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WO2009103680A1 - Matériaux poreux solides à structure coeur-écorce à base de polymères et de biopolymères synthétiques, procédés pour les produire et leur utilisation - Google Patents

Matériaux poreux solides à structure coeur-écorce à base de polymères et de biopolymères synthétiques, procédés pour les produire et leur utilisation Download PDF

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Publication number
WO2009103680A1
WO2009103680A1 PCT/EP2009/051791 EP2009051791W WO2009103680A1 WO 2009103680 A1 WO2009103680 A1 WO 2009103680A1 EP 2009051791 W EP2009051791 W EP 2009051791W WO 2009103680 A1 WO2009103680 A1 WO 2009103680A1
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solid
liquid
porous materials
porous
biopolymers
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German (de)
English (en)
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Simon Champ
Robert Chapman
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BASF SE
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BASF SE
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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
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • 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
    • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
    • 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
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • Solid, porous materials with core-shell structure based on synthetic polymers and biopolymers, process for their preparation and their use
  • the present invention relates to novel, solid, porous materials having a core-shell structure based on synthetic polymers and biopolymers. Moreover, the present invention relates to a novel process for the preparation of solid, porous materials based on synthetic polymers and biopolymers. Last but not least, the present invention relates to the use of the novel, solid, porous materials having a core-shell structure based on synthetic polymers and biopolymers and solid, porous materials produced by the novel process.
  • a polysaccharide in particular cellulose, optionally dissolved together with additives in an ionic liquid.
  • the solution is introduced into a liquid medium which is miscible with the ionic liquid, but which is unable to dissolve the polysaccharide.
  • Suitable liquid media include or consist of water, alcohols, nitriles, ethers or ketones.
  • water is used, because then can be dispensed with the use of volatile organic solvents.
  • the regenerated polysaccharide accumulates in the form of a gel. Upon drying, the regenerated polysaccharide gel shrinks, resulting in a polysaccharide-based solid. It is not known whether the formed solids have a core-shell structure and whether they are porous.
  • US Pat. No. 5,328,603 discloses a process for producing cellulose-based porous beads having a particle size of at least 0.3 in which one dissolves cellulose in a chaotropic liquid, in particular in a saturated solution of lithium chloride or calcium thiocyanate in a polar organic solvent such as dimethylacetamide, atomizing the resulting solution and introducing the resulting droplets into a liquid which is miscible with the chaotropic liquid is, but which does not solve cellulose.
  • a chaotropic liquid in particular in a saturated solution of lithium chloride or calcium thiocyanate in a polar organic solvent such as dimethylacetamide
  • a polar organic solvent such as dimethylacetamide
  • water, methanol or water-methanol mixtures are used as liquid media.
  • the droplets solidify and form globules which can be washed with water and isolated.
  • these beads are porous, they have no core-shell structure.
  • US 2006/0151 170 A1 discloses a process for stimulating petroleum and natural gas sources.
  • a thickened liquid medium containing deformable particles in the form of spheres, cylinders, cubes, rods, cones or irregular shapes of a particle diameter of 850 ⁇ m is press-fitted into a wellbore.
  • new cracks and fissures are formed in the oil or natural gas formation, through which the oil or natural gas easily gets back to the borehole.
  • This method for well stimulation is also called “fracturing” in natural gas and oil well technology.
  • the deformable particles serve as support particles or proppants which prevent the newly formed cracks and crevices from being closed again by the pressure of the overlying rock.
  • proppants These supporting particles or supporting materials are also referred to as "proppants" in the natural gas and crude oil extraction technology.
  • the deformability of the proppants to some extent prevents the formation of finely divided material by abrasion of rock material, and / or by breaking the proppants, as with the use of hard proppants such as e.g. Fracturing sand is common.
  • the deformable proppants thus effectively have the effect of support pillows.
  • deformable proppants are made from shredded natural products such as, for example, sliced, ground or crushed Nutshells, fruit seeds, plant trays or wooden parts.
  • these must be provided with a protective layer in order to adapt the elastic modulus of the proppants to the respective requirements.
  • the known deformable proppants have the disadvantage that their chemical compositions and mechanical properties vary widely, so that elaborate tests are required to check whether a delivered batch is suitable for a given petroleum or natural gas formation.
  • the cores of these new, solid, porous materials should be comparatively hard and have a uniform, porous structure.
  • the shells of these new, solid, porous materials should be softer and more compact than the cores and have a uniform thickness.
  • novel, solid, porous materials based on synthetic polymers and biopolymers with core-shell structure should also have a high mechanical stability in the swollen state. They should have a higher absorption capacity than the known materials based on synthetic polymers and biopolymers. They should be in a variety of three-dimensional shapes, such as
  • Example spherical particles, irregular or regularly shaped, non-spherical particles, plates, rods, cylinders, needles, flakes, threads, fabrics or films, provide all of which should have a high mechanical stability.
  • the new process should provide solid, porous materials based on synthetic polymers and biopolymers with core-shell structure in a simple and highly reproducible manner.
  • these process products should have the desired property profile described above.
  • the new, solid, porous materials with a core-shell structure based on synthetic polymers and biopolymers, as well as the solid, porous materials based on synthetic polymers and biopolymers produced according to the new process are said to be particularly wide, especially in the synthetic one and analytical chemistry, biochemistry and genetic engineering, biology, pharmacology, medical diagnostics, cosmetics, natural gas and petroleum extraction technology, process technology, paper technology, packaging technology, electrical engineering, magnetic engineering,
  • Communication technology radio and television technology, agricultural technology, aerospace technology and textile technology and construction, land and sea transport and mechanical engineering, be used with advantage.
  • they are said to be outstandingly suitable as support particles, support materials or proppants, construction materials, insulations, fabrics, absorbents, adsorbents, membranes, release materials, barrier layers, controlled release materials, catalysts, cultivation media, catalysts and also colorant, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame retardant materials or for their preparation are suitable.
  • novel, solid, porous materials having a core-shell structure based on synthetic polymers and / or biopolymers (A), soluble in chaotropic liquids (C) and in protic polar inorganic liquids (D1) and in protic polar organic liquids (D2) are insoluble, found.
  • novel solid porous materials will be referred to as "materials of the invention”.
  • Liquid (D1) and optionally the at least one additive (B) contains or consists thereof, and a liquid phase (F) containing or consisting of chaotropic liquid (C) and liquid (D1),
  • the inventive method provided materials according to the invention with a core-shell structure.
  • the cores of the inventive materials were relatively hard and had a uniform, porous structure.
  • the shells of the materials according to the invention were softer and more compact than the cores and had a uniform thickness.
  • the materials according to the invention also exhibited a high mechanical stability in the swollen state. They had a higher absorption capacity than the known materials based on polysaccharides. They were available in a wide variety of three-dimensional shapes, such as spherical particles, irregular or regularly shaped, non-spherical particles, plates, rods, cylinders, needles, flakes, threads, cloths, or films, all of which had high mechanical stability.
  • the process according to the invention provided the materials according to the invention in a simple and highly reproducible manner, these surprisingly having the desired property profile described above.
  • the materials according to the invention and the solid, porous materials produced on the basis of synthetic polymers and biopolymers (A), in particular the materials according to the invention were particularly broad, in particular in synthetic and analytical chemistry, biochemistry and genetic engineering, Biology, pharmacology, medical diagnostics, cosmetics, natural gas and oil production technology, process technology, paper technology, packaging technology, electrical engineering, magnetic engineering, communication technology, radio and television technology, agricultural engineering, aerospace engineering and textile technology, as well as construction, land and sea transport and mechanical engineering, usable with advantage.
  • support particles support materials or proppants
  • construction materials insulations, fabrics
  • absorbents adsorbents
  • membranes release materials
  • barrier layers controlled-release materials
  • catalysts culture media
  • catalysts also colorant, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame retardant materials or for their manufacture.
  • the powdery solid materials based on synthetic polymers and / or biopolymers prepared by the process of the invention were outstandingly suitable as abrasion-resistant, pressure-resistant, deformable proppants in liquid media for fracturing for the purpose of highly effective and particularly long-lasting well stimulation in the production of Natural gas and petroleum.
  • the flow rates could be significantly increased.
  • the materials of the invention are solid. This means that they are up to at least 50 0 C, preferably to at least 100 0 C, preferably to at least 200 ° C and in particular up to at least 250 0 C are fixed and do not have a phase transition to a liquid or gaseous state.
  • the materials according to the invention are porous. This means that they have a foamy or sponge-like structure.
  • the structure may be closed-pored or open-pored. Preferably, it is open-pore, ie, it is permeable to gases and liquids.
  • the materials of the invention have a core-shell structure. Although the cores and the shells may have different material compositions. Preferably, the cores and shells have the same material composition. But they differ in their internal structure or their structure. Preferably, the shells are firmly bonded to the cores so that they do not disengage from the cores under mechanical stress.
  • the cores of the materials according to the invention are preferably coarse-pored or fine-pored. These properties are referred to Römpp Online 2008, "Pores”.
  • the pores have a diameter of 50 nm to 10 .mu.m, more preferably 500 nm to 8 .mu.m, most preferably 1 .mu.m to 7 .mu.m and in particular 1 .mu.m to 5 .mu.m.
  • the cores of the materials of the invention may be harder or softer than their shells. That is, the shells can be deformed more easily or more severely than the cores or, in other words, the material is more or less rigid to the cores than the material of the shells.
  • the cores are harder than the shells.
  • the cores and the shells of the materials according to the invention may have a different porosity. So the shells can be more compact than the cores and vice versa.
  • the cups are more compact than the cores, that is, they have a lower porosity than the cores.
  • porosity see Römpp Online 2008, "Porosity”.
  • the pores of the shells have a diameter of 1 to ⁇ 50 nm.
  • the thickness of the shells of the materials according to the invention can vary widely.
  • they have a thickness of 1 to 100 .mu.m, preferably 5 to 90 .mu.m, more preferably 10 to 80 .mu.m and in particular 15 to 70 microns.
  • the materials according to the invention can be used in any three-dimensional forms,
  • Sizes and morphologies are present.
  • the size varies from 100 nm to 10 mm. This means that the three-dimensional shapes are micro or macro forms.
  • the materials of the present invention can not, for example, be spherical particles, irregular or regularly shaped spherical particles, plates, rods, cylinders, needles, flakes, threads, fabrics or films.
  • the materials according to the invention are preferably in the form of spherical particles, more preferably spheres or beads.
  • the particle size of the spheres or beads according to the invention can be varied very widely and thereby be excellently adapted to the requirements of the individual case.
  • they Preferably, they have an average particle size of from 0.1 to 10 mm, preferably 0.2 to 5 mm and especially 0.3 to 2 mm, measured by sedimentation in a gravitational field.
  • the particle size distribution may be multimodal or monomodal. Preferably, it is monomodal.
  • the particle size distribution may be narrow or ready. Preferably, it is narrow, that is, the spheres or beads of the invention have only very small fines and coarse fractions.
  • the basis of the materials according to the invention forms at least one, in particular one, synthetic polymer and / or biopolymer (A).
  • a given material according to the invention consists of a synthetic polymer and / or biopolymer (A) or that a given material according to the invention contains a synthetic polymer and / or biopolymer (A), but the synthetic polymer and / or biopolymer (A) the three-dimensional structure determined substantially or alone.
  • polymer (A) the synthetic polymer and / or biopolymer are also collectively referred to as “polymer (A)” or “polymers (A)”.
  • all synthetic polymers and biopolymers (A) are suitable for this purpose as long as they are soluble in one of the chaotropic liquids (C) described below and insoluble in the protic polar inorganic liquids (D1) and protic polar organic liquids (D2) described below are.
  • the synthetic polymers (A) are preferably selected from the group consisting of random, alternating and block-like, linear, branched and comb-like, oligomeric and polymeric (co) polymers of ethylenically unsaturated monomers, polyaddition resins and polycondensation resins (see Rompp Lexikon Lacke and Printing Inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457: “Polyaddition” and “Polyaddition Resins (Polyadducts)", pages 463 and 464: "polycondensates", "polycondensation” and “polycondensation resins”).
  • Preference is given to using (meth) acrylate (co) polymers, polyurethanes and polyesters, particularly preferably polyesters.
  • the biopolymers (A) are selected from the group consisting of nucleic acids which are composed essentially or exclusively of nucleotides, proteins which are composed essentially or exclusively of amino acids, and polysaccharides which are composed essentially or exclusively of monosaccharides ,
  • "essentially” means that the relevant biopolymers (A) may contain other structural units or building blocks than those mentioned, but that the structures and the essential chemical and physical properties of the relevant biopolymers (A) of the nucleic acids, the amino acids or the Monosaccharides are determined (see Thieme Römpp Online 2008, »Biopolymers«)
  • the synthetic polymers and biopolymers (A) can be prepared in situ in the process according to the invention in the chaotropic liquid (C) described below.
  • Polysaccharides (A) are preferably used.
  • the polysaccharides (A) include homopolysaccharides or heteropolysaccharides as well as proteoglycans, wherein the polysaccharide portion outweighs the protein content.
  • structural polysaccharides (A) are used. They are characterized by largely elongated, unbranched and therefore easily crystallizable chains, which ensure the mechanical strength. Examples of suitable structural polysaccharides
  • (A) are cellulose, lignocellulose, chitin, chitosan, glucosaminoglycans, in particular
  • the materials according to the invention may also contain at least one additive (B).
  • gaseous, liquid and solid, preferably liquid and solid, materials can be used as additives (B), as long as they are not undesirable with the polysaccharides (A) and in the context of chaotropic liquids (C) and / or liquid media (D1) and / or (D2) used in the method according to the invention described below, such as substances with strong positive redox potential such as platinum hexafluoride or strong negative redox potential such as metallic potassium, and / or uncontrolled decompose explosively, such as heavy metal azides.
  • substances with strong positive redox potential such as platinum hexafluoride or strong negative redox potential such as metallic potassium
  • uncontrolled decompose explosively such as heavy metal azides.
  • the additives (B) are selected from the group consisting of low molecular weight, oligomeric and polymeric, organic, inorganic and organometallic compounds, organic, inorganic and organometallic nanoparticles and microscopic and macroscopic particles and moldings, biomolecules, cell compartments, cells and cell aggregates.
  • the choice of the additive (B) or of the additives (B) depends primarily on what technical, sensory and / or aesthetic effects it wants to achieve in or with the materials according to the invention.
  • the additives (B) may have the physical or structural properties, such as density, strength, flexibility, nanoporosity, microporosity, macroporosity, absorbency, adsorptivity and / or barrier to gases and liquids, of the materials of the present invention as such, and vary appropriately.
  • plasticizers e.g. Structural proteins such as keratin, urea, monosaccharides such as glucose, polysaccharides such as polyoses or cyclodextrins
  • the flexibility and permeability of materials of the invention are varied.
  • the additives (B) may also impart properties to the materials of the invention containing them which comprise the additives (B) as such.
  • the additives (B) dyes, catalysts, colorants, fluorescent, phosphorescent, electrically conductive, magnetic or microwave radiation absorbing pigments, light stabilizers, vitamins, provitamins, antioxidants, Peroxidzersetzer, repellent, radioactive and non-radioactive non-metal and / or metal ions containing compounds , Compounds that have such ions absorb, flame retardants, hormones, diagnostics, pharmaceuticals, biocides, insecticides, fungicides, acaricides, fragrances, flavorings, flavorings, food ingredients, engineering plastics, enzymatically or non-enzymatically active proteins, structural proteins, antibodies, antibody fragments, nucleic acids, genes, cell nuclei, Mitochondria, cell membrane materials, ribosomes, chloroplasts, cells or blastocysts.
  • additives (B) are known from international patent application WO 2004/084627 A2 or US patent application US 2007/0006774 A1.
  • the additives (B) can be used in the matrix formed by the polymer (A), in particular in the polysaccharide matrix, the materials according to the invention and the solid, porous materials based on polymers (A), in particular polysaccharides, produced by the process according to the invention (A), more or less homogeneously distributed.
  • fibrous additives (B) may have an inhomogeneous distribution in order to vary mechanical properties in the desired manner.
  • catalytically active additives (B) whose accessibility in the matrix formed by the polymer (A), in particular in the polysaccharide matrix, can be improved by an inhomogeneous distribution.
  • the most homogeneous possible distribution in the matrix formed by the polymer (A), in particular in the polysaccharide matrix is advantageous, for example when softening additives (B) are used.
  • the additives (B) may be more or less firmly bonded to the matrix formed by the polymer (A), in particular the polysaccharide matrix.
  • polymeric or particulate additives (B) can be permanently bonded to the matrix formed by the polymer (A), in particular the polysaccharide matrix.
  • the amount of additive (B) or additives (B) contained in a given material according to the invention can vary widely and depends mainly on their physical, chemical and structural properties on the one hand and on the technical, sensory and / or aesthetic effects , the you want to adjust.
  • the person skilled in the art can therefore adjust suitable quantitative ratios in a simple manner on the basis of his general technical knowledge, if appropriate with the aid of a few orienting experiments.
  • the materials of the invention can be prepared by conventional and known methods. According to the invention, it is advantageous to prepare them by the processes according to the invention.
  • At least one, in particular one, of the above-described polymers (A) is optionally in the presence of at least one of the above-described additives (B) in at least one, in particular one, substantially or completely anhydrous chaotropic liquid (C) solubilized.
  • Chaotropic is understood to mean the property of substances, in particular of liquids, of dissolving supermolecular associates of macromolecules by disrupting or influencing the intermolecular interactions, such as, for example, hydrogen bonds, without influencing the intramolecular covalent bonds (cf. Römpp Online 2008, “Chaotropic”).
  • the chaotropic liquids (C) used in the process according to the invention are essentially or completely free of water.
  • substantially anhydrous means that the water content of the chaotrope liquids (C) is ⁇ 5% by weight, preferably ⁇ 2% by weight, preferably ⁇ 1% by weight and in particular ⁇ 0.1% by weight.
  • Fully anhydrous means that the water content is below the detection limits of conventional and known methods for the quantitative determination of water.
  • the chaotropic liquids (C) are in a temperature range of -
  • the chaotrope liquids (C) have a melting point of preferably at most 150 0 C, preferably at most 130 0 C and in particular at most 100 0 C have.
  • Especially effective chaotropic liquids (C) are the so-called ionic liquids. They are therefore used with very particular preference.
  • Ionic liquids consist exclusively of ions (cations and anions). They may consist of organic cations and organic or inorganic anions or of inorganic cations and organic anions.
  • ionic liquids are molten salts with a low melting point. It is not only expected that the liquid at ambient temperature, but also all salt compounds, which preferably below 150 0 C, preferably below 130 0 C and especially below 100 ° C melt. Unlike conventional inorganic salts such as sodium chloride (melting point 808 0 C), ionic liquids are reduced by charge delocalization lattice energy and symmetry, which may for solidification points down to -80 0 C and run underneath. Due to the numerous possible combinations of anions and cations, ionic liquids with very different properties can be prepared (cf a Römpp Online 2007, "ionic liquids").
  • Organic cations can be any cations commonly used in ionic liquids. Preferably, they are noncyclic or heterocyclic onium compounds.
  • noncyclic and heterocyclic onium compounds from the group consisting of quaternary ammonium, oxonium, sulfonium and phosphonium cations and of uronium, thiouronium and guanidinium cations, in which the single positive charge is delocalized over several heteroatoms used ,
  • heterocyclic quaternary ammonium cations are selected from the group consisting of pyrrolium, imidazolium, 1H-pyrazolium, 3H-pyrazolium, 4H-
  • Pyrazolium 1-pyrazolinium, 2-pyrazolinium, 3-pyrazolinium, 2,3-dihydro- imidazolinium, 4,5-dihydroimidazolinium, 2,5-dihydroimidazolinium, pyrrolidinium, 1, 2,4-triazolium (quaternary nitrogen atom in 1-position), 1, 2,4-triazolium ( 4-position quaternary nitrogen atom), 1, 2,3-triazolium (1-position quaternary nitrogen atom), 1, 2,3-triazolium (4-position quaternary nitrogen atom), oxazolium, isooxazolium, thiazolium , Isothiazolium, pyridinium, pyridazinium, pyrimidinium, piperidinium, morpholinium, pyrazinium, indolium, quinolinium, isoquinolinium, quinoxaline and indolinium cations.
  • imidazolium cations in particular the 1-ethyl-3-methylimidazolium cation (EMIM) or the 1-butyl-3-methylimidazolium cation (BMIM), in which the quaternary nitrogen in each case in 1 - Position is used.
  • EMIM 1-ethyl-3-methylimidazolium cation
  • BMIM 1-butyl-3-methylimidazolium cation
  • Suitable inorganic cations are all cations which do not form crystalline salts with the organic anions of the ionic liquids (C) whose melting point is above 150 ° C.
  • suitable inorganic cations are the cations of the lanthanides.
  • inorganic anions are basically all anions into consideration, which do not form crystalline salts with the organic cations of ionic liquids (C) whose melting point is above 150 0 C, and which also no undesirable interactions with the organic cations, such as chemical reactions, received.
  • the inorganic anions are selected from the group consisting of halide, pseudohalide, sulfide, halometalate, cyanometalate, carbonylmetalate, haloborate, halophosphate, haloarsenate, and haloantimonate anions and the anions of the halide, sulfur, of nitrogen, phosphorus, carbon, silicon, boron and transition metals.
  • Fluoride, chloride, bromide and / or iodide ions are preferred as halide anions, cyanide, cyanate, thiocyanate, isothiocyanate and / or azide anions as pseudohalide anions, sulfide, hydrogen sulfide, polysulfide and / or hydrogen polysulfide anions as sulfide anions, as halometalatanions chloro- and / or bromoaluminates and / or -ferrate, as cyanometallate anions hexacyanoferrate (II) and / or - (III) anions, as carbonylmetalate anions tetracarbonylferratanions, as haloborate anions tetrachloro- and / or tetrafluoroborate anions, as halophosphate, haloarsenate anions and Haloantimonate anions hexafluorophosphate, he
  • organic anions are basically all anions into consideration, which do not form crystalline salts with the organic or inorganic cations of ionic liquids (C) whose melting point is above 150 0 C, and which also no undesirable interactions with the organic or inorganic cations, such as chemical reactions.
  • the organic anions of aliphatic, cycloaliphatic and aromatic acids are derived from the group consisting of carboxylic acids, sulfonic acids, acidic sulfate esters, phosphonic acids, phosphinic acids, acidic phosphate esters, hypodiphosphinic acids, hypodiphosphonic acids, acidic boric acid esters, boronic acids, acidic silicic acid esters and acidic silanes they are selected from the group consisting of aliphatic, cycloaliphatic and aromatic thiolate, alcoholate, phenolate, methide, bis (carbonyl) imide, bis (sulfonyl) imide and
  • Carbonylsulfonylimidanionen selected.
  • EMIM Ac 1-ethyl-3-methylimidazolium acetate
  • the temperature at which the polymers (A) described above and optionally the additives (B) described above are solubilized in the chaotropic liquid (C) depends primarily on the temperature range in which the chaotrope liquid (C) is liquid , according to the thermal stability and chemical reactivity of the substances to be solubilized (A) and (B) as well as the rate of solubilization. Thus, the temperature should not be so high that it comes in the solubilization to a thermal decomposition of the substances (A) and (B) and / or undesirable reactions between them.
  • the temperature should not be so low that the speed of solubilization becomes too low for practical needs.
  • the solubilization at temperatures from 0 to 100 0 C, preferably 10 to 70 0 C, more preferably 15 to 50 ° C and in particular 20 to 30 0 C performed.
  • the solubilization in the first process step has no special features, but can be carried out batchwise or continuously using the customary and known mixing units, such as stirred tanks, Ultraturrax, inline dissolvers, homogenization units such as homogenizing nozzles, kneaders or extruders.
  • mixing units such as stirred tanks, Ultraturrax, inline dissolvers, homogenization units such as homogenizing nozzles, kneaders or extruders.
  • the content of polymers (A) of the solution or dispersion (AC) or (ABC) resulting in the first process step may likewise vary widely.
  • the upper limit of the content is determined on a case-by-case basis in such a way that the viscosity of the solution or dispersion (AC) or (ABC) in question can not be so high that it can no longer be processed.
  • the content is from 0.1 to 10 wt .-%, preferably 0.25 to 5 wt .-% and in particular 0.5 to 3 wt .-%, each based on (AC) or (ABC).
  • the solution or dispersion (AC) or (ABC) obtained in the first process step is contacted with a protic polar inorganic liquid (D1).
  • the protic polar inorganic liquid (D1) is miscible with the above-described chaotropic liquid (C), preferably without a miscibility gap, ie in any quantitative ratio.
  • the polymer (A) in (D1) is substantially or completely insoluble.
  • the optionally present additives (B) may be soluble or insoluble in (D1).
  • the protic polar inorganic liquid (D1) used is in particular water.
  • the solution or dispersion (AC) or (ABC) may be contacted in different ways with (D1), in particular with water, for example by pouring the solution or dispersion (AC) or (ABC) into the liquid (D1) , drips, sprayed or extruded or in the form of a film with the liquid (D1) or its vapor (D1) brings into contact. This can be carried out continuously or batchwise in batch mode.
  • the solution or dispersion (AC) or (ABC) is dripped or sprayed into the liquid (D1) in the form of droplets so that beads or beads may form in contact with (D1).
  • the ratio of solution or dispersion (AC) or (ABC) to liquid (D1) may vary widely from case to case. It is essential that the quantitative ratio is selected such that the polymer (A), in particular the polysaccharide (A), is quantitatively precipitated or regenerated.
  • the person skilled in the art can therefore easily determine the required quantitative ratio on the basis of his general knowledge, where appropriate with the aid of a few orienting experiments.
  • the temperature at which the second process step is carried out may also vary widely. In the first place, the temperature depends on the temperature range in which the liquid (D1) is liquid. Also, the solution or dispersion (AC) or (ABC) on contact with (D1) should not have too high temperatures, because otherwise it can lead to a sudden evaporation and / or to a decomposition of the liquid (D1).
  • the second process step is also carried out at temperatures of 0 to 100 0 C, preferably 10 to 70 0 C, more preferably 15 to 50 ° C and in particular 20 to 30 0 C.
  • phase (E) the solid polymer (A), in particular solid polysaccharide (A), chaotropic liquid (C) and liquid (D1) and optionally contains or consists of at least one additive (B), and a liquid phase (F) containing or consisting of chaotrope liquid (C) and liquid (D1).
  • the phase (E) already has the preferred form of beads or beads.
  • the phase (E) is kept in contact with the liquid (D1) for a certain time, preferably for 10 minutes to 24 hours, more preferably 20 minutes to 10 hours and especially 30 minutes to 2 hours , so that the desired shape of the phase (E), in particular the spherical shape or bead shape completely form and mature.
  • the phase (E) is separated from the phase (F). This can be done in different ways, preferably by decanting, centrifuging and / or filtering. This process step can also be carried out continuously or batchwise in batch mode.
  • the chaotropic liquid (C) is removed from the phase (E) with the aid of the liquid (D1), whereby a moist gel (G) based on the polymer (A), in particular the polysaccharide ( A) results.
  • the chaotrope liquid (C) is removed by washing the phase (E) at least once with the liquid (D1), after which the washing liquid (D1) is separated from the phase (E).
  • the above-described continuous or discontinuous methods can be used.
  • the washing and separation is continued until no more chaotropic liquid (C) can be detected in the moist gel (G) and / or in the washing liquid (D1).
  • the fourth process step is carried out at temperatures at which the resulting moist gel (G) is not thermally damaged, in particular does not age rapidly.
  • the resulting wet gel (G) already has the three-dimensional shape as the inventive material to be produced therefrom.
  • Preferred protic polar organic liquids (D2) are alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and / or 2-butoxyethanol, but especially ethanol ,
  • the gel (G) containing (D2) is treated with the liquid (D1), in particular with water.
  • the treatment is preferably carried out by bringing the (D2) -containing gel (G) into contact with the liquid (D1) at least once, followed by (D1) for a certain time, preferably 1 minute to 2 hours (G). allowed to act and then separated.
  • this is preferably carried out by stirring the spheres or beads according to the invention in (D1) and subsequently separating off by centrifuging, decanting and / or filtering.
  • the moist material according to the invention can be dried in the eighth process step.
  • the moist or dried material according to the invention which is free of additives (B), at least one additive (B) or the moist or dried material according to the invention, which already contains at least one additive (B), at least one further additive (B) are added.
  • At least one of the process steps can be carried out at a pressure greater than 100 kPa.
  • the process according to the invention is carried out overall at atmospheric pressure.
  • the process according to the invention directly supplies the materials according to the invention in a very reproducible manner.
  • the method according to the invention makes it possible to produce the materials according to the invention in a wide variety of predefined three-dimensional forms, such as the forms described above, in a targeted manner and with very good reproducibility. Due to the precise adjustability of their dimensions, the materials according to the invention can be assembled safely and reliably into even more complex three-dimensional moldings.
  • the materials according to the invention and the solid, porous materials based on polymers (A) prepared in accordance with the method of the invention can therefore be advantageously used in a wide variety of technical fields within the scope of the inventive use. They can be used in synthetic and analytical chemistry, biochemistry and genetic engineering, biology, pharmacology, medical diagnostics, cosmetics, natural gas and petroleum extraction technology, process technology, paper technology, packaging technology, electrical engineering, magnetic engineering,
  • Communication technology radio and television technology, agricultural technology, aerospace technology and textile technology and construction, land and sea transport and engineering, in particular as support particles, proppants or materials, construction materials, insulation, fabrics, absorbents, adsorbents, membranes, release materials, barrier layers, Controlled release materials, catalysts, culture media, catalysts and colorants, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame retardant materials or used for their preparation.
  • the materials according to the invention and the solid, porous materials based on biopolymers (A) prepared in the process according to the invention are used in the natural gas and petroleum extraction technology.
  • the solid materials are preferably used as powder, in particular powder with spherical particles such as spheres or beads. They are preferably used as deformable, pressure-resistant support particles, support materials or proppants in liquid media for fracturing or borehole stimulation. In this case, liquid media based on water or oil can be used.
  • the resulting liquid media according to the invention for The fracturing - in short: "fracturing media" - in addition to the proppants according to the invention, other conventional and known components, such as the proppants described in US Patent Application US 2006/0151 170 A1, protective layers, substances for weight modification, gelling agents, crosslinking agents, yellowing Contain agents, curable resins, curing agents, surface-active compounds, foaming agents, means for separating emulsions, clay stabilizers and / or acids.
  • other conventional and known components such as the proppants described in US Patent Application US 2006/0151 170 A1
  • protective layers substances for weight modification, gelling agents, crosslinking agents, yellowing Contain agents, curable resins, curing agents, surface-active compounds, foaming agents, means for separating emulsions, clay stabilizers and / or acids.
  • the fracturing medium according to the invention with the proppants according to the invention is pumped under pressure into the production horizon to break up the rock. If the hydrostatic pressure of the fracturing medium exceeds the fracturing gradient of the production horizon, it breaks up at defects, and the fracturing medium according to the invention penetrates into the rupturing or already torn gaps, cracks and channels. After reducing the hydrostatic pressure of the fracturing medium according to the invention, the proppants according to the invention effectively and for a long time prevent the closing of the formed crevices, cracks and channels by the overlying rock. There is also no or only a very small formation of finely divided abrasion of rock and / or crumbs of proppants. Overall, a better long-term exploitation of the funding horizon results.
  • a one percent solution of cellulose in EMIM Ac was added dropwise with stirring to a beaker filled with water.
  • a drop of a wetting agent had been added to the water to lower the surface tension of the water and to allow the formation of beads.
  • the beads were ripened for one hour each.
  • the contents of the beaker were stirred uniformly to prevent deformation of the beads.
  • the beads were separated from the water-EMI M Ac solution by filtration, treated with ethanol for one hour, and rinsed with water for 20 minutes. Subsequently, the water-moist beads were dried for 2 hours at 80 0 C in a convection oven.
  • the shells had a uniform thickness in the range of 30 to 50 microns. They were clear and transparent and a bit softer than the seeds.
  • the cores were opaque and harder than the shells and had a substantially uniform porous structure with pore diameters in the range of 1 to 5 ⁇ m.
  • Example 2 and Comparative Experiment V3 The Absorbency of the Cellulose Beads 1 of Example 1 (Example 2) and the Cellulose Beads V1 of Comparative Experiment V1 (Comparative Experiment V3)
  • Example 2 the cellulose beads 1 of Example 1 were used.
  • the cellulose beads 1 (Example 2) and V1 (Comparative Experiment V3) were separately swollen in a one percent aqueous solution of a dye (trisodium salt of pyrentrisulfonic acid) for one hour. Subsequently, the swollen cellulose beads 1 and V1 were dried for 2 hours in a circulating air oven at 80 0 C. In each case 5 of the dried, dye-loaded cellulose beads 1 and V1 were added separately in each case in a water-filled cuvette. Subsequently, the leaching behavior of the dye-loaded cellulose beads 1 and V1 was measured by UVA / IS spectroscopy by the change in the intensity of absorption of the dye at 207 nm in water.
  • a dye trisodium salt of pyrentrisulfonic acid
  • Example 1 was repeated to give cellulose beads having particle sizes of 800 ⁇ m to 1.6 mm. Subsequently, the performance properties essential for use as a proppant were measured (Example 3). For purposes of comparison, the corresponding performance properties of commercial proppants were measured. It was in the comparative experiment V4 sintered bauxite (high pressure resistant, ceramic material) and in the Comparative experiment V5 used an uncoated fracturing sand. The following results were obtained.
  • the compressive strength of the cellulose beads 3 was determined according to ISO 13502-2. For this purpose, 40 g each of the proppants were introduced into a 2 inch (5.02 cm) diameter steel cell and loaded with the pressure given in Table 1. Subsequently, the amount of the resulting fines was determined.
  • the proppants fill out the channels introduced into the rock. It is important here that the permeability of the channels is maintained and is reduced as little as possible by the proppants. This is achieved above all by using round, spherical particles as far as possible. Therefore, roundness and sphericity of the proppants were determined according to ISO 13502-2.
  • the apparent specific gravity and bulk density are also essential. A low density prevents settling of the proppants.
  • Conductivity and permeability Ultimately, it is crucial for the use of the cellulose beads 3 of Example 3 as proppants, whether the conductivity and the permeability of the rock columns are maintained over a longer period. Therefore, the conductivity and permeability of a model gap in Ohio sandstone at a loading of 2 lb / ft 2 (95.76 Pa) were determined using a 2% potassium chloride solution according to API RP 61. The results are shown in Table 4. They supported that at moderate pressures and temperatures, even after 10 hours, a significant residual conductivity remained, which meant that the cellulose beads 3 of Example 3 were suitable as proppants.

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Abstract

L'invention concerne des matériaux poreux solides présentant une structure coeur-écorce à base de polymères et/ou de biopolymères synthétiques (A) qui sont solubles dans des liquides chaotropes (C) et insolubles dans des liquides inorganiques polaires protogènes (D1) et dans des liquides organiques polaires protogènes (D2). L'invention concerne également des procédés permettant de les produire et leur utilisation.
PCT/EP2009/051791 2008-02-22 2009-02-16 Matériaux poreux solides à structure coeur-écorce à base de polymères et de biopolymères synthétiques, procédés pour les produire et leur utilisation Ceased WO2009103680A1 (fr)

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EP08101892.1 2008-02-22

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
US20140199352A1 (en) * 2013-01-14 2014-07-17 Xerox Corporation Porous nanoparticles produced by solvent-free emulsification
AT515180A1 (de) * 2013-10-15 2015-06-15 Chemiefaser Lenzing Ag Dreidimensionaler cellulosischer Formkörper, Verfahren zu seiner Herstellung und seine Verwendung
EP3167005A4 (fr) * 2014-07-11 2017-12-06 Rhodia Operations Complexes polymères électriquement conducteurs et dispositifs électroniques contenant de tels complexes

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US5328603A (en) * 1990-03-20 1994-07-12 The Center For Innovative Technology Lignocellulosic and cellulosic beads for use in affinity and immunoaffinity chromatography of high molecular weight proteins
US6328443B1 (en) * 2000-06-30 2001-12-11 Eastman Kodak Company Ink jet printing method
DE10063197A1 (de) * 2000-06-28 2002-01-10 Leder Kunstledertech Forsch Verfahren zur Herstellung von partikulärem Gelmaterial mit gesteuertem Permeationsverhalten
US6492006B1 (en) * 2000-06-30 2002-12-10 Eastman Kodak Company Ink jet recording element
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WO2007085624A1 (fr) * 2006-01-24 2007-08-02 Basf Se Structures polymères pour la fabrication de tissus artificiels
US20070287760A1 (en) * 2006-06-08 2007-12-13 James Charles Bohling Process for macroporous acrylic resins
WO2008003623A1 (fr) * 2006-07-06 2008-01-10 Basf Se Procédé de fabrication de pièces de forme nanoporeuses
WO2009048514A1 (fr) * 2007-10-11 2009-04-16 Eastman Kodak Company Procédé de fabrication de particules poreuses à enveloppe non poreuse

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US5328603A (en) * 1990-03-20 1994-07-12 The Center For Innovative Technology Lignocellulosic and cellulosic beads for use in affinity and immunoaffinity chromatography of high molecular weight proteins
DE10063197A1 (de) * 2000-06-28 2002-01-10 Leder Kunstledertech Forsch Verfahren zur Herstellung von partikulärem Gelmaterial mit gesteuertem Permeationsverhalten
US6328443B1 (en) * 2000-06-30 2001-12-11 Eastman Kodak Company Ink jet printing method
US6492006B1 (en) * 2000-06-30 2002-12-10 Eastman Kodak Company Ink jet recording element
DE102004002206A1 (de) * 2004-01-15 2005-08-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Gelpartikel und Verfahren zu deren Herstellung
WO2007085624A1 (fr) * 2006-01-24 2007-08-02 Basf Se Structures polymères pour la fabrication de tissus artificiels
US20070287760A1 (en) * 2006-06-08 2007-12-13 James Charles Bohling Process for macroporous acrylic resins
WO2008003623A1 (fr) * 2006-07-06 2008-01-10 Basf Se Procédé de fabrication de pièces de forme nanoporeuses
WO2009048514A1 (fr) * 2007-10-11 2009-04-16 Eastman Kodak Company Procédé de fabrication de particules poreuses à enveloppe non poreuse

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140199352A1 (en) * 2013-01-14 2014-07-17 Xerox Corporation Porous nanoparticles produced by solvent-free emulsification
US9309114B2 (en) * 2013-01-14 2016-04-12 Xerox Corporation Porous nanoparticles produced by solvent-free emulsification
AT515180A1 (de) * 2013-10-15 2015-06-15 Chemiefaser Lenzing Ag Dreidimensionaler cellulosischer Formkörper, Verfahren zu seiner Herstellung und seine Verwendung
AT515180B1 (de) * 2013-10-15 2016-06-15 Chemiefaser Lenzing Ag Dreidimensionaler cellulosischer Formkörper, Verfahren zu seiner Herstellung und seine Verwendung
EP3167005A4 (fr) * 2014-07-11 2017-12-06 Rhodia Operations Complexes polymères électriquement conducteurs et dispositifs électroniques contenant de tels complexes

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