Classifications

• • 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
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
• • 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
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
  • B01J31/063—Polymers comprising a characteristic microstructure
  • B01J31/067—Molecularly imprinted polymers
• • 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
  • B01J31/40—Regeneration or reactivation
  • B01J31/4007—Regeneration or reactivation of catalysts containing polymers
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/02—Carriers therefor
  • C08F4/027—Polymers
• • 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
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
  • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
• • 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
  • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
  • B01J2531/002—Materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/584—Recycling of catalysts

Definitions

• the present invention relates to a new type of solid catalytic composition, which is in the form of a mesoporous solid, which can be used in particular in an aqueous medium.
• mesoporous solid is meant, in the sense of the present description, a porous solid whose pores, called “mesopores”, have at least a characteristic dimension of between 2 and 250 nm, typically less than 100 nm, and especially between 2 and 50 nm, for example a material comprising pores or hollow channels of diameter included in these ranges of values.
• a mesoporous solid composition for catalysis has so-called "open" porosity, ie at least a portion of the surface of its mesopores is accessible by chemical species (as opposed to closed porous structure, where the pores are included in a solid matrix, without possible exchange with the outside).
• a mesoporous character associated with open structure gives the material in particular a high specific surface, allowing important contacts with the external environment.
• Materials having a pore size greater than 20 nm are also particularly useful on the one hand for facilitating the transport of material within the pores, and on the other hand for allowing the grafting of macromolecules, such as enzymes or proteins.
• compositions or of "catalytic” character within the meaning of the present invention, as well as the terms “catalyst” or composition or function capable of “catalyzing” a chemical reaction are understood in their broadest sense, that is, a composition is considered to be catalytic, or to provide a so-called catalytic effect, if it is capable of promoting a chemical reaction in which it does not intervene as a reagent, this composition preferably being unchanged at the end of the reaction. chemical reaction.
• a catalyst within the meaning of the present description means any composition capable of promoting a chemical reaction when it is introduced into a reaction medium, and whether or not it plays a catalytic role in the strictest sense of the term.
• the mesoporous solids are particularly interesting insofar as the contact between the reagents and the surface functions of the catalyst takes place within the confined environment of the mesopores, which can in particular promote contact between reagents, increase the efficiency of catalysis or even allow reactions that can not be envisaged under other conditions.
• the known mesoporous catalysts are essentially, if not exclusively, solids of inorganic nature, typically based on inorganic oxides, generally based on silica, alumina or titanium oxide, of those described, for example, in J. Am. Chem. Soc., Vol. 1, 14, pp. 10834-10843 (2002), Science, Vol. 279, pp. 548-552 (1998), or Nature, vol. 359, pp. 710-712 (1992).
• inorganic mesoporous catalysts generally have a rather poor mechanical strength. Friable and brittle, they are almost exclusively used in a granular or pulverulent form, which reduces their possible modes of implementation and makes their recycling difficult. In addition, when they are used in a liquid medium, especially in aqueous media, they tend to disintegrate over time, which makes them very poorly adapted for example to the treatment of a continuous aqueous flow, which tends to erode these catalysts over time.
• An object of the present invention is to provide mesoporous catalysts having the advantages of the aforementioned inorganic mesoporous catalysts, but which do not have their disadvantages.
• the invention aims to provide mesoporous solid catalysts whose functionalization can be adapted to a large extent and which have a higher mechanical strength than those of inorganic mesoporous catalysts, allowing, inter alia, their implementation in aqueous medium .
• the present invention proposes a novel type of mesoporous solid catalyst, namely a material based on a mesoporous organic polymer whose pore surface carries functional functions for catalyzing a chemical reaction.
• mesoporous polymers without catalytic character which are prepared by self-organization of polymers comprising immiscible blocks (organization by phase segregation according to a hexagonal cylindrical phase or the like), then degradation of one of the blocks to generate a mesoporosity in the material. It has also been described, for example in Langmuir, vol 21, pp. 9322-9326 (2005) or in J. Am. Chem. Soc., Vol. 129, pp.
• Chem. Res. flight. 34, pp. 973-980 which uses lyophilic amphiphilic monomers capable of forming hexagonal cylindrical phases, which leads to polymers with a porous structure and bearing polar groups (the polymer having the structure of the cylindrical phase formed by lyotropic monomers).
• this technique is mainly limited to obtaining microporous polymer (very small pore diameter, less than 2 nm ) and is not transferable to the synthesis of polymers having larger pores, in other words, this technique is not exploitable for the synthesis of functionalized mesoporous polymers.
• the present invention provides, conversely, the means of obtaining organic materials having on the one hand a mesoporous character and whose functionality of the walls can be modulated to a very large extent.
• the subject of the present invention is a process for preparing a solid catalyst composition based on a mesoporous polymeric material whose mesopore walls carry reactive functions R capable of catalyzing a reaction. which comprises the following successive steps:
• a self-assembly of organogelling compounds is carried out in the form of fibrillar structures having a diameter of 10 nm to 100 nm, whereby a gel comprising said fibrillar structures is formed; dispersed in a dispersing medium comprising the monomers; then
• reactive functions R capable of catalyzing a chemical reaction whose presence is sought on the material
• step (D) converting, where appropriate, all or part of the functions R 'present at the mesopore walls of the polymeric material (M 0 ) resulting from step (C) into reactive functions R, and recovering a composition comprising a porous polymeric material (M) carrying reactive functions R within its mesopores, as a catalytic composition.
• the invention also relates to solid catalyst compositions based on a mesoporous polymeric material whose mesopore walls carry reactive functions R capable of catalyzing a chemical reaction, which have the specific characteristics obtained. by implementing the steps (A) to (D) above.
• the mesoporosity is obtained very easily, namely simply by carrying out the polymerization of the monomers in the presence of organogelling compounds which, in the polymerization medium, self-associate in the form of fibrillary objects (tubular) of mesoscopic dimensions, these objects acting as "template” during the synthesis of the polymer, then being removed at the end of the polymerization, which leads to obtaining in the final material mesopores corresponding to the fingerprint of the fibrillar objects formed by the organogelators.
• organogelling compounds which, in the polymerization medium, self-associate in the form of fibrillary objects (tubular) of mesoscopic dimensions, these objects acting as "template” during the synthesis of the polymer, then being removed at the end of the polymerization, which leads to obtaining in the final material mesopores corresponding to the fingerprint of the fibrillar objects formed by the organogelators.
• the organogelators used in this context generally have the advantage of being able to be recycled, which has a significant advantage of the process, which is reflected in terms of reduced process costs, and which makes the process adapted in particular to an implementation of the process on an industrial scale.
• the method of the invention has in this context an undeniable advantage over the currently known methods of synthesis of inorganic mesoporous materials, which use organic molecules as a template (surfactants associating in a typical hexagonal phase) . Indeed, in the case of organic materials, generally sensitive to washing operations, the template used is generally removed by calcination, which prohibits any possibility of recycling.
• steps (A) to (C) allows the implementation of a very large number of functions R ', themselves modifiable in step (D) into an even wider range of R reactive functions, which opens the way to a modularity of functionalization incomparable with that, much more restricted, offered by inorganic catalysts.
• the materials obtained according to steps (A) to (D) have mechanical properties which are substantially those of the organic polymers which constitute them, generally independently of the R functions which they carry.
• the materials obtained according to the steps (A) to (D) in particular have a higher mechanical strength than the inorganic mesoporous catalysts, of which they do not exhibit the friable character and brittle. They can also be used in liquid media where the polymer is not soluble, especially in aqueous medium, without leading to erosion phenomena encountered with inorganic mesoporous catalysts.
• mesoporous organic catalysts according to the invention can be used in more macroscopic forms.
• the gel prepared in step (A) can be shaped very modulably before the polymerization step (B), whereby various forms can be obtained for the mesoporous material (M) obtained at the outcome of step (D).
• the gel prepared in step (A) may be introduced into a mold, whereby the material (M) obtained in fine is in the form of a molded mesoporous mass piece having the shape of the mold used.
• the gel prepared in step (A) can be deposited in the form of a film, on various supports, with the possibility of controlling the thickness of the film, which allows for example to obtain the catalytic material (M) in the form of a surface coating on different types of substrates, in particular in the form of internal reactor coating.
• This possibility of shaping the catalysts, combined with their capacity to be used in a liquid medium, is particularly suitable for recycling the catalyst (shaping in the form of a mass object or particles of sufficiently large size ( millimeter balls for example) facilitates the extraction of the catalyst which can then optionally be subjected to washing steps without risk of erosion).
• the process of the invention is carried out using monomers bearing R 'functions as defined above, associated with organogellators capable of forming fibrillar objects in a medium comprising these monomers.
• the functions R 'present on the monomers employed in step (A) of the process are the reactive functions R whose presence is sought on the final material in a protected form.
• protected form of a reactive function R is meant, within the meaning of the present invention, a function which is capable of being easily converted into the function R, generally in a single step, by a reaction which can be implementation in the step (D) without harming the integrity of the porous polymer structure (M 0) prepared in step (C).
• step (D) comprises a reaction of deprotection of all or part of the functions R' in the reactive functions R sought.
• the functions R ' can for example be ester functions and the step (D) then comprises a deprotection reaction (conversion) of all or part of these esters to carboxylate-COO " reactive functions, typically by treatment of the polymeric material (M 0 ) obtained at the end of step (C) with a base, for example a soda or potassium hydroxide solution.
• the functions R 'present on the monomers employed in step (A) are functions, generally non-reactive as such, making it possible to fix on the material (M 0 ) such reactive functions R, in a grafting step or optionally in several successive synthesis steps.
• step (D) the functions R are fixed on the surface of the mesopores of the material (M 0 ) by means of these hooked functions R ', generally by reaction of the material (M 0 ) with compounds carrying both functions R '"capable of forming a covalent bond with the functions R' and of R functions, optionally in protected form, in particular if they are otherwise capable of reacting with the R functions or R '", then, where appropriate, deprotection of the functions R.
• the functions R' present on the monomers employed in the step (A) may for example be ester functions, in which case in step (D), these functions are at least partly deprotected to carboxylic acid or carboxylate functions, then the R functions are introduced, typically by reaction of the material (M 0 ) with a compound carrying an amine function or alcohol
• the functions R 'present on the monomers employed in step (A) may be protected amino functions which, in step (D), are at least partly deprotected into primary or secondary amine functions, then the R functions are introduced, typically by reaction of the material (MO) with a compound carrying a carboxylic acid function, acid chloride (sulfonyl chloride for example), or and at least one function
• R or more generally, by reaction with a reagent of formula R-A, where A is a leaving group, for example a halide or mesylate group.
• step (A) of the process of the invention which appear to be particularly interesting in the embodiments of the two preceding paragraphs, there may be mentioned monomers carrying ester functions, which lead to the formation, in step (B), of polymers carrying these same ester functions as functions R '.
• a mixture of difunctional monomers, ie carriers of two (meth) acrylic polymerizable groups, optionally in admixture with monomers carrying a single (meth) acrylic polymerizable group is used.
• step (A) whatever the nature of the monomers used in step (A), they are used in this step in the presence of organogelling compounds, under conditions in which these organogellants form, in the monomer mixture, structures fibrillary having a diameter of 10 nm to 100 nm, which, used as a template in the method of the invention, lead to a mesoporosity calibrated and controlled in the material (M) obtained at the end of the process.
• organogelling compounds or “organogelators” of a given liquid medium, is meant in the sense of the present description, a set of identical organic molecules generally non-polymeric, or a mixture of several generally non-polymeric organic molecules, which, when introduced into said liquid medium are capable, at least under certain concentration and temperature conditions, of establishing physical interactions with each other such that they self-associate, generally by weak reversible bonds ( hydrogen bonds typically), so as to form within the apolar medium three-dimensional supramolecular structures associating several molecules, which generally leads to gelation of the medium.
• organogelators we can refer in particular to Chem. Rev. flight. 97, pp. 3133-3159 (1997) or at "P.
• organogellators employed in the context of the present invention are those molecules which are capable of forming fibrillar type associations within the medium of step (A).
• fibrillar structure is meant a cylindrical or substantially cylindrical morphology structure, characterized by a length along a longitudinal axis and a radius perpendicular to this longitudinal axis, with a ratio of length to radius preferably greater than 10: 1, more preferably greater than 20: 1, and even more preferably greater than 40: 1, or even 50: 1.
• the organogelators employed in the context of step (A) are molecules capable of forming fibrillar structures with a diameter of 10 and 100 nm, for example from 15 to 80 nm, in particular from 20 to 50 nm.
• the length of these Fibrillar structures are preferably at least 200 nm, and more preferably at least 300 nm, typically in the range of 400 nm to 5 microns.
• organogelators employed in the context of the present invention are moreover compatible with the monomers employed.
• the organogelators which are dissolved or precipitate in the monomers employed are in particular to be banned.
• Suitable organogellators in this context are, in a non-limiting manner, the organogelling systems employed in Langmuir's articles, theft
• the medium of step (A) is a polar medium and the organogelling compounds used are compounds capable of self-association in an apolar medium.
• the medium of step (A) may comprise apolar compounds, in which case the organogelling compounds employed are compounds capable of self-association in an apolar medium.
• step (A) are molecules of 3,5-bis- (5-hexylcarbamoylpentyloxy) benzyl decylate (also called BHPB compound), corresponding to the following formula:
• nanotubular type structures having a controlled diameter, very little polydispersed, of the order of 30 nm and a length from 400 nm to a few microns, observable in particular by electron microscopy and neutron scattering at small angles.
• organogelling agent in step (A) analogous compounds of the abovementioned BHPB family, corresponding to the following formula (I):
• x is an integer ranging from 2 to 7,
• y is an integer ranging from 1 to 10, such that the sum (x + y) ranges from 8 to 12;
• z is an integer greater than 7, generally between 8 and 16, for example between 8 and 12.
• the compounds corresponding to the general formula (I) lead to the formation of nanotubes in an apolar medium, these nanotubes typically having a diameter of the order of 20 to 40 nm.
• organogellators in step (A) it is possible to use other organogelling compounds capable of forming the desired fibrillar structures in the medium of step (A), for example:
• step (A) a specific texturing of the material is obtained, with in particular a mesopore diameter characteristic of the organogelling compounds employed. It is thus possible to modify the structure of the material (M) prepared according to the invention in a fine way, and in particular to modulate the diameter of its mesopores by a judicious choice of the organogelling compounds employed.
• obtaining the fibrillar structures in step (A) is optionally subject to specific conditions of concentration and / or temperature.
• the mass ratio BHPB / monomers it is generally desirable for the mass ratio BHPB / monomers to be greater than 0.05: 1, the porosity and the specific surface area of the material (M) obtained in fine increasing with this ratio.
• the BHPB / monomer weight ratio it is preferable, in most cases, for the BHPB / monomer weight ratio to remain below 2: 1.
• this mass ratio is preferably between 0.5: 1 and 1.5: 1, typically of the order of 1: 1.
• a similar problem is encountered with all the organogellators. It is the skill of the person skilled in the art to adapt, on a case by case basis, the concentration of organogelators to be used to obtain the desired porosity and mechanical strength.
• fibrillar structures based on BHPB are formed spontaneously at room temperature but disappear at a limiting temperature, known as the "gelling temperature", which depends on the concentration of organogelators in the medium (this temperature is for example 58 ° C for a content of 5% by weight of BHPB).
• BHPB-based fibrillar structures are typically made by dissolving hot BHPB in the monomer mixture and then cooling the medium to room temperature (typically 25 ° C).
• room temperature typically 25 ° C
• the steps (A) and (B) are conducted at room temperature as soon as the fibrillar structures are formed so as not to risk affecting the integrity of these structures.
• step (B) is carried out by photoinitiation, which allows implementation of step (B) at low temperature, typically at room temperature.
• photoinitiation allows implementation of step (B) at low temperature, typically at room temperature.
• step (B) by photopolymerization can be carried out according to any embodiment known per se to those skilled in the art.
• a photo-activable polymerization initiator namely a compound capable of forming free radicals when irradiated (typically in the UV range), and the photopolymerization is obtained by subjecting the mixture to this irradiation.
• the extraction of the organogelling compounds which is carried out in step (C) can be carried out according to any means known per se, it being understood that this extraction must not be of a kind to affect the synthesized polymer, and in particular that it must not inhibit the possibility of ultimately obtaining the reactive functions R sought on the surface of the mesopores of the polymer.
• the extraction of the organogelling compounds in step (C) is generally carried out by washing, typically using a solvent capable of dissociating the fibrillar structures formed by the organogelators, preferably by conducting several successive washes of the polymer, preferably by soaking in successive washing baths.
• Such an embodiment generally makes it possible to extract quantitatively or substantially (typically more than 90%, and generally at least 95%), the organogelling compounds out of the mesopores of the polymer formed in the step (B) without affecting neither the structure of the polymer nor the organogelling compounds which are easily recoverable from the washing solvents, by simple evaporation of the solvent.
• the organogelling compounds thus extracted are recycled, in particular to be used again in a step (A) for forming a material according to the invention, after a possible purification of the organogelators. This possibility of recycling the organogellators is still an advantage of the method of the invention, which is reflected in particular in terms of reduced production costs.
• step (C) can typically be conducted by washing the polymer from step (B) in a solvent capable of dissociating the hydrogen bonds associating the BHPB molecules. in the nano tubes formed by these organogelators.
• a suitable dissociating solvent for this purpose is, for example, chloroform, which allows substantial extraction of the organogelators (typically, immersion of the polymer in three chloroform wash baths leads to extraction of more than 95% of the BHPB out of the polymer (typically of the order of 99%), the BHPB thus extracted can be recovered and reused, for example, as an organogelling agent in step (A) of synthesis of another polymeric mesoporous material according to the invention.
• the solid catalyst compositions of the present invention are based on a mesoporous polymeric material, where the mesopores are typically in the form of calibrated and controlled diameter channels of between 5 and 5 microns. and 150 nm, most often between 10 and 100 nm, more generally between 15 and 80 nm, especially between 20 and 50 nm (typically around 30 nm when BHPB is used as organogelator)
• a catalytic composition according to the invention is, moreover, most often in the form of a hard polymer resin and mechanically resistant. These mechanical properties make it possible to reduce the composition in particles of millimeter dimensions without affecting the structure of the mesopores of the material (M) and without leading to the formation of fine particles of the type of those present in compositions based on inorganic mesoporous materials, much more brittle.
• a composition according to the invention may be:
• step (A) in the form of a solid polymer part, for example a molded polymer part such as a hollow tube, a container or a plate (to do this, the gel prepared in step (A) is placed in a suitable mold before the polymerization of step (B)); or
• step (A) in the form of a catalytic coating deposited on all or part of a support, for example on the inner face of a pipe or a container (for this purpose, the gel prepared in step (A) is deposited on a support prior to the implementation of step (B)); or
• millimeter-sized particles for example with an average diameter of the order of 0.5 to 10 mm.
• compositions obtained according to the process of the invention can be used as solid catalyst compositions to promote various chemical reactions.
• compositions obtained according to the above-mentioned stages (A) to (D) are particularly advantageous for use in a liquid medium, especially in an aqueous medium.
• a composition according to the invention can be in the form of sufficiently divided particles to provide an exchange surface adapted to catalysis, but of sufficiently large size to allow easy separation of the products obtained and the catalyst, for example in the form of particles of dimensions of the order of a millimeter.
• This possibility of obtaining the catalyst in a form of easily separable particles is a significant advantage over inorganic catalysts in powder form, which include inevitable very fine particles (micron or submicron) likely to pollute the products obtained.
• particles of composition according to the invention can be agglomerated (in particular by sintering), which makes it possible to obtain porous materials with a high specific surface area.
• the facile extraction of the catalyst allows washing and recycling of the catalyst after the catalysis of the reaction, generally without substantial loss of catalytic efficiency.
• compositions according to the invention in the form of a tube or a container or in the form of a catalytic coating on the inner surface of a pipe or a container can be used to continuously treat a liquid flow, especially aqueous, during transport or transfer.
• the compositions of the invention may for example be used for the treatment of wastewater or industrial chemical effluents.
• BHPB 3,5-bis (5-hexylcarbamoylpentyloxy) decyl benzoate
• Irgacure 651 2,2-dimethoxy-1,2) - diphenyl-ethanone
• the dissolution was carried out by introducing the compounds into a closed vessel, heating the resulting mixture to 70 ° C until complete dissolution of BHPB and photoinitiator in benzene diacrylate.
• the gel thus formed was subjected to UV irradiation, whereby a photopolymerization of the ethylene diacrylate was obtained around the BHPB nanotubes present in the reaction medium, in the form of of a polyacrylate resin.
• the purified BHPB thus recovered can be recycled to form a resin again.
• the resin R 0 was crushed in the form of particles of dimensions of the order of 1 mm.
• the resin thus ground was immersed for 260 minutes in a 1 mol / l solution of NaOH in a 1: 1 v / v methanol / water mixture, which led to a partial hydrolysis of the ester functions of the resin into functional groups.
• carboxylate which can be demonstrated by Fourier transform infrared spectrometry
• the resin was removed from the treatment bath and was rinsed with water and then with methanol using an extractor. Soxhlet.
• the resin R was thus obtained in the form of grains with a diameter of the order of 1 mm based on a hard and vitreous material.
• Resin R of Example 1 was employed as a catalyst in a model reaction, Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate, below:
• the resin was recovered by simple filtration, and washing with ethanol. The resin thus recovered and was again tested under the same conditions as above. A new cycle of recovery and reuse of the resin was then carried out again.
• Comparative test 1 experimental conditions of Example 2 reproduced, but replacing the resin R with the resin R 0 of Example 1 (non-functionalized mesoporous resin within its pores).
• Comparative test 2 experimental conditions of Example 2 reproduced, but replacing the resin R with a resin, called R ', obtained under the conditions of Example 1 but in the absence of BHPB (non-mesoporous resin, treated with NaOH, carrier of carboxylate function at the surface)
• a resin R " was prepared analogously to the resin R of Example 1, with 0.2 g of BHPB, 0.1 g of butylidenediacrylate, 0.1 g of terbutylacrylate and 3 mg of Irgacure 651 (2, 2-dimethoxy-1,2-diphenylethanone)
• the BHPB is extracted to give a mesoporous resin with a pore size of the order of 30 nm and having tert-butyl ester functions.
• the resin thus obtained is milled in the form of particles having a size of approximately 1 mm. These particles are immersed in 5 ml of a solution of trifluoroacetic acid in dichloromethane and left without stirring for 24 hours. They are then rinsed for 24 h in dichloromethane and then dried at 50 ° C. for 48 hours.
• the FTIR spectra in ATR mode show that the R "resin thus obtained contains carboxylic acid functions, an assay of these functions showing that their amount is 1.5 mmol / g.
• the resin R described in Example 1 is suspended (0.15 g) in a solution of 21 mg of 1-prop-2-ynyloxy-undecylammonium chloride and 2.5 mg of hydroxybenzotriazole (HOBt) in 5 mL of dichloromethane, then 46 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDCI) is added at 0 ° C. The suspension is stirred for 10 min at 0 ° C and then for 24 hours at 25 ° C. The resin obtained is filtered and washed with dichloromethane, then acetone and dried under vacuum. The presence of the amide functions formed is highlighted by FTIR. The alkyne functions introduced onto the resin can then be modified by cycloaddition of Huisgen.
• HOBt hydroxybenzotriazole
• EDCI 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide

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