WO2009103680A1

WO2009103680A1 - Solid, porous materials with a core-shell structure on the basis of synthetic polymers and biopolymers, method for their production and use thereof

Info

Publication number: WO2009103680A1
Application number: PCT/EP2009/051791
Authority: WO
Inventors: Simon Champ; Robert Chapman
Original assignee: Basf Se
Priority date: 2008-02-22
Filing date: 2009-02-16
Publication date: 2009-08-27

Abstract

The invention relates to solid, porous materials with a core-shell structure on the basis of synthetic polymers and/or biopolymers (A), which are soluble in chaotropic liquids (C) and insoluble in protic polar inorganic liquids (D1) and protic polar organic liquids (D2). The invention also relates to a method for their production and to the use thereof.

Description

Solid, porous materials with core-shell structure based on synthetic polymers and biopolymers, process for their preparation and their use

Field of the invention

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.

State of the art

The preparation of solid materials based on biopolymers such as polysaccharides, which may also contain additives, using chaotropic liquids, in particular ionic liquids, is known from international and US patent applications and US Patents WO 03/029329 A2, US 2003/0157351 A1 , WO 2004/084627 A2, US 2004/0038031 A1, US Pat. No. 6,824,599, US Pat. No. 6,808,557, US 2004/0006774 A1, WO 2007/057235 A2 and WO 2007/085624 A1.

In these known methods, a polysaccharide, in particular cellulose, optionally dissolved together with additives in an ionic liquid. Subsequently, the solution is introduced into a liquid medium which is miscible with the ionic liquid, but which is unable to dissolve the polysaccharide. As a result, the polysaccharide is regenerated again. Suitable liquid media include or consist of water, alcohols, nitriles, ethers or ketones. Preferably, water is used, because then can be dispensed with the use of volatile organic solvents. Usually, 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. In particular, 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. Although these beads are porous, they have no core-shell structure. In addition, there is a risk in these known processes of producing irregular beads having a broad particle size distribution.

On the whole, disadvantages of the specific and reproducible production of powder particles on the basis of regenerated polysaccharide make it more difficult, so that the powder particles are not suitable for numerous applications for technical and economic reasons.

US 2006/0151 170 A1 discloses a process for stimulating petroleum and natural gas sources. In this method, 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 μm is press-fitted into a wellbore. Here, 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. 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.

In the known fracturing process, deformable proppants are made from shredded natural products such as, for example, sliced, ground or crushed Nutshells, fruit seeds, plant trays or wooden parts. However, these must be provided with a protective layer in order to adapt the elastic modulus of the proppants to the respective requirements. Moreover, 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.

task

It is an object of the present invention to provide novel, solid, porous materials based on synthetic polymers and biopolymers having a core-shell structure. In addition, the cores of these new, solid, porous materials should be comparatively hard and have a uniform, porous structure. Furthermore, the shells of these new, solid, porous materials should be softer and more compact than the cores and have a uniform thickness.

Overall, the 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.

In addition, it was the object of the present invention to propose a novel process for the preparation of solid, porous materials based on synthetic polymers and biopolymers, which no longer has the disadvantages of the prior art.

Above all, 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. In particular, these process products should have the desired property profile described above. Last but not least, 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. In particular, 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.

Inventive solution

Accordingly, the 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.

Hereinafter, the novel solid porous materials will be referred to as "materials of the invention".

In addition, the new process for the production of solid, porous materials based on synthetic polymers and / or biopolymers (A) by

(1) solubilization of at least one synthetic polymer and / or biopolymer (A) or at least one synthetic polymer and / or biopolymer (A) and at least one additive (B) in at least one substantially or completely anhydrous chaotropic liquid (C), (2) contacting the solution or dispersion (AC) or (ABC) obtained in process (1) with a protic polar inorganic liquid (D1) which is miscible with the chaotropic liquid (C) but wherein at least the polymer ( A) is substantially or completely insoluble, whereby a phase (E), the solid polymer (A), chaotropic liquid (C) and protic polar inorganic

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),

(3) separation of the phase (E) from the phase (F),

(4) removing the chaotropic liquid (C) from the phase (E) using the liquid (D1), resulting in a wet gel (G) based on synthetic polymer and / or biopolymer (A),

(5) treating the moist gel (G) containing (D1) with a protic polar organic liquid (D2) which is miscible with both the chaotropic liquid (C) and the liquid (D1) but wherein at least the polymer ( A) is substantially or completely insoluble,

(6) treating the wet gel (G) containing the liquid (D2) with the liquid (D1) and

(7) Separating the Resulting Wet, Solid, Porous Material (A) or (AB) Based on Synthetic Polymers and / or Biopolymers (A)

found.

In the following, the new process for producing solid, porous materials based on synthetic polymers and / or biopolymers (A) is referred to as the "process according to the invention".

In addition, the use of the materials according to the invention and of the solid, porous materials according to the invention based on synthetic polymers and biopolymers (A) and materials according to the invention in synthetic and analytical chemistry, biochemistry and genetic engineering, Biology, pharmacology, medical diagnostics, cosmetics, natural gas and petroleum extraction technology, process technology, paper technology, electrical engineering, magnetic engineering, communications technology, radio and television technology, agricultural engineering, aerospace and textile technology and construction, land and sea transport and mechanical engineering found what hereinafter referred to collectively as "inventive use".

Advantages of the invention

In view of the prior art, it was surprising and unforeseeable for the skilled person that the object underlying the present invention could be achieved by means of the materials according to the invention, the method according to the invention and the use according to the invention.

In particular, it was surprising that the inventive method provided materials according to the invention with a core-shell structure. As desired, the cores of the inventive materials were relatively hard and had a uniform, porous structure. Furthermore, the shells of the materials according to the invention were softer and more compact than the cores and had a uniform thickness.

Overall, 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.

It was also surprising that the process according to the invention no longer had the disadvantages of the prior art.

Above all, 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. Last but not least, 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. In particular, they were outstandingly suitable as support particles, support materials or proppants, construction materials, insulations, fabrics, absorbents, adsorbents, membranes, release materials, barrier layers, controlled-release materials, catalysts, culture media, catalysts and also colorant, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame retardant materials or for their manufacture.

In particular, 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. As a result, the flow rates could be significantly increased.

Detailed description of the invention

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". Preferably, 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. Preferably, 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. Preferably, the cups are more compact than the cores, that is, they have a lower porosity than the cores. For the term porosity, see Römpp Online 2008, "Porosity". Preferably, 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.

Preferably, 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. Preferably, the size varies from 100 nm to 10 mm. This means that the three-dimensional shapes are micro or macro forms.

As for the three-dimensional shapes, 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. 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. In addition, 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). This means that 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.

Hereinafter, the synthetic polymer and / or biopolymer are also collectively referred to as "polymer (A)" or "polymers (A)".

Basically, 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.

Preferably, 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 , Here, "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.

In particular, 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

Chondroitin sulphates and keratan sulphates, as well as alginic acid and alginates. In particular, will

Cellulose used.

The materials according to the invention may also contain at least one additive (B).

Basically all 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.

Preferably, 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 range of suitable additives (B) is therefore virtually unlimited. Therefore, the materials according to the invention can be varied almost arbitrarily in the desired manner, which is one of their very special advantages.

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.

Thus, 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. For example, with the help of 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.

However, the additives (B) may also impart properties to the materials of the invention containing them which comprise the additives (B) as such. Thus, 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.

Examples of 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. For example, it may be advantageous if fibrous additives (B) have an inhomogeneous distribution in order to vary mechanical properties in the desired manner. The same applies to 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. In many cases, on the other hand, 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. Thus, in particular polymeric or particulate additives (B) can be permanently bonded to the matrix formed by the polymer (A), in particular the polysaccharide matrix. In contrast, it may be advantageous, in particular, for the low molecular weight additives (B), if they are not permanently bound to the matrix, but are released again in the sense of a "slow release" or "controlled release".

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.

In the first process step of the process 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.

The term "solubilized" or the term "solubilization" in the context of the present invention mean that the polymer (A) is dissolved in the chaotropic liquid (C) in a molecularly disperse manner or at least as finely divided and homogeneously dispersed as possible. The same applies to the additives (B), if they are used with.

"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.

Preferably, the chaotropic liquids (C) are in a temperature range of -

100 ⁰ C to +150 ⁰ C, preferably -50 ° C to +130 ⁰ C, in particular -20 ° C to + 100 ° C liquid. That is, 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.

In principle, 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.

Preference is given to 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 ,

Particular preference is given to using quaternary ammonium cations and very particularly preferably heterocyclic quaternary ammonium cations.

In particular, the 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.

The organic cations described above are per se known species which are described, for example, in the German and international patent applications and in the American patent application

DE 10 2005 055 815 A, page 6, paragraph [0033], to page 15, paragraph [0074],

- DE 10 2005 035 103 A1, page 3, paragraph [0014], to page 10, paragraph [0051], and

DE 103 25 050 A1, the paragraphs overlapping pages 2 and 3 [0006] in connection with page 3, paragraph [0011], to page 5, paragraph [0020],

- WO 03/029329 A2, page 4, last paragraph, to page 8, second paragraph,

WO 2004/052340 A1, page 8, first paragraph, to page 10, first paragraph,

WO 2004/084627 A2, page 14, second paragraph, to page 16, first paragraph, and page 17, first paragraph, to page 19, second paragraph,

WO 2005/017252 A1, page 1 1, line 20, to page 12, line 19,

WO 2005/017001 A1, page 7, last paragraph, to page 9, fourth last paragraph,

WO 2005/023873 A1, page 9, line 7, to page 10, line 20,

WO 2006/116126 A2, page 4, line 1, to page 5, line 24,

- WO 2007/057253 A2, page 4, line 24, to page 18, line 38, WO 2007/085624 A1, page 14, line 27, to page 18, line 11, and

US 2007/0006774 A1 page 17, paragraph [0157], to page 19, paragraph [0167],

will be described in detail. The listed passages of the patent applications are expressly incorporated by reference for purposes of further explanation of the present invention.

Of the organic cations described above, especially 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.

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. Examples of suitable inorganic cations are the cations of the lanthanides.

As 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.

Preferably, 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, hexafluoroarsenate, hexachloroantimonate and / or hexafluoroantimonate anions, and as anions of the haloacids, sulfur, nitrogen, phosphorus, carbon, silicon, boron and transition metals chlorate, perchlorate, bromate, iodate, sulphate, hydrogensulphate, sulphite, bisulphite, thiosulphate, nitrite, nitrate, phosphinate, phosphonate, phosphate, hydrogenphosphate, dihydrogenphosphate, carbonate, bicarbonate, glyoxylate, oxalate , Delta seed, square, croconate, rhodizonate, silicate, borate, chromate and / or permanganate anions.

In the same way come as 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.

Preferably, 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.

Examples of suitable inorganic and organic anions are from international patent applications

WO 2005/017252 A1, page 7, page 14, to page 1 1, page 6, and

- WO 2007/057235 A2, page 19, line 5, to page 23, page 23,

known. Very particular preference is given to using acetate anions.

In particular, 1-ethyl-3-methylimidazolium acetate (EMIM Ac) is used as the ionic liquid (C). 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. On the other hand, the temperature should not be so low that the speed of solubilization becomes too low for practical needs. Preferably, 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.

From a methodological point of view, 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.

The content of polymers (A) of the solution or dispersion (AC) or (ABC) resulting in the first process step may likewise vary widely. In general, 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. Preferably, 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).

In the further course of the process according to the invention, in the second process step, 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. In contrast, 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.

Preferably, 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). Preferably, 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.

In the second process step results in a 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). Preferably, the phase (E) already has the preferred form of beads or beads. Preferably, prior to carrying out the third process step, 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.

In the third process step, 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.

In the further course of the process according to the invention, in the fourth process step, 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. Preferably, 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). In this case, the above-described continuous or discontinuous methods can be used. Preferably, 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).

Preferably, 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. Preferably, temperatures of 0 to 100 ⁰ C, preferably 10 to 70 ⁰ C, particularly preferably 15 to 50 ⁰ C and in particular 20 to 30 ⁰ C applied.

Preferably, the resulting wet gel (G) already has the three-dimensional shape as the inventive material to be produced therefrom.

In the further course of the process according to the invention, in the fifth process, the moist gel (G) rode with a protic polar organic liquid (D2) which is miscible both with the chaotropic liquid (C) and with the liquid (D1), but wherein at least the polymer (A), in particular the polysaccharide (A), substantially or completely insoluble, treated. 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 ,

In the further course of the process according to the invention, in the sixth process step, 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. In the case of the preferred spheres or beads according to the invention, 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.

In the last separation of (D1), i.e., in the seventh process step, the wet material of the invention results.

The moist material according to the invention can be dried in the eighth process step.

In addition, in a further 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.

In the method according to the invention, at least one of the process steps can be carried out at a pressure greater than 100 kPa. Preferably, the process according to the invention is carried out overall at atmospheric pressure.

It is a very particular advantage of the process according to the invention that it directly supplies the materials according to the invention in a very reproducible manner. In addition, 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.

By the additives (B) described above, the materials according to the invention for the inventive use can be modified in many ways.

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.

In particular, 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.

In the context of this use according to the invention, 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.

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.

All this underpins the extraordinary advantages of the materials according to the invention and of the process according to the invention and of the solid, porous materials based on polymers (A) produced therewith.

Example and comparative experiments

Comparative Experiments V1 and V2

The production of cellulose beads without core-shell structure

A one percent solution of cellulose in 1-ethyl-3-methylimidazolium acetate (EMIM Ac) was added dropwise with stirring into a water-filled beaker (Comparative Experiment V1) or in a beaker filled with ethanol (Comparative Experiment V2). When using water (Comparative Experiment V1) it was necessary to add a drop of wetting agent to lower the surface tension of the water and to allow the formation of pearls. In the time in which the resulting pearls the Reached the bottom of the beakers, they had stabilized so far that there was no danger of deformation. After completion of the addition of the cellulose solution, the beads were ripened for one hour each. The contents of the beakers were stirred uniformly to prevent deformation of the beads. Subsequently, the beads of the water-EM IM Ac solution (Comparative Experiment V1) and the ethanol-EMIM Ac solution (Comparative Experiment V2) were separated by filtration and dried for 2 hours in a convection oven at 80 ⁰ C.

Both Comparative Experiments resulted in dried beads of about 1 mm in diameter with a compact, uniform structure without a core-shell structure.

example 1

The production of cellulose beads with a uniform core-shell structure

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. By the time the resulting beads reached the bottom of the beaker, they had stabilized to such an extent that there was no danger of deformation. After completion of the addition of the cellulose solution, the beads were ripened for one hour each. The contents of the beaker were stirred uniformly to prevent deformation of the beads. Subsequently, 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.

This resulted in dried beads of about 1 mm in diameter with a pronounced and uniform core-shell structure. 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 μm.

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)

For Example 2, the cellulose beads 1 of Example 1 were used.

For the comparative experiment V4, the cellulose beads V1 of Comparative Experiment V1 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. It was found that the dye was leached from the cellulose beads 1 and V1 at substantially the same rate, but that the cellulose beads 1 had absorbed considerably more dye than the cellulose beads V1, so that it took significantly longer for the dye to completely precipitate out of the cellulose beads Cellulose beads 1 was leached. This corroborated that the cellulose beads 1 had a much higher absorbency than the cellulose beads V1.

Example 3 and Comparative Experiments V4 and V5

The preparation of cellulose beads 3 of Example 3 and their performance properties with respect to their use as proppants

Example 1 was repeated to give cellulose beads having particle sizes of 800 μm 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.

Compressive strength:

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.

Table 1: Measurement of compressive strength

The results of Table 1 supported that the cellulose-based powder (A) was clearly superior in compressive strength to commercial proppants.

Roundness and sphericity:

As is known, 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 results are shown in Table 2. The results supported that the cellulose beads 3 of Example 3 had a significantly better sphericity and a significantly better roundness than the commercial fracturing sand (Comparative Experiment V5). and were in this respect the sintered bauxite (Comparative Experiment V4) equal.

Table 2: Measurement of sphericity and roundness

Apparent Specific Gravity and Bulk Density:

For the effectiveness of the proppants used, the apparent specific gravity and bulk density are also essential. A low density prevents settling of the

Proppants as soon as the fracturing medium penetrates into the formed rock channel.

If the material does not penetrate deep enough into the channel or gap, it can penetrate into the channel

Close areas where no proppant is present. A low apparent specific gravity is therefore advantageous. Therefore, the apparent specific gravity and bulk density were measured according to API (American Petroleum Institute) RP 60,

Section 9, "Bulk density and specific gravity" measured.

The results are shown in Table 3. They supported that the cellulose beads 3 of Example 3 were clearly superior to the commercial proppants in this respect.

Table 3: Measurement of bulk density and apparent specific gravity

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.

Table 4: Measurement of conductivity and permeability (Example 3)

Claims

claims

1. Solid, porous materials with core-shell structure based on synthetic polymers and biopolymers (A), which are soluble in chaotropic liquids (C) and insoluble in protic polar inorganic liquids (D1) and protic polar organic liquids (D2) are.

2. Solid, porous materials according to claim 1, characterized in that they are porous.

3. Solid, porous materials according to claim 1 or 2, characterized in that their cores are coarse-pored or fine-pored.

4. Solid, porous materials according to claim 3, characterized in that their cores are finely porous.

5. Solid, porous materials according to claim 4, characterized in that the pores of the cores have a diameter of 50 nm to 10 microns.

6. Solid, porous materials according to one of claims 1 to 5, characterized in that their cores are harder than their shells.

7. Solid, porous materials according to one of claims 1 to 6, characterized in that their shells are more compact than their cores.

8. Solid, porous materials according to claim 7, characterized in that the pores of the shells have a diameter of 1 to <50 nm.

9. Solid, porous materials according to one of claims 1 to 8, characterized in that their shells have a thickness of 1 to 100 microns.

10. Solid, porous materials according to one of claims 1 to 9, characterized in that they have the form of spherical particles, irregular or regularly shaped, non-spherical particles, plates, rods, cylinders, needles, flakes, threads, fabrics or films ,

1 1. Solid, porous materials according to claim 10, characterized in that they have the form of spherical particles.

12. Solid, porous materials according to claim 1 1, characterized in that the spherical particles have the shape of spheres or beads.

13. Solid, porous materials according to claim 1 1, characterized in that the balls or beads have a measured by sedimentation in a gravitational field mean particle size of 0.1 to 10 mm.

14. Solid, porous materials according to one of claims 1 to 13, characterized in that the biopolymers (A) are polysaccharides.

15. Solid, porous materials according to claim 14, characterized in that the polysaccharides (A) are structural polysaccharides.

16. Solid, porous materials according to one of claims 1 to 15, characterized in that they contain at least one additive (B) selected from the group consisting of low molecular weight, oligomeric and polymeric, organic, inorganic and organometallic compounds, organic, inorganic and organometallic nanoparticles as well as microscopic and macroscopic particles and moldings, biomolecules, cell compartments, cells and cell aggregates.

17. Solid, porous materials according to one of claims 1 to 16, characterized in that the chaotrope liquid (C) in a temperature range from -100 ⁰ C to +150 ⁰ C is liquid.

18. Solid, porous materials treated claims 1 to 17, characterized in that the chaotrope liquid (C) is an ionic liquid.

19. Solid, porous materials according to one of claims 1 to 18, characterized in that the protic polar inorganic liquid (D1) is water.

20. Solid, porous materials according to one of claims 1 to 19, characterized in that the protic polar organic liquid (D1) is an alcohol.

21. Solid, porous materials according to claim 20, characterized in that the alcohol (DI) is ethanol.

22. A process for the preparation of solid, porous materials based on synthetic polymers and / or biopolymers (A) by

(1) solubilization of at least one synthetic polymer and / or biopolymer (A) or at least one synthetic polymer and / or biopolymer (A) and at least one additive (B) in at least one substantially or completely anhydrous chaotropic liquid (C),

(2) contacting the solution or dispersion (AC) or (ABC) obtained in process step (1) with a protic polar inorganic liquid (D1) which is miscible with the chaotropic liquid (C) but wherein at least the polymer (A) is essentially or completely insoluble, causing a

Phase (E) comprising or consisting of solid polymer (A), chaotropic liquid (C) and protic polar inorganic liquid (D1) and optionally the at least one additive (B), and a liquid phase (F), the chaotropic liquid (C) and liquid (D1) contains or consists of

(3) separation of the phase (E) from the phase (F),

(5) treating the moist gel (G) containing (D1) with a protic polar organic liquid (D2) which is miscible both with the chaotropic liquid (C) and with the liquid (D1), but wherein at least the polymer ( A) is substantially or completely insoluble, (6) treating the wet gel (G) containing the liquid (D2) with the liquid (D1) and

(7) separating the resulting wet, solid, porous material (A) or

(AB) based on synthetic polymers and / or biopolymers (A)

23. The method according to claim 22, characterized in that

(8) drying the wet, solid, porous material (A) or (AB).

24. The method according to claim 22 or 23, characterized in that

(9a) the wet or dried solid porous material (A) at least one additive (B) or

(9b) at least one further additive (B) is added to the moist or dried, solid, porous material (AB).

25. The method according to any one of claims 22 to 24, characterized in that in the process seh rode (2) in the process step (1) obtained solution or dispersion (AC) or (ABC) contacted with the liquid (D1) by pouring, dropping, spraying or extruding the solution or dispersion (AC) or (ABC) into the liquid (D1) or contacting it in the form of a film with the liquid (D1) or the vapor of the liquid (D1).

26. The method according to claim 25, characterized in that in the process seh rode (2) in the process step (1) obtained solution or dispersion (AC) or (ABC) drips or sprayed into the liquid (D1) in the form of droplets ,

27. The method according to any one of claims 22 to 26, characterized in that in step (3) the phase (E) from the phase (F) by decantation, centrifuging and / or filtration is separated.

28. The method according to any one of claims 22 to 27, characterized in that in step (4) the phase (E) washes at least once with the liquid (D1), after which the washing liquid is separated from the phase (E) and the resulting moist gel (G) isolated.

29. The method according to any one of claims 22 to 28, characterized in that the content of the solution or dispersion (AC) or (ABC) of polymer (A) 0.1 to 10 wt .-%, based on (AC) or ( ABC).

30. The method according to any one of claims 22 to 29, characterized in that solid, porous materials with core-shell structure on the basis of synthetic polymers and / or biopolymers (A), as defined in any one of claims 1 to 29 result ,

31. Use of the solid, porous materials with core-shell structure based on synthetic polymers and / or biopolymers (A) according to any one of claims 1 to 21 and the solid, porous produced by the method according to any one of claims 22 to 30 Materials based on synthetic polymers and / or biopolymers (A) 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, communications technology, radio and television technology, agricultural engineering, aerospace technology and textile technology and construction, land and sea transport and

Mechanical engineering.

32. Use according to claim 31, characterized in that the solid, porous materials based on synthetic polymers and / or biopolymers (A) as support particles, support materials or proppants,

Construction materials, insulations, fabrics, absorbents, adsorbents, membranes, release materials, barrier layers, controlled release materials, catalysts, culture media, catalysts, as well as colorant, fluorescent, phosphorescent, electroconductive, magnetic, microwave radiation absorbing and flame retardant materials or for their manufacture ,

33. Use according to claim 32, characterized in that the support particles, support materials or proppants are used in liquid fracturing media for Bohrlochstimulierung in the natural gas and petroleum production.