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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.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Analytical Chemistry (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2008
  • 2008-05-19 FR FR0853231A patent/FR2931157B1/fr not_active Expired - Fee Related
• 2009
  • 2009-05-18 WO PCT/FR2009/050919 patent/WO2009150358A1/fr active Application Filing
  • 2009-05-18 EP EP09761909A patent/EP2285878A1/de not_active Withdrawn

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