Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/06—Aluminium compounds
  • C07F5/069—Aluminium compounds without C-aluminium linkages

Definitions

• the present invention relates to a process for preparing an MOF solid of a porous and crystallized aluminum aromatic azocarboxylate, in a nonaqueous organic medium.
• references in brackets [] refer to the list of references at the end of the text.
• the Metal-Organic Framework is a new class of microporous solids (or even mesoporous for some of them). It is based on the concept of three-dimensional assembly of rigid organic ligands (including a benzene ring, for example) with metal centers. The latter can arrange to form isolated clusters, infinite chains or inorganic layers that connect to one another via organic ligands via carboxylate or amine linkages.
• This type of material is usually characterized by their specific surface (which gives a precise idea of their accessible porosity for the incorporation of molecules). These specific surface values (expressed in m 2 per gram of material) are measured by the Brunauer-Emmett-Teller (or BET) methods which make it possible to examine the surface of the pores by chemistry-nitrogen sorption at 77 K ( multilayer model) or Langmuir using the same process with a single layer model. These new materials prove to be very good adsorbents for gases such as hydrogen [4-6], methane [7, 8] or even carbon dioxide [8]. They can therefore be used instead of active carbons or zeolites. In addition, this type of solids (some of which are biocompatible) may find applications for encapsulation and controlled release of drug molecules [9].
• trimesic acid 1,4-naphthalenedicarboxylic acid, 1,2,4-acid, 5-benzenetetracarboxylic
• ligands eg trimesic acid, 1,4-naphthalenedicarboxylic acid, 1,2,4-acid, 5-benzenetetracarboxylic
• trimesic acid 1,4-naphthalenedicarboxylic acid, 1,2,4-acid, 5-benzenetetracarboxylic
• aluminum-based materials can have large storage capacities for molecules such as H 2 , CH 4 , CO 2 , etc.
• the MOFs based on aluminum azocarboxylates in a crystallized form, have proved particularly interesting in terms of porosity and purity.
• MOF materials In general, it is difficult to control the structural organization and porosity of MOF materials. This may be related for example to the risks of interpenetration and entanglement of the networks during the formation of these materials may lead to a dense material with reduced pores. The material obtained may therefore have a heterogeneous structure with inadequate porosity.
• MOFs based on aluminum azocarboxylates for which the structures can be controlled so as to obtain specific properties, in particular a crystallized structure, a "customized" pore diameter adapted to the molecules to be adsorbed. , a specific surface area and / or an improved adsorption capacity, etc.
• the aluminum-based MOF solids obtained by most known methods may be unsuitable for the desired application because they may comprise several phases, be in amorphous form or contain undesirable secondary substances obtained and not eliminated during of the preparation of the MOF solid.
• said solids do not always have a porosity and therefore a sufficient adsorption capacity.
• the present invention is specifically intended to meet this need by providing a process for preparing an MOF solid of a porous and crystallized aluminum aromatic azocarboxylate, comprising at least the following steps:
• Ci-i alkyl O, C 2- ioalcène, C 2- ioalcyne, C 3- iocycloalkyle, Ci-i 0 heteroalkyl, Ci-I0 haloalkyl, C 6- ioaryle, C 3- 2ohcierocyclique, Ci-ioalkylCe-ioaryle, Ci-ioalkylCs-iohcieroaryle, F, Cl, Br, I, -NO 2, -CN, - CF 3 , -CH 2 CF 3 , -OH, -CH 2 OH, -CH 2 CH 2 OH, -NH 2 , -CH 2 NH 2 , -NHCHO, -COOH, -CONH 2 , -SO 3 H, - PO 3 H 2 , q 2 to 4;
• crystal solid in which atoms, ions or molecules form long-range ordered arrangements in the three dimensions of the space, leading to a unique signature constituted by a specific succession of diffraction peaks (X-rays for example) for each solid.
• An "amorphous solid” is a solid where atoms, ions or molecules, although locally ordered, pile up in a disordered manner at long distances. This results in a signature of one or more diffraction peaks (X-rays for example) very wide which does not allow the precise identification of the material (since several solids can co-exist and lead to the same signature by diffraction).
• atoms, ions or molecules can adopt several arrangements depending on the conditions of their formation. These different arrangements constitute the different "phases" of the solid existing in a given chemical system. The physical properties such as the melting point and the density of the different phases are different, which allows the differentiation of solids.
• alkyl means an optionally substituted saturated linear or branched, carbon radical comprising 1 to 12 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, for example.
• an alkyl radical may be a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl or tert-pentyl radical.
• alkene means a linear or branched, cyclic or acyclic unsaturated hydrocarbon radical comprising at least one carbon-carbon double bond.
• the alkenyl radical may comprise from 2 to 20 carbon atoms, for example from 2 to 10 carbon atoms, more particularly from 2 to 8 carbon atoms, even more particularly from 2 to 6 carbon atoms.
• an alkenyl radical may be an allyl, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl radical or similar radicals.
• alkyne refers to a linear or branched, cyclic or acyclic unsaturated hydrocarbon radical comprising at least one carbon-carbon triple bond.
• the alkynyl radical may comprise from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms, more particularly from 1 to 8 carbon atoms, even more particularly from 2 to 6 carbon atoms.
• an alkynyl radical may be an ethynyl, 2-propynyl (propargyl), 1-propynyl radical or similar radicals.
• aryl means an aromatic system comprising at least one ring which satisfies Hekel's aromaticity rule. Said aryl is optionally substituted and may comprise from 6 to 50 carbon atoms, for example 6 to 27 carbon atoms, especially from 6 to 14 carbon atoms, more particularly from 6 to 12 carbon atoms.
• an aryl radical may be a phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl or similar group.
• heteroaryl in the sense of the present invention, a system comprising at least one aromatic ring of 4 to 50 carbon atoms, for example from 4 to 20 carbon atoms, and at least one heteroatom selected from the group including sulfur, oxygen, nitrogen. Said heteroaryl may be substituted.
• a heteroaryl radical may be pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and similar radicals.
• cycloalkyl in the sense of the present invention, a cyclic carbon radical, saturated or unsaturated, optionally substituted, which may comprise 3 to 10 carbon atoms.
• cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclobutyl, 2,3-dimethylcyclobutyl, 4-methylcyclobutyl and 3-cyclopentylpropyl.
• haloalkyl in the sense of the present invention, an alkyl radical as defined above, said alkyl system comprising at least one halogen selected from the group consisting of fluorine, chlorine, bromine, iodine.
• heteroalkyl in the sense of the present invention, an alkyl radical as defined above, said alkyl system comprising at least one heteroatom, especially selected from the group consisting of sulfur, oxygen, nitrogen, phosphorus.
• heterocycle in the sense of the present invention, a cyclic carbon radical comprising at least one heteroatom, saturated or unsaturated, optionally substituted, and which may comprise 3 to 20 carbon atoms, preferably 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms.
• the heteroatom may for example be selected from the group consisting of sulfur, oxygen, nitrogen and phosphorus.
• a heterocyclic radical may be pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, or tetrahydrofuryl.
• an alkoxy radical may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, n-hexoxy, or a similar radical.
• substituted denotes, for example, the replacement of a hydrogen atom in a given structure with a group as defined above. When more than one position may be substituted, the substituents may be the same or different at each position.
• the organic solvent may consist of a single solvent or a mixture of organic solvents.
• non-aqueous solvent advantageously refers to one or a mixture of solvent (s) containing at most 5% by weight, preferably 1% by weight, more preferably 0.1% by weight and even more preferably at most 0%. , 01% by weight of water relative to the total weight of all the solvents.
• the non-aqueous organic solvent may be chosen from the group comprising N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), dioxane, methanol, ethanol, n-propanol and isopropanol.
• DMF N-dimethylformamide
• DEF diethylformamide
• dioxane methanol, ethanol, n-propanol and isopropanol.
• DMSO dimethyl sulfoxide
• the non-aqueous organic solvent is more particularly chosen from the group comprising DMF, DEF, dioxane, methanol, ethanol and DMSO.
• the inorganic metal precursor in step (i) may be in the form of Al metal, an Al 3+ metal salt or a coordination complex comprising the Al 3+ metal ion.
• the counterion may be an inorganic ion selected from the group consisting of sulphate, nitrate, nitrite, sulphite, bisulphite, phosphate, phosphite, fluoride, chloride , bromide, iodide, perchlorate, carbonate, bicarbonate.
• the counterion may also be an organic ion selected from the group consisting of acetates, formates, oxalates, citrates, ethoxy, isoproxy.
• the inorganic metal precursor is in the form of an Al 3+ metal salt.
• the crystalline spatial organization of the solids of the present invention is the basis of the particular characteristics and properties of these materials. In particular, it governs the size of the pores, which has an influence on the specific surface of the materials and on the adsorption characteristics. It also governs the relatively low density of materials, the proportion of metal in these materials, the stability of materials, the stiffness and flexibility of structures, and so on.
• the pore size can be adjusted by choosing appropriate ligands L.
• the ligand L is more particularly an aromatic azodi- or azotetracarboxylic acid, chosen from the group comprising: Ci 2 H 8 N 2 (CO 2 "4 (4,4'-azobenzene dicarboxylate), Ci 2 H 6 Cl 2 N 2 (CO 2 " ) 2 (dichloro-4,4'-azobenzene dicarboxylate), Ci 2 H 6 N 2 (CO 2 " ) 4 (3,3 ', 5,5'-azobenzene) tetracarboxylate), Ci 2 H 6 N 2 (OH) 2 (CO 2 " ) 2 (dihydroxo-4,4'-azobenzene dicarboxylate).
• step (i) the inorganic metal precursor and the organic precursor of the ligand L can be mixed in a molar ratio of between 1 and 5.
• the MOF solids according to the invention have a crystallized structure which gives these materials specific properties.
• the crystallization is carried out in a very precise temperature range.
• the mixture is heated at a temperature ranging from 50 ° C. to 150 ° C.
• the mixture may be heated for 1 to 10 days. One day is 24 hours.
• the mixture can be heated in a closed cell.
• Step (ii) can be carried out at an autogenous pressure greater than 10 5 Pa. "Autogenous" pressure is the pressure generated by the reactants at a given temperature in a closed reaction cell.
• step (ii) may, in addition, be subjected to an activation step (iii) in which said solid is heated to a temperature of 100 ° C. to 300 ° C., preferably from 100 ° C to
• the solid can be heated for 1 to 48 hours.
• the activation step (iii) may optionally be carried out in a mixture of solvent (s) chosen (s) from the group comprising DMF, DEF, methanol, ethanol, DMSO or water.
• This activation step (iii) makes it possible in particular to empty the pores of the MOF solid of the invention and to make them accessible for the intended use of said solid.
• the emptying can be done, for example, by the departure of water molecules, solvent and / or optionally L ligand molecules present in the reaction medium.
• the resulting MOF solids will then have a higher adsorption and storage capacity.
• the subject of the present invention is also an MOF solid of a porous and crystalline aluminum aromatic azocarboxylate obtainable by the process according to the invention, comprising a three-dimensional succession of units of formula (I):
• D Al represents the metal ion Al 3+ ;
• D m is 1 to 15, for example 1 to 8;
• D k is 0 to 15, for example 1 to 8;
• D is 0 to 10, for example 1 to 8;
• D p is 1 to 10, for example 1 to 5;
• m, k, I and p are chosen so as to respect the neutrality of the charges of said pattern;
• MOF solids of aromatic aluminum azocarboxylates prepared by the process of the invention have certain advantages, in particular:
• X is selected from the group consisting of OH “ , CI “ , F “ , CIO 4 -.
• the MOF solids according to the invention preferably comprise a mass percentage of Al of 5 to 50%.
• the MOF solids obtainable by the process of the invention have pores, and more particularly micro- and / or mesopores.
• the micropores can be defined as pores having a diameter less than or equal to 2 nm (diameter ⁇ 2 nm) and mesopores as pores with a diameter greater than 2 nm and up to 50 nm (2 nm ⁇ diameter ⁇ 50 nm).
• the pore diameter of the MOF solid of the invention is 0.2 to 6 nm.
• the presence of micro- and mesopores can be followed by sorption measurements to determine the capacity of the MOF solid to absorb nitrogen at 77K according to DIN 66131.
• the specific surface area of the solids constituted by organic-metal networks (MOF) of porous and crystallized aluminum aromatic azocarboxylates that can be obtained by the process of the invention can be measured by the BET method and determined and calculated by the model.
• Said solids may have a BET specific surface area ranging from 50 to 4200 m 2 / g, more particularly from 100 to 3000 m 2 / g. They may also have a Langmuir specific surface ranging from 50 to 6000 m 2 / g, more particularly from 150 to 3500 m 2 / g.
• the MOF solids according to the invention advantageously have a pore volume of from 0.3 to 4 cm 3 / g.
• the pore volume means the accessible volume for the gas or liquid molecules.
• the MOF solids may have a gas loading capacity of 0.5 to 50 mmol of gas per gram of dry solid.
• the carrying capacity means the gas storage capacity or the amount of gas adsorbed by the solid.
• the MOF solids of the present invention may in particular have the advantage of having a thermal stability up to a temperature of 500 ° C. More particularly, these solids may have a thermal stability between 250 ° C. and 450 ° C.
• the MOF solids of the invention are crystallized and may preferably be in the form of crystallites with a length which varies from 0.05 ⁇ m to 100 ⁇ m, more particularly from 0.05 ⁇ m to 20 ⁇ m. They are preferably in the form of small crystals having a particular morphology (needles, platelets, octahedra ...) which also allows their precise identification by examination using a scanning electron microscope (SEM).
• SEM scanning electron microscope
• the MOF solids according to the invention have a crystallized structure and a high purity which provide these materials with specific properties.
• the MOF solids of aluminum azocarboxylates according to the invention consist of a single phase. This means that the other phases that may exist in the chemical system in question are not present in a mixture with the solid.
• the MOF solids of aluminum azocarboxylates that can be obtained by a preparation process as described above also having a degree of purity of at least 95%, in particular of at least 98% by weight.
• the purity of the MOF solids of the invention can be determined in particular by elemental chemical analysis, X-ray diffraction, scanning electron microscopy.
• the MOF solids obtained contain no or little secondary product, for example aluminum hydroxide of formula AI (OH) 3 or AlO (OH), or the other phases of the chemical system considered appearing in other conditions of synthesis.
• the particular structural characteristics of the solids of the present invention make them adsorbents with high loading capacity, high selectivity and high purity. They thus make possible the selective adsorption and thus the selective separation of gas molecules such as molecules of NO, N 2 , H 2 S, H 2 , CH 4 , O 2 , CO, CO 2, etc.).
• the present invention also relates to the use of a solid consisting of a metal-organic network (MOF) of porous and crystallized aluminum azocarboxylates for the storage of liquid or gaseous molecules, for the selective separation of gases [25]. ] or for catalysis [26].
• MOF metal-organic network
• Figure 1 shows the X-ray diffraction pattern of the MIL-130 (Al) (CuK D ) phase.
• the abscissa represents the angular variation in 2D (°).
• the ordinate represents the relative intensity of the diffraction peaks.
• Figure 2 shows the N 2 adsorption isotherm at 77K of the MIL-130 phase.
• the ratio p / p ° which corresponds to the relative pressure is given on the abscissa.
• the volume of adsorbed gas per gram of product (cm 3 .g -1 ) is represented in ordinate.
• Fig. 3 shows the thermogravimetric analysis curve of MIL-130 (Al) (under 02 flow, 3 ° C.min -1 ) The percentage of mass loss is plotted on the ordinate. Heating is represented on the abscissa.
• FIG. 4 shows the photograph (scanning electron microscopy) of a sample of MIL-130 (A1) showing crystallites in hexagonal rod form.
• FIG. 5 shows the photograph (scanning electron microscopy) of a sample of MIL-130 (A1) showing crystallites in the form of aggregates of ovoid crystallites.
• Figure 6 shows the photograph (scanning electron microscopy) of a sample of MIL-130 (A1) showing crystallites in the form of ovoid platelets.
• the diffraction diagrams were recorded using a diffractometer (Siemens D5000) in Bragg-Brentano geometry in reflection on a 2theta angular domain of 2 to 40 ° with a pitch and a counting time of 0.02 ° and 1 second respectively (CuK radiation D i, 2 ).
• Thermogravimetric analysis (TA Instrument 2050) was carried out from a sample of 5 or 20 mg heated on a scale of 20 to 600 0 C under an oxygen flow with a heating rate of 3 ° C.min " 1.
• the compound MIL-130 (Al) is obtained from a mixture of 3.6 g of aluminum nitrate (Al (NO 3 ) 3-9H 2 O), 1.2 g of 4,4 'acid. azodibenzenedicarboxylic acid and 70 ml of DMF (N, N'-dimethylformamide) placed in a Teflon cell with a volume of 125 ml and then inserted into a steel autoclave of Parr trademark (trademark). The reaction is carried out at 100 ° C. for 7 days in an oven. 2 g of MIL-130 (Al) is obtained. The product is activated by heating at 200 ° C overnight.
• a second preparation can be made from a mixture of
• a third preparation can be made from a mixture of 0.19 g of aluminum chloride hexahydrate (Al (Cl) 3-6H 2 O), 0.1 g of 4,4'-azodibenzenedicarboxylic acid, ml of DMF (N, N'-dimethylformamide) placed in a teflon cell with a volume of 23 ml and then a steel autoclave of Parr trademark (trademark). The reaction is carried out at 100 ° C. for 7 days in an oven. 0.07 g of MIL-130 (Al) is obtained.
• a fourth preparation can be made from a mixture of 0.1 g of anhydrous aluminum chloride (Al (Cl) 3), 0.1 g of 4,4'-azodibenzenedicarboxylic acid, 5 ml of DMF ( N, N'-dimethylformamide) placed in a teflon cell with a volume of 23 ml and then a steel autoclave of trademark Parr (trademark). The reaction is carried out at 100 ° C. for 7 days in an oven. 0.07 g of MIL-130 (Al) is obtained.
• Al (Cl) 3 anhydrous aluminum chloride
• DMF N, N'-dimethylformamide
• a fifth preparation can be made from a mixture of 0.1 g of anhydrous aluminum chloride (Al (Cl) 3), 0.1 g of 4,4'-azodibenzenedicarboxylic acid, 5 ml of DMF ( N, N'-dimethylformamide) placed in a teflon cell with a volume of 23 ml and then a steel autoclave of trademark Parr (registered trademark). The reaction takes place at 100 ° C for 4 hours in an oven. 0.07 g of MIL-130 (Al) is obtained.
• Thermogravimetric analysis indicates that the MIL-100 (Al) material is stable up to 420 ° C. (FIG. 3).
• MIL-96 a Porous Aluminum Trimesate 3D Structure Constructed from a Hexagonal Network of 18-Membered Rings and ⁇ 3-Oxo

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