WO2009150358A1 - Solid material containing an active load and enabling easy access to said load - Google Patents

Solid material containing an active load and enabling easy access to said load Download PDF

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Publication number
WO2009150358A1
WO2009150358A1 PCT/FR2009/050919 FR2009050919W WO2009150358A1 WO 2009150358 A1 WO2009150358 A1 WO 2009150358A1 FR 2009050919 W FR2009050919 W FR 2009050919W WO 2009150358 A1 WO2009150358 A1 WO 2009150358A1
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Prior art keywords
polymer
polymers
substances
filler
poly
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PCT/FR2009/050919
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French (fr)
Inventor
Christian Gondard
Laurent Cauret
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Institut Superieur De Plasturgie D'alencon - Entreprises
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Priority to EP09761909A priority Critical patent/EP2285878A1/en
Publication of WO2009150358A1 publication Critical patent/WO2009150358A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • 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
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
    • 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
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28095—Shape or type of pores, voids, channels, ducts
    • B01J20/28097—Shape or type of pores, voids, channels, ducts being coated, filled or plugged with specific compounds
    • 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
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/308—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/311—Porosity, e.g. pore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • C08J2201/0462—Elimination of a polymeric phase using organic solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open

Definitions

  • the present invention relates to a solid material containing an active charge and allowing great accessibility to this load; it also relates to a method of manufacturing such a material.
  • It can be absorbent, reactive, insulating substances, etc.
  • these substances are dispersed, as charges, in the vicinity of the surface of the wall of the structure (tube for example) intended to contain or convey the product with which these charges must react.
  • the object of the present invention is to remedy these drawbacks and to do this, it proposes a solid material, containing an active charge and allowing great accessibility to this load; this material is characterized in that it comprises, on the one hand, a matrix of shapeable material, this matrix being microporous and with open pores, and, on the other hand, a particulate filler of which at least a part is housed in the free state in at least a portion of the pores of said matrix.
  • the matrix may for example be constituted by a thermoplastic (co) polymer, in which case the particulate filler is thermostable.
  • the material according to the invention has many advantages. It is light because of its microporous structure. It combines a considerable surface area due to the microporosity of the matrix (and possibly the charge) to an optimum accessibility to the particulate load, resulting from the pores open network of porosity; these pores, and thus the charge which is lodged there, are thus easily affected by any substance which one would seek to make act or react on this load.
  • the matrix of this material consists of a shapeable material, in particular a thermoplastic (co) polymer
  • this material in the form desired by conventional shaping techniques, such as extrusion, injection molding, thermoforming, for example, this shape can be that of a tube, a sheet, a container, ...
  • the particulate filler being in the free state, that is to say not completely coated by the matrix and not chemically bonded thereto, it is more easily accessible and therefore of optimum efficiency.
  • the particulate filler content of the material according to the invention may vary within wide limits. It will be a function of the nature of this load and the function it is intended to fill, but nevertheless limited to maintain sufficient mechanical strength of the material and allow the implementation of conventional shaping techniques mentioned above. Generally, the weight ratio of matrix to particulate filler is in the range of 0.1 to 4.
  • the filled material according to the invention preferably has a porosity corresponding to a density of 0.3 to 1.2, the matrix having for its part preferably a porosity corresponding to a density of 0.1 to 0.8.
  • the particle size of the particulate filler is preferably in the range of 1 to 200 ⁇ m.
  • the particulate filler is polar and the constituent material of the matrix is a non-polar (co) polymer or having a polarity lower than that of the charge.
  • said (co) polymer may for example be a polypropylene (PP) or a polyamide (PA).
  • the particulate filler may be non-polar and the constituent material of the matrix may be a polar (co) polymer.
  • the material according to the invention finds applications in the most diverse fields depending on the nature of the particulate filler.
  • this charge can be: an absorbent or adsorbent substance, in which case the material can be used for the collection of water, water vapor, gas, odors, dust, etc.,
  • the material can then be used in reactions involving a substrate sensitive to these properties, or - a substance with conduction properties or electrical, thermal or acoustic insulation, the material then finding applications in the electrical field, electronics, heat exchange and insulation.
  • a substrate sensitive to these properties or - a substance with conduction properties or electrical, thermal or acoustic insulation, the material then finding applications in the electrical field, electronics, heat exchange and insulation.
  • zeolites By way of non-limiting examples of absorbing or adsorbent substances, mention will be made of zeolites, CaO, CaSO 4 , silica gel and alginates.
  • the particulate filler may be constituted by the abovementioned substances themselves or by those substances supported by a particulate substrate.
  • the subject of the present invention is also a process for the manufacture of the above material in which the matrix consists of a (co) polymer, characterized in that it comprises the operations of: mixing in the molten state, under shear, two
  • thermoplastic (co) polymers and a particulate filler, these two (co) polymers being incompatible with each other and chosen to be divided into two co-continuous phases in the mixture obtained, the filler being for its part selected to be essentially distributed within the phase formed by one of the two (co) polymers, - possibly shaping said mixture to give it the desired shape, and - after solidification of said mixture, selectively removing at least partially the phase of polymer in which the charge is distributed.
  • the level of dispersion one in the other of the two (co) polymers is molecular order, that is to say with no nodules of one of the (co) polymers, dispersed in the other (co) polymer.
  • the weight ratio between the two (co) polymers used in the initial mixing operation may vary within wide limits; However, it is preferable that the initial concentration of polymer to be removed is as high as possible to obtain, after its selective removal, a matrix as porous as possible, the limit may however be the desired strength of the final material.
  • the weight ratio between the (co) polymer to be selectively removed and the other (co) polymer may be from 1 to 9, and preferably from 2 to 4.
  • the weight ratio of the (co) polymers / particulate filler will advantageously be from 1 to 9, and preferably from 2 to 4.
  • shear it is usually such that the shear rate is in the range of 10 to 300 s -1 .
  • (Co) polymers have different polarities, the charge having a polarity such that after the initial mixing operation, it is essentially found in the phase of the (co) polymer to be eliminated selectively.
  • the charge will be chosen to be polar.
  • the pair of (co) polymers may for example be polypropylene (PP) / poly (vinyl chloride) (PVC), polypropylene
  • PA poly (methyl methacrylate)
  • PMMA poly (methyl methacrylate)
  • the pair of (co) polymers can easily be determined by those skilled in the art on the basis of the following parameters: ratio of the respective viscosities of the (co) polymers: equal to or close to 1, and ratio of the respective surface tensions of the (co) polymers: equal to or close to 1.
  • the operation of shaping the molten mixture obtained according to the process may, for example, be an injection, extrusion, coextrusion or thermoforming operation.
  • bilayer tubular material could be obtained by eliminating the (co) polymer phase to be extracted, only over a certain thickness from the inner face of the tube.
  • the selective disposal operation can take different forms.
  • the aforementioned decomposition thus allows the creation of porosity without resorting to an extraction solvent.
  • the presently preferred form of removal is an extraction with an appropriate solvent capable of selectively dissolving the (co) polymer to be removed and having little or no effect on the other (co) polymer.
  • this solvent may be tetrahydrofuran and in the case where this (co) polymer is a PMMA, the solvent may be acetone.
  • the extraction can also be carried out using a supercritical fluid (in particular supercritical CO 2 ), the advantage of this technique over those using an organic solvent being that it can be exonerated any removal operation of the solvent after extraction, since this fluid (CO 2 ) is removed spontaneously by passage to the gas phase, without leaving a toxic residue.
  • a supercritical fluid in particular supercritical CO 2
  • molten ternary mixture consisting of 64% by weight of PVC, 16% by weight of PP and 20% by weight of zeolite.
  • This molten mixture is brought into the form of a plate (or film) by compression at 190 ° C. (maximum pressure: 9 tons).
  • the plate thus obtained once cooled, is introduced into an Erlenmeyer flask containing THF and extraction of the PVC phase is carried out at 23 ° C. with gentle stirring.
  • the extraction can alternatively be carried out by means of a Soxhlet extractor.
  • the zeolite has not been extracted and it will be noted that the porosity of the organic phase, that is to say of the PP matrix, is of the order of 80%.
  • the core morphology of the final material or outer surfaces thereof was observed by SEM (low pressure scanning electron microscopy) and microtomography.
  • the porosity of the matrix is regular, the average pore diameter is of the order of 21 ⁇ m (the mean distance between two nearest cavities being 35 ⁇ m) and the zeolite is retained in the pores of the matrix without being chemically bound thereto. .
  • the resulting molten ternary mixture consists of 56% weight of PMMA, 24% by weight of PP and 20% by weight of zeolite.
  • the PMMA is then extracted using the technique described in Example 1, but using acetone instead of THF.
  • the material obtained has a porosity corresponding to a density of 0.41, the average pore diameter is 28 ⁇ m and the average distance between two closest cavities is 38 ⁇ m, the matrix (PP) having a porosity of 30 ⁇ m. 70%.
  • Example 3 Preparation of an Absorbent Microporous Material from a PA / PMMA / Zeolite Ternary Mixture
  • the resulting ternary mixture consists of 42% PMMA, 28% PA and 30% zeolite.
  • Example 2 It was brought in the form of a plate (or a film) as in Example 1, but operating at 230 ° C. instead of 190 ° C. The PMMA phase is then extracted as in Example 2.
  • Example 4 Water Absorption Properties of the Materials Subject of Examples 1 to 3
  • thermogravimetric analysis This measurement is performed under an air atmosphere until a maximum shelf: isotherm at 40 0 C for 150 min in air at a rate of 451 / min under 50% humidity.
  • the tested materials have a moisture absorption kinetics equivalent to that of pure zeolite.

Abstract

The invention relates to a solid material containing an active load and enabling easy access to said load. The material comprises a matrix made of a microporous workable material with open pores, and a particular active load having at least a portion thereof contained in a free state in at least a portion of the pores of said matrix. The invention also relates to a method for making such a material.

Description

« Matériau solide contenant une charge active et permettant une grande facilité d'accès à cette charge ». "Solid material containing an active charge and allowing great ease of access to this charge".
La présente invention a pour objet un matériau solide, contenant une charge active et permettant une grande accessibilité à cette charge ; elle a également pour objet un procédé de fabrication d'un tel matériau.The present invention relates to a solid material containing an active charge and allowing great accessibility to this load; it also relates to a method of manufacturing such a material.
On utilise dans de nombreux domaines (industriel, médical, cosmétique, agroalimentaire, ...) , des substances dotées de propriétés diverses (physiques, chimiques, biologiques, ...) pour effectuer des tâches variées.In many fields (industrial, medical, cosmetic, food, ...), substances with various properties (physical, chemical, biological, ...) are used to perform various tasks.
Il peut s'agir de substances absorbantes, réactives, isolantes, etc.It can be absorbent, reactive, insulating substances, etc.
Celles-ci sont généralement utilisées sous une forme particulaire et selon leur nature, peuvent être fixées ou non sur un support pour en faciliter la mise en œuvre.These are generally used in particulate form and depending on their nature, can be fixed or not on a support to facilitate implementation.
Dans certaines applications, il est particulièrement avantageux que ces substances soient dispersées, en tant que charges, au voisinage de la surface de la paroi de la structure (tube par exemple) destinée à contenir ou véhiculer le produit avec lequel doivent réagir ces charges.In some applications, it is particularly advantageous that these substances are dispersed, as charges, in the vicinity of the surface of the wall of the structure (tube for example) intended to contain or convey the product with which these charges must react.
Les solutions de ce type proposées à ce jour sont peu satisfaisantes dans la mesure où ledit produit ne parvient que lentement et/ou de manière limitée en contact avec la charge en raison de la faible perméabilité, à ce produit, de ladite paroi.The solutions of this type proposed to date are unsatisfactory insofar as said product reaches only slowly and / or in a limited way in contact with the load because of the low permeability, to this product, of said wall.
Le but de la présente invention est de remédier à ces inconvénients et pour ce faire, elle propose un matériau solide, contenant une charge active et permettant une grande accessibilité à cette charge ; ce matériau est caractérisé en ce qu'il comprend d'une part une matrice en matière façonnable, cette matrice étant microporeuse et à pores ouverts, et d'autre part une charge particulaire dont une partie au moins est logée à l'état libre dans au moins une partie des pores de ladite matrice.The object of the present invention is to remedy these drawbacks and to do this, it proposes a solid material, containing an active charge and allowing great accessibility to this load; this material is characterized in that it comprises, on the one hand, a matrix of shapeable material, this matrix being microporous and with open pores, and, on the other hand, a particulate filler of which at least a part is housed in the free state in at least a portion of the pores of said matrix.
On notera que la matrice peut par exemple être constituée par un (co) polymère thermoplastique, auquel cas la charge particulaire est thermostable.Note that the matrix may for example be constituted by a thermoplastic (co) polymer, in which case the particulate filler is thermostable.
Le matériau selon l'invention présente de multiples avantages. II est léger en raison de sa structure microporeuse. Il allie une surface spécifique considérable due à la microporosité de la matrice (et éventuellement de la charge) à une accessibilité optimum à la charge particulaire, résultant du réseau de pores ouverts de la porosité ; ces pores, et donc la charge qui y est logée, est donc aisément atteinte par toute substance que l'on chercherait à faire agir ou réagir sur cette charge.The material according to the invention has many advantages. It is light because of its microporous structure. It combines a considerable surface area due to the microporosity of the matrix (and possibly the charge) to an optimum accessibility to the particulate load, resulting from the pores open network of porosity; these pores, and thus the charge which is lodged there, are thus easily affected by any substance which one would seek to make act or react on this load.
La matrice de ce matériau étant constituée par une matière façonnable, notamment par un (co) polymère thermoplastique, il est possible de produire ce matériau sous la forme voulue par les techniques de façonnage classiques, telles que l'extrusion, l'injection, le thermoformage, par exemple, cette forme pouvant être celle d'un tube, d'une feuille, d'un récipient,...Since the matrix of this material consists of a shapeable material, in particular a thermoplastic (co) polymer, it is possible to produce this material in the form desired by conventional shaping techniques, such as extrusion, injection molding, thermoforming, for example, this shape can be that of a tube, a sheet, a container, ...
De plus, la charge particulaire étant à l'état libre, c'est-à- dire non enrobée totalement par la matrice et non liée chimiquement à cette dernière, elle est plus aisément accessible et donc d'une efficacité optimale.In addition, the particulate filler being in the free state, that is to say not completely coated by the matrix and not chemically bonded thereto, it is more easily accessible and therefore of optimum efficiency.
La teneur en charge particulaire du matériau selon l'invention peut varier dans de larges limites. Elle sera fonction de la nature de cette charge et de la fonction qu'elle est destinée à remplir, mais néanmoins limitée pour conserver une résistance mécanique suffisante du matériau et permettre la mise en œuvre des techniques classiques de façonnage susmentionnées . Généralement, le rapport en poids matrice/charge particulaire est situé dans la plage de 0,1 à 4.The particulate filler content of the material according to the invention may vary within wide limits. It will be a function of the nature of this load and the function it is intended to fill, but nevertheless limited to maintain sufficient mechanical strength of the material and allow the implementation of conventional shaping techniques mentioned above. Generally, the weight ratio of matrix to particulate filler is in the range of 0.1 to 4.
Le matériau chargé selon l'invention présente de préférence une porosité correspondant à une densité de 0,3 a 1,2, la matrice ayant pour sa part de préférence une porosité correspondant à une densité de 0,1 à 0,8.The filled material according to the invention preferably has a porosity corresponding to a density of 0.3 to 1.2, the matrix having for its part preferably a porosity corresponding to a density of 0.1 to 0.8.
Par ailleurs, la granulométrie de la charge particulaire est de préférence située dans la plage de 1 à 200 μm.Furthermore, the particle size of the particulate filler is preferably in the range of 1 to 200 μm.
Selon un mode de réalisation de l'invention, la charge particulaire est polaire et la matière constitutive de la matrice est un (co) polymère non polaire ou présentant une polarité inférieure à celle de la charge. Dans ce cas, ledit (co) polymère peut être par exemple un polypropylène (PP) ou un polyamide (PA) .According to one embodiment of the invention, the particulate filler is polar and the constituent material of the matrix is a non-polar (co) polymer or having a polarity lower than that of the charge. In this case, said (co) polymer may for example be a polypropylene (PP) or a polyamide (PA).
En variante, la charge particulaire peut être non polaire et la matière constitutive de la matrice un (co) polymère polaire. Le matériau selon l'invention trouve des applications dans les domaines les plus divers selon la nature de la charge particulaire. Ainsi, cette charge peut être : une substance absorbante ou adsorbante, auquel cas le matériau peut être utilisé pour le captage d' eau, de vapeur d'eau, de gaz, d'odeurs, de poussières, etc.,Alternatively, the particulate filler may be non-polar and the constituent material of the matrix may be a polar (co) polymer. The material according to the invention finds applications in the most diverse fields depending on the nature of the particulate filler. Thus, this charge can be: an absorbent or adsorbent substance, in which case the material can be used for the collection of water, water vapor, gas, odors, dust, etc.,
- une substance dotée de propriétés chimiques ou biologiques, le matériau pouvant alors être mis en œuvre dans des réactions faisant intervenir un substrat sensible à ces propriétés, ou - une substance dotée de propriétés de conduction ou d'isolation électrique, thermique ou acoustique, le matériau trouvant alors des applications dans le domaine électrique, électronique, d'échange thermique et de l'isolation. A titre d'exemples non limitatifs de substances absorbantes ou adsorbantes, on citera les Zéolithes, le CaO, le CaSO4, le gel de silice et les alginates.- a substance with chemical or biological properties, the material can then be used in reactions involving a substrate sensitive to these properties, or - a substance with conduction properties or electrical, thermal or acoustic insulation, the material then finding applications in the electrical field, electronics, heat exchange and insulation. By way of non-limiting examples of absorbing or adsorbent substances, mention will be made of zeolites, CaO, CaSO 4 , silica gel and alginates.
Des exemples de substances dotées de propriétés chimiques ou biologiques sont la poudre de fer (capteur de l'oxygène), les enzymes, les catalyseurs, les électrolytes, les bactéries. On notera que la charge particulaire pourra être constituée par les substances susvisées elles-mêmes ou par ces substances supportées par un substrat particulaire.Examples of substances with chemical or biological properties are iron powder (oxygen sensor), enzymes, catalysts, electrolytes, bacteria. It will be noted that the particulate filler may be constituted by the abovementioned substances themselves or by those substances supported by a particulate substrate.
La présente invention a par ailleurs pour objet un procédé de fabrication du matériau ci-dessus dans lequel la matrice est constituée d'un (co) polymère, caractérisé en ce qu'il comprend les opérations consistant à : mélanger à l'état fondu, sous cisaillement, deuxThe subject of the present invention is also a process for the manufacture of the above material in which the matrix consists of a (co) polymer, characterized in that it comprises the operations of: mixing in the molten state, under shear, two
(co) polymères thermoplastiques et une charge particulaire, ces deux (co) polymères étant incompatibles entre eux et choisis pour être répartis en deux phases co-continues dans le mélange obtenu, la charge étant pour sa part sélectionnée pour être répartie pour l'essentiel au sein de la phase constituée par l'un des deux (co) polymères, - façonner éventuellement ledit mélange pour lui conférer la forme souhaitée, et - après solidification dudit mélange, éliminer sélectivement au moins partiellement la phase de polymère dans laquelle est répartie la charge.thermoplastic (co) polymers and a particulate filler, these two (co) polymers being incompatible with each other and chosen to be divided into two co-continuous phases in the mixture obtained, the filler being for its part selected to be essentially distributed within the phase formed by one of the two (co) polymers, - possibly shaping said mixture to give it the desired shape, and - after solidification of said mixture, selectively removing at least partially the phase of polymer in which the charge is distributed.
Comme cela est parfaitement connu dans le domaine des polymères, dans un mélange de deux (co) polymères incompatibles répartis en deux phases co-continues, le niveau de dispersion l'un dans l'autre des deux (co) polymères est de l'ordre moléculaire, c'est-à-dire avec absence de nodules de l'un des (co) polymères, dispersés dans l'autre (co) polymère .As is well known in the field of polymers, in a mixture of two incompatible (co) polymers divided into two co-continuous phases, the level of dispersion one in the other of the two (co) polymers is molecular order, that is to say with no nodules of one of the (co) polymers, dispersed in the other (co) polymer.
Il s'ensuit que par élimination sélective de l'une des phases de (co) polymère, il y a formation d'une matrice polymère microporeuse à pores ouverts, la charge restant logée au moins partiellement dans une partie au moins des pores ainsi formés.It follows that by selectively removing one of the (co) polymer phases, an open pored microporous polymer matrix is formed, the charge remaining housed at least partially in at least a portion of the pores thus formed. .
Le rapport pondéral entre les deux (co) polymères mis en œuvre dans l'opération de mélange initiale, peut varier dans de larges limites ; il est cependant préférable que la concentration initiale en polymère destiné à être éliminé soit la plus élevée possible pour obtenir, après son élimination sélective, une matrice la plus poreuse possible, la limite pouvant cependant être la résistance mécanique souhaitée pour le matériau final. Ainsi, le rapport pondéral entre le (co) polymère destiné à être éliminé sélectivement et l'autre (co) polymère peut être de 1 à 9, et de préférence de 2 à 4.The weight ratio between the two (co) polymers used in the initial mixing operation may vary within wide limits; However, it is preferable that the initial concentration of polymer to be removed is as high as possible to obtain, after its selective removal, a matrix as porous as possible, the limit may however be the desired strength of the final material. Thus, the weight ratio between the (co) polymer to be selectively removed and the other (co) polymer may be from 1 to 9, and preferably from 2 to 4.
Le rapport pondéral somme des (co) polymères / charge particulaire, sera avantageusement de 1 à 9, et de préférence de 2 à 4.The weight ratio of the (co) polymers / particulate filler will advantageously be from 1 to 9, and preferably from 2 to 4.
Quant au cisaillement, il est habituellement tel que le taux de cisaillement soit situé dans la plage de 10 à 300 s"1.As for shear, it is usually such that the shear rate is in the range of 10 to 300 s -1 .
Selon un mode réalisation du procédé selon l'invention, lesAccording to one embodiment of the method according to the invention,
(co) polymères ont des polarités différentes, la charge ayant pour sa part une polarité telle qu'après l'opération de mélange initiale, elle se retrouve pour l'essentiel dans la phase du (co) polymère destiné à être éliminé sélectivement. Ainsi, par exemple, si le (co) polymère à éliminer sélectivement est polaire, le (co) polymère restant étant non polaire, la charge sera choisie pour être polaire.(Co) polymers have different polarities, the charge having a polarity such that after the initial mixing operation, it is essentially found in the phase of the (co) polymer to be eliminated selectively. Thus, for example, if the (co) polymer to be selectively removed is polar, the remaining (co) polymer being non-polar, the charge will be chosen to be polar.
Le couple de (co) polymères peut par exemple être polypropylène (PP) /poly (chlorure de vinyle) (PVC), polypropylèneThe pair of (co) polymers may for example be polypropylene (PP) / poly (vinyl chloride) (PVC), polypropylene
(PP) /poly (méthacrylate de méthyle) (PMMA) ou polyamide(PP) / poly (methyl methacrylate) (PMMA) or polyamide
(PA) /poly (méthacrylate de méthyle) (PMMA), PP étant un polymère non polaire et PA, PVC et PMMA étant des polymères polaires.(PA) / poly (methyl methacrylate) (PMMA), PP being a nonpolar polymer and PA, PVC and PMMA being polar polymers.
En fait, le couple de (co) polymères peut aisément être déterminé par l'homme de métier sur la base des paramètres suivants : rapport des viscosités respectives des (co) polymères : égal ou proche de 1, et rapport des tensions superficielles respectives des (co) polymères : égal ou proche de 1.In fact, the pair of (co) polymers can easily be determined by those skilled in the art on the basis of the following parameters: ratio of the respective viscosities of the (co) polymers: equal to or close to 1, and ratio of the respective surface tensions of the (co) polymers: equal to or close to 1.
L'opération consistant à façonner le mélange fondu obtenu selon le procédé, peut par exemple être une opération d'injection, d'extrusion, de co-extrusion ou de thermofaçonnage.The operation of shaping the molten mixture obtained according to the process may, for example, be an injection, extrusion, coextrusion or thermoforming operation.
Il peut notamment s'agir d'une co-extrusion dudit mélange fondu avec un (co) polymère non poreux pouvant être de même nature chimique que le (co) polymère non sélectivement éliminé dans le procédé susmentionné .It can in particular be a coextrusion of said molten mixture with a nonporous (co) polymer that can be of the same chemical nature as the (co) polymer not selectively removed in the aforementioned process.
On peut ainsi obtenir par exemple un tube dont la partie interne est constituée par le matériau microporeux selon l'invention et dont la résistance mécanique globale peut être élevée en raison de la partie tubulaire fortement résistante entourant la partie tubulaire interne microporeuse relativement plus fragile.It is thus possible to obtain, for example, a tube whose inner part is constituted by the microporous material according to the invention and whose overall mechanical strength can be high because of the highly resistant tubular part surrounding the relatively fragile microporous inner tubular part.
On ajoutera que le même type de matériau tubulaire bicouche pourrait être obtenu par une élimination de la phase (co) polymère à extraire, uniquement sur une certaine épaisseur à partir de la face interne du tube.It will be added that the same type of bilayer tubular material could be obtained by eliminating the (co) polymer phase to be extracted, only over a certain thickness from the inner face of the tube.
L'opération d'élimination sélective peut prendre différentes formes .The selective disposal operation can take different forms.
Il peut s'agir d'une décomposition du (co) polymère à éliminer, par exemple une décomposition thermique (catalysée ou non) ou une décomposition chimique mettant en œuvre un agent de décomposition approprié dont la nature est fonction de la composition chimique dudit (co) polymère .It may be a decomposition of the (co) polymer to be removed, for example a thermal decomposition (catalyzed or not) or a chemical decomposition using a decomposition agent the nature of which is a function of the chemical composition of said (co) polymer.
Ce type de décomposition conduit à une dépolymérisation du (co) polymère concerné. Ainsi, à partir de 1800C, le PMMA va se dépolymériser en libérant le monomère de départ, le méthacrylate de méthyle, aisément éliminable .This type of decomposition leads to depolymerization of the (co) polymer concerned. Thus, from 180 0 C, the PMMA will depolymerize by releasing the starting monomer, methyl methacrylate, easily removed.
La décomposition susmentionnée permet donc la création d'une porosité sans avoir recours à un solvant d'extraction. La forme d'élimination actuellement préférée est toutefois une extraction par un solvant approprié apte à dissoudre sélectivement le (co) polymère à éliminer et n'affectant pas ou que faiblement l'autre (co) polymère .The aforementioned decomposition thus allows the creation of porosity without resorting to an extraction solvent. The presently preferred form of removal, however, is an extraction with an appropriate solvent capable of selectively dissolving the (co) polymer to be removed and having little or no effect on the other (co) polymer.
Ainsi, dans le cas où le (co) polymère à éliminer est constitué par un PVC, ce solvant peut être le tétrahydrofurane et dans le cas où ce (co) polymère est un PMMA, le solvant peut être l'acétone.Thus, in the case where the (co) polymer to be removed consists of PVC, this solvent may be tetrahydrofuran and in the case where this (co) polymer is a PMMA, the solvent may be acetone.
En variante, l'extraction peut également être réalisée par mise en œuvre d'un fluide supercritique (notamment le CO2 supercritique), l'avantage de cette technique par rapport à celles faisant appel à un solvant organique, étant de pouvoir s'exonérer d'une quelconque opération d'élimination du solvant après l'extraction, puisque ce fluide (CO2) est éliminé spontanément par passage à la phase gazeuse, sans laisser de résidu toxique.As a variant, the extraction can also be carried out using a supercritical fluid (in particular supercritical CO 2 ), the advantage of this technique over those using an organic solvent being that it can be exonerated any removal operation of the solvent after extraction, since this fluid (CO 2 ) is removed spontaneously by passage to the gas phase, without leaving a toxic residue.
La présente invention est illustrée ci-après par quelques exemples non limitatifs de préparation du matériau selon 1' invention.The present invention is illustrated hereinafter by some nonlimiting examples of preparation of the material according to the invention.
Exemple 1 : Préparation d'un matériau microporeux absorbant à partir d'un mélange ternaire PP/PVC/Zéolithe.Example 1 Preparation of an absorbent microporous material from a ternary mixture PP / PVC / Zeolite
41,6g de PVC, 10,4g de PP et 13g de Zéolithe (granulométrie : 1 à 200 μm) sont mélangés dans un mélangeur du type Rhéocord Haake® 90, à une température d'environ 19O0C, à une vitesse des rotors d'environ 40 tours/min et pendant environ 5 min.41.6 g of PVC, 10.4 g of PP and 13 g of zeolite (particle size: 1 to 200 μm) are mixed in a Rhéocord Haake® 90 type mixer, at a temperature of about 190 ° C., at a speed of the rotors about 40 rpm and about 5 min.
Il en résulte un mélange ternaire fondu constitué par 64% en poids de PVC, 16% en poids de PP et 20% en poids de Zéolithe. Ce mélange fondu est amené sous forme de plaque (ou de film) par compression à 190°C (pression maximale : 9 tonnes) . La plaque ainsi obtenue une fois refroidie, est introduite dans un erlenmeyer contenant du THF et une extraction de la phase PVC est réalisée à 23°C sous faible agitation.This results in a molten ternary mixture consisting of 64% by weight of PVC, 16% by weight of PP and 20% by weight of zeolite. This molten mixture is brought into the form of a plate (or film) by compression at 190 ° C. (maximum pressure: 9 tons). The plate thus obtained once cooled, is introduced into an Erlenmeyer flask containing THF and extraction of the PVC phase is carried out at 23 ° C. with gentle stirring.
L'extraction peut en variante être réalisée au moyen d'un extracteur de Soxhlet.The extraction can alternatively be carried out by means of a Soxhlet extractor.
Après extraction du PVC par le THF, les analyses effectuées sur le matériau final montre que le PVC a été extrait en totalité ; on notera cependant que les caractéristiques physico-chimiques du PP différent faiblement de celles du PP pur, en raison de la forte porosité du matériau, qui correspond à une densité de 0,37.After extraction of the PVC with THF, the analyzes carried out on the final material shows that the PVC was extracted in full; It should be noted, however, that the physico-chemical characteristics of PP differ slightly from those of pure PP, due to the high porosity of the material, which corresponds to a density of 0.37.
On soulignera que la Zéolithe n'a pas été extraite et on notera que la porosité de la phase organique, c'est-à-dire de la matrice de PP, est de l'ordre de 80%.It should be noted that the zeolite has not been extracted and it will be noted that the porosity of the organic phase, that is to say of the PP matrix, is of the order of 80%.
La morphologie à cœur du matériau final ou des surfaces externes de celui-ci a été observée par des analyses MEB (microscopie électronique à balayage à faible pression) et par microtomographie .The core morphology of the final material or outer surfaces thereof was observed by SEM (low pressure scanning electron microscopy) and microtomography.
La porosité de la matrice est régulière, le diamètre moyen des pores est de l'ordre de 21μm (la distance moyenne entre deux cavités les plus proches étant de 35μm) et la Zéolithe est retenue dans les pores de la matrice sans y être liée chimiquement.The porosity of the matrix is regular, the average pore diameter is of the order of 21 μm (the mean distance between two nearest cavities being 35 μm) and the zeolite is retained in the pores of the matrix without being chemically bound thereto. .
Exemple 2 : Préparation d'un matériau microporeux absorbant a partir d'un mélange ternaire PP/PMMA/Zéolithe.Example 2 Preparation of an Absorbent Microporous Material from a PP / PMMA / Zeolite Ternary Mixture
38,1g de PMMA, 16,3g de PP et 13,6g de Zéolithe (granulométrie : 1 à 200μm) sont mélangés comme dans l'Exemple 1, si ce n'est que l'on opère à 2200C au lieu de 1900C.38.1 g of PMMA, 16.3 g of PP and 13.6 g of zeolite (particle size: 1 to 200 μm) are mixed as in Example 1, except that the operation is carried out at 220 ° C. instead of 190 0 C.
Le mélange ternaire fondu résultant est constitué de 56% un poids de PMMA, 24% en poids de PP et 20% en poids de Zéolithe.The resulting molten ternary mixture consists of 56% weight of PMMA, 24% by weight of PP and 20% by weight of zeolite.
Il est amené sous la forme d'une plaque (ou d'un film) comme dans l'Exemple 1, mais en travaillant à 22O0C en lieu de 190°C.It is brought in the form of a plate (or a film) as in Example 1, but working at 22O 0 C instead of 190 ° C.
On procède ensuite à l'extraction du PMMA selon la technique décrite dans l'Exemple 1, mais en utilisant de l'acétone en lieu et place du THF.The PMMA is then extracted using the technique described in Example 1, but using acetone instead of THF.
Le matériau obtenu a une porosité correspondant à une densité de 0,41, le diamètre moyen des pores est de 28μm et la distance moyenne entre deux cavités les plus proches est de 38μm, la matrice (PP) ayant pour sa part une porosité de l'ordre de 70%. Exemple 3 : Préparation d'un matériau microporeux absorbant à partir d'un mélange ternaire PA/PMMA/Zéolithe .The material obtained has a porosity corresponding to a density of 0.41, the average pore diameter is 28 μm and the average distance between two closest cavities is 38 μm, the matrix (PP) having a porosity of 30 μm. 70%. Example 3 Preparation of an Absorbent Microporous Material from a PA / PMMA / Zeolite Ternary Mixture
27,3g de PMMA, 18,2g de PA et 19,5g de Zéolithe (granulométrie : 1 a 200μm) sont mélangés comme dans l'Exemple 1, si ce n'est que le mélange est réalisé à 2300C au lieu de 1900C.27.3 g of PMMA, 18.2 g of PA and 19.5 g of zeolite (particle size: 1 to 200 μm) are mixed as in Example 1, except that the mixing is carried out at 230 ° C. instead of 190 0 C.
Le mélange ternaire résultant est constitué de 42% de PMMA, de 28% de PA et de 30% de Zéolithe.The resulting ternary mixture consists of 42% PMMA, 28% PA and 30% zeolite.
Il a été amené sous la forme d'une plaque (ou d'un film) comme dans l'Exemple 1, mais en opérant à 2300C au lieu de 1900C. La phase PMMA est ensuite extraite comme dans l'Exemple 2.It was brought in the form of a plate (or a film) as in Example 1, but operating at 230 ° C. instead of 190 ° C. The PMMA phase is then extracted as in Example 2.
Le matériau obtenu a une forte porosité correspondant à une densité de 0,51, le diamètre moyen des pores de ce matériau étant de 30μm et la distance moyenne entre deux cavités les plus proches de ce matériau est de 31μm. Exemple 4 : Propriétés d'absorption d'eau des matériaux objet des Exemples 1 à 3.The material obtained has a high porosity corresponding to a density of 0.51, the average pore diameter of this material being 30 μm and the average distance between two cavities closest to this material is 31 μm. Example 4: Water Absorption Properties of the Materials Subject of Examples 1 to 3
La technique utilisée pour mesurer l'absorption d'humidité de ces matériaux, est l'analyse thermogravimétrique (ATG) . Cette mesure est effectuée sous atmosphère d'air jusqu'à obtention d'un plateau maximum : isotherme à 400C pendant 150 min sous air à raison de 451/min sous 50% d'hygrométrie.The technique used to measure the moisture absorption of these materials is thermogravimetric analysis (TGA). This measurement is performed under an air atmosphere until a maximum shelf: isotherm at 40 0 C for 150 min in air at a rate of 451 / min under 50% humidity.
On peut ainsi tracer pour chaque matériau, la courbe de la masse d'eau absorbée par rapport au poids du matériau (en %) en fonction du temps (en minutes) . On a représenté sur la figure unique annexée les courbes obtenues pour les matériaux suivants :It is thus possible to plot for each material, the curve of the mass of absorbed water relative to the weight of the material (in%) as a function of time (in minutes). The attached single figure shows the curves obtained for the following materials:
O matériau obtenu à partir du mélange ternaire PP/PVC/Zéolithe où PP/PVC = 20/80 et (PP + PVC) / Zéolithe = 70/30. x matériau obtenu à partir du mélange ternaire PMMA/PP/Zéolithe où PMMA/PP = 70/30 et (PMMA + PP) /Zéolithe = 70/30. + matériau selon l'exemple 3.O material obtained from the ternary mixture PP / PVC / Zeolite where PP / PVC = 20/80 and (PP + PVC) / zeolite = 70/30. x material obtained from the ternary mixture PMMA / PP / zeolite where PMMA / PP = 70/30 and (PMMA + PP) / zeolite = 70/30. + material according to Example 3.
Les matériaux testés ont une cinétique d'absorption d'humidité équivalente à celle de la Zéolithe pure.The tested materials have a moisture absorption kinetics equivalent to that of pure zeolite.
Par ailleurs, ces mêmes matériaux présentent des vitesses d'absorption d'humidité très supérieures à celles des produits existants actuellement sur le marché et dont il a été fait mention au début de cette description. Moreover, these same materials have moisture absorption rates much higher than existing products currently on the market and which was mentioned at the beginning of this description.

Claims

REVENDICATIONS
1. Procédé de fabrication d'un matériau solide comprenant une matrice en (co) polymère thermoplastique, microporeuse et à pores ouverts, et une charge active particulaire thermostable dont une partie au moins est logée à l'état libre dans au moins une partie des pores de ladite matrice, caractérisé en ce qu'il comprend les étapes consistant à : mélanger à l'état fondu, sous cisaillement, deux (co) polymères thermoplastiques et une charge active particulaire thermostable, ces deux (co) polymères étant incompatibles entre eux et choisis pour être répartis en deux phases co-continues dans le mélange obtenu, la charge étant pour sa part sélectionnée pour être répartie pour l'essentiel au sein de la phase constituée par l'un des deux (co) polymères, façonner éventuellement ledit mélange pour lui conférer la forme souhaitée, etA method of manufacturing a solid material comprising a microporous, open-pored thermoplastic (co) polymer matrix, and a heat-stable particulate active filler of which at least a portion is free-housed in at least a portion of pore of said matrix, characterized in that it comprises the steps of: melt blending, under shear, two thermoplastic (co) polymers and a thermostable particulate active filler, these two (co) polymers being incompatible with one another and chosen to be divided into two co-continuous phases in the mixture obtained, the charge being for its part selected to be essentially distributed within the phase constituted by one of the two (co) polymers, possibly forming said mixture to give it the desired shape, and
- après solidification dudit mélange, éliminer sélectivement au moins partiellement la phase de (co) polymère dans laquelle est répartie la charge.after solidification of said mixture, selectively removing at least partially the (co) polymer phase in which the charge is distributed.
2. Procédé selon la revendication 1, caractérisé en ce que le rapport pondéral (co) polymère destiné à être éliminé sélectivement/ (co) polymère non éliminé est situé dans la plage de 1 à 9. 2. Method according to claim 1, characterized in that the weight ratio (co) polymer to be eliminated selectively / (co) polymer not eliminated is in the range of 1 to 9.
3. Procédé selon la revendication 1 ou 2 , caractérisé en ce que le rapport pondéral somme des (co) polymères/charge particulaire est situé dans la plage de 1 à 9.3. Method according to claim 1 or 2, characterized in that the sum weight ratio of (co) polymers / particulate filler is in the range of 1 to 9.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les (co) polymères ont des polarités différentes, la charge ayant une polarité telle qu'après l'opération de mélange initial, elle se retrouve pour l'essentiel répartie au sein de la phase du (co) polymère destiné à être éliminé.4. Method according to any one of the preceding claims, characterized in that the (co) polymers have different polarities, the charge having a polarity such that after the initial mixing operation, it is found for the most part distributed within the (co) polymer phase to be eliminated.
5. Procédé selon la revendication 4, caractérisé en ce que la charge particulaire est polaire et le (co) polymère non éliminé est non polaire ou présente une polarité inférieure à celle de ladite charge . 5. Method according to claim 4, characterized in that the particulate filler is polar and the non-eliminated (co) polymer is nonpolar or has a polarity lower than that of said filler.
6. Procédé selon la revendication 4, caractérisé en ce que la charge particulaire est non polaire et le (co) polymère non éliminé est polaire.6. Method according to claim 4, characterized in that the particulate filler is non-polar and the non-eliminated (co) polymer is polar.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le couple des (co) polymères est choisi dans le groupe constitué par les couples polypropylène (PP) /poly (chlorure de vinyle) (PVC), polypropylène (PP) /poly (méthacrylate de méthyle) (PMMA) et polyamide (PA)/ poly (méthacrylate de méthyle) (PMMA) . 7. Method according to any one of the preceding claims, characterized in that the pair of (co) polymers is selected from the group consisting of polypropylene (PP) / poly (vinyl chloride) (PVC), polypropylene (PP) ) / poly (methyl methacrylate) (PMMA) and polyamide (PA) / poly (methyl methacrylate) (PMMA).
8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la charge comprend ou est constituée d'une substance choisie dans le groupe constitué par les substances absorbantes ou adsorbantes, les substances dotées de propriétés chimiques, les substances dotées de propriétés biologiques, les substances dotées de propriétés de conduction ou d'isolation électrique, les substances dotées de propriétés thermiques et les substances dotées de propriétés acoustiques.8. Method according to any one of the preceding claims, characterized in that the filler comprises or consists of a substance selected from the group consisting of absorbing or adsorbent substances, substances with chemical properties, substances with properties biological substances, substances with conductive properties or electrical insulation, substances with thermal properties and substances with acoustic properties.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'opération d'élimination sélective est choisie dans le groupe constitué par une décomposition thermique, une décomposition chimique et une extraction par un solvant approprié.9. Process according to any of the preceding claims, characterized in that the selective removal operation is selected from the group consisting of thermal decomposition, chemical decomposition and extraction with a suitable solvent.
10. Procédé selon la revendication 9 dans lequel l'élimination sélective est constituée par une extraction par un solvant, caractérisé en ce que le couple (co) polymère à éliminer/solvant est constitué par poly (chlorure de vinyle) (PVC) /tétrahydrofurane (THF) ou poly (méthacrylate de méthyle) (PMMA) /acétone . 10. The method of claim 9 wherein the selective removal is constituted by extraction with a solvent, characterized in that the (co) polymer to eliminate / solvent pair consists of poly (vinyl chloride) (PVC) / tetrahydrofuran (THF) or poly (methyl methacrylate) (PMMA) / acetone.
PCT/FR2009/050919 2008-05-19 2009-05-18 Solid material containing an active load and enabling easy access to said load WO2009150358A1 (en)

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FR3038240B1 (en) * 2015-07-02 2019-08-09 Arkema France ARTICLE COMPRISING ZEOLITIC PARTICLES CONNECTED WITH A RESIN

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FR2931157A1 (en) 2009-11-20
FR2931157B1 (en) 2011-02-18

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