EP3164208A1 - Process for the synthesis of hybrid allophane - Google Patents

Process for the synthesis of hybrid allophane

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Publication number
EP3164208A1
EP3164208A1 EP15734346.8A EP15734346A EP3164208A1 EP 3164208 A1 EP3164208 A1 EP 3164208A1 EP 15734346 A EP15734346 A EP 15734346A EP 3164208 A1 EP3164208 A1 EP 3164208A1
Authority
EP
European Patent Office
Prior art keywords
base
aluminum
reactor
allophane
medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP15734346.8A
Other languages
German (de)
French (fr)
Inventor
Olivier Poncelet
Antoine THILL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication of EP3164208A1 publication Critical patent/EP3164208A1/en
Ceased legal-status Critical Current

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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow

Definitions

  • the present invention aims to provide a process for the preparation of hollow particles of allophane-type aluminosilicate hybrid core. More specifically, it proposes a process for synthesizing aluminosilicates of spherical and hollow form, and whose internal silicon atoms are at least 90% by number, and preferably at 100% by number, functionalized by a radical. hydrophobic hydrocarbon.
  • Allophans are aluminosilicate spheres (OH ⁇ AhCbSiOH) and exist naturally in natural deposits, and are related to imogolites of the same formula and chemical anisotropy, but in the form of hollow filaments still called nanotubes.
  • the outer surface of the allophanes is covered with Al-OH while their inner surface is covered with Si-OH.
  • the inside of the spheres is filled with water and on the wall of the nanospheres are pores of 0.7 to 1 nm which allow the water to be exchanged with the outside.
  • US Pat. No. 6,254,845 describes a process for preparing hollow spheres of amorphous aluminosilicate polymers.
  • the method comprises blending a silicon-based compound at high speed with an aluminum compound to form a slurry comprising precursor particles and a salt in solution. The latter is then removed and the particles of the precursor subjected to a heat treatment to obtain the hollow spheres of expected luminosilicates.
  • the document FR 2 845 515 describes the synthesis of so-called partially hybrid allophanes, insofar as the interior of the hollow spheres is covered with 50% by number of Si-OH and by 50% by number of SR with R being a methyl group or vinyl. It should be noted that the presence of non-hydrolysable groups on the inner surface has the consequence of generating an increase in the diameter of these partially hybrid spheres. Their diameter changes from 5 nm to 10 nm.
  • the present invention is specifically intended to provide a method according to this expectation.
  • the present invention relates to a process for preparing hollow particles of spherical aluminosilicates of the allophane and hybrid-core type comprising at least the steps of
  • all the steps (a) to (d) are carried out consecutively within the same reactor.
  • the material constituting said reactor is devoid of silanol group and free fluorine atom.
  • the constituent material of the reactor is different from glass and teflon.
  • the material constituting the reactor is selected from stainless steel, polypropylene, inert porcelains including those conforming to those used in industrial chemistry reactors.
  • the silicon alkoxide is of formula RSi (OR ') 3 in which R' is a C 1 -C 2 alkyl group and R is a saturated or unsaturated C 1 -C 2 hydrocarbon group.
  • OCKb methyltrimethoxysilane
  • OCH 3 vinyltrimethoxysilane
  • the inventors have found that the choice of a particular material for the reactor dedicated to the preparation of the aluminosilicate provides access to an aluminosilicate reproducing advantageously the allophane isotropy, while being hybrid heart.
  • hybrid heart intends to qualify the fact that at least 90% by number of silicon atoms present on the internal face of said cavity are functionalized with a hydrocarbon radical.
  • This functionalization rate control may in particular be carried out by thermogravimetric analysis called TGA technology coupled to spectrometry or ⁇ infra-red.
  • the hollow particles of aluminosilicates obtained according to the invention are of course compatible with a wide variety of applications, in particular taking advantage of their internal cavity to convey or trap a wide variety of hydrophobic molecules of interest (cosmetic active agents , pharmaceuticals, plasticizers, pesticides, hormones ).
  • a substance is said to be hydrophobic when it has a very weak or even a total lack of affinity for an aqueous medium. This lack of affinity also results in a very low or even a lack of aqueous solubility.
  • a compound is said to be immiscible in water if less than 3%, preferably less than 2%, for example less than 1% by weight of this compound is in solubilized form in water.
  • the precursor of the aluminum used during step (a) is chosen from aluminum perchlorate A1 (C10 4 ) 3> aluminum nitrate A1 (N0 3 ) 3 or aluminum chloride AICI3, and preferably is aluminum perchlorate A1 (C1C ⁇ 4) 3.
  • the molar ratio Al / Si of step (a) is between 1.5 and 2.5.
  • the aluminum concentration of the aqueous solution in step (a) may be from 0.01 to 1 mol.L -1 and preferably from 0.05 to 0.1 mol.L -1.
  • the silicon alkoxide or the mixture of silicon alkoxides hydrolyzed in step (b) corresponds to the formula R-Si (OR ') 3 in which R' is a linear alkyl or alkenyl group or branched C 1 -C 6 , or a phenyl group, said group R possibly being able to carry a substituent chosen from -OH, -NH 2 , -COOH, a phenyl group or a halogen atom, and R is a linear alkyl group or branched to C1-C12.
  • R ' is methyl, ethyl, propyl, butyl or vinyl and even more preferably R is methyl or vinyl.
  • R is a methyl, ethyl or propyl group and, even more preferably, R is a methyl group.
  • the preferred silicon alkoxides are methyltrimethoxysilane (OCH 3 ) 3 SiCH and vinyltrimethoxysilane
  • the base / aluminum molar ratio (ratio between the concentration of added base and the amount of aluminum initially present) still means that the hydrolysis ratio is a synthesis parameter well known to those skilled in the art which can be determined at all. along the reaction from pH.
  • the base added in step (b) may be selected from sodium hydroxide, potassium hydroxide or lithium hydroxide and, preferably, said base is sodium hydroxide. Its concentration may be between 0.1 and 3 mol L "1.
  • the addition of the base is advantageously carried out at a rate of between 50 and 300 mL.1T 1, and preferably, between 100 and 280 ml / hr.
  • the mixture thus obtained is stirred at room temperature, that is to say at a temperature likely to vary from 18 to 25 ° C until the medium becomes completely clear.
  • This clarity can in particular be controlled by spectroscopy. It corresponds to 95% to 100% of visible transmission measured by UV-visible spectrometry in a 1 cm cell on the entire visible spectrum. This clarity can be obtained after 8 to 12 hours of agitation.
  • This stirring time is indeed likely to vary according to the chemical nature of the silicon alkoxide retained for the process.
  • step (d) can be carried out at a temperature between 70 and 150 ° C. and preferably between 80 and 100 ° C., either in an autoclave, in an oven or at reflux.
  • the duration of the heating step (d) is between 4 and 8 days.
  • the method of the invention may further comprise a step (e) washing or concentration of the solution obtained at the end of step (d).
  • the washing step serves to remove from the reaction medium the by-products formed in the previous steps, such as residual ions from the base used in step (b) or the alcohols from the hydrolysis of alkoxide.
  • Step (d) can therefore be carried out by dialysis, either by concentration and preferably by ultrafiltration.
  • the hollow particles of hybrid aluminosilicates thus purified can be recovered according to conventional techniques.
  • Another subject of the invention relates to the allophane-type hybrid spherical hollow-shaped particles as such that can be obtained according to the process of the invention, and simultaneously comprising a hydrophilic external surface and a hydrophobic internal surface at 100.degree. %.
  • the presence of an internal cavity in these spheres can also be characterized by S AXS analysis.
  • S AXS analysis by comparing the signal obtained by diffusion of X-rays to a homogeneous electron density model, it can be deduced that the hybrid allophanes have a wall of the order of 5 to 7 ⁇ thick and therefore a hydrophobic cavity with a size of between 2.5 and 5 nm.
  • the particles according to the invention are particularly advantageous as vehicles or for the trapping of molecules of interest and in particular hydrophobic.
  • Another aspect of the invention relates to the use of spherical hollow aluminosilicate hollow particles according to the claims for vehicle purposes or trapping at least one molecule of hydrophobic interest.
  • a substance is said to be hydrophobic when it has a very weak or even a total lack of affinity for an aqueous medium. This lack of affinity also results in a very low or even a lack of aqueous solubility.
  • a compound is said to be immiscible in water if less than 3%, preferably less than 2%, for example less than 1% by weight of this compound is in solubilized form in water.
  • the invention furthermore aims at a particle according to the invention containing at least one molecule of hydrophobic interest, chosen for example from therapeutic, phytosanitary, surfactant, insecticidal, dyestuff or marker agents. .
  • a fresh sodium hydroxide solution (5.33 g of NaOH in 1333 ml of DI water) is then added to the dropping funnel. The addition is at a rate of 250 mL per minute.
  • the reaction medium is clear after 1 ⁇ 4 hour.
  • the reaction mixture is stirred for 12 hours at room temperature before being heated for 5 days at 90 ° C. in a container. polypropylene or stainless steel. After cooling to room temperature, the reaction medium is washed (diaf ltré) and concentrated by ultrafiltration on a lOkD membrane.
  • the yield is 76% (average measurement over three batches: two in a polypropylene bottle and one in a stainless steel container).
  • Example 2 The procedure used is that of Example 1 except that 50 ml of EtOH were added to the aqueous medium to achieve the "solubility / dispersion" of (OMe) 3 -ivinyl.
  • the yield compared to ⁇ introduced aluminum is 67% (obtained on three lots: 2 in a stainless steel container and 1 in a polypropylene container.
  • the zeta potential is + 37mV.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention relates to a process for preparing hollow particles of spherically shaped hybrid aluminosilicates of allophane type with a core, comprising at least the steps consisting in: (a) providing, at ambient temperature, an aqueous medium containing at least one aluminium precursor and one silicon alkoxide in an Al/Si mole ratio ranging from 1 to 3, (b) carrying out, with stirring, the alkaline hydrolysis of said medium with gradual addition of at least one base in a base/Al mole ratio of 2.3 to 3, (c) at the end of the addition of all of said base, maintaining the stirring at ambient temperature until said medium is obtained in the clear state and (d) heating the solution obtained at a temperature ranging from 50 to 150°C, for 2 to 8 days, characterized in that all of steps (a) to (d) are carried out in a reactor consisting of a material which is chemically inert with respect to the reagents and to said expected aluminosilicate.

Description

PROCEDE DE SYNTHESE D' ALLOPHANE HYBRIDE  PROCESS FOR THE SYNTHESIS OF HYBRID ALLOPHANE
La présente invention vise à proposer un procédé de préparation de particules creuses d'aluminosilicate de type allophane hybride à cœur. Plus précisément, elle propose un procédé permettant de synthétiser des aluminosilicates à forme sphérique et creuse, et dont les atomes de silicium internes sont à raison d'au moins 90 % en nombre, et de préférence à 100 % en nombre, fonctionnalisés par un radical hydrocarboné hydrophobe. The present invention aims to provide a process for the preparation of hollow particles of allophane-type aluminosilicate hybrid core. More specifically, it proposes a process for synthesizing aluminosilicates of spherical and hollow form, and whose internal silicon atoms are at least 90% by number, and preferably at 100% by number, functionalized by a radical. hydrophobic hydrocarbon.
Les allophancs sont des sphères d'aluminosilicate (OH^AhCbSiOH et existent naturellement dans des gisements naturels. Elles sont apparentées aux imogolites de même formule et de même anisotropie chimique mais qui se présentent en revanche sous la forme de filaments creux encore qualifiés de nanotubes.  Allophans are aluminosilicate spheres (OH ^ AhCbSiOH) and exist naturally in natural deposits, and are related to imogolites of the same formula and chemical anisotropy, but in the form of hollow filaments still called nanotubes.
La surface externe des allophanes est recouverte d'Al-OH alors que leur surface interne est recouverte de Si-OH. L'intérieur des sphères est rempli d'eau et sur la paroi des nanosphères figurent des pores de 0,7 à 1 nm qui permettent à l'eau de s ' échanger avec l'extérieur.  The outer surface of the allophanes is covered with Al-OH while their inner surface is covered with Si-OH. The inside of the spheres is filled with water and on the wall of the nanospheres are pores of 0.7 to 1 nm which allow the water to be exchanged with the outside.
Ces matériaux présentent un grand intérêt notamment au regard de leur transparence.  These materials are of great interest especially in view of their transparency.
Pour répondre au besoin industriel en ce type de matériaux, de nombreux procédés ont ainsi été développés.  To meet the industrial need for this type of material, many processes have been developed.
Ainsi, le brevet US 6 254 845 décrit un procédé de préparation de sphères creuses de polymères d'aluminosilicate amorphe. Ce procédé consiste à mélanger à vitesse élevée un composé à base de silicium avec un composé à base d'aluminium pour former une suspension comprenant des particules de précurseur et un sel en solution. Ce dernier est ensuite éliminé et les particules du précurseur soumises à un traitement thermique pour obtenir les sphères creuses d' luminosilicates attendues.  Thus, US Pat. No. 6,254,845 describes a process for preparing hollow spheres of amorphous aluminosilicate polymers. The method comprises blending a silicon-based compound at high speed with an aluminum compound to form a slurry comprising precursor particles and a salt in solution. The latter is then removed and the particles of the precursor subjected to a heat treatment to obtain the hollow spheres of expected luminosilicates.
Plus récemment, il a été constaté que l'introduction de fonctions organiques au sein d'aluminosilicate de type allophane ou imogolite permet d'accéder à des nouvelles propriétés par rapport aux aluminosilicates conventionnels. Ces nouveaux polymères synthétiques sont alors dits hybrides.  More recently, it has been found that the introduction of organic functions in aluminosilicate of the allophane or imogolite type provides access to new properties compared with conventional aluminosilicates. These new synthetic polymers are then called hybrid.
Ainsi, le document FR 2 845 515 décrit la synthèse d' allophanes dits partiellement hybrides, dans la mesure où l'intérieur des sphères creuses est recouvert de 50 % en nombre de Si-OH et de 50 % en nombre de S-R avec R étant un groupe méthyle ou vinyle. Il est à noter que la présence de groupes non hydrolysables sur la surface interne a pour conséquence de générer une augmentation du diamètre de ces sphères partiellement hybrides. Leur diamètre évolue de 5 nm à 10 nm. Thus, the document FR 2 845 515 describes the synthesis of so-called partially hybrid allophanes, insofar as the interior of the hollow spheres is covered with 50% by number of Si-OH and by 50% by number of SR with R being a methyl group or vinyl. It should be noted that the presence of non-hydrolysable groups on the inner surface has the consequence of generating an increase in the diameter of these partially hybrid spheres. Their diameter changes from 5 nm to 10 nm.
A la connaissance des inventeurs, il n'existe toutefois pas, à ce jour, de procédé permettant d'accéder à des particules creuses d'aluminosilicates de type ailophane et à cavité totalement hybride.  To the inventors' knowledge, however, there is currently no method for accessing hollow particles of aluminosilicates of the allophane type and totally hybrid cavity.
La présente invention a précisément pour objet de proposer un procédé conforme à cette attente.  The present invention is specifically intended to provide a method according to this expectation.
Plus précisément, la présente invention concerne un procédé pour préparer des particules creuses d'aluminosilicates à forme sphérique de type ailophane et à cœur hybride comprenant au moins les étapes consistant à  More specifically, the present invention relates to a process for preparing hollow particles of spherical aluminosilicates of the allophane and hybrid-core type comprising at least the steps of
(a) disposer à température ambiante d'un milieu aqueux contenant au moins un précurseur d'aluminium et un alcoxyde de silicium dans un rapport molaire Al/Si variant de 1 à 3.  (a) disposing at ambient temperature an aqueous medium containing at least one aluminum precursor and a silicon alkoxide in an Al / Si molar ratio ranging from 1 to 3.
(b) procéder sous agitation à l'hydrolyse alcaline dudit milieu avec addition progressive d'au moins une base dans un rapport molaire base/ Aluminium de préférence de (b) stirring the alkaline hydrolysis of said medium with progressive addition of at least one base in a molar ratio base / aluminum preferably
2,3 à 3, 2,3 to 3,
(c) maintenir, à l'issue de l'addition de la totalité de la base, l'agitation à température ambiante jusqu'à obtention dudit milieu à l'état limpide et  (c) maintaining, after the addition of all of the base, stirring at room temperature until said medium in the limpid state and
(d) chauffer la solution obtenue à une température variant de 50 à 150 °C, pendant 2 à 8 jours,  (d) heating the resulting solution to a temperature ranging from 50 to 150 ° C for 2 to 8 days,
caractérisé en ce que l'ensemble des étapes (b) à (d) réalisés au sein d'un réacteur constitué d'un matériau inerte chimiquement vis-à-vis des réactifs et dudit aluminosilicate attendu.  characterized in that all of the steps (b) to (d) carried out in a reactor consisting of a material chemically inert with respect to the reactants and said expected aluminosilicate.
Selon une variante préférée, l'ensemble des étapes (a) à (d) est réalisé consécutivement au sein d'un même réacteur.  According to a preferred variant, all the steps (a) to (d) are carried out consecutively within the same reactor.
Plus particulièrement, le matériau constitutif dudit réacteur est dénué de groupe silanol et d'atome de fluor libre.  More particularly, the material constituting said reactor is devoid of silanol group and free fluorine atom.
Plus précisément, le matériau constitutif du réacteur est différent du verre et du téflon. Avantageusement, le matériau constitutif du réacteur est choisi parmi l'inox, le polypropylène, des porcelaines inertes notamment conformes à celles mises en œuvre dans les réacteurs de chimie industrielle. More specifically, the constituent material of the reactor is different from glass and teflon. Advantageously, the material constituting the reactor is selected from stainless steel, polypropylene, inert porcelains including those conforming to those used in industrial chemistry reactors.
Ainsi, le procédé selon l'invention est avantageusement réalisé en l'absence de groupe silanol libre.  Thus, the process according to the invention is advantageously carried out in the absence of free silanol group.
Selon une autre variante préférée, l'alcoxyde de silicium est de formule RSi(OR')3 dans laquelle R' est un groupe alkyle en Ci à C2 et R un groupe hydrocarboné saturé ou insaturé en Ci à C2. According to another preferred variant, the silicon alkoxide is of formula RSi (OR ') 3 in which R' is a C 1 -C 2 alkyl group and R is a saturated or unsaturated C 1 -C 2 hydrocarbon group.
Plus préfércntiellement, il s'agit du méthyltriméthoxysilane {OCKb^SiCEb et/ou du vinyltriméthoxysilane (OCH3)3Si(CH=CH2). More preferably, it is methyltrimethoxysilane (OCKb) SiCEb and / or vinyltrimethoxysilane (OCH 3 ) 3Si (CH = CH 2 ).
Contre toute attente, les inventeurs ont ainsi constaté que le choix d'un matériau particulier pour le réacteur dédié à la préparation de l'aluminosilicate permet d'accéder à un aluminosilicate reproduisant avantageusement Fanisotropie de l'allophane, tout en étant à cœur hybride. Unexpectedly, the inventors have found that the choice of a particular material for the reactor dedicated to the preparation of the aluminosilicate provides access to an aluminosilicate reproducing advantageously the allophane isotropy, while being hybrid heart.
Au sens de l'invention, l'expression à cœur hybride entend qualifier le fait qu'au moins 90 % en nombre des atomes de silicium présents sur la face interne de ladite cavité sont fonctionnalisés par un radical hydrocarboné. Ce contrôle de taux de fonctionnalisation peut notamment être réalisé par analyse thermogravimétrie dite technologie TGA couplée à la spectrométrie ou Γ infra-rouge.  Within the meaning of the invention, the term hybrid heart intends to qualify the fact that at least 90% by number of silicon atoms present on the internal face of said cavity are functionalized with a hydrocarbon radical. This functionalization rate control may in particular be carried out by thermogravimetric analysis called TGA technology coupled to spectrometry or Γ infra-red.
Les particules creuses d' aluminosilicates obtenues selon l'invention s'avèrent bien entendu compatibles avec une grande variété d'applications, notamment tirant profit de leur cavité interne pour véhiculer ou piéger une grande diversité de molécules d'intérêt à caractère hydrophobe (actifs cosmétiques, pharmaceutiques, plastifiants, pesticides, hormones...).  The hollow particles of aluminosilicates obtained according to the invention are of course compatible with a wide variety of applications, in particular taking advantage of their internal cavity to convey or trap a wide variety of hydrophobic molecules of interest (cosmetic active agents , pharmaceuticals, plasticizers, pesticides, hormones ...).
De manière générale, une substance est dite hydrophobe lorsqu'elle présente une très faible voire un total défaut d'affinité pour un milieu aqueux. Ce défaut d'affinité se traduit également par une très faible voire un défaut de solubilité aqueux. A titre indicatif un composé est dit immiscible dans l'eau si moins de 3 %, de préférence moins de 2 %, par exemple moins de 1 % en poids de ce composé est sous forme solubilisée dans l'eau. Selon un mode de réalisation avantageux, le précurseur de l'aluminium mis en œuvre lors de l'étape (a) est choisi parmi le perchlorate d'aluminium A1(C104)3> le nitrate d'aluminium A1(N03)3 ou le chlorure d'aluminium AICI3, et de préférence est le perchlorate d'aluminium A1(C1C<4)3. In general, a substance is said to be hydrophobic when it has a very weak or even a total lack of affinity for an aqueous medium. This lack of affinity also results in a very low or even a lack of aqueous solubility. As a guide, a compound is said to be immiscible in water if less than 3%, preferably less than 2%, for example less than 1% by weight of this compound is in solubilized form in water. According to an advantageous embodiment, the precursor of the aluminum used during step (a) is chosen from aluminum perchlorate A1 (C10 4 ) 3> aluminum nitrate A1 (N0 3 ) 3 or aluminum chloride AICI3, and preferably is aluminum perchlorate A1 (C1C <4) 3.
Selon un mode de réalisation particulier, le rapport molaire Ai/Si de l'étape (a) est compris entre 1 ,5 et 2,5.  According to a particular embodiment, the molar ratio Al / Si of step (a) is between 1.5 and 2.5.
La concentration en aluminium de la solution aqueuse en étape (a) peut être comprise entre 0,01 et 1 mol.L"1 et, de préférence, entre 0,05 et 0,1 mol.L '. The aluminum concentration of the aqueous solution in step (a) may be from 0.01 to 1 mol.L -1 and preferably from 0.05 to 0.1 mol.L -1.
De manière avantageuse, l'alcoxyde de silicium ou le mélange d'alcoxydes de silicium hydrolysé lors de l'étape (b) répond à la formule R-Si(OR')3 dans laquelle R' est un groupe alkyle ou alcényle linéaire ou ramifié en Ci-C6, ou un groupe phényle, ledit groupe R pouvant éventuellement porter un substituant choisi parmi -OH, -NH2, -COOH, un groupe phényle ou un atome d'halogène, et R est un groupe alkyle linéaire ou ramifié en C1-C12. Advantageously, the silicon alkoxide or the mixture of silicon alkoxides hydrolyzed in step (b) corresponds to the formula R-Si (OR ') 3 in which R' is a linear alkyl or alkenyl group or branched C 1 -C 6 , or a phenyl group, said group R possibly being able to carry a substituent chosen from -OH, -NH 2 , -COOH, a phenyl group or a halogen atom, and R is a linear alkyl group or branched to C1-C12.
De préférence, R' représente un groupe méthyle, éthyle, propyle, butyle ou vinyle et, de manière encore plus préférée, R est un groupe méthyle ou vinyle. De préférence, R est un groupe méthyle, éthyle ou propyle et, de manière encore plus préférée, R est un groupe méthyle.  Preferably, R 'is methyl, ethyl, propyl, butyl or vinyl and even more preferably R is methyl or vinyl. Preferably, R is a methyl, ethyl or propyl group and, even more preferably, R is a methyl group.
Comme énoncé précédemment, les alcoxydes de silicium préférés sont le méthyltriméthoxysilane (OCH3)3SiCH et le vinyltriméthoxysilane As stated above, the preferred silicon alkoxides are methyltrimethoxysilane (OCH 3 ) 3 SiCH and vinyltrimethoxysilane
Le rapport molaire base/aluminium (ratio entre la concentration en base ajoutée et la quantité d'aluminium initialement présent) dit encore rapport d'hydrolyse est un paramètre de synthèse bien connu de l'homme de l'art qui peut être déterminé tout au long de la réaction à partir du pH. The base / aluminum molar ratio (ratio between the concentration of added base and the amount of aluminum initially present) still means that the hydrolysis ratio is a synthesis parameter well known to those skilled in the art which can be determined at all. along the reaction from pH.
La base ajoutée lors de l'étape (b) peut être choisie parmi l'hydroxyde de sodium, l'hydroxyde de potassium ou l'hydroxyde de lithium et, de préférence, ladite base est l'hydroxyde de sodium. Sa concentration peut être comprise entre 0,1 et 3 mol.L"1. Lors de l'étape (b), l'ajout de la base est avantageusement réalisé à un débit compris entre 50 et 300 mL.1T1 et, de préférence, entre 100 et 280 mL.h'! . Le mélange ainsi obtenu est maintenu sous agitation à température ambiante c'est-à-dire à une température susceptible de varier de 18 à 25 °C jusqu'à ce que le milieu devienne totalement limpide. Cette limpidité peut notamment être contrôlée par spectroscopie. Elle correspond entre 95 % et 100 % de transmission dans le visible mesurée par une spectrométrie UV- visible dans une cellule de 1cm de côté sur tout le spectre du visible. Cette limpidité peut être obtenue au terme de 8 à 12 heures d'agitation. Ce temps d'agitation est en effet susceptible de varier selon la nature chimique de l'alcoxyde de silicium retenu pour le procédé. The base added in step (b) may be selected from sodium hydroxide, potassium hydroxide or lithium hydroxide and, preferably, said base is sodium hydroxide. Its concentration may be between 0.1 and 3 mol L "1. In step (b), the addition of the base is advantageously carried out at a rate of between 50 and 300 mL.1T 1, and preferably, between 100 and 280 ml / hr. The mixture thus obtained is stirred at room temperature, that is to say at a temperature likely to vary from 18 to 25 ° C until the medium becomes completely clear. This clarity can in particular be controlled by spectroscopy. It corresponds to 95% to 100% of visible transmission measured by UV-visible spectrometry in a 1 cm cell on the entire visible spectrum. This clarity can be obtained after 8 to 12 hours of agitation. This stirring time is indeed likely to vary according to the chemical nature of the silicon alkoxide retained for the process.
Le chauffage de l'étape (d) peut être réalisé à une température comprise entre 70 et 150 CC et, de préférence, entre 80 et 100 °C, soit en autoclave, soit en étuve, soit à reflux. The heating of step (d) can be carried out at a temperature between 70 and 150 ° C. and preferably between 80 and 100 ° C., either in an autoclave, in an oven or at reflux.
Selon un mode de réalisation avantageux, la durée de l'étape (d) de chauffage est comprise entre 4 et 8 jours.  According to an advantageous embodiment, the duration of the heating step (d) is between 4 and 8 days.
Le procédé de l 'invention peut, en outre, comprendre une étape (e) de lavage ou de concentration de la solution obtenue à l'issue de l'étape (d). L'étape de lavage sert à éliminer du milieu réactionnel les sous-produits formés au cours des étapes précédentes, tels que les ions résiduels provenant de la base utilisée lors.de l'étape (b) ou les alcools provenant de l'hydrolyse de l'alcoxyde. L'étape (d) peut donc être effectuée par dialyse, soit par concentration et de préférence par ultrafiltration. Les particules creuses d'aluminosilicates hybrides ainsi purifiées peuvent être récupérées selon des techniques conventionnelles.  The method of the invention may further comprise a step (e) washing or concentration of the solution obtained at the end of step (d). The washing step serves to remove from the reaction medium the by-products formed in the previous steps, such as residual ions from the base used in step (b) or the alcohols from the hydrolysis of alkoxide. Step (d) can therefore be carried out by dialysis, either by concentration and preferably by ultrafiltration. The hollow particles of hybrid aluminosilicates thus purified can be recovered according to conventional techniques.
La caractérisation de leur potentiel de surface mesuré par zétamétrie montre qu'il est conforme à celui de sphères allophane non fonctionnalisées. D varie de +30 mV à The characterization of their surface potential measured by zetametry shows that it is consistent with that of unfunctionalized allophane spheres. D varies from +30 mV to
+40 mV. +40 mV.
Un autre objet de l'invention concerne les particules creuses à forme sphérique hybrides de type allophane en tant que telles, susceptibles d'être obtenues selon le procédé de l'invention, et comprenant simultanément une surface externe hydrophile et une surface interne hydrophobe à 100 %. Another subject of the invention relates to the allophane-type hybrid spherical hollow-shaped particles as such that can be obtained according to the process of the invention, and simultaneously comprising a hydrophilic external surface and a hydrophobic internal surface at 100.degree. %.
La présence d'une cavité interne en ces sphères peut par ailleurs être caractérisée par analyse S AXS. Ainsi, en comparant le signal obtenu par diffusion des rayons X à un modèle de densité électronique homogène, il peut être déduit que les allophanes hybrides ont une paroi de l'ordre de 5 à 7 Â d'épaisseur et donc une cavité hydrophobe de taille comprise entre 2,5 et 5 nm. The presence of an internal cavity in these spheres can also be characterized by S AXS analysis. Thus, by comparing the signal obtained by diffusion of X-rays to a homogeneous electron density model, it can be deduced that the hybrid allophanes have a wall of the order of 5 to 7 Å thick and therefore a hydrophobic cavity with a size of between 2.5 and 5 nm.
Les particules selon l'invention s'avèrent particulièrement avantageuses à titre de véhicules ou pour le piégeage de molécules d'intérêt et notamment hydrophobes.  The particles according to the invention are particularly advantageous as vehicles or for the trapping of molecules of interest and in particular hydrophobic.
Ainsi, un autre aspect de l'invention concerne l'utilisation des particules creuses d'aluminosilicatcs à forme sphérique selon les revendications à des fins de véhicule ou de piégeage d'au moins une molécule d'intérêt hydrophobe.  Thus, another aspect of the invention relates to the use of spherical hollow aluminosilicate hollow particles according to the claims for vehicle purposes or trapping at least one molecule of hydrophobic interest.
De manière générale, une substance est dite hydrophobe lorsqu'elle présente une très faible voire un total défaut d'affinité pour un milieu aqueux. Ce défaut d'affinité se traduit également par une très faible voire un défaut de solubilité aqueux. A titre indicatif un composé est dit immiscible dans l'eau si moins de 3 %, de préférence moins de 2 %, par exemple moins de 1 % en poids de ce composé est sous forme solubilisée dans l'eau.  In general, a substance is said to be hydrophobic when it has a very weak or even a total lack of affinity for an aqueous medium. This lack of affinity also results in a very low or even a lack of aqueous solubility. As a guide, a compound is said to be immiscible in water if less than 3%, preferably less than 2%, for example less than 1% by weight of this compound is in solubilized form in water.
L'invention vise en outre une particule conforme à l'invention contenant au moins une molécule d'intérêt hydrophobe en particulier choisi par exemple parmi les actifs thérapeutiques, phytosanitaires, les tensio-actifs, les insecticides, les matières colorantes, les marqueurs...  The invention furthermore aims at a particle according to the invention containing at least one molecule of hydrophobic interest, chosen for example from therapeutic, phytosanitary, surfactant, insecticidal, dyestuff or marker agents. .
Les exemples ci-après sont présentés à titre illustratif et non limitatif de la présente invention.  The following examples are presented for illustrative and not limiting of the present invention.
Exemple 1 Example 1
Synthèse du (OH^AbC SiMe  Synthesis of (OH) AbC SiMe
Dans un récipient en polypropylène ou en inox, on ajoute à 700 mL d'eau DI, 32,46 g d'Al(C104)3,9H20. Le milieu est laissé sous agitation l/2h. On ajoute ensuite 4,53 g de MeSi(OMe)3. Le milieu réactionnel homogène est maintenu sous agitation à température ambiante. In a polypropylene or stainless steel container, 32.46 g of Al (C10 4 ) 3,9H 2 0 are added to 700 ml of DI water. The medium is left stirring for 1 h / 2h. 4.53 g of MeSi (OMe) 3 are then added . The homogeneous reaction medium is stirred at room temperature.
On ajoute ensuite à l'ampoule à brome une solution de soude fraîche (5,33 g de NaOH dans 1 333 ml d'eau DI). L'addition se fait à la vitesse de 250 mL par minute. Le milieu réacîionnel est limpide après ¼ heure. Le milieu réactionnel est agité 12 heures à température ambiante avant d'être chauffé pendant 5 jours à 90 °C dans un récipient en polypropylènc ou en inox. Après refroidissement à température ambiante, le milieu réactionnel est lavé (diaf ltré) et concentré par ultrafiltration sur une membrane lOkD. A fresh sodium hydroxide solution (5.33 g of NaOH in 1333 ml of DI water) is then added to the dropping funnel. The addition is at a rate of 250 mL per minute. The reaction medium is clear after ¼ hour. The reaction mixture is stirred for 12 hours at room temperature before being heated for 5 days at 90 ° C. in a container. polypropylene or stainless steel. After cooling to room temperature, the reaction medium is washed (diaf ltré) and concentrated by ultrafiltration on a lOkD membrane.
Le rendement e (OF sA OîSiMe par rapport à l'aluminium introduit est de 76 % (mesure moyenne sur trois lots : deux en bouteille polypropylènc et une en récipient inox).  The yield is 76% (average measurement over three batches: two in a polypropylene bottle and one in a stainless steel container).
A 10 % massique en (Off^AhCbSiMe, le sol colloïdal aqueux est totalement transparent et limpide. Le potentiel de surface mesuré par zétamétrie est de +40mV ce qui est comparable à un allophane classique. Le S AXS révèle également qu'il s'agit de sphères creuses.  At 10% by mass (Off ^ AhCbSiMe), the aqueous colloidal sol is completely transparent and limpid, the surface potential measured by zetametry is + 40mV, which is comparable to a conventional allophane.The S AXS also reveals that it is acts hollow spheres.
Exemple 2 Example 2
Synthèse de fOH)3AhQ3Sivinyle. Synthesis of fOH 3 AhQ 3 Sivinyl.
Le mode opératoire retenu est celui de l'exemple 1 à la différence que 50 ml d'EtOH ont été ajoutés au milieu aqueux pour y réaliser la « solubilité/dispersion » de (OMe)3Sivinyle. The procedure used is that of Example 1 except that 50 ml of EtOH were added to the aqueous medium to achieve the "solubility / dispersion" of (OMe) 3 -ivinyl.
Le rendement en par rapport à Γ aluminium introduit est de 67 % (obtenu sur trois lot : 2 dans un récipient inox et 1 dans un récipient polypropylène. Le potentiel zêta est de +37mV. The yield compared to Γ introduced aluminum is 67% (obtained on three lots: 2 in a stainless steel container and 1 in a polypropylene container.The zeta potential is + 37mV.

Claims

REVENDICATIONS
1 . Procédé pour préparer des particules creuses d ' aluminosilicates à forme sphérique de type allophane et hybrides à cœur comprenant au moins les étapes consistant à : 1. A process for preparing hollow particles of allophane-type spherical aluminosilicates and core hybrids comprising at least the steps of:
(a) disposer à température ambiante d'un milieu aqueux contenant au moins un précurseur d'aluminium et un alcoxyde de silicium dans un rapport molaire Ai/Si variant de 1 à 3,  (a) disposing at ambient temperature an aqueous medium containing at least one aluminum precursor and a silicon alkoxide in an Al / Si molar ratio ranging from 1 to 3,
(b) procéder sous agitation à l'hydrolyse alcaline dudit milieu avec addition progressive d'au moins une base dans un rapport molaire base/ Al de 2,3 à 3,  (b) stirring the alkaline hydrolysis of said medium with progressive addition of at least one base in a base / Al molar ratio of 2.3 to 3,
(c) maintenir à l'issue de l'addition de la totalité de ladite base, l'agitation à température ambiante jusqu'à obtention dudit milieu à l'état limpide et  (c) maintaining at the end of the addition of all of said base, stirring at room temperature until said medium is in a clear state and
(d) chauffer la solution obtenue à une température variant de 50 à 150 °C, pendant 2 à 8 jours,  (d) heating the resulting solution to a temperature ranging from 50 to 150 ° C for 2 to 8 days,
caractérisé en ce que l 'ensemble des étapes (b) à (d) est réalisé au sein d'un réacteur constitué d'un matériau inerte chimiquement vis-à-vis des réactifs et dudit aluminosilicate attendu.  characterized in that all of the steps (b) to (d) are performed in a reactor consisting of a material chemically inert with respect to the reagents and said expected aluminosilicate.
2. Procédé selon la revendication 1 dans lequel l'ensemble des étapes (a) à (d) est réalisé consécutivement au sein d'un même réacteur.  2. The method of claim 1 wherein all of the steps (a) to (d) is carried out consecutively within the same reactor.
3. Procédé selon l'une quelconque des revendications 1 ou 2 dans lequel le matériau constitutif dudit réacteur est dénué de groupe silanol et d'atome de fluor libre.  3. Method according to any one of claims 1 or 2 wherein the constituent material of said reactor is devoid of silanol group and free fluorine atom.
4. Procédé selon l'une quelconque des revendications 1 à 3 dans lequel le matériau constitutif du réacteur est choisi parmi l'inox, le polypropylène et des porcelaines inertes.  4. Method according to any one of claims 1 to 3 wherein the constituent material of the reactor is selected from stainless steel, polypropylene and inert porcelains.
5. Procédé selon l'une quelconque des revendications 1 à 4 dans lequel l 'alcoxyde de silicium est de formule RSi(OR')3 dans laquelle R' est un groupe alkyle en Cl à i et R un groupe hydrocarboné saturé ou insaturé en Ci à Ci. 5. Process according to any one of claims 1 to 4 wherein the silicon alkoxide is of formula RSi (OR ') 3 in which R' is a C1 to C4 alkyl group and R a saturated or unsaturated hydrocarbon group in Ci to Ci.
6. Procédé selon l'une quelconque des revendications 1 à 5 dans lequel F alcoxyde de silicium est le méthyltriméthoxysilanc (OCH3)3SiCH3 et/ou le vinyltriméthoxysilane (OCH3)3Si(CH=CH2). 6. Process according to any one of claims 1 to 5 wherein F silicon alkoxide is methyltrimethoxysilanc (OCH 3 ) 3 SiCH 3 and / or vinyltrimethoxysilane (OCH 3 ) 3Si (CH = CH 2 ).
7. Procédé selon l'une quelconque des revendications 1 à 6 dans lequel le précurseur de l'aluminium est choisi parmi le perchlorate d'aluminium A1(C!04)3, le nitrate d'aluminium AI(N03)3 ou le chlorure d'aluminium AICI3 et de préférence est le perchlorate d'aluminium A1(C104)3. 7. Method according to any one of claims 1 to 6 wherein the precursor of aluminum is selected from aluminum perchlorate A1 (C! 0 4 ) 3, nitrate aluminum Al (N0 3 ) 3 or aluminum chloride AICI3 and preferably is aluminum perchlorate A1 (C10 4 ) 3.
8. Procédé selon l'une des revendications 1 à 7 dans lequel le rapport molaire Ai/Si de l'étape (a) est compris entre 1,5 et 2,5.  8. Method according to one of claims 1 to 7 wherein the molar ratio Al / Si of step (a) is between 1.5 and 2.5.
9. . Procédé selon l'une des revendications 1 à 8 dans lequel la base ajoutée lors de l'étape (b) est choisie parmi l'hydroxyde de sodium, l'hydroxyde de potassium ou l'hydroxyde de lithium.  9.. Process according to one of claims 1 to 8 wherein the base added in step (b) is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide.
10. Procédé selon l'une des revendications 1 à 9 dans lequel l'ajout de la base lors de l'étape (b) est réalisé à un débit compris entre 50 et 300 mL.h"1 et, de préférence, entre 100 et 280 mL.h"1. 10. Method according to one of claims 1 to 9 wherein the addition of the base during step (b) is carried out at a flow rate of between 50 and 300 mL.h -1 and preferably between 100 and 280 mL.h -1 .
11. Procédé selon l'une des revendications 1 à 10 dans lequel l'étape (d) de chauffage est réalisée à une température comprise entre 70 et 150 °C, et de préférence entre 80 et 100 °C.  11. Method according to one of claims 1 to 10 wherein the step (d) of heating is carried out at a temperature between 70 and 150 ° C, and preferably between 80 and 100 ° C.
12. Procédé selon l'une des revendications 1 à 1 1, caractérisé en ce qu'il comprend consécutivement à l'étape (d), une étape (e) d'ultrafîltration.  12. Method according to one of claims 1 to 1 1, characterized in that it comprises consecutively in step (d), a step (e) ultrafltration.
13. Particules creuses d'aluminosilicate à forme sphérique, hybride de type allophane susceptibles d'être obtenues selon le procédé des revendications 1 à 12 comprenant simultanément une surface externe hydrophile et une surface interne hydrophobe à 100 %,  13. Allophane-type hybrid spherical aluminosilicate hollow particles obtainable according to the method of claims 1 to 12 simultaneously comprising a hydrophilic external surface and a 100% hydrophobic internal surface,
14. Utilisation des particules creuses d'aluminosilicates à forme sphérique obtenus selon les revendications 1 à 12 ou selon la revendication 13 à des fins de véhicule ou de piégeage d'au moins une molécule d'intérêt hydrophobe.  14. Use of hollow particles of spherical aluminosilicates obtained according to claims 1 to 12 or claim 13 for the purpose of vehicle or trapping at least one hydrophobic molecule of interest.
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