Classifications

• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/005—Processes for mixing polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
  • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
• • 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
  • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
• • 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
  • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase

Definitions

• the present invention relates to the field of crystalline organic-inorganic hybrid materials (MHOIC) and, in particular, that of their shaping for use in industrial applications for catalysis, storage for example of gas, or the separation. More specifically, this invention relates to a new composite material comprising at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material having a high content of an organic hybrid material. inorganic crystalline material and the process for preparing said novel material, said method comprising at least one step of mixing at least one powder of at least one crystalline organic-inorganic hybrid material with at least one powder of at least one polymer.
• MHOIC crystalline organic-inorganic hybrid materials
• crystallized organic-inorganic hybrid materials are understood to mean any crystallized material containing organic and inorganic entities (atoms, clusters) connected by chemical bonds.
• MOF Metal Organic Framework according to the English terminology
• coordination polymers ZIFs (or Zeolitic Imidazolate Frameworks according to the English terminology)
• MILs or Materials of the Lavoisier Institute
• IRMOFs or IsoReticular Metal Organic Framework according to the English terminology.
• organic-inorganic mixed matrix porous hybrid materials are quite similar to porous inorganic skeleton materials. Like the latter, they associate chemical entities by giving rise to porosity. The main difference lies in the nature of these entities. This difference is particularly advantageous and is at the origin of all the versatility of this category of hybrid materials. Indeed, the size of the pores becomes, through the use of organic ligands, adjustable through the length of the carbon chain of said organic ligands.
• the framework which in the case of inorganic porous materials, can accept only a few elements (Si, Al, Ge, Ga, P possibly Zn) can, in this case, accommodate the majority of the cations.
• the solvent (and / or the ligand) plays this effect alone.
• the crystallized organic-inorganic hybrid materials comprise at least two elements called connectors and ligands whose orientation and the number of binding sites are determinants in the structure of said hybrid material. From the diversity of these natt ligands and connectors, as already mentioned, an immense variety of hybrid materials.
• Connector means the inorganic entity of said hybrid material. It can be a single cation, a dimer, trimer or tetramer or a chain or a plane.
• the teams of Yaghi and Férey have thus described a large number of new hybrid materials (series of MOFs - "Metal Organic Framework” - and series of MIL - “Materials of the Lavoisier Institute” - respectively). Many other teams have followed this path and today the number of new hybrid materials described is expanding. Most often, the studies are aimed at developing ordered structures with extremely large pore volumes, good thermal stability, and adjustable chemical functionality.
• Yaghi et al. disclose a series of boron structures in US patent application 2006/0154807 and indicate their interest in the field of gas storage.
• US Pat. No. 7,202,385 discloses a particularly complete summary of the structures described in the literature and perfectly illustrates the multitude of hybrid materials existing to date.
• MHOIC crystalline organic-inorganic hybrid materials
• MHOIC crystalline organic-inorganic hybrid materials
• Finsy et al. (Finsy et al., Separation of CO 2 / CH 4 mixtures vvith the MIL53 (AI) metal-organic framework, Microporous and mesoporous materials, 120 (2009) 221-227) describes the preparation of MIL-53 materials shaped by stirring evaporation of the solvent in which the polymer (polyvinyl alcohol PVA, present at a level of 13% by weight relative to the total mass of the material) was previously dissolved and studied the column separation properties of the agglomerates obtained. Finsy et al. describes the preparation of objects of size between 500 and 630 microns. No details on the mechanical properties of obtained granules and in particular on the crush resistance is provided but it is observed that the reduction of the microporous volume is 32% after activation at 190oC.
• the polymer polyvinyl alcohol PVA
• Patent Application US2003 / 0222023A1 discloses shaped materials of the MOF type prepared by shaping a composition comprising a crystallized organic-inorganic hybrid material and a binder. All shaping techniques are described: pelletizing, kneading, extrusion, granulation, etc.
• the materials described as binders in the text are inorganic compounds, minerals such as silica, alumina, clay or graphite and organic compounds such as silanes.
• Hydrophilic polymers such as PVA (polyvinyl alcohol) and PVP (polyvinylpyrrolidone) are cited as a thickener of the preparation prior to shaping.
• the examples of the application US2003 / 0222023A 1 mention only the shaping of such materials by pelletizing.
• the materials obtained have a crush strength of 2 to 100 N.
• US Pat. No. 3,737,983B1 discloses membranes comprising a continuous polymer organic phase and a crystallized organic-inorganic hybrid material dispersed in the continuous polymer phase, their method of preparation and a process for separating gas by bringing a gas into contact with said membrane .
• the membranes are prepared by mixing a polymer solution with a crystalline organic-inorganic hybrid material powder to form a dispersion and the mixture is then cast to form a membrane.
• the examples of US Pat. No. 3,737,983 mention membranes containing 20 to 30% of hybrid organic-inorganic material crystallized with a polyimide matrix (Matrimid, Ultem).
• the patent application WO 201 1/100501 A1 also describes composite membranes intended for the separation of gases.
• the membrane consists of an organometallic phase and a polymeric phase.
• the self associative polymers (organization by non-covenant bonds: hydrogen bond, ionic, intermolecular) are described.
• the compositions contain from 1 to 70% by weight of crystallized organic-inorganic hybrid material.
• Chapter 15 of the book "Metal-Organic Frameworks: Applications from Catalysis to Gas Storage” published by Wiley takes the techniques of shaping hybrid organic-inorganic material crystallized according to the intended applications.
• An object of the present invention is to provide a new composite material comprising at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material having a high content of one crystallized organic-inorganic hybrid material,
• Another object of the present invention is to provide a new process for preparing said material comprising at least one crystallized organic-inorganic hybrid material (MHOIC) shaped as extrudates with a binder formulation comprising at least one polymer.
• MHOIC crystallized organic-inorganic hybrid material
• the present invention relates to a material comprising at least one crystallized organic-inorganic hybrid material shaped in the form of an extrusion with a binder formulation comprising at least one polymeric binder, said material consisting of 80 to 99% by weight of at least one crystalline organic-inorganic hybrid material and from 1 to 20% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
• the present invention also relates to a process for preparing said material comprising at least the following steps:
• MHOIC crystalline organic-inorganic hybrid material
• An advantage of the present invention is to provide a material and its preparation process allowing its shaping with a content of high crystallized organic-inorganic hybrid material and in particular between 80 and 99% by weight relative to the mass of the material, said obtained material having both a good mechanical strength and a loss of microporous volume with respect to the porosity of the starting crystallized organic-inorganic hybrid material limited.
• the material thus obtained is suitable for use in an industrial process over long periods.
• the material according to the present invention comprises at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material consisting of 80 to 99% by weight of at least one crystallized organic-inorganic hybrid material and from 1 to 20% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
• the crystalline organic-inorganic hybrid material (s) used (MHOIC) used in the material according to the present invention are preferably selected from the MOF (Metal Organic Framework according to US Pat. English terminology), the ZlFs (or Zeolitic Imidazolate Frameworks according to the English terminology), the MILs (or Materials of the Lavoisier Institute), the IRMOFs (or isoReticular Metal Organic Framework according to the English terminology), only or in mixture.
• MOF Metal Organic Framework according to US Pat. English terminology
• ZlFs or Zeolitic Imidazolate Frameworks according to the English terminology
• MILs or Materials of the Lavoisier Institute
• IRMOFs or isoReticular Metal Organic Framework according to the English terminology
• said crystalline organic-inorganic hybrid material (s) used (MHOIC) in the material according to the present invention are chosen from the following list: 1, HKUST, CAU-1, MOF-5, MOF-38, MOF-305, MOF-37, MOF-12, IRMOF-2 to -16, MIL-53, MIL-68, MIL-101, ZIF-8 , ZIF-1 1, ZIF-67, ZIF-90, alone or in admixture.
• the said hybridized organic-inorganic hybrid material (s) used (MHOIC) in the material according to the present invention are chosen from SIM-1, HKUST and ZIF-8, alone or mixed.
• the said crystallized organic-inorganic hybrid material (s) (MHOIC) are used in step a) of the preparation process according to the invention in powder form.
• the said (s) binder (s) polymer (s) is (are) advantageously chosen (s) among the polymers well known to those skilled in the art.
• the said polymer (s) is (are) chosen from polyvinylpyrrolidones, cellulosic polymers and their derivatives, preferably chosen from cellulose ethers such as, for example, Methocel, sold by Dow Chemical, polyvinyl alcohols, polyethylene glycols, polyacrylamides, polysaccharides, natural polymers and their derivatives such as, for example, alginates, polyesters, polyamides and aromatic polyamides, polyethers poly (aryether), polyurethanes, polysulfones such as polyether sulfones, heterocylic polymers, preferably selected from polyimides, polyether imides, polyesters imides, polyamide imides, and polybenzimidazoles.
• the said binder (s) polymer (s) is (are) chosen from polyvinylpyrrolidones, heterocyclic polymers and cellulosic polymers and very preferably from polyvinylpyrrolidones, polyimides and cellulose ethers.
• polymer By polymer is meant a compound having at least 20 repeating units or a molecular weight greater than 500 g.mol -1 .
• said material consists of 85 to 99% by weight of at least one crystallized organic-inorganic hybrid material and 1 to 15% by weight of at least one polymeric binder, and preferably from 90 to 99% by weight of at least one crystallized organic-inorganic hybrid material and from 1 to 10% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
• said material is in the form of extrudates.
• said material is in the form of extrudates with a diameter of between 0.8 and 5 mm and preferably between 0.9 and 4 mm.
• Said materials according to the invention having a high content of crystallized organic-inorganic hybrid material have increased mechanical properties, especially in terms of mechanical strength, regardless of the content used, and are resistant to a rise in moderate temperature, which allows to consider the implementation of said material in processes at relatively high temperatures but still limited by the temperature resistance of the hybrid organic-inorganic crystalline material (MHOIC) and / or the polymer.
• MHOIC crystallized organic-inorganic hybrid material
• Said materials according to the invention can therefore be used for applications in catalysis and separation.
• said materials according to the invention have a mechanical resistance measured by the grain-to-grain crushing test, noted by EGG at least greater than 0.4 daN / mm and preferably at least greater than 0.9 daN / mm and preferably at least greater than 1 daN / mm.
• the mechanical strength of the material according to the invention determined by the grain-to-grain (GGE) crushing test.
• GGE grain-to-grain
• ASTM D4179-01 standardized test that involves subjecting a material as a millimeter object, such as a ball, pellet, or extrusion, to a compressive force that causes the breakage. This test is therefore a measure of the tensile strength of the material. The analysis is repeated on a number of solids taken individually and typically on a number of solids between 10 and 200.
• the average of the lateral forces of rupture measured constitutes the average EGG which is expressed in the case of the granules in unit of force (N), and in the case of extrusions in unit of force per unit length (daN / mm or decaNewton per millimeter of extruded length).
• said materials according to the invention exhibit a loss of microporous volume of less than 35%, preferably less than 30%, preferably less than 25 and more preferably less than 15%.
• the loss of micro porosity is calculated taking into account the dilution due to the presence of polymer binder in the final material in extruded form: the microporous volume of the material obtained in extruded form is compared with that of the MHOIC powder. starting point, weighted with the dilution factor which is equal to the mass percentage of MHOIC present in the material obtained in extruded form.
• the loss of microporosity [(microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100 - microporous volume of the final material obtained under extruded form] x 100 / (microporous volume of the starting MHOIC x% by mass of MHOIC present in the final material obtained in extruded form) / 100).
• the present invention also relates to a process for the preparation of said material according to the invention.
• the method of preparing the material comprising at least the following steps: a) a step of mixing at least 80 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC) with at least 1 to 20% by weight of a powder of at least one polymer and a solvent to obtain a mixture, the weight percentages being expressed relative to the total amount of powders introduced in said step a), b) a step of extrusion shaping of the mixture obtained at the end of step a), c) a step of heat treatment of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and 300 ° C., for a period of time between 1 minute and 72 hours.
• MHOIC crystalline organic-inorganic hybrid material
• the sum of the amounts of each of the powders introduced in said step a) is equal to 100%.
• said step a) consists of mixing at least 80 to 99% by weight and preferably at least 85 to 99% by weight and preferably at least 90 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC), with at least 1 to 20% by weight and preferably with at least 1 to 15% by weight and more preferably at least 1 to 10% by weight of a powder of at least one polymer and a solvent to obtain a mixture.
• MHOIC crystallized organic-inorganic hybrid material used in powder form in the process for preparing the material according to the present invention and the polymers are described. upper.
• Said solvent is advantageously chosen from water, the alcohols preferably chosen from ethanol and methanol, amines, ethers, esters, ketones, lactones, phenols, cresols, polar aprotic solvents such as DMF, DMAC, NMP for example.
• the polymer (s) may be mixed in powder form or in solution in said solvent.
• the order in which the mixture of the powders of at least one crystalline organic-inorganic hybrid material (MHOIC), at least one polymer and the solvent is produced is indifferent.
• the mixture of said powders and of said solvent can advantageously be produced at one time.
• said powders of at least one crystalline organic-inorganic hybrid material (MHOIC), of at least one polymer, in the case where they are mixed in the form of powders, are firstly prepared. -mixed, dry, before the introduction of the solvent.
• MHOIC crystalline organic-inorganic hybrid material
• the polymers may previously be in solution or suspension in said solvent when said solvent is brought into contact with the powders of at least one crystalline organic-inorganic hybrid material (MHOIC). Contacting with said solvent leads to obtaining a mixture which is then kneaded.
• MHOIC crystalline organic-inorganic hybrid material
• said mixing step a) is carried out by mixing, batchwise or continuously.
• said step a) is advantageously carried out in a kneader preferably equipped with Z-arms, or with cams, or in any other type of mixer such as for example a planetary mixer, Said step a) of mixing makes it possible to obtain a homogeneous mixture of powder constituents and of the solvent,
• said step a) is carried out for a period of between 5 and 60 minutes, and preferably between 10 and 50 minutes.
• the rotation speed of the kneader arms is advantageously between 10 and 75 revolutions / minute. preferred way between 25 and 50 rpm.
• said step b) consists in shaping by extrusion of the mixture obtained at the end of step a) of mixing.
• Said step b) is advantageously carried out in a piston, single-screw or twin-screw extruder.
• an organic adjuvant may optionally be added in the mixing step a). The presence of said organic adjuvant facilitates extrusion shaping.
• said mixing step a) can be coupled with the extrusion shaping step b) in the same equipment.
• the extrusion of the mixture also called “kneaded paste” can be carried out either by directly extruding the end of continuous twin-screw kneader for example, or by connecting one or more batch kneaders to an extruder.
• the geometry of the die, which confers their shape to the extrudates can be chosen from the well-known dies of the skilled person. They can thus be, for example, cylindrical, multilobed, fluted or slotted.
• step a) the amount of solvent added in step a) of mixing is adjusted so as to obtain, at the end of this step and whatever the variant used, a mixture or a paste that does not flow but is not too dry to allow its extrusion under suitable conditions of pressure and temperature well known to those skilled in the art and dependent on the extrusion equipment used.
• said extrusion forming step b) is carried out at an extrusion pressure greater than 1 MPa and preferably between 3 MPa and 10 MPa.
• said step c) consists of a step of heat treatment of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and 300 ° C, preferably between 25 and 200 ° C and preferably between 25 and 150 ° C for a period of between 1 minute and 72 hours, preferably between 30 minutes and 72 hours, and preferably between 1 hour and 48 h and more preferably between 1 and 12 h.
• Said heat treatment step is preferably a maturation step and can advantageously be carried out under inert gas or under vacuum.
• said maturation step is carried out under air.
• the material obtained is in the form of extrudates of size between 0.8 and 5 mm and preferably between 0.9 and 4 mm.
• said materials obtained are then, for example, introduced into equipment for rounding their surface, such as a bezel or other equipment allowing their spheronization.
• Said method of preparation according to the invention makes it possible to obtain materials according to the invention having mechanical strength values measured by grain-to-grain crushing greater than 0.4 daN / mm, preferably greater than 0.9 daN / mm and preferably greater than 1 daN / mm, regardless of the content of (MHOIC) implemented.
• the material obtained at the end of the preparation process according to the invention can be used for applications in catalysis, separation, purification, capture ...
• Said material is brought into contact with the gaseous feedstock to be treated in a reactor, which can be either a fixed bed reactor, a radial reactor, or a fluidized bed reactor.
• the expected EGG value is greater than 0.9 daN.mm -1 , preferably greater than 1.0 daN.mm -1 .
• the viscous paste is introduced into a hand extruder (3 mm diameter die) and a sufficient pressure is applied to obtain a rod which is cut into extrudates of 1 cm in length.
• the extrudates are subjected to a heat treatment of 5 hours at 140 ° C. under a vacuum of a vane pump.
• the viscous paste is introduced into a hand extruder (die ⁇ 3 mm) and sufficient pressure is applied to obtain a rod which is cut into extruded 1 cm in length.
• the extrudates are subjected to a heat treatment of 5 hours at 140 ° C. under a vacuum of a vane pump.
• a polyvinylpyrrolidone (PVP) powder marketed by Aldrich (representing 8.25% by weight expressed relative to the total amount of powders introduced into said stage are introduced into a glass reactor equipped with mechanical stirring. a)) and 3.64 g of methanol. The mixture is stirred until complete solubilization of the polymer and 4 g of a ZIF-8 powder (Basolite Z1200) (representing 91.75% by weight relative to the total amount of powders introduced in said step a) are added. Stirring is then continued until a suspension assimilated to a viscous paste is obtained.
• PVP polyvinylpyrrolidone
• the viscous paste is introduced into a hand extruder (die ⁇ 3 mm) and sufficient pressure is applied to obtain a rod which is cut into extruded 1 cm in length.
• Step a) 2 g of a polyvinylpyrrolidone (PVP) powder marketed by Aldrich (representing 10% by weight relative to the total amount of powders introduced in said step a) are introduced into a glass reactor equipped with mechanical stirring. ) and 19 ml of water. Stirring until complete solubilization of the polymer.
• PVP polyvinylpyrrolidone
• the paste is introduced into a capillary rheometer type piston extruder (die ⁇ 3 mm) and a sufficient pressure is applied to obtain a rod.
• the extrudates are subjected to a heat treatment of 16 hours at 80 ° C. and then 120 ° C. or 200 ° C. for 16 hours.
• the paste is introduced into a capillary rheometer type piston extruder (die ⁇ 3 mm) and a sufficient pressure is applied to obtain a rod.
• the extrudates are subjected to a heat treatment of 16 hours at 80 ° C. and then 120 ° C. for 16 hours.
• Step a) In a kneader equipped with cam shafts, 3.1 g of a K15M methocel powder marketed by DOW Chemicals (representing 5% by weight relative to the total quantity of powders introduced in said stage a)), 62.5 g (95% by weight relative to the total amount of powders introduced in said step a) of a SIM-I powder and 34.2 ml of water are mixed. The mixing is then continued until a paste is obtained.
• a K15M methocel powder marketed by DOW Chemicals (representing 5% by weight relative to the total quantity of powders introduced in said stage a)
• 62.5 g (95% by weight relative to the total amount of powders introduced in said step a) of a SIM-I powder and 34.2 ml of water are mixed. The mixing is then continued until a paste is obtained.
• the paste is introduced into a capillary rheometer type piston extruder (die ⁇ 3 mm) and a sufficient pressure is applied to obtain a rod.
• the extrudates are subjected to a heat treatment of 16 hours at 40 ° C. and then 120 ° C. for 16 hours.
• the loss of microporosity is calculated taking into account the dilution due to the presence of polymeric binder in the final material in extruded form: the microporous volume of the material obtained in extruded form is compared with that of the MHOIC powder of starting, weighted dilution factor which is equal to the mass percentage of MHOIC present in the material obtained in the form of extruded.
• the loss of microporosity [(microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100 - microporous volume of the final material obtained under extruded form] x 100 / (microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100).

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