HK1166035B - Hybrid inorganic/organic polymer catalytic membrane materials comprising immobilized molecular catalysts and their preparation - Google Patents

Description

Hybrid inorganic/organic high molecular catalytic membrane material comprising immobilized molecular catalyst and preparation thereof

Technical Field

The present invention relates to novel catalytic hybrid inorganic/polymeric materials, in particular catalytic hybrid inorganic/polymeric membranes, which show high selectivity, activity, stability, recyclability and low metal leaching (leaching) in various catalytic chemical reactions. More particularly, the invention relates to the manufacture of low-cost hybrid materials of the polyvinyl alcohol type, in particular membranes, and to the immobilization of selective catalysts on said materials, to the production of catalytic materials exhibiting the above specific properties, to their components in reactors (assembly) and to their use in chemical processes. The use of such materials is particularly useful for asymmetric hydrogenation of prochiral, unsaturated organic substrates, but is not limited thereto.

Background

Sustainable, i.e. cost-effective and environmentally friendly, high-selectivity process development for the production of fine chemicals (pharmaceuticals, agrochemicals, fragrances, etc.) is a major concern at the current industrial level.

Currently, most commercial processes showing high activity and selectivity, in particular stereo-or enantioselectivity, are based on the use of homogeneous, molecular catalysts. These compounds are generally composed of heavy (noble) metal complexes comprising highly complex (chiral) ligands. In addition to being complex and expensive to prepare, these catalysts suffer from the difficulty of their recovery from the reaction mixture and their reuse. Furthermore, the separation of the products from the catalyst and the solution (usually an organic solvent) always leads to the evolution of volatile contaminants.

On the other hand, heterogeneous catalysts are easier to handle, separate, reuse and integrate in reactor equipment than homogeneous catalysts, and therefore the chemical industry has a strong tendency towards heterogeneous catalysts. Heterogeneous catalysts, however, generally do not provide comparable selectivity.

Therefore, in order to meet both environmental and economic objectives, there is a clear need to develop new concepts bridging heterogeneous and homogeneous catalysts and to apply these to the engineering of catalytic plants for the industrial production of fine chemicals. This problem is most important in asymmetric catalysis where the cost of the chiral ligand often exceeds the cost of the noble metal used.

In the processes developed over the last decades, the immobilization of chemical catalysts onto solid insoluble support materials provides significant benefits in view of the thorough separation of the expensive catalyst from the reaction product and its reuse. Chem.rev., 102, 3215-3216 (2002); science, 299, 1702-1706 (2003); adv.synth.cat., 348, 1337-.

The preformed molecular catalyst may be conveniently immobilized by non-covalent bonding. This process is commonly referred to as "heterogenisation of the homogeneous catalyst". More recently, for example, in top, cat, 25, 71-79 (2003); top, cat, 40, 3-17 (2006); hem.eur.j., 12, 5666-; ind, eng, chem, res, 44, 8468-8498 (2005); J.mol.Cat.A: this subject is reviewed in Chemical, 177, 105-. The advantages of this approach are many: a) potentially enabling the preparation of heterogeneous catalysts with predictable selectivity, b) without the need for chemical modification of the support or catalyst, c) minimizing problems arising from metal loading, d) enabling easy characterization of the catalyst active sites. The usual disadvantages are the lower activity and the occurrence of metal leaching compared to corresponding homogeneous catalysts.

For the purpose of immobilizing molecular catalysts, various solids have been developed which are generally highly complex, including inorganic substances (e.g. as reviewed in chem.rev., 102, 3495-. In terms of focusing on the practical use of the catalyst, in addition to the effect of the support on the catalyst efficiency (both activity and selectivity), the chemical, mechanical and thermal stability of the material is also of paramount importance.

The physical form of the solid is also of importance. When using lumps (monolith) or beads (from 30 μm diameter), the shape and size of the material allow easy and quantitative recovery of the catalyst by means of simple filtration or decantation. In contrast, when powdery materials having a size of about 1 μm or less are used, they do not settle in a short time in a solution, and it is difficult to collect them for recycling. Separation of the catalyst therefore requires centrifugal separation or ultrafiltration. The extremely fine powders also clog or poison the reactors or autoclaves used in the catalytic tests.

In addition to their common use as separation media, polymeric fibers and membranes are the most useful solids for use as supports for the engineering of catalytic materials. When exhibiting catalytic activity, the membrane is often referred to as a "catalytic membrane". Their classification, preparation, performance and application are reviewed in several recent articles such as: total, 56, 147-; chem.rev., 102, 3779-3810 (2002); adv. synth. cat., 348, 1413-; top, cat, 29, 59-65 (2004); top. cat., 29, 3-27 (2004); app.cat.a: general, 307, 167-; top. cat, 29, 67-77 (2004). Compared to other support materials, the films offer the following additional opportunities: (i) the polymer membrane drives catalytic reaction due to different adsorption and diffusion of reagents and products in the membrane; (ii) polymeric membranes can be prepared by controlling their mechanical, chemical and thermal stability to produce the desired permeability and affinity for reagents and products; (iii) the shape and size of the polymeric membrane allows for easy engineering of a variety of reactor types; (iv) the use of a catalytic membrane allows the reaction to be carried out in a membrane reactor (CMR) in which the reaction and separation processes can be combined in one stage.

However, at present, it is known that rarely are examples related to the preparation and use of polymeric catalytic membranes for highly (enantioselective processes. In these cases, the membrane is generally composed of a chemical catalyst (transition metal catalyst) embedded in a polymer.

Chem.Comm.，388-389(2002)；Angew.Chem.，Int.Ed.Engl.，35，1346-1347(1996)；Commu., 2407-2408(1999), Tetrahedron: asymmetry, 8, 3481, 3487(1997) and chem. Commun, 2323, 2324(1997) describe [ ((R, R) -MeDuPHOS) Rh (COD)]CF₃SO₃((S) -BINAP) Ru (p-isopropyltoluene) Cl and ((S, S) -SALEN) MnCl complex [ DuPHOS ═ 1, 2-bis- (2R, 5R) -dimethyl (cyclopentyl (phospho)) -benzene, COD ═ cyclooctadiene, BINAP ═ 2,2 ' -bis (diphenylphosphino) -1,1 ' -binaphthyl, SALEN ═ N, N ' -bis (3, 5-di-tert-butylsalicylidene) -1, 2-cyclohexanediamine]Occlusions in Polydimethylsiloxane (PDMS) films and their use in the asymmetric hydrogenation of methyl 2-acetamidoacrylate (MAA), methyl acetoacetate, and in the epoxidation of olefins, respectively. From both activity and selectivity (in water/heptane) considerations, in the case of epoxidation the efficiency of the immobilized catalyst can be comparable to that of the corresponding homogeneous catalyst, whereas in the case of hydrogenation catalysts (in water, methanol or glycols) significantly lower activities (typically 1-2 orders of magnitude) are observed. In the latter case, the conversion is increased (up to 4-fold) by incorporating silica or p-toluenesulfonic acid into the membrane, possibly due to the reduced hydrophobicity of the membrane. However, due to the complexity of the interaction of the catalyst with the polymer, solvent, matrix and product, these systems are not sufficiently stable with respect to leaching. Careful selection of the solvent can effectively reduce metal leaching (as low as 1%) of the epoxidation catalyst without being completely avoided. Acceptable metal leaching (about 0.2%) is observed for ruthenium-based hydrogenation catalysts, whereas leaching from low to high amounts (0.9-31%) is observed for rhodium complexes, which is strongly dependent on the solvent (preferably water and less preferably methanol). Regeneration and reuse of the catalyst is possible by washing the membrane with the reaction solvent before adding new reaction mixture.

Tetrahedron: asymmetry, 13, 465-468(2002) describes [ ((R, R) -MeDuPHOS) Rh (COD)]CF₃SO₃Immobilization in polyvinyl alcohol (PVA) membranes and their use for enantioselective hydrogenation of MAAs. The metal catalyst is trapped in the polymer during membrane synthesis. Lightly crosslinked (3%) PVA was used for this purpose. Andlower conversions were obtained with corresponding homogeneous catalysts than with membrane-assisted catalysts. The leaching of rhodium into solution is directly related to the swellability of the membrane and the solubility of the metal complex in the solvent used in the hydrogenation reaction, higher for methanol (47%) and lower for xylene (0.7%). The choice of water as reaction solvent (leaching 4.2%) is driven by the requirement to minimize leaching while maintaining catalyst activity, but this choice actually limits the applicability of the process due to poor solubility of the organic matrix. Reuse of the catalyst is possible as described above.

A limited number of other applications using polymer-based membranes embedded with molecular chemical catalysts are described, however, this is limited to non-selective chemical reactions. For example, j.mol.cat.a: chemical, 282, 85-91(2008) and appl.cata.a: general, 335, 37-47(2008) describes the use of perfluorinated polymeric membranes containing ruthenium porphyrin complexes in the catalytic aziridination of styrene. Membrane sci, 114, 1-11(1996) and fact, polym, 14, 205-11(1991) report the catalytic hydrogenation of cinnamaldehyde, 1, 3-and 1, 5-cyclooctadiene by means of Pd, Rh, Ru and Ni nanoparticles embedded in PVA films.

In Augustine et al 1998(WO 9828074; US 6005148) a method is disclosed based on the use of Heteropolyacids (HPAs) as binding agents (anchoring agents) for anchoring preformed heterogeneous catalysts to various solid supports. Ruthenium complexes and rhodium complexes are used as homogeneous catalysts, while materials such as alumina, carbon, silica and clay are used as supports. HPA phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, and silicomolybdic acid were used as binders. Anchored catalysts are typically prepared by sequential treatment of the support with a HPA solution followed by treatment of the resulting material with a metal complex solution. Immobilization is achieved by the interaction of the metal atoms of the catalyst with the support promoted by means of HPA. As in app.cat.a: general, 256, 69-76 (2003); commu., 1257-; J.mol.Cat.A: this technique was successfully applied to the asymmetric catalytic hydrogenation of prochiral olefins using ethanol as solvent and using an anchored rhodium chiral diphosphine catalyst, as described in Chemical 216, 189-197 (2004). These catalysts are active and selective as homogeneous analogues (analogs) and can be reused several times with almost constant efficiency. Catalyst leaching is typically on the ppm level.

The same process was used continuously to produce small amounts of a selective, heterogenized catalyst. J.Catal., 227, 428-. Appl.cat.: a: general, 303, 29-34(2006) describes the incorporation of Al₂O₃Enantioselective hydrogenation of (Z) - α -acetamidocinnamic acid of the PTA-immobilized rhodium chiral complex.

PVA membranes that capture HPAs, but do not anchor any molecular catalyst, show catalytic activity in limited non-selective chemical processes. Polymer 16, 209-215(1992) describes PVA-PTA membranes that catalyze ethanol dehydration reactions. J.Membrane Sci., 159, 233-. Membrane sci, 202, 89-95(2002) reported dehydration of butanediol to tetrahydrofuran catalyzed by PVA-PTA membranes. Total. today, 82, 187-.

The current state of the art clearly shows that no polymeric catalytic membranes for highly (stereoselective) selective chemical reactions have been successfully developed, as have neither reactors nor processes for the production of catalytic membranes based on these polymeric catalytic membranes. Hybrid inorganic/polymeric membranes embedded with preformed chemical catalysts are a promising strategy in view of the mechanical, thermal, chemical stability and recyclability of the catalyst and low metal leaching into solution.

One of the inventors of the present invention has proposed a new hybrid inorganic/polymeric membrane in Electrochemistry, 72, 111-116(2004), JP 3889605, US 7101638, JP 3856699. These membranes are composed of a hybrid composite of inorganic oxide and polyvinyl alcohol (PVA) in which the inorganic oxide is chemically bonded to PVA through its hydroxyl groups. These materials are produced in aqueous solution by a simple process in which the salt of the inorganic oxide is neutralized with an acid in the co-presence of PVA. By this method, the nascent, active inorganic oxide produced by neutralization binds to PVA and hybridizes to form a hybrid complex. Hybrid compounds are different from mixtures of inorganic oxides and PVA, i.e. their chemical properties are significantly altered by their starting materials. For example, once hybridized, the material is insoluble in any solvent including hot water.

However, these membranes have been designed and developed for use as solid electrolytes, particularly initially in fuel cells. Therefore, their use as supports to immobilize molecular catalysts requires their modification and the development of appropriate techniques for heterogenisation processes.

Disclosure of Invention

The present invention relates to the preparation and use of catalytic materials, in particular catalytic membranes, for selective chemical reactions. The term "catalytic material (membrane)" is used hereinafter to denote a hybrid inorganic/PVA material (membrane) on which a preformed metal catalyst is immobilized. The "preformed metal catalyst" is any catalytically active material, typically a metal complex, comprising at least one transition metal atom or ion from group IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII of the periodic table of elements to which one or more ligands are attached. The ligands, both chiral and achiral, may be capable of coordinating transition metal atoms or ions and include phosphines, amines, imines, ethers, carbonyls, alkenes, halides and mixtures thereof. When a chiral catalyst comprising a chiral ligand is used, the catalytic material or catalytic membrane obtained so far is denoted as "chiral catalytic material" or "chiral catalytic membrane", respectively.

One aspect of the invention relates to the preparation of catalytic materials by contacting a preformed hybrid inorganic/PVA material with an appropriate solution of a preformed metal catalyst.

Another aspect of the invention relates to the aforementioned catalytic materials in chemical reactors, in particular membrane modules, and their use in chemical processes such as hydrogenation, dehydrogenation, hydrogenolysis, hydroformylation, carbonylation, oxidation, dihydroxylation, epoxidation, amination, phosphonation, carboxylation, silylation, isomerization, allylic alkylation, cyclopropanation, alkylation, allylation, arylation, metathesis and other C-C bond forming reactions. The use of such catalytic materials is particularly useful for, but not limited to, asymmetric hydrogenation of prochiral, unsaturated organic substrates such as substituted α, β unsaturated acids or esters.

In another aspect of the invention, the preparation and use of the catalytic material in a chemical process is performed by a one-step process. These processes may be in solution or in a liquid-gas two-phase system; in a batch reactor using a fixed bed catalytic module or a rotating catalytic membrane module, or a continuous flow reactor.

Detailed Description

The invention allows the easy preparation and use of new catalytic materials, in particular membranes, for highly selective organic reactions in two successive, separate steps or by a one-step process. The catalytic material (membrane) of the invention comprises two components: a "preformed hybrid inorganic/polymeric material (membrane)" and a preformed homogeneous chemical catalyst. The homogeneous catalysts are typically molecular "metal complexes" comprising a metal atom and an organic ligand, the activity and selectivity of which in the homogeneous phase is known.

The "preformed hybrid inorganic/polymeric material" is preferably a hybrid of an inorganic oxide and a polymer having hydroxyl groups. Further, the inorganic oxide is preferably a silicic acid compound, a tungstic acid compound, a molybdic acid compound and a stannic acid compound. Silicic acid means containing SiO₂As its basic groupA unit and a compound containing water molecules, and may be made of SiO₂·xH₂And O represents. In the present invention, the silicic acid compound means silicic acid and derivatives thereof or any compound containing silicic acid as a main component. Tungstic acid is meant to comprise WO₃As basic constituent units thereof and compounds containing water molecules, and may be prepared from WO₃·xH₂And O represents. In the present invention, the tungstic acid compound means tungstic acid and derivatives thereof or any compound containing tungstic acid as a main component. Molybdic acid means comprising MoO₃As its basic constituent unit and a compound containing water molecules, and may be composed of MoO₃·xH₂And O represents. In the present invention, the molybdic acid compound refers to molybdic acid and derivatives thereof or any compound containing molybdic acid as a main component. Stannic acid is meant to comprise SnO₂As basic constituent units thereof and compounds containing water molecules, and may be composed of SnO₂·xH₂And O represents. In the present invention, the stannic acid compound means stannic acid and derivatives thereof or any compound containing stannic acid as a main component. More preferably, silicic acid compounds and tungstic acid compounds are used to make the material of the invention.

Silicic acid compounds, tungstic acid compounds, molybdic acid compounds and stannic acid compounds are allowed to contain other elements as substituents, thereby having a non-stoichiometric composition and/or having certain additives as long as the initial properties of silicic acid, tungstic acid, molybdic acid and stannic acid can be maintained. Certain additives such as phosphoric acid, sulfonic acid, boric acid, titanic acid, zirconic acid, alumina and derivatives thereof are also permissible.

For the inorganic/polymeric hybrid material, a polymer having a hydroxyl group is suitable as the polymer component because the hydroxyl group is available for binding to the inorganic oxide. In addition, a water-soluble polymer is more preferable because in most cases, the hybridization process is carried out in an aqueous environment. From these viewpoints, PVA is considered to be most suitable. However, absolute (perfect) PVA is not necessarily required, and certain modifications such as partial substitution of hydroxyl groups by certain other groups or partial block copolymerization are permissible.

In addition, it is permissible to mix other polymers such as polyolefin polymers such as polyethylene and polypropylene, polyacrylic polymers, polyether polymers such as polyethylene oxide and polypropylene oxide, polyester polymers such as polyethylene terephthalate and polybutylene terephthalate, fluorine polymers such as polytetrafluoroethylene and polyvinylidene fluoride, sugar-containing polymers such as methyl cellulose, polyvinyl acetate polymers, polystyrene polymers, polycarbonate polymers, epoxy resin polymers or other organic and inorganic additives to the hybrid material.

Inorganic/polymeric hybrid materials are prepared by a simple aqueous phase process (aquous process) in which salts of inorganic oxides such as silicates, tungstates, molybdates and stannates are neutralized by an acid in an aqueous solution containing a polymer having a hydroxyl group such as PVA. In the method, silicate, tungstate, molybdate and stannate are changed into silicic acid compound, tungstic acid compound, molybdic acid compound and stannic acid compound, respectively, by neutralization. These nascent compounds are so active that they have a tendency to bind to each other. However, in this method, since a polymer and an inorganic compound coexist in proximity to each other, a nascent compound is bonded to a hydroxyl group of the polymer by dehydration bonding. The film can be prepared by a general casting method using the above precursor solution after the co-existence neutralization process (co-existence neutralization). The fibers of the hybrid composite can be prepared by, for example, a spunbond process, a melt-blown process, or an electrospinning process.

The inorganic/polymeric hybrid material shows high affinity for water or other solvents having high polarity, and swells by absorbing these solvents. The degree of swelling of the membrane can be adjusted by aldehyde treatment (Electrochemistry, 72, 111-116(2004), JP4041422, US 7396616). The aldehyde treatment refers to binding of free hydroxyl groups of macromolecules remaining in the inorganic/polymeric hybrid with aldehydes such as glutaraldehyde, phthalaldehyde, glyoxal, and butyraldehyde by contacting the membrane with a solution or gaseous reactant including an aldehyde. By the aldehyde treatment, the high molecular component is crosslinked or becomes nonpolar (hydrophobic) to adjust the swelling degree.

For reinforcing the inorganic/polymeric hybrid membrane, certain porous substrates such as cloth, nonwoven fabric or paper can be used. Any material such as polyester, polypropylene, polyethylene, polystyrene, and nylon may be used as the matrix for reinforcement as long as sufficient durability is exhibited.

According to the present invention, molecular "metal complex" means any catalytically active material comprising at least one transition metal atom or ion from group IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII of the periodic table of the elements to which one or more ligands are attached. Suitable transition metal atoms or ions include Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au. The ligand may be any organic or metal-inorganic species comprising one or more donor atoms with free electron pairs, for example at phosphorus, nitrogen, oxygen, sulfur, halogen atoms or mixed donor atom sets, as well as any organic or metal-inorganic species comprising carbonyls, carboxylic acids, alkanes, alkenes, dienes, alkynes or any other moiety capable of coordinating a metal atom or ion. Mixtures of the above ligands are also contemplated herein. Suitable chiral ligands include, but are not limited to: phosphines, amines, imines, cyclopentadiene (Cp), Cyclooctadiene (COD), Norbornadiene (NBD), methanol, acetonitrile, dimethyl sulfoxide. Suitable chiral ligands include, but are not limited to: (R, R) or (S, S) -BINAP [2,2 '-bis (diphenylphosphino) -1, 1'. binaphthalene](R, R) or (S, S) -DIOP [2, 3-O-isopropylidene-2, 3-dihydroxy-1, 4-bis (diphenylphosphino) butane](R) or (S) -monophosphorus [ (3, 5-dioxa-4-phospha-cyclohepta [2, 1-a; 3, 4-a)]Dinaphthalen-4-yl) dimethylamine](R, R) or (S, S) -TMBTP [4,4 '-bis (diphenylphosphino) -2, 2', 5,5 '-tetramethyl-3, 3' -bithiophene]. Examples of metal complexes contemplated by the present invention include, but are not limited to: [ (-) - (TMBTP) Rh (NBD)]PF₆、[(-)-BINAP)Rh(NBD)]PF₆、[(-)-DIOP)Rh(NBD)]PF₆(-) -monophosphorus [)₂Rh(NBD)]PF₆。

The catalytic material (membrane) is obtained by immobilizing the homogeneous catalyst onto a preformed support material (membrane) by a direct method avoiding any chemical treatment (chemical manipulation) of the support material, which is neither ligand nor complex, and adding any binding or chemical modifying agent. The catalytic material thus obtained is used as a heterogeneous catalyst, which exhibits selectivities comparable to those observed in homogeneous phases, but has the great advantage of being insoluble in the reaction solvent and, therefore, easily removable from the reaction mixture by simple decantation and re-use. The leaching of metals in solution is extremely low when the respective catalyst is reused. For the reasons stated above, the catalytic material (membrane) of the invention is particularly useful in a variety of organic transformations, in particular in highly (enantioselective reactions foreseen for applications in the pharmaceutical, agrochemical or perfumery industries.

The interaction that allows the immobilization of the pre-formed homogeneous catalyst to the hybrid material may be based on a combination of non-covalent electrostatic bonds, van der waals forces, donor-acceptor interactions or other adsorption phenomena, which are strong enough to result in an efficient anchoring of the metal complex to the support material and the catalytic material thus obtained may be used for a variety of organic chemical reactions with minimal loss of the metal complex in solution, regardless of the exact nature of the interaction, even when using solvents in which the homogeneous catalyst is soluble. On the other hand, the interactions do not interfere with the stereoselective or enantioselective ability of a molecular complex immobilized on a support material, and therefore the selectivity offered by the catalyst is generally maintained from homogeneous to heterogeneous. This makes the invention particularly suitable for the design and production of catalytic materials characterized by predictable selectivity.

The immobilization step, which essentially consists of stirring a solution of the desired metal complex in the presence of the preformed hybrid material (membrane) followed by washing, is extremely simple, low cost, modular (in view of the immobilized catalyst used and the preformed membrane) and versatile (in view of the various catalytic reactions that can be achieved). Depending on the molecular catalyst to be immobilized and the support used, the catalytic membrane obtained is preformed differently: based on a suitable combination of support and metal complex, the choice of catalytic material for the chosen application and with the desired properties is thus feasible.

The catalytic membrane of the present invention can be prepared and used in a two-step process or a single-step process. The former involves a first step of obtaining and storing the catalytic membrane under an inert atmosphere, followed by a second step of using the catalytic membrane in an autoclave or chemical reactor for the selected chemical reaction. The latter involves the direct preparation of the catalytic membrane in the same autoclave in which the subsequent catalytic reaction is carried out, without the need to remove the catalytic membrane or open the reactor before its use. This latter method is particularly useful, but not limited to, in the case where the catalytic membrane must be used for liquid-gas phase reactions carried out under high pressure gaseous reactants.

Catalytic membranes can be employed in fixed bed (in the case of stirred reaction solutions) or rotating membrane module reactors. In both cases, the catalytic membrane can be easily and directly reused by: the reaction solution of the previous reaction cycle is removed, for example by simple decantation, under a suitable gas atmosphere and a new batch of solution containing the substrate is added. The heterogeneous nature of the catalytic membrane (material) ensured by the absence of any catalytic activity of the reaction solution and by the negligible metal loss, minimizes any impurities leached in the reaction solvent containing the desired product and therefore does not require any further purification steps in its recovery.

According to the invention, the catalytic material (membrane) is prepared by: the solution of the metal complex is stirred in a suitable solvent and in the presence of a preformed hybrid inorganic/polymeric material (membrane) at a temperature of-40 ℃ to 150 ℃ for 0.5 to 48 hours. Agitation is accomplished using either a fixed membrane and an agitated solution or a rotating membrane immersed in a solution of the metal complex described above. Suitable solvents include, but are not limited to: alcohols (preferably methanol), glycols, water, ethers, ketones, esters, aliphatic and aromatic hydrocarbons, alkyl halides. The concentration range of the metal complex solution is 1 to 10^-4M to 1.10^-2M，While the typical amount of inorganic/polymeric material ranges from 20g to 200g based on 1g of metal in the metal complex, and the typical area of the inorganic/polymeric film ranges from 0.5 to 20cm². The catalytic material was washed repeatedly with the solvent used for immobilization before being dried under a stream of nitrogen gas. Depending on whether the metal complex is air-sensitive or not, all of the above treatments required for the preparation of the catalytic material (membrane) must be carried out under an inert atmosphere. The catalytic material (membrane) thus obtained can be stored under nitrogen and ready for subsequent reactions. For the purpose of evaluating the metal supported in the catalytic material (membrane), the material (membrane) was dried overnight under high vacuum and analyzed to give a typical metal content of about 0.1 wt% to 20 wt%.

According to the present invention, the catalytic material prepared as described above may be used to catalyze various chemical reactions including, but not limited to: hydrogenation, dehydrogenation, hydrogenolysis, hydroformylation, carbonylation, oxidation, dihydroxylation, epoxidation, amination, phosphonation, carboxylation, silylation, isomerization, allylic alkylation, cyclopropanation, alkylation, allylation, arylation, metathesis and other C-C bond forming reactions. These reactions can be carried out in solution or in a liquid-gas two-phase system. Furthermore, it is possible for the person skilled in the art to adapt the catalytic membranes to engineering in batch reactors operating in fixed bed or in rotating membrane mode, or in continuous flow reactors. When used in a batch mode, the catalytic material is typically introduced into the reactor in the presence of a solution comprising the substrate and the reactants. When a gaseous reactant is to be used, it is introduced into the reactor at a desired pressure in the range of from 0.01MPa to 8 MPa. Suitable solvents include, but are not limited to: alcohols (preferably methanol), glycols, water, ethers, ketones, esters, aliphatic and aromatic hydrocarbons, alkyl halides. Typical substrate concentrations are between 1 and 10^-2M-10M. Based on the measured metal content in the catalytic membrane, the matrix: the catalyst ratio may be from 10: 1 to 100.000: 1. The reaction can be carried out with stirring in a temperature range from-40 ℃ to 150 ℃. Since the catalytic material is an insoluble solid and is fixed to itThe fact that the agent is heterogeneous, the reaction solution can be easily recovered at any time by simple decantation and the catalytic material recycled by simple addition of a fresh solution containing the substrate and the reactants. The feasibility of using water as a solvent is also worth emphasizing due to its environmental compatibility.

According to another aspect of the invention, the catalytic membrane may be prepared and used by a one-step process as described below. The hybrid inorganic/polymeric membrane is introduced into the reactor and then a solution of the metal complex in a suitable solvent is added. The concentration range of the metal complex solution is 1 to 10^-4M to 1.10^-2M, and the typical area of the inorganic/polymeric membrane ranges from 0.5 to 20cm². The mixture is stirred at a temperature of-40 ℃ to 150 ℃ for 0.5 to 48 hours. Thereafter, the in-situ prepared catalytic membrane was repeatedly washed using the solvent for immobilization. All of the above treatments must be carried out under an inert atmosphere depending on whether the metal complex used is air sensitive or not. A solution comprising a substrate and a reactant is introduced into a reactor. When a gaseous reactant is to be used, it will be introduced into the reactor at the desired pressure. Suitable solvents include, but are not limited to: alcohols (preferably methanol), glycols, water, ethers, ketones, esters, aliphatic and aromatic hydrocarbons, alkyl halides. Typical substrate concentrations are between 1 and 10^-2M-10M. Based on the metal content in the catalytic membrane, the matrix: the catalyst ratio may be from 10: 1 to 100.000: 1. The reaction may be carried out at a temperature ranging from-40 ℃ to 150 ℃ with stirring. The reaction solution can be easily recovered at any time by simple decantation and the catalytic material recycled by simple addition of fresh solution containing the substrate and the reactants.

In a preferred embodiment of the invention, the catalytic membranes of the invention are used for enantioselective hydrogenation of prochiral substrates including, but not limited to: olefins, imines, enamines, ketones, alpha, beta-unsaturated alcohols, ketones, esters or acids. Preferred immobilized metal complexes are, but not limited to, those of Ir, Rh, Ru, Pd with chiral phosphino, amino or amino-phosphino ligands or mixtures thereof. According to this aspect of the invention, prochiral olefins having the formula below are hydrogenated by the catalytic membrane of the invention to preferentially give one enantiomer of the product:

wherein R is hydrogen, an alkyl group containing from 1 to about 30 carbon atoms, an aryl group containing from about 6 to 18 carbon atoms, R₁、R₂And R₃The same or different and includes hydrogen, alkyl groups containing 1 to about 30 carbon atoms, alkenyl groups containing 1 to about 30 carbon atoms, alkynyl groups containing 1 to about 30 carbon atoms, aryl groups containing about 6 to 18 carbon atoms, amides, amines, alkoxides (alkoxide) containing 1 to about 30 carbon atoms, esters containing 1 to about 30 carbon atoms, ketones containing 1 to about 30 carbon atoms. Aryl substituents may also be bicyclic fused species or contain heteroatoms such as sulfur, oxygen, nitrogen, phosphorus. The prochiral olefin is introduced into the reactor containing the catalytic membrane as a solution in a suitable solvent, preferably, but not limited to, methanol. The hydrogenation reaction is carried out in a temperature range of-40 ℃ to 150 ℃ and in a hydrogen pressure range of 0.01MPa to 5MPa for 0.5 to 48 hours. Prochiral olefins are preferably, but not limited to: 2-acetaminoacrylic acid methyl ester, 2-acetaminoacrylic acid, itaconic acid dimethyl ester, itaconic acid, 2-acetamino cinnamic acid methyl ester and 2-acetamino cinnamic acid.

In summary, the present invention describes the preparation and use, even by means of a one-step process, of catalytic materials (membranes) based on hybrid inorganic/polymeric macromolecules, which catalyze various chemical reactions, in particular highly selective reactions, in mild reaction conditions and with low metal leaching. The catalytic material (membrane) is suitable for the engineering of reactors and can be easily and efficiently reused.

The following examples are given to illustrate the scope of the invention. Further, the embodiments of the present invention are not limited to the examples given below.

Example I

This example illustrates the general procedure for the preparation of immobilized hybrid inorganic/polymeric materials, especially membranes, for preformed molecular catalysts. The aqueous solution of the raw material is prepared by mixing predetermined amount of sodium silicate and/or sodium tungstate dihydrate (Na)₂WO₆·2H₂O) to 100ml of a 10% by weight polyvinyl alcohol solution. PVA had an average degree of polymerization of 3100-3900 and a degree of saponification of 86 to 90%. A hydrochloric acid solution having a concentration of 2.4M was added dropwise to the raw material aqueous solution under stirring to coexist and neutralize, which induced the hybridization reaction.

The precursor solution was cast onto a polyester film in a coating apparatus under heating the plate to a temperature of 60-80 ℃. The coating apparatus was an R K PrintCoat Instruments ltd. electric coater (K control coater) having a doctor blade (sector blade) for adjusting the gap with a micrometer and a polyester film disposed on the coating plate. Immediately after the precursor solution was cast on the plate, the precursor solution was swept at a constant speed by a doctor blade whose gap was adjusted to 0.5mm in order to smooth the precursor solution to a predetermined thickness. Under this condition, water evaporated from the precursor solution. After the fluidity of the precursor solution had almost disappeared, additional precursor solution was again poured thereon, brushed by a doctor blade, and then the panel was heated at 110-125 ℃ for 1-2 hours. Thereafter, the hybrid inorganic/polymeric film thus formed is peeled off from the plate to be washed by hot water and dried. Although this is an example method for fabricating a membrane, the hybrid inorganic/polymeric material can be formed from the precursor solution into any shape and size.

The aldehyde treatment was performed by immersing the inorganic/polymeric hybrid membrane into a 1.2M-concentrated hydrochloric acid solution containing terephthalaldehyde at room temperature. Certain additives such as polystyrene sulfonic acid or polyethylene glycol can be added as components of the hybrid inorganic/polymeric material by mixing them into the precursor solution. In the case of reinforcement by the matrix sheet, the polyester nonwoven fabric is sandwiched between the first casting layer and the second casting layer of the precursor solution.

Table 1 reports the composition of the hybrid inorganic/polymeric support membrane.

Example II

This example illustrates: general procedure for the preparation of catalytic membranes by immobilization of a preformed metal catalyst on a hybrid inorganic/polymeric membrane prepared as described in example I, according to the process of the present invention as described above.

Will be at 21cm clamped between windows²The sample of hybrid inorganic/PVA membrane support was introduced into a round bottom glass flask equipped with a lateral piston (lateralstopcock). Methanol (10mL) was introduced into the flask which was degassed with three vacuum/nitrogen cycles. The preformed metal complex catalyst (3.10) in methanol (5mL) was then added^-3mmol) of a nitrogen degassed solution under a nitrogen streamCapillary transfer to flask after stirring the flask at room temperature for 24h with the aid of an orbital shaker (orbitalshaker), the methanol solution was removed from the flask by decantation under nitrogen flow, the membrane was carefully washed with successive additions/removals of degassed MeOH fractions (3 × 15mL) and dried under nitrogen flow for 4h the catalytic membrane module thus obtained could be stored under nitrogen and ready for use in the subsequent autoclave for hydrogenation reactions.

Table 2 reports the supported amount of anchored metal on various, representative catalytic membrane samples prepared as described in example II.

Example III

This example illustrates: according to the process of the invention as described in the preceding examples, based on the immobilization of a preformed rhodium catalyst [ (-) -BINAP) Rh (NBD) on a hybrid inorganic/polymeric membrane NK-1 type]PF₆A step of preparing a catalytic membrane.

Will be at 21cm clamped between windows²(6.76mg) hybrid inorganic/PVA membrane carrier type NK-1 was introduced into a round bottom glass flask equipped with a side piston. Methanol (10mL) was introduced into the flask which was degassed with three vacuum/nitrogen cycles. The preformed rhodium catalyst [ (-) -BINAP) Rh (NBD) in methanol (5mL) was then added]PF₆(3.00mg，3.1·10^-3mmol) of a nitrogen degassed solution under a nitrogen streamCapillary transfer to flask after stirring the flask at room temperature for 24h with an orbital shaker, the methanol solution was removed from the flask by decantation under nitrogen flow, the membrane was carefully washed with sequential additions/removals of degassed MeOH fractions (3 × 15mL) and dried under nitrogen flow for 4 h.

Example IV

This example illustrates: general procedure for hydrogenation reactions of various substrates using catalytic membranes prepared as described in example II.

Will be composed of a catalytic membrane andthe catalytic membrane module, which is constructed with a holder and prepared as described in example II, is introduced into a reactor equipped with a magnetic stirrer and a manometer and the inner wall thereof is usedCovered 100mL stainless steel autoclave. The autoclave was degassed with 3 vacuum/nitrogen cycles. 1.7.10 of hydrogen degassing of the substrate (molar ratio of substrate: anchored metal 164: 1, based on the data reported in Table 2)^-2M methanol solution under nitrogen flow throughThe capillary was transferred to an autoclave. The autoclave was flushed with hydrogen for 10 minutes and then filled with the desired hydrogen pressure. The solution in the autoclave was stirred at room temperature (140RPM) for the desired time. After that, the autoclave was depressurized and the reaction solution was removed from the bottom discharge valve under a nitrogen stream. A sample of this solution (0.5 μ L) was analyzed by gas chromatography using appropriate columns and conditions to determine both conversion and enantiomeric excess (ee). The remaining solution aliquot (aliquot) was used to determine the amount of metal leached into the solution via ICP-AES analysis.

Example V

This example illustrates: using the process according to the invention described in example III by means of a preformed rhodium catalyst [ (-) -BINAP) Rh (NBD)]PF₆Immobilized to a catalytic membrane prepared on a hybrid inorganic/polymeric membrane, type NK-1, and following the procedure used for the hydrogenation of methyl 2-acetamidoacrylate (MAA) carried out according to the procedure described in example IV.

Will consist of a catalytic membrane (having [ (-) -BINAP) Rh (NBD)]PF₆NK-1 type of immobilized catalyst, Rh content 2.91 w/w%) andthe catalytic membrane module, which is constructed with a holder and prepared as described in example II, is introduced into a reactor equipped with a magnetic stirrer and a manometer and the inner wall thereof is usedCovered 100mL stainless steel autoclave. The autoclave was degassed with 3 vacuum/nitrogen cycles. Deairing MAA (46.6mg, 0.32mmol, MAA: rhodium molar ratio 164: 1) with hydrogen gas 1.7.10^-2M methanol solution (19mL) was passed under a stream of nitrogenCapillary transfer into the autoclave was purged with hydrogen for 10 minutes and then filled with 5bar hydrogen gas pressure the solution in the autoclave was stirred at room temperature (140RPM) for 2 hours after which the autoclave was depressurized and the reaction solution was removed from the bottom drain valve under a stream of nitrogen a sample of this solution (0.5 μ L) was analyzed by gas chromatography using a 50m × 0.25mm ID Lipodex-E (Macherey-Nagel) capillary column (helium carrier gas 24 cm/sec, isothermal 140 ℃) to determine both conversion (35.0%) and enantiomeric excess (10.4%) an aliquot of the remaining solution was analyzed via ICP-AES to determine the amount of metal leached into the solution (0.350 ppm).

Example VI

This example illustrates: according to the method of the present invention as described above, a catalytic membrane is prepared by fixing a preformed metal catalyst to a hybrid inorganic/polymeric membrane, and is applied to a conventional one-step process for hydrogenation reaction of various substrates.

Will be at 22cm clamped between windows²Hybrid inorganic/PVA film carrier sample insertAt the bottom end of the mechanical stirrer. The assembly was introduced into a chamber equipped with a bottom discharge valve and a pressure gauge and having an inner wall forCovered 100mL stainless steel autoclave. The autoclave was charged with methanol (20mL) and degassed with 3 vacuum/nitrogen cycles. Then the preformed metal complex catalyst (6.10)^-3mmol) of a degassed solution of nitrogen in methanol (10mL) under a stream of nitrogenThe capillary was transferred to an autoclave. The solution in the autoclave is passed throughAfter the membrane module was mechanically stirred at room temperature (140RPM) for 24h under a nitrogen atmosphere, the solution was removed from the autoclave under a stream of nitrogen and the membrane module was passed through with a degassed MeOH fraction (3 × 30mL) viaThe capillary tubes were carefully washed by sequential addition/removal to the autoclave. In this case, the catalytic membrane thus obtained is ready for the subsequent hydrogenation reaction and is immediately used as such without removing it from the autoclave.

For the purpose of evaluating the metal supported in the catalytic membrane, the autoclave was purged with a stream of nitrogen for 2 hours; the membrane can be removed from the Teflon mount and autoclave and dried overnight under high vacuum. The dried catalyst can be analyzed by ICP-AES.

When continuing the one-step hydrogenation step, the substrate (substrate: fixed metal molar ratio 164: 1, based on the data reported in table 2) was degassed by hydrogen to 1.7 · 10^-2M methanol solution under nitrogen flow throughThe capillary was transferred to an autoclave containing a catalytic membrane.The autoclave was purged with hydrogen for 10 minutes and then filled with the desired hydrogen pressure. The solution in the autoclave was passed through at room temperatureThe catalytic membrane module was mechanically agitated (140RPM) for a desired time. After that, the autoclave was depressurized and the reaction solution was removed from the bottom discharge valve under a stream of hydrogen. A sample of this solution (0.5 μ L) was analyzed by gas chromatography using appropriate columns and conditions to determine both conversion and enantiomeric excess (ee). The remaining solution aliquot was analyzed via ICP-AES to determine the amount of metal leached into the solution. Cycling experiments were performed as follows: 1.7-10 of hydrogen degassing of the substrate (substrate: anchored metal molar ratio 164: 1, based on the data reported in table 2) after its use in the preceding hydrogenation reaction^-2M methanol solution under nitrogen flow throughThe capillary was transferred to an autoclave containing a catalytic membrane. The autoclave was filled with the desired hydrogen gas pressure and the solution was mechanically stirred (140RPM) at room temperature for the desired time. After that, the autoclave was depressurized and the reaction solution was removed from the bottom discharge valve under a stream of hydrogen. A sample of this solution (0.5 μ L) was analyzed by gas chromatography to determine both conversion and enantiomeric excess (ee). The remaining solution aliquot was analyzed via ICP-AES to determine the amount of metal leached into the solution.

The results of certain hydrogenation reactions of MAA using catalytic membranes prepared and used as described in example V are reported in table 3. Representative data for 5 cycle experiments are also reported.

Example VII

This example illustrates: according to the process of the invention described in example VI, by reacting a preformed rhodium catalyst [ (-) -BINAP) Rh (NBD)]PF₆Preparation of catalyst fixed on hybrid inorganic/polymeric membrane NK-1Membrane formation and the application of the catalytic membrane to a one-step process in the hydrogenation of MAA.

Will be at 22cm clamped between windows²Hybrid inorganic/PVA film NK-1 type insert in holothurianAt the bottom end of the mechanical stirrer. The assembly was introduced into a chamber equipped with a bottom discharge valve and a pressure gauge and having an inner wall forCovered 100mL stainless steel autoclave. The autoclave was charged with methanol (20mL) and degassed with 3 vacuum/nitrogen cycles. The preformed rhodium complex [ (-) -BINAP) Rh (NBD) is then reacted]PF₆(6.00mg，6.2·10^-3mmol) of a degassed solution of nitrogen in methanol (10mL) under a stream of nitrogenThe capillary was transferred to an autoclave. The solution in the autoclave is passed throughAfter the membrane module was stirred at room temperature (140RPM) for 24h under nitrogen atmosphere, the solution was removed from the autoclave under a stream of nitrogen and the membrane module was passed through with degassed MeOH fraction (3 × 30mL) viaThe capillary tubes were carefully washed by sequential addition/removal to the autoclave. The catalytic membrane thus obtained is ready for the subsequent hydrogenation reaction and is immediately used as such without opening or removing the autoclave.

1.7-10 of hydrogen degassing MAA (93.2mg, 0.65mmol, MAA: rhodium molar ratio 164: 1, based on the data reported in Table 2)^-2M methanol solution (38mL) was passed under a stream of hydrogenThe capillary was transferred to an autoclave containing a catalytic membrane. The autoclave was purged with hydrogen for 10 minutes and then filled with 5bar hydrogen pressure. The solution in the autoclave was passed through at room temperatureAfter mechanical stirring (140RPM) of the catalytic membrane module for the desired time, the autoclave was depressurized and the reaction solution was removed from the bottom drain valve under a stream of hydrogen gas A sample (0.5 μ L) of this solution was analyzed by gas chromatography using a 50m × 0.25mm ID Lipodex-E (Macherey-Nagel) capillary column (helium carrier gas 24 cm/sec, isothermal 140 ℃ C.) to determine both conversion (22.33%) and ee (15.0%)^-2M methanol solution (38mL) was passed under a stream of hydrogenThe capillary was transferred to an autoclave containing a catalytic membrane. The autoclave was filled with 5bar hydrogen gas pressure and the solution was mechanically stirred (140RPM) at room temperature for the desired time. After that, the autoclave was depressurized and the reaction solution was removed from the bottom discharge valve under a stream of hydrogen. A sample of this solution (0.5 μ L) was analyzed by gas chromatography to determine both conversion and enantiomeric excess (ee). The remaining solution aliquot was analyzed via ICP-AES to determine the amount of metal leached into the solution. The results of 5 hydrogenation cycles are reported in table 3.

TABLE 1

^aIn-film WO₃And PVThe weight ratio of A.

^bSiO in film₂Weight ratio to PVA.

^cWeight ratio of polystyrene sulfonic acid to PVA in the membrane.

^dThe weight ratio of polyethylene glycol to PVA in the membrane.

^ePolyester paper substrate for reinforcement, P: presence, A: is absent.

^fDegree of saponification.

^gAldehyde treatment, H: heavy treatment, L: and (5) lightly treating.

TABLE 2^a

^aExamples of data obtained using the catalytic membrane prepared using the procedure described in example II. ICP-AES, average of three samples.

TABLE 3^a

Claims (22)

1. A catalytic material consisting of a pre-formed hybrid inorganic/polymeric support material and a molecular catalyst immobilized on the pre-formed hybrid inorganic/polymeric support material, wherein the pre-formed hybrid inorganic/polymeric support material is composed of a hybrid inorganic/polymeric composite in which a silicic acid compound and/or a tungstic acid compound is chemically bound with polyvinyl alcohol, and the immobilized molecular catalyst is a pre-formed metal catalyst comprising at least one metal atom or ion to which at least one chiral ligand is attached.

2. Catalytic material according to claim 1, wherein the pre-formed hybrid inorganic/polymeric support material is a hybrid inorganic/polymeric membrane and the catalytic material is a catalytic membrane.

3. Catalytic material according to claim 1, wherein the immobilized molecular catalyst is a molecular enantioselective catalyst.

4. Catalytic material according to claims 1, 2 and 3, wherein the hybrid inorganic/polymeric composite comprises a polymer with sulfonic acid groups.

5. Catalytic material according to claim 4, wherein the polymer having sulfonic acid groups is polystyrene sulfonic acid.

6. Catalytic material according to claims 1, 2 and 3, wherein the hybrid inorganic/polymeric composite comprises polyethylene glycol.

7. Catalytic material according to claim 2, wherein the hybrid inorganic/polymeric membrane has a porous substrate for reinforcement.

8. Catalytic material according to claim 1, wherein the preformed metal catalyst is any catalytically active material comprising at least one transition metal atom or ion selected from groups IB, IIB, IVB, VB, VIB, VIIB, VIII of the periodic table of the elements to which one or more ligands are attached.

9. Catalytic material according to claim 8, wherein the transition metal atom or ion comprises at least one transition metal atom or ion selected from Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au.

10. Catalytic material according to claim 8, wherein the ligands are selected from organic or metal-organic species comprising one or more donor atoms having at least a free electron pair or any other donor moiety capable of coordinating the transition metal atom or ion.

11. Catalytic material according to claim 10, wherein the donor atoms comprise phosphorus atoms, nitrogen atoms, oxygen atoms, sulfur atoms, carbon atoms, halogen atoms and/or mixed donor atom sets.

12. Catalytic material according to claim 10, wherein the ligand comprises phosphines, amines, imines, ethers, carbonyls, alkenes, alkadienes, methanol, nitriles, dimethylsulfoxide, halides and mixtures thereof.

13. Catalytic material according to claim 1, wherein the preformed metal catalyst comprises at least one transition metal atom or ion selected from Ru, Rh, Pd, Ir, Ni, Pt, Au and at least one chiral ligand selected from organic species or metal-organic species comprising phosphino, amino or amino-phosphino species or mixtures thereof.

14. Catalytic material according to claim 3 or 8, wherein the immobilized catalyst is a preformed metal complex comprising at least one ligand selected from (R, R) or (S, S) -BINAP [2,2 ' -bis (diphenylphosphino) -1,1 '. binaphthalene ], (R, R) or (S, S) -DIOP [2, 3-O-isopropylidene-2, 3-dihydroxy-1, 4-bis (diphenylphosphino) butane ], (R) or (S) -monophospho [ (3, 5-dioxa-4-phospha-cyclohepta [2, 1-a; 3,4-a ] dinaphthalen-4-yl) dimethylamine ], (R, R) or (S, S) -TMBTP [4,4 ' -bis (diphenylphosphino) -2,2 ', 5,5 ' -tetramethyl-3, 3 ' -dithiophene ].

15. Catalytic material according to claim 3 or 8, wherein the catalyst immobilized is selected from [ (-) - (TMBTP) Rh (NBD)]PF₆、[(-)-(BINAP)Rh(NBD)]PF₆、[(-)-(DIOP)Rh(NBD)]PF₆And [ (-) - (monophosphorus)₂Rh(NBD)]PF₆A preformed metal complex of (a).

16. The catalytic material of any of claims 1, 2, and 3, for use in hydrogenation, dehydrogenation, hydroformylation, carbonylation, oxidation, dihydroxylation, epoxidation, amination, phosphonation, carboxylation, silylation, isomerization, allylalkylation, cyclopropanation, alkylation, arylation, metathesis, and other C-C bond forming reactions.

17. Catalytic material according to claims 1, 2 and 3 for the enantioselective hydrogenation of prochiral substrates comprising olefins, imines, enamines, ketones, α, β -unsaturated alcohols, esters or acids.

18. Catalytic material according to claims 1, 2 and 3 for the enantioselective hydrogenation of prochiral olefins of formula:

wherein R is hydrogen, an alkyl group containing 1 to 30 carbon atoms, an aryl group containing 6 to 18 carbon atoms, R₁、R₂And R₃Including hydrogen, alkyl groups containing 1 to 30 carbon atoms, alkenyl groups containing 1 to 30 carbon atoms, alkynyl groups containing 1 to 30 carbon atoms, aryl groups containing 6 to 18 carbon atoms, amidesAmines, alkoxides comprising 1 to 30 carbon atoms, esters comprising 1 to 30 carbon atoms, ketones comprising 1 to 30 carbon atoms, the aryl groups being of the bicyclic fused type or comprising heteroatoms selected from sulfur, oxygen, nitrogen or phosphorus.

19. A method for manufacturing catalytic material according to claim 1, wherein the hybrid inorganic/polymeric composite is formed by casting and drying a precursor solution prepared by neutralizing at least one inorganic oxide salt selected from silicate and tungstate by means of an acid in a solution containing polyvinyl alcohol.

20. A method of manufacturing catalytic material according to claim 1, by contacting a preformed hybrid inorganic/polymeric support material with a suitable solution of a preformed metal catalyst.

21. Catalytic material according to claim 2, for use as a fixed bed catalytic membrane or a rotating catalytic membrane.

22. Catalytic material according to any of claims 1, 2 and 3, wherein the manufacture of the catalytic material and the chemical reaction using the catalytic material are carried out in a two-separate step process or in a one-step process according to claim 20.