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
  • B01J20/02—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
  • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
• • 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
  • B01J20/26—Synthetic macromolecular compounds
  • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes

Definitions

• the invention relates to the field of zeolitic adsorbents, more particularly that of composite materials comprising zeolitic adsorbents, and in particular composite materials comprising zeolitic adsorbents dispersed in organic matrices.
• the role of the polymer matrix is then limited to that of an agglomeration binder for shaping the zeolite into an adsorbent article, for example in the form of adsorbent strips, molded or extruded parts, gaskets.
• Patent application FR2939330 describes a zeolitic adsorbent material with an organic binder containing from 65% to 99% of zeolite in the form of crystals which are incorporated directly into the polymer matrix.
• the technique of incorporating the crystals into the polymer is mixing in a twin-screw extruder. This technique requires a relatively large amount of energy and shows the low compatibility between the zeolite and the organic matrix.
• zeolites Due to this "incompatibility" generally observed between mineral zeolites and organic polymer matrices, zeolites are generally only incorporated at a relatively low content in polymer matrices. This is one of the reasons why zeolite crystals are often used as a filler material, for example in flame-retardant compositions, as for example described in documents EP0629678, FR3062390 and EP1375594). The zeolite content by weight in the material then generally does not exceed 10%.
• Zeolites can also serve as a carrier agent for the active principle, for example amines capable of controlling the crosslinking of a composition.
• Crosslinkable polymer based on a polymer having groups of maleic anhydride type (US Pat. No. 5,792,816). The zeolite content is again generally less than 20%.
• zeolites are used at low content, for example to provide occasional dehydration properties, for example during the manufacture of polyurethanes, to eliminate traces of water in formulations of polyols and isocyanates and to avoid thus the formation of bubbles in the polymer, or else to trap traces of residual monomers in the polymer material.
• the zeolite confers particular properties on the composition, as is for example the case in document FR2811304, where fungistatic packaging based on polyolefins or polystyrenes containing up to 30% zeolite crystals partially exchanged for silver.
• Application WO2009032869 describes a dehydrating composition obtained by mixing an organic binder of polyolefin type and of an adsorbent component of zeolitic type present in an amount of 55% to 77%.
• This composition is used for the manufacture of desiccant gaskets for double glazing.
• the use of such compositions is however difficult: the times for incorporation of the adsorbent solid into the preparation are long and the mixture is very viscous.
• one of the objectives of the present invention is to provide zeolites with improved compatibility with organic materials, such as organic polymers.
• Another objective of the present invention is to provide zeolites with improved compatibility with organic materials, and to incorporate large amounts of said zeolites into said organic materials.
• Yet another objective is to provide zeolites with improved compatibility, which can be easily prepared and used in industry, with relatively low production costs and controlled energy consumption.
• the present invention relates to modified zeolite crystals comprising zeolite crystals and from 0.5% to 20%, preferably from 0.5% to 15%, more preferably from 1% to 10%, and advantageously from 1% to 5%, by weight, limits included, relative to the total weight of modified zeolite crystals, of at least one polymer compatibilizer, in particular a functional polyolefin.
• the zeolite crystals are zeolitic adsorbent materials well known to those skilled in the art and can be of all types used in the field of adsorption, and preferred examples of zeolites include, without limitation, zeolites of LTA type, preferably 3A, 4A and 5A, zeolites of FAU type, preferably of X, LSX, MSX, Y type, zeolites of MFI type, preferably of MFI type.
• ZSM-5 and silicalites P zeolites, SOD type zeolites (such as sodalites), MOR type zeolites, CFIA type zeolites (such as chabazites), FIEU type zeolites (such as clinoptilolites), and mixtures of two or more of them in all proportions.
• the preferred zeolites are chosen from zeolites of LTA type, preferably 3A, 4A and 5A, zeolites of FAU type, preferably of type X, LSX, MSX, Y, P zeolites, SOD-type zeolites (such as sodalites), MOR-type zeolites, CHA-type zeolites (such as chabazites), HEU-type zeolites (such as clinoptilolites), and mixtures of two or several of them in all proportions.
• zeolites of LTA type preferably 3A, 4A and 5A
• zeolites of FAU type preferably of type X, LSX, MSX, Y, P zeolites
• SOD-type zeolites such as sodalites
• MOR-type zeolites such as CHA-type zeolites (such as chabazites)
• HEU-type zeolites such as clinoptilolites
• the aforementioned zeolites can be natural, artificial or synthetic, that is to say natural, modified or synthesized. Zeolites most often contain one or more types of cations in order to ensure electronic neutrality.
• the cations present in zeolites naturally or after one or more cationic exchanges are well known to those skilled in the art. Non-limiting examples of such cations include cations of hydrogen, alkali metals, alkaline earth metals, metals of Groups VIII, IB and IIB, and mixtures of two or more of them, and most often examples of cations include cations of lithium, potassium, sodium, barium, calcium, silver, copper, zinc, and mixtures of two or more thereof, in all proportions.
• the number-average size of the crystals can vary widely and is generally between 0.05 ⁇ m and 20 ⁇ m, preferably between 0.1. pm and 20 pm, more preferably between 0.1 pm and 10 pm, advantageously between 0.2 pm and 10 pm, more preferably between 0.3 pm and 8 pm, more preferably between 0.5 pm and 5 pm.
• the modified zeolite crystals of the present invention further comprise at least one polymer compatibilizer, in particular a functional polyolefin, as indicated above.
• the compatibilizer used preferably said at least one functional polyolefin, for the preparation of the modified zeolite crystals has a melt flow index (MFI, or "Melt Flow Index" in English) greater than 250 g / 10 min, measured according to standard ASTM D1238 (190 ° C, 2.16 kg), preferably between 250 g / 10 min and 1000 g / 10 min, more preferably between 300 g / 10 min and 950 g / 10 min, better still between 500 g / 10 min and 900 g / 10 min and, most preferably, between 550 g / 10 min and 900 g / 10 min.
• MFI melt flow index
• the melting temperature of said compatibilizing agent is less than 150 ° C, more preferably less than 120 ° C, advantageously less than 110 ° C, and better still less than 100 ° C.
• the compatibilizer is a polymer, preferably a polyolefin and more specifically a functional polyolefin.
• polyolefins is meant the homopolymers or copolymers of alpha-olefins or diolefins. These olefins are, by way of example, ethylene, propylene, butene-1, octene-1, butadiene, styrene, and others, as well as mixtures of two or more of them, in all proportions.
• polyolefins also encompasses mixtures of two or more homopolymers and / or copolymers mentioned above.
• polyolefins mention may be made of polyethylene (HDPE, LDPE or VLDPE), polypropylene, and their copolymers.
• the number molecular weight of the polyolefins can vary widely, and is generally between 1000 g / mol and 1,000,000 g / mol.
• polyolefins or copolyolefins can also be grafted or "functionalized” with various functional groups, well known to those skilled in the art, such as for example anhydrides of unsaturated carboxylic or dicarboxylic acids such as maleic anhydride or unsaturated epoxides such as glycidyl methacrylate.
• the polyolefins thus functionalized can be prepared by homopolymerization of functionalized monomers or copolymerization of olefins with functionalized comonomers or else copolymerization of functionalized olefins with optionally functionalized comonomers, said functionalized monomers or comonomers being advantageously and most generally chosen from unsaturated carboxylic acids, their salts and their esters, such as alkyl (meth) acrylate, for example methyl acrylate, vinyl esters of saturated carboxylic acids such as vinyl acetate, unsaturated dicarboxylic acids, their salts, esters, half-esters, anhydrides, unsaturated epoxides, and the like, as well as mixtures of two or more of them, in all proportions .
• unsaturated carboxylic acids such as alkyl (meth) acrylate, for example methyl acrylate
• vinyl esters of saturated carboxylic acids such as vinyl acetate
• the term “functionalized polyolefin” or “functional polyolefin” is understood to mean a polyolefin known in the English language under the generic term “functionalized polyolefin” and as being an olefin polymer (s) with at least one polar functionality or not. polar linked to the polymer chain. According to a preferred aspect of the present invention, preferred are olefin polymers with at least one polar functionality. According to another preferred aspect of the present invention, the term “functional polyolefin” does not include halogenated polyolefins.
• the compatibilizing agent is a copolymer, and preferably a copolymer with an olefinic component
• the latter is advantageously chosen from olefin / carboxylic acid copolymers (optionally under salt form or ester form) and copolymers of olefins and vinyl esters of carboxylic acids, to name only the most common olefinic copolymers.
• olefin / carboxylic acid copolymers (optionally in salt form or in ester form), olefin / unsaturated carboxylic acid copolymers, optionally in salt form or in ester form.
• carboxylic acids, salts or esters suitable for the purposes of the present invention include in particular acrylic and methacrylic acids, their salts or esters, and most particularly methyl acrylate or butyl acrylate.
• copolymers of olefins and vinyl esters of carboxylic acids mention may be made of copolymers of olefins and of vinyl esters of saturated carboxylic acids, and in particular olefin / vinyl acetate copolymers.
• the polymer compatibilizing agent can comprise one or more polymers and / or copolymers as they have just been defined, and in particular polymers and / or olefinic copolymers such that they have just been defined.
• the content (in number, determined by infrared spectrometry) of functionalized comonomers is from 10 to 40% in the copolymer.
• the zeolite crystals modified according to the present invention are in the form of free crystals (that is to say of free powder) or in the form of friable aggregates of crystals.
• the crystals according to the present invention are crystals which are not integral with each other, with the exception of possible aggregates of crystals, these crystals which are not integral with each other are zeolite crystals comprising at least one polymer compatibilizer, preferably at least one functional polyolefin.
• the number-average size of the modified crystals (more simply "size of the modified crystals" in the remainder of the description) according to the present invention is generally between 0.07 ⁇ m and 25 ⁇ m, preferably between 0.1 ⁇ m. and 20 ⁇ m, more preferably between 0.1 ⁇ m and 10 ⁇ m, advantageously between 0.2 ⁇ m and 10 ⁇ m, more preferably between 0.3 ⁇ m and 8 ⁇ m, more preferably between 0.5 ⁇ m and 5 ⁇ m.
• the present invention relates to the process for preparing the modified zeolite crystals according to the invention, that is to say zeolite crystals comprising at least one compatibilizing agent.
• This process is characterized in that it comprises the following steps: a) mixing the zeolite crystals with said at least one compatibilizer, and b) recovering the modified zeolite crystals.
• the compatibilizer used in step a) can be either melted or ground, for example by cryogrinding, prior to mixing with the zeolite crystals.
• the compatibilizer can be in the solid state or in the molten state before and / or during mixing.
• the modified zeolite crystals recovered are in the form of pulverulent crystals, and / or in the form of friable aggregates, as indicated above.
• the modified zeolite crystals are pulverulent crystals, and / or in the form of friable aggregates most often and most generally obtained in a melting step after or during mixing with at least one compatibilizing agent, as defined above, which is either a fusion of said at least one compatibilizing agent by supplying an external heat source, and / or an at least partial fusion of said at least one compatibilizing agent by the friction forces in the mixer, during mixing.
• the mixing of the zeolite crystals with said at least one compatibilizing agent can be carried out in batch or continuously, by means of suitable mixers and well known to those skilled in the art, and which include, by way of examples not limiting, the Brabender type mixers, for example with rotating blades and of various shapes adapted to each type of die, the devices of the Banbury type in which two spiral rotors rotate in opposite directions at a variable speed of rotation, the extruders, mono screw or twin screw, such as for example the BUSS type mixers, which are generally equipped with an axially oscillating screw with a sinusoidal movement.
• Extruders are particularly well suited for continuous processes, while mixers of the Brabender or Banbury type are more suitable for batch processes. These various types of mixers can withstand the temperatures applied and adapted to the melting temperature of the compatibilizer, if applicable.
• the zeolite crystals can be introduced in one or more times or, better, by fractions in the mixture.
• the mixers used comprise several feed zones, this making it possible to favor and greatly facilitate mixtures with a high content of zeolite crystals.
• various additives and / or fillers to the zeolite crystals, before and / or during and / or after the addition of said at least one compatibilizing agent.
• the additives and fillers which can thus be incorporated form part of those well known to those skilled in the art and generally include, and by way of nonlimiting examples, crosslinking agents, antibacterial agents, fungicides, anti-fog agents. , blowing agents, dispersants, flame retardants, pigments, lubricants, impact modifiers, anti-oxidants, and the like, and mixtures thereof, to name only the main ones.
• zeolite crystals that is to say desorbed from the water adsorbed by heat treatment, and more generally having a very residual water. low, typically at a Loss On Ignition (PAF) of less than 2%.
• PAF Loss On Ignition
• the Loss on Ignition is determined in an oxidizing atmosphere, by calcining the crystals in air, at a temperature of 950 ° C ⁇ 25 ° C, as described in standard NF EN 196-2 (April 2006). The standard deviation of the measurement is less than 0.1%.
• modified zeolite crystals are obtained, that is to say a zeolite in the form of crystals and comprising said at least one compatibilizing agent. These modified zeolite crystals are ready to be used, after optional storage, under conditions well known to those skilled in the art for the storage of adsorbent materials.
• the modified zeolite crystals comprise at least one compatibilizer, said at least one compatibilizer being able to be present and visible by scanning electron microscopy (SEM) in various forms, and for example in the form of particles intimately mixed with zeolite crystals, and / or in a thin layer of compatibilizing agent on the surface of the crystals, and / or others, as well as the combinations of these various forms.
• SEM scanning electron microscopy
• the compatibilizer when the compatibilizer is in the form of particles intimately mixed with the zeolite crystals, said particles have a number-average size of less than 100 ⁇ m, preferably less than 80 ⁇ m, of more preferably less than 60 ⁇ m, preferably of number-average size between 0.1 ⁇ m and 100 ⁇ m, of preferably between 0.5 ⁇ m and 80 ⁇ m, more preferably between 1 ⁇ m and 60 ⁇ m, the number-average size being measured by SEM as indicated below.
• Such sizes of compatibilizing agent particles can be obtained by any means well known to those skilled in the art and for example by cryogrinding, as indicated above.
• the compatibilizer is in the form of a thin layer partially or totally covering the surface of the zeolite crystals, said layer preferably having a thickness, observed by means of a Scanning Electron Microscope (SEM) or even a Transmission Electron Microscope (TEM or “TEM” in English) less than 1.0 ⁇ m, advantageously less than 0.5 ⁇ m, preferably less than 0.2 ⁇ m.
• SEM Scanning Electron Microscope
• TEM Transmission Electron Microscope
• the compatibilizing agent layer partially or totally covering the surface of the zeolite crystals is generally obtained by mixing said zeolite crystals with the compatibilizing agent at a temperature preferably at least above the melting temperature of said agent. compatibilizing.
• the zeolite crystals comprising at least one compatibilizing agent according to the invention are zeolite crystals or aggregates of crystals. friable, and exhibit completely unexpected properties in terms of compatibility with organic matrices, in particular polymer matrices.
• modified zeolite crystals according to the invention are incorporated much more easily into polymer matrices, this having for direct implication a very large number of advantages, among which one can quote, between others, reduced energy consumption, greater incorporation speed, better rheological behavior (for example reduction in viscosity), a higher rate of zeolite crystals in the polymer matrices.
• the polymer matrices in which it may be advantageous to incorporate the modified zeolite crystals according to the present invention can be of any type and in particular the polymer matrices known to be loaded with zeolite crystals but also other types of polymer matrices which, until now, could not contain, or only contain small amounts of zeolite crystals.
• the polymer materials which can serve as a matrix for the modified zeolite crystals according to the invention can be in particular, and preferably thermoplastic polymers, among which there may be mentioned, by way of nonlimiting examples, polyethylenes, ethylene elastomers, propylene rubbers (EPR), ethylene, propylene and diene elastomers (EPDM), their mixtures, polyisobutylenes, silicones, polyurethanes, as well as copolymers, and mixtures of these polymers.
• Said polymer matrices comprising the modified zeolite crystals can then optionally be crosslinked or vulcanized, according to conventional techniques and well known to those skilled in the art.
• modified zeolite crystals according to the invention into the polymer matrices is generally carried out according to techniques known to those skilled in the art, and generally according to conventional and known techniques for processing plastics, such as kneading , extrusion, extrusion-molding, kneading-molding, and the like, as well as combinations of these techniques.
• incorporation techniques can also include the incorporation of various additives and fillers, also well known in the art, to impart additional properties to the zeolite loaded polymer matrix.
• additives and fillers mention may be made, by way of nonlimiting examples, of crosslinking agents, antibacterial agents, fungicides, anti-fogging agents, swelling agents, dispersants, flame retardants, pigments, etc. lubricants, impact modifiers, anti-oxidants, and the like, and mixtures thereof, to name just the main ones.
• the modified zeolite crystals of the present invention thus allow access to polymer matrices loaded with zeolite endowed with remarkable properties. It has in particular been demonstrated, surprisingly, that the modified zeolite crystals according to the invention are incorporated much more easily into polymer matrices, this having for direct implication a very large number of advantages, among which one can quote, among others, a consumption reduced energy, higher incorporation rate, better rheological behavior (for example reduction in viscosity), a higher rate of zeolite crystals in the polymer matrices.
• the invention also relates to the use of the modified zeolite crystals according to the invention as a filler in a polymer matrix, in particular for the preparation of composite materials.
• the modified zeolite crystals according to the invention find very interesting applications in a very large number of industrial fields, and in particular as fillers in polymer matrices (or polymer compositions).
• the modified zeolite crystals according to the invention can be incorporated into polymer matrices in large or even very large amounts, for example contents of at least 40%, or even at least. at least 60%, or even at least 80% and more.
• the modified zeolite crystals according to the invention can therefore be used as fillers in polymer matrices, and find quite interesting applications, in the field of double-glazing, in the field of coating compositions, for example, polyurethane coatings or coatings for metal supports such as aluminum or coatings for glass, or in the field of ready-to-polymerize formulations, ready-to-crosslink formulations, but also as filler in materials with reinforced mechanical properties, flame-retardant, phonic, as well as for applications in the electrical and electronic fields, such as cables, connectors, and others.
• coating compositions for example, polyurethane coatings or coatings for metal supports such as aluminum or coatings for glass, or in the field of ready-to-polymerize formulations, ready-to-crosslink formulations, but also as filler in materials with reinforced mechanical properties, flame-retardant, phonic, as well as for applications in the electrical and electronic fields, such as cables, connectors, and others.
• the size of the various materials is estimated by observation with a Scanning Electron Microscope (SEM). To this end, a set of images is taken at a magnification of at least 5000. The size of at least 200 elements is then measured using dedicated software, for example the publisher's Smile View software. LoGraMi. The accuracy is in the order of 3%. "Size” is defined as the largest dimension of the element. The resulting particle size distribution is equivalent to the average of the particle size distributions observed on each of the images. The number-average size is calculated according to conventional methods known to those skilled in the art, by applying the statistical rules of Gaussian distribution.
• the morphology of the crystals as well as the modification of the surface of the crystals are qualified from SEM photos taken at the magnification suited to the size of the crystals (for example magnification between 4000 and 20,000).
• Example 1 Preparation of crystals of 3A zeolite modified with a functional polyolefin
• a Lotryl ® 28BA700T grade polyolefin from Arkema in the form of granules (10 g) is introduced into a mixer of the Brabender Rheomix ® 600 type of the HAAKE TM brand, at 100 ° C. and 50 revolutions per minute. After melting lapolyarchyarchfine at this temperature, the 3A type zeolite crystals grade Siliporite ® NK30AP Arkema (190 g) in powder form are added to the mixer by fractions. After 20 minutes of mixing, a homogeneous mixture of modified zeolite crystals (200 g) is obtained in the form of free powder and very friable aggregates, which are left to cool to room temperature away from humidity in a Schlenk.
• Figure 1 shows a photograph obtained by SEM (5000 magnification) showing 3A zeolite crystals covered almost entirely by a thin layer of polyolefin.
• Example 1a comparative: Preparation of crystals of 3A zeolite modified with a non-functional polyolefin
• Polypropylene (Sigma Aldrich, isotactic grade, Mw -250,000, Mn -67,000) in the form of granules (10 g) is introduced into a mixer of the Brabender Rheomix ® 600 type of the HAAKE TM brand, at 160 ° C and 50 revolutions per minute. After melting the polyolefin at this temperature, the 3A type zeolite crystals grade Siliporite ® NK30AP Arkema (190 g) in powder form are added to the mixer by fractions. After 20 minutes of mixing, a mixture of agglomerates of crystals stuck in polypropylene and unmodified, free zeolite crystals is obtained. invention.
• a peroxide-type crosslinking agent, Arkema's Luperox P (3.6 g) is first added with stirring to 200 g of modified zeolite crystals obtained in Example 1.
• This premix is then introduced into 190 g of a silicone polymer matrix (Silicone 4-7155 from Dow Corning) using a twin-cylinder mixer. Mixing is carried out for approximately 15 minutes at room temperature (20 ° C.). The rotational speeds of the cylinders (diameter 150 mm) are different 18 revolutions per minute (rpm) for the rear cylinder and 24 rpm for the front cylinder. The spacing between the two cylinders is approximately 3mm. A homogeneous mixture is obtained in the form of a sheet about 60 cm long and about 15 cm wide and 3 mm thick.
• a crosslinking agent for peroxide, Luperox P Arkema (3.6 g) was added in 190 g of 3A grade type zeolite crystals Siliporite ® NK30AP Arkema.
• the mixture obtained is then introduced into 200 g of a silicone polymer matrix (Silicone 4-7155 from Dow Corning) using a twin-cylinder mixer. The mixing is carried out for approximately 15 min at room temperature.
• the rotational speeds of the cylinders (diameter 150 mm) are different and 18 rpm for the rear cylinder and 24 rpm for the front cylinder.
• the spacing between the two cylinders is approximately 3 mm.
• the homogeneous mixture is obtained in the form of a sheet approximately 60 cm long and approximately 15 cm wide and 3 mm thick.
• Measurements of the rheological behavior are then carried out on the sheets obtained using a plane-plane rheometer with oscillating matrix (MDR-C type of the France Scientifique brand) at 130 ° C for 45 min, duration for which crosslinking of the silicone matrix.
• MDR-C oscillating matrix
• the rheometer is operated according to ISO 6502 and ASTM D5289 standards.
• the sheet prepared with the modified zeolite crystals according to the invention has a minimum torque lower than that obtained with the unmodified zeolite crystals (reduction of the order of 30%, or even less), which demonstrates that a smaller amount of energy is required to mix the modified zeolite crystals according to the invention with the polymer matrix.
• greater fluidity (lower viscosity) of the mixture with the modified crystals according to the invention is observed.

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