursor including an aromatic ring and a transition metal compound represented by M(L B ) x , and the transition metal compound It may include forming a porous organic polymer by performing a Friedel Craft reaction with the frame ligand precursor and the linker precursor. The same thing as the manufacturing method of the heterogeneous hydrogenation catalyst according to the above embodiment is omitted.
  • the supercrosslinked polymer unit precursor may further include performing a Friedel Craft reaction with the linker precursor.
  • a Lewis acid catalyst may be added during the Friedel Craft reaction.
  • a homogeneous hydrogenation catalyst which is a complex in which a transition metal compound is coordinated with a frame ligand
  • a Lewis acid catalyst such as AlCl 3
  • Lewis acid catalysts Is a hard acid
  • transition metal (M) is a soft acid (soft acid)
  • ligand (L) is a soft base (soft base)
  • Lewis acid is the coordination between the frame ligand (FL) and the transition metal compound. Since it may not interfere with bonding, there are methodological advantages.
  • the frame ligand (FL) to which the transition metal compound is coordinated may be a homogeneous hydrogenation catalyst that has been reported to have high activity and stability in the related art. Therefore, by performing the Friedel Craft reaction using the existing homogeneous hydrogenation catalyst, a heterogeneous hydrogenation catalyst using a porous organic polymer as a support can be prepared, so the manufacturing method is simple, and the conventionally manufactured homogeneous hydrogenation catalyst The utilization of can be increased.
  • Bathophenanthroline ((1) in Scheme 1) (500 mg, 1.5 mmol) under N 2 was added to a 50 mL round-bottom flask (RBF) equipped with a condenser that was dried in an oven. This was cooled to 0° C., and 15 ml of a pale yellow transparent solution, dichloromethane, was added. After stirring for 5 minutes, AlCl 3 (3.2 g, 24.06 mmol) was added and stirred for 4 hours to obtain a light brown mixture.
  • the mixture was heated and stirred at 30° C. for 8 hours to obtain a light brown mixture.
  • the mixture was heated and stirred at 40° C. for 12 hours to obtain a brownish red mixture.
  • the mixture was heated and stirred at 80° C. for 24 hours to obtain a brownish red mixture.
  • FIG. 1 is a scanning electron microscope (SEM) photograph of a [Phen-POP] hydrogenation catalyst synthesized according to Example 1-1 of the present invention
  • FIG. 2 is a graph of the EDS analysis result thereof.
  • the surface area of the catalyst was reduced from 587 m 2 /g to 496 m 2 /g, and the pore volume was 0.32 cm 3 /g to 0.26 cm 3 /g It can be seen that the hydrogenation catalyst has sufficient porosity even when it is reduced to, but exists in a complex state.
  • FIG. 3 is a graph showing a nitrogen adsorption isotherm of a hydrogenation catalyst synthesized according to an embodiment of the present invention.
  • P/P 0 relative pressure
  • a hydrogenation experiment of carbon dioxide was performed using the catalyst prepared according to Preparation Example 1-2.
  • the hydrogenation of carbon dioxide was carried out under basic conditions to overcome the thermodynamic barrier.
  • the catalyst, triethylamine and water were added to a 100 mL autoclave and tightly sealed.
  • carbon dioxide was first injected and pressurized to 40 bar, and then hydrogen was injected to pressurize to 80 bar. It was also heated at 120° C. for 2 hours, cooled to room temperature, and then the pressure was removed.
  • the reaction mixture was filtered through a 0.2 micron filter, and then injected into HPLC.
  • Table 3 uses the [Pnen-POP-RuCl 3 ] catalyst prepared according to Example 1-1, and summarizes the catalytic activity according to the present invention under various reaction conditions.
  • Table 4 uses the [Pnen-POP-RuCl 3 ] and [bpy-CTF-RuCl 3 ] catalysts prepared according to Example 1-2 and Comparative Example 1-2, according to the present invention under various reaction conditions. This is a summary of catalytic activity.

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Abstract

La présente invention concerne un catalyseur d'hydrogénation hétérogène. Le catalyseur d'hydrogénation hétérogène comprend un polymère organique poreux, et un composé de métal de transition représenté par M(LB)x et coordonné avec le polymère organique poreux, un monomère du polymère organique poreux comprenant un ligand de cadre, qui contient un cycle aromatique, et un groupe de liaison lié par une réaction Friedel-Crafts à l'anneau aromatique contenu dans le ligand de cadre, M représente un ou plusieurs éléments choisis dans le groupe constitué par Ir, Pt, Pd, Ru, Rh, Ni, Fe, Cu, V, Co, Cr, Au, Re, W, Zr et Mo, LB est un ligand anionique ou un ligand neutre, et x peut être un nombre entier de 1 à 5.
PCT/KR2020/003745 2019-03-19 2020-03-19 Catalyseur d'hydrogénation hétérogène, son procédé de préparation, et procédé d'hydrogénation de dioxyde de carbone à l'aide du catalyseur Ceased WO2020190047A1 (fr)

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