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

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

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
liquid
solid
characterized
porous materials
d1
Prior art date
Application number
PCT/EP2009/051791
Other languages
German (de)
French (fr)
Inventor
Simon Champ
Robert Chapman
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP08101892.1 priority Critical
Priority to EP08101892 priority
Application filed by Basf Se filed Critical Basf Se
Publication of WO2009103680A1 publication Critical patent/WO2009103680A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28Working-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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions or lattices by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09Making solutions, dispersions or lattices by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091Making solutions, dispersions or lattices by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096Nitrogen containing compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/80Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2201/00Foams characterised by the foaming process
    • C08J2201/04Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/054Precipitating the polymer by adding a non-solvent or a different solvent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2205/00Foams characterised by their properties
    • C08J2205/02Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02Cellulose; Modified cellulose

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 having a core-shell structure on the basis of synthetic polymers and biopolymers, methods for their preparation and their use

Field of the Invention

The present invention relates to novel, solid, porous materials having a core-shell structure on the basis of 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. Not least, the present invention relates to the use of the new, solid, porous materials having a core-shell structure on the basis of synthetic polymers and biopolymers as well as the solid, porous materials produced by the new process.

State of the art

The preparation of solid materials on the basis of biopolymers such as polysaccharides, which optionally also contain additives, using chaotropic liquids, particularly ionic liquids is known from the international and US Patent Applications and US Patents WO 03/029329 A2, US 2003/0157351 A1 WHERE 2004/084627 A2, US 2004/0038031 A1, US 6,824,599, US 6,808,557, US 2004/0006774 A1, WO 2007/057235 A2 and WO 2007/085624 A1.

In these known processes is a polysaccharide, in particular cellulose, optionally together with additives dissolved in an ionic liquid. Subsequently, the solution is introduced into a liquid medium which is miscible with the ionic liquid, but not capable of dissolving the polysaccharide. Thus, the polysaccharide is regenerated. Suitable liquid media include water, alcohols, nitriles, ethers or ketones, or consist thereof. Preferably, water is used because can then be dispensed with the use of volatile organic solvents. Typically, the regenerated polysaccharide is obtained in the form of a gel. When drying the regenerated polysaccharide gel shrinks and the result is a solid state on the basis of polysaccharide. It is not known if the solids formed have a core-shell structure, and whether they are porous.

From the American patent US 5,328,603 a method for the production of porous beads based on cellulose having a particle size of at least 0.3 mm is known, in which polar cellulose in a chaotropic liquid, in particular in a saturated solution of lithium chloride or calcium thiocyanate in a organic solvent such as dimethylacetamide, dissolves, atomizes the resulting solution and introducing the resulting droplets in a liquid which is miscible with the chaotropic liquid, but not capable of dissolving cellulose. Suitable liquid media, especially water, methanol or water-methanol mixtures. In this case, the droplets solidify and form beads, which can be washed with water and isolated. Although these spheres are porous, however, they have no core-shell structure. Furthermore, with these known methods the risk of irregular beads are formed with a wide particle size distribution.

Total dese disadvantages complicate the targeted and reproducible production of powder particles on the basis of regenerated polysaccharide, so that the powder particles for various applications for technical and economic reasons, are not eligible.

From the American patent application US 2006/0151 170 A1 a method of stimulating oil and gas sources indicate. In this method, a thickened liquid medium, the deformable particles contains, in the form of spheres, cylinders, cubes, rods, cones or irregular shapes having a particle diameter of 850 .mu.m, is pressed under pressure into a wellbore. Here, new cracks and fissures in the oil or gas formation are formed, through which passes the oil or natural gas back to the borehole more readily. This method of well stimulation is known in the oil and gas handling technology as "fracturing". The deformable particles serve as support particles or support materials which prevent the newly formed cracks and fissures are closed again by the pressure of the overlying rock. These supporting particles or support materials are referred to in the natural gas and oil producing art as "proppants". The deformability of the proppants prevented to a certain degree the formation of finely divided material through abrasion of rock material and / or by breaking the proppants, as is common in the use of hard proppants such as sand fracturing. The deformable proppants have thus to some extent the effect of support pads.

In the known fracturing techniques are deformable proppants of crushed natural products such as geschitzelte, ground or crushed nut shells, fruit seeds, plants shells or wood parts may be used. However, they must be provided with a protective layer to adjust the elastic modulus of the proppants to the respective requirements. In addition, the known deformable proppants the disadvantage that their chemical compositions and mechanical properties vary greatly, so that extensive tests are necessary to check whether a delivered batch is suitable given oil or gas formation for one.

task

The present invention was therefore based on the object to provide novel, solid, porous materials based on synthetic polymers and biopolymers which have a core-shell structure. In addition, the cores of these new, solid, porous materials should be relatively hard and have a uniform porous structure. It also aims to be the shells of these novel solid, porous materials softer and more compact than the seeds and have a uniform thickness.

Overall, the new, solid, porous materials based on synthetic polymers and biopolymers with a core-shell structure in the swollen state should have a high mechanical stability. 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

For example, spherical particles, irregularly or regularly shaped, non-spherical particles, plates, rods, cylinders, needles, flakes, threads, fabrics, or films, can be made available, which are all have a high mechanical stability.

Moreover, it was the object of the present invention to provide 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 longer.

Above all, the new process is intended to provide in a simple and very well reproducible manner, solid, porous materials based on synthetic polymers and biopolymers with a core-shell structure. In particular, this process products are intended to have the above described desired properties. Not least, the new, solid, porous materials having a core-shell structure on the basis of synthetic polymers and biopolymers as well as those produced by the new process solid, porous materials based on synthetic polymers and biopolymers are particularly wide, in particular in the synthetic and analytical chemistry, biochemistry and genetic engineering, biology, pharmacology, medical diagnostics, cosmetics, oil and gas handling equipment, process technology, paper technology, packaging technology, electrical engineering, magnet technology,

Communication technology, radio and television technology, agricultural technology, aviation and space technology and textile technology, as well as construction, land and sea transport system and engineering, be used with advantage. Here, they are particularly suited as support particles supporting materials or proppants, construction materials, insulation, fabrics, absorbents, adsorbents, membranes, separating materials, barrier layers, controlled release materials, catalysts, cultivation media, catalysts and color pigments, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame-retardant materials or are suitable for their preparation.

inventive solution

Accordingly, the new, solid, porous materials having a core-shell structure on the basis of synthetic polymers and / or biopolymers (A), which in chaotropic liquids (C) soluble and in protic polar inorganic liquids (D1), and in protic polar were organic liquids (D2) are insoluble found.

The following are the new solid porous materials will be referred to as "inventive materials."

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

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

Liquid (D1) and optionally the at least one additive (B) contains or consists of, and a liquid phase (F), the chaotropic liquid (C) and liquid (D1) contains or consists result,

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

(4) removing the chaotropic liquid (C) from the phase (E) using the liquid (D1), whereby a wet gel (G) results on the basis of synthetic polymer and / or biopolymer (A),

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

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

(7) separating the resulting wet, solid, porous material (A) or (AB) on the basis of synthetic polymers and / or biopolymers (A)

found.

In the following, the novel process for the preparation of solid, porous materials based on synthetic polymers and / or biopolymers (A) will be referred to as "the invention".

Moreover, the use of the materials according to the invention as well as the solid, porous materials produced by the inventive method has been based on synthetic polymers and biopolymers (A) and the inventive materials in synthetic and analytical chemistry, biochemistry and genetic engineering, biology, pharmacology and medical diagnostics, cosmetics, oil and gas handling equipment, process technology, paper, electrical, magnetic equipment, communications equipment, radio and television technology, agricultural technology, aviation and space technology and textile technology, as well as construction, land and sea transport beings and mechanical engineering found what hereinafter collectively as " inventive use "is called.

Advantages of the Invention

In view of the prior art it was surprising and unforeseeable for the skilled person that the task at the present invention is based could be achieved by using the inventive materials, the inventive method and the inventive use.

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

Overall, the inventive materials in the swollen state had a high mechanical stability. They had a higher absorption capacity than the known materials based on polysaccharides. They could be in a variety of three-dimensional shapes, such as spherical particles, irregularly or regularly shaped, providing non-spherical particles, plates, rods, cylinders, needles, flakes, threads, fabrics or films, which all had a high mechanical stability.

Also surprising that the inventive method not having the disadvantages of the prior art longer.

Above all, the method of the invention gave the inventive materials in a simple and very well reproducible manner, which surprisingly showed the above described desired properties. Not least, were materials of the invention and prepared by the process of the invention solid, porous materials based on synthetic polymers and biopolymers (A), in particular materials of the invention, particularly wide, in particular in synthetic and analytical chemistry, biochemistry and genetic engineering, biology, pharmacology, medical diagnostics, cosmetics, oil and gas handling equipment, process technology, paper technology, packaging, electrical, magnetic equipment, communications equipment, radio and television technology, agricultural technology, aviation and space technology and textile technology, as well as construction, land and sea transport beings and mechanical engineering, can be used with advantage. Here they lent themselves particularly suited as support particles supporting materials or proppants, construction materials, insulation, fabrics, absorbents, adsorbents, membranes, separating materials, barrier layers, controlled release materials, catalysts, cultivation media, catalysts and color pigments, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame-retardant materials or their manufacture.

More specifically, appropriated those prepared by the novel process pulverförm strength solid materials based on synthetic polymers and / or biopolymers suited as a wear-resistant, pressure-resistant, deformable proppants in liquid media for fracturing for the purpose of a highly effective and particularly long-lasting well stimulation in promoting natural gas and oil. Thus, the flow rates could be significantly increased.

Detailed Description of the Invention

The inventive materials 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 inventive materials are porous. This means that they have a foam-like or sponge-like structure. The structure may be closed cell or open-pore. Preferably, it is porous, 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 the shells have the same material composition. but they differ in their internal structure or its structure. Preferably, the shells are firmly bonded with the cores so that they do not dissolve during mechanical loading of the cores.

Preferably, the cores of the inventive materials are coarsely porous or finely porous. These properties will pore "refer to Römpp Online 2008,". the pores preferably have a diameter of 50 nm to 10 .mu.m, particularly preferably 500 nm to 8 microns, most preferably 1 micron to 7 microns and especially from 1 .mu.m to 5 .mu.m.

The nuclei of the materials of the invention may be harder or softer than their shells. This means that the shells can be deformed easier or harder than the cores or, in other words, that the material is the seeds rigid or less rigid than the material of the shells. Preferably, the cores are harder than the shells.

The cores and the shells of the materials of the invention may have a different porosity. So the shells can be more compact than the cores and vice versa. Preferably, the shells are more compact than the cores, that is, they have a lower porosity than the cores. To the term porosity is porosity "refer to Römpp Online 2008,". Preferably, the pores of the shells have a diameter of 1 to <50 nm.

The strength of the shells of the materials of the invention may vary widely.

Preferably they have a thickness of 1 to 100 .mu.m, preferably 5 to 90 .mu.m, particularly preferably 10 to 80 microns and especially 15 to 70 microns.

The invention materials may in any three-dimensional shapes,

Sizes and morphologies are present. Preferably, the size of 100 nm to 10 mm varies. This means that the three-dimensional shapes micro or macro forms.

As for the three-dimensional shapes, materials of the invention can be present for example as spherical particles, irregularly or regularly shaped, non-spherical particles, sheets, rods, cylinders, needles, flakes, threads, fabrics or films.

Preferred materials of this invention are as spherical particles, particularly preferably as beads or pearls, before.

The particle size of the balls or beads according to the invention may vary very widely and are thereby excellently adapted to the requirements of the case. Preferably, they have a measured by sedimentation in a gravitational field average particle size of 0.1 to 10 mm, preferably 0.2 to 5 mm and in particular 0.3 to 2 mm. The particle size distribution can be multimodal or monomodal. Preferably, it is monomodal. In addition, the particle size distribution may be narrow or ready. it is closely preferably, ie, balls or the inventive beads have only minor fine and coarse fractions on.

The base materials of the present invention forms at least one, in particular a synthetic polymer and / or biopolymer (A). This means exists or that a given material of the invention contains a synthetic polymer and / or biopolymers (A) that a given material of the invention from a synthetic polymer and / or biopolymer (A), but the synthetic polymer and / or biopolymer (A) the three dimensional structure substantially or alone determined.

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

Virtually all synthetic polymers and biopolymers (A) are suitable for this purpose, provided that they in one of the chaotropic liquids described below (C) soluble, and in the below-described protic polar inorganic liquids (D1) and protic polar organic liquids (D2) insoluble are.

Preferably, the synthetic polymers (A) selected from the group consisting constructed from random, alternating and block, linear, branched, and comb, oligomeric and polymeric (co) polymers of ethylenically unsaturated monomers, polyaddition resins and polycondensation resins (see FIG. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition" and "polyaddition resins (polyadducts)", pages 463 and 464, "polycondensates", "polycondensation" and "polycondensation resins") selected. (Meth) acrylate (co) polymers are preferred, polyurethanes and polyesters, more preferably polyesters used.

Preferably the biopolymers are (A) from the group consisting of nucleic acids, which are composed substantially or exclusively of nucleotides, proteins, which are composed substantially or entirely of amino acids and polysaccharides, which are composed substantially or exclusively from monosaccharides selected , Here, "essentially means" that the biopolymers relevant even as that may contain mentioned (A) other structural units or building blocks, however, that the structures and the essential chemical and physical properties of the respective biopolymers (A) of the nucleic acids, amino acids or monosaccharides are determined (see. Thieme Römpp online 2008, "biopolymers")

The synthetic polymers and biopolymers (A) can be prepared in the process according to the invention in situ as described below chaotropic liquid (C).

Polysaccharides are preferably used (A). Here, the polysaccharides (A) homopolysaccharides or heteropolysaccharides and proteoglycans include wherein the Polysacharidanteil outweighs the protein portion.

In particular, structural polysaccharides are used (A). They are characterized by largely stretched, unbranched and therefore well crystallizable chains that ensure the mechanical strength. Examples of suitable structural polysaccharides

(A) are cellulose, lignocellulose, chitin, chitosan, glycosaminoglycans, in particular

Chondroitin sulfates and keratan sulfates, and alginic acid and alginates. In particular,

Cellulose used.

The invention materials may further comprise at least one additive (B).

As additives (B) may be basically used in gaseous, liquid and solid, preferably liquid and solid materials as long as they do not undesirably with the polysaccharides (A) and the chaotropic liquids used in the process according to the invention described below, (C react), and / or liquid media (D1) and / or (D2), such as substances with a strong positive redox potential such as platinum hexafluoride or strongly negative redox potential such as metallic potassium, and / or explosively decompose in an uncontrolled manner, such as Schwermetallazide.

Preferably, the additives (B) selected from the group consisting of low molecular mass, 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 selected.

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

The selection of the additive (B) or the additives (B) is aimed primarily after which technical, sensory and / or aesthetic effects one wants to achieve in or with the inventive materials.

Thus, the additives may be (B), the physical or structural properties, such as density, strength, flexibility, nanoporosity, the microporosity, the macroporosity, the absorption capacity, the adsorption ability and / or the barrier effect against gases and liquids, the materials of the invention influence as such and may vary appropriately. So can be varied for example by means of plasticizers, such as structural proteins such as keratin, urea, monosaccharides such as glucose, polysaccharides such as cyclodextrins or polyoses, the flexibility and permeability of the inventive materials.

The additives (B) but can impart having the additives (B) as such the materials of the invention, they contain properties. Thus, the additives (B) compounds dyes, catalysts, colorants, fluorescent, phosphorescent, electrically conductive, magnetic or microwave radiation absorbing pigments, light stabilizers, vitamins, provitamins, antioxidants, peroxide decomposers, repellent, radioactive and non-radioactive non-metal and / or metal ion-containing , compounds absorb such ions, flameproofing agents, hormones, diagnostic agents, pharmaceuticals, biocides, insecticides, fungicides, acaricides, fragrances, flavoring agents, flavoring agents, ingredients of food, engineering plastics, enzymatically or non-enzymatically active proteins, structural proteins, antibodies, antibody fragments, nucleic acids , be genes, nuclei, mitochondria, membrane materials, ribosomes, chloroplasts, cells, or blastocyst.

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) may be produced in the polymer (A) formed matrix, in particular in the polysaccharide matrix, the materials according to the invention and using the method of the invention, solid porous materials on the basis of polymers (A), especially of polysaccharides (A) present more or less homogeneously distributed. For example, it may be advantageous if fibrous additives (B) have a non-homogeneous distribution in order to vary mechanical properties in the desired manner. The same is true for catalytically active additives (B), their accessibility can be improved in the polymer (A) formed matrix, in particular in the polysaccharide matrix by an inhomogeneous distribution. In many cases, however, is a very homogeneous distribution in the polymer (A) formed matrix, in particular in the polysaccharide matrix, an advantage be used for example when softening additives (B).

The additives (B) may be formed with the polymer (A) matrix, in particular of the polysaccharide matrix to be more or less permanently connected. In particular, can be polymeric or particulate additives (B) formed on the duration from the polymer (A) matrix, in particular the polysaccharide matrix, respectively. In contrast, it may be particularly in the low molecular weight additives (B) of advantage if they are not connected permanently with the matrix, but to be released again in terms of a "slow release" or "controlled release".

The amount of additive (B) or additives (B) contained in a given material of this invention, may vary very widely and depends mainly on their physical, chemical and structural properties on the one hand and according to the technical, physiological and / or aesthetic effects that you want to adjust. The skilled worker is therefore set in individual cases suitable ratios in a simple manner on the basis of his general knowledge optionally with the aid of a few exploratory experiments.

The invention materials may be produced using conventional and known methods. According to the invention it is advantageous to prepare them according to the inventive method.

In the first step of the method according to the invention is at least one, especially one, of the above-described polymers (A), optionally in the presence of at least one of the above-described additives (B) in at least one, especially one, entirely or substantially anhydrous chaotropic liquid (C) solubilized.

The verb "solubilized" or the term "solubilization" mean in the context of the present invention that the polymer (A) in the chaotropic liquid (C) molecularly dissolved or at least so finely divided and homogeneous as possible is dispersed. The same applies to the additives (B), when used with.

Under "chaotropic" is the property of substances, particularly liquids, to understand supramolecular assemblies of macromolecules by disrupting or influencing the intermolecular interactions such as hydrogen bonds dissolve, without affecting the intramolecular covalent bonds (see a.. Römpp online 2008, "chaotrope").

The chaotropic liquids used in the inventive process (C) are entirely or substantially anhydrous. "Substantially anhydrous" means that the water content of the chaotropic liquids (C) <5 wt .-%, preferably <2 wt .-%, preferably <1 wt .-% and in particular <0.1 wt .-%. "Completely free of water" means that the water content below the detection limits of the conventional methods is for the quantitative determination of water.

Preferably, the chaotropic liquids (C) 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 in liquid form. That is, the chaotropic liquids (C) has a melting point of preferably not more than 150 0 C, preferably not more than 130 0 C and in particular at most 100 0 C.

Very particularly effective chaotropic liquids (C) are the so-called ionic liquids. They are therefore very particularly preferably used.

Ionic liquids consist entirely of ions (cations and anions). They may consist of organic cations and organic or inorganic anions or cations of inorganic and organic anions.

In principle, ionic liquids are molten salts with a low melting point. It not only converts the liquid at the ambient temperature, but also all salt compounds to the preferred melt preferably below 150 0 C 130 0 C and in particular below 100 ° C. 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 (Römpp Online 2007, "ionic liquids" see. A.) Can be produced.

Suitable organic cations all the cations are concerned, as they are commonly used in ionic liquids. Preferably, it is non-cyclic or heterocyclic onium compounds.

Preferred are non-cyclic and heterocyclic onium compounds from the group consisting of quaternary ammonium, oxonium, sulfonium and phosphonium cations as well as from uronium, thiouronium and guanidinium cations, in which the simple positive charge is delocalized over more heteroatoms used ,

quaternary ammonium cations and most preferably heterocyclic quaternary ammonium cations are particularly preferred.

In particular, the heterocyclic quaternary ammonium cations from the group consisting of Pyrrolium-, imidazolium, 1-pyrazolium H, 3H-pyrazolium, 4H be

Pyrazolium, 1-pyrazolinium, 2-pyrazolinium, 3-pyrazolinium, 2,3-dihydro imidazolinium, 4,5-dihydro-imidazolinium, 2,5-dihydro-imidazolinium, pyrrolidinium, 1, 2,4-triazolium (quaternary nitrogen atom in the 1-position), 1, 2,4-triazolium (quaternary nitrogen atom in 4-position), 1, 2,3-triazolium (quaternary nitrogen atom in the 1-position), 1 , 2,3-triazolium (quaternary nitrogen atom in 4-position), oxazolium, Isooxazolium-, thiazolium, Isothiazolium-, pyridinium, pyridazinium, pyrimidinium, piperidinium, morpholinium, pyrazinium, indolium, quinolinium -, isoquinolinium, Chinoxalinium- and indolinium cations selected.

The organic cations described above are conventional species, for example, in the German and international patent applications as well as 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 sides 2 and 3, inter-paragraph [0006], in conjunction 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, last paragraph, fourth,

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],

are described in detail. The listed passages of patent applications is expressly made for the purpose of clarifying the present invention.

From the above-described organic cations are especially imidazolium cations, in particular the 1-ethyl-3-methylimidazolium cation (EMIM) or the 1-butyl-3-methylimidazolium cation (BMIM), wherein the quaternary nitrogen in each case 1 - position is used.

Suitable inorganic cations all the cations are concerned, the (C) form with the organic anions of the ionic liquids no crystalline salts whose melting point is above 150 0 C. Examples of suitable inorganic cations are the cations of the lanthanides.

Suitable inorganic anions are basically all of the anions are concerned, the (C) form with the organic cations of the ionic liquids no crystalline salts whose melting point is above 150 0 C, and no undesirable interactions with the organic cations, such as chemical reactions, received.

Preferably, the inorganic anions from the group consisting of halide, pseudohalide, sulfide, Halometallat-, cyanometalate, Carbonylmetallat-, Haloborat-, halophosphate, and Haloarsenat- Haloantimonatanionen and the anions of oxygen acids of halides of sulfur, of nitrogen, phosphorus, carbon, silicon, boron and the transition metals selected.

are preferred as the halide fluoride, chloride, bromide and / or iodide ions, pseudohalide as cyanide, cyanate, thiocyanate, isothiocyanate and / or Azidanionen, sulfide anions as sulfide, hydrosulfide, polysulfide and / or Hydrogenpolysulfidanionen, Halometallatanionen as chlorine and / or Bromaluminate and / or -ferrate as Cyanometallatanionen hexacyanoferrate (II) - and / or - (III) anions, as Carbonylmetallatanionen Tetracarbonylferratanionen as Haloboratanionen tetrachloro- and / or Tetrafluoroboratanionen, as halophosphate, Haloarsenat- and Haloantimonatanionen hexafluorophosphate, hexafluoroarsenate, Hexachlorantimonat- and / or Hexafluorantimonatanionen as well as anions of oxygen acids of halides, sulfur, nitrogen, phosphorus, carbon, silicon, boron and the transition metal chlorate, perchlorate, bromate , lodat-, sulfate, bisulfate, sulfite, bisulfite, thiosulfate, nitrite, nitrate, phosphinate, P hosphonat-, phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, glyoxylate, oxalate, Deltaat-, square, Krokonat-, rhodizonate, silicate, borate, chromate and / or Permanganatanionen used.

In the same way, suitable organic anions are basically all anions into consideration, the (C) form with organic or inorganic cations of the ionic liquids no crystalline salts whose melting point above 150 0 C, is located, and the no undesirable interactions with the organic or inorganic cations such as chemical reactions go.

Preferably, the organic anions of aliphatic, cycloaliphatic and aromatic acids from the group lead, consisting of carboxylic acids, sulfonic acids, acidic Sulfatestern, phosphonic acids, phosphinic acids, acidic phosphate esters, Hypodiphosphinsäuren, Hypodiphosphonsäuren, acidic esters of boric acid, boronic acids, acidic Kieselsäureestern and acidic silanes from or 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 from the 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 particularly preferably acetate anions can be used.

In particular, 1-ethyl-3-methylimidazolium acetate (EMIM Ac) as the ionic liquid (C). The temperature are solubilized in which the above-described polymers (A) and optionally the above-described additives (B) in the chaotropic liquid (C) depends primarily on the temperature range in which the chaotropic liquid (C) is liquid , according to the thermal stability and chemical reactivity of the materials to be solubilised (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 set so low that the rate of solubilization for practical requirements is too low. Preferably, the solubilization at temperatures of 0 to 100 0 C, preferably 10 to 70 0 C, particularly preferably from 15 to 50 ° C and especially 20 to 30 0 C.

In terms of method, has the solubilization in the first step has no special features but can using conventional mixing units such as stirred tanks, Ultraturrax, inline dissolvers, Homogenisierungsaggregate as homogenizing nozzles, kneader or extruder, continuously or discontinuously in batch mode.

The content of polymer (A) of the first process step the resulting solution or dispersion (AC) or (ABC) may also vary widely. In general, the upper limit of the content in each individual case is determined by the fact that the viscosity of its solution or dispersion (AC) or (ABC) must not be so high that they can not be processed. Preferably, the content is 0.1 to 10 wt .-%, preferably 0.25 to 5 wt .-% and in particular 0.5 to 3 wt .-%, based on (AC) or (ABC).

In the further course of the process according to the invention, the solution obtained in the first step or dispersion (AC) or (ABC) with an inorganic protic polar liquid (D1) is contacted in the second step.

The inorganic protic polar liquid (D1) is connected to the above-described chaotropic liquid (C), preferably without miscibility gap, that is, in each ratio, miscible. In contrast, the polymer (A) in (D1) is substantially or completely insoluble. The optional additives (B) may be soluble or insoluble in (D1). As inorganic protic polar liquid (D1) is used in particular water.

The solution or dispersion (AC) or (ABC) can be used in different ways with (D1), in particular with water, are brought into contact, for example by pouring the solution or dispersion (AC) or (ABC) in the liquid (D1) , is added dropwise, einsprüht or extruded, or in the form of a film with the liquid (D1) or its vapor (D1) into contact. This can be performed continuously or discontinuously in batch mode of operation.

Preferably, the solution or dispersion is (AC) or (ABC) in the liquid (D1) was dropped in the form of droplets or sprayed such that can form in the contact with (D1) balls or beads.

Here, the ratio of solution or dispersion (AC) or (ABC) to liquid (D1) from case to case, can vary widely. It is essential that the amount ratio is chosen so that the polymer (A), particularly the polysaccharide (A), is quantitatively precipitated or regenerated. The expert can thus easily determine the required amount of money based on his general knowledge optionally with the aid of a few exploratory experiments.

The temperature at which the second process step is carried out may also vary widely. Primarily, the temperature depends on the fact in which temperature range the liquid (D1) is liquid. Also, the solution or dispersion should (AC) or (ABC) upon contact with (D1) have too high temperatures because there may otherwise an abrupt evaporation and / or 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, particularly preferably from 15 to 50 ° C and especially 20 to 30 0 C.

In the second step a phase results (E), the solid polymer (A), in particular solid polysaccharide (A), chaotropic liquid (C) and liquid (D1) and optionally the at least one additive (B) or consists of, as well as a liquid phase (F), the chaotropic liquid (C) and liquid (D1) contains or consists of. Preferably, the phase (E) already has the preferred form of spheres or beads. the phase (E), preferably is preferably kept for 10 minutes to 24 hours, particularly preferably 20 minutes to 10 hours and especially 30 minutes to 2 hours, in contact with the liquid (D1) before carrying out the third process step during a certain time , so may that the desired shape of the phase (e), in particular the spherical form or the form of beads form complete and mature.

In the third method step, the phase (E) of the phase (F) is separated off. This can be done in different ways, preferably by decantation, centrifugation and / or filtration. This process step also can be continuously or discontinuously in batch mode.

In the further course of the process in the fourth method step, the chaotropic liquid (C) from the phase (E) using the liquid (D1), thereby a wet gel (G) on the basis of the polymer (A), in particular polysaccharide ( A) results. Preferably, the chaotropic liquid is removed (C) by washing out the phase (E) at least once with the liquid (D1), after separating the washing liquid (D1) of the phase (E). The continuous or discontinuous methods described above may be used. Preferably, the washing and separation is continued until in the wet gel (G) and / or in the washing liquid can be detected more (D1) no chaotropic liquid (C).

Preferably, the fourth step is carried out at temperatures at which the resulting wet gel (G) is not thermally damaged, especially not aging rapidly. Preferably, temperatures from 0 to 100 0 C, preferably 10 to 70 0 C, particularly preferably applied from 15 to 50 0 C and in particular 20 to 30 0 C.

Preferably, also, the resulting wet gel (G) on the three-dimensional shape as the already produced therefrom material of the invention.

In the further course of the process of the invention see in the fifth method rode the wet gel (G) with a protic polar organic liquid (D2) which is miscible with both the chaotropic liquid (C) and with the liquid (D1), but wherein at least the polymer (A), particularly the polysaccharide (A), completely insoluble substantially or is treated. As protic polar organic liquids (D2) are preferably alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and / or 2-butoxyethanol, but particularly ethanol, in consideration ,

In the further course of the process according to the invention is in the sixth step, the (D2) containing gel (G) with the liquid (D1), in particular with water, treated. Preferably, the treatment takes place in that the (D2) containing gel is brought into contact (G) at least once with the liquid (D1), followed by (D1) in each case for a certain time, preferably 1 minute to 2 hours, at (G) allowed to act and then separated. In the case of the preferred spheres or beads according to the invention this is preferably done in that one stirs balls or the beads in the present invention (D1), and then separated by centrifugation, decantation and / or filtration.

At the last separating (D1), that is, in the seventh method step, the wet material according to the invention results.

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

Moreover, in a further method step, at least one further additive can the wet or dried material according to the invention, which is free from additives (B), at least one additive (B) or the wet or dried material according to the invention which already contains at least one additive (B) (B) are added.

In the inventive method, at least one of the process steps can be carried out kPa greater than 100 at a pressure. Preferably, the method of the invention is carried out generally at normal pressure.

It is a very special advantage of the method is that it directly provides the inventive materials in very reproducible manner. It also allows the inventive method, the inventive materials in a wide variety of predetermined three-dimensional shapes such as the shapes described above, targeted and highly reproducible manufacture. Due to the precise adjustment of its dimensions materials of the invention can be safely and reliably assembled into more complex three-dimensional moldings.

Through the above-described additives (B) materials of the invention for use in the invention in vielfältigster way can be modified.

The materials of the invention as well as the solid, porous materials produced by the novel procedure on the basis of polymers (A) can therefore be used in the context of the use according to the different technical areas with advantage. So they can in synthetic and analytical chemistry, biochemistry and genetic engineering, biology, pharmacology, medical diagnostics, cosmetics, oil and gas handling equipment, process technology, paper technology, packaging technology, electrical engineering, magnet technology,

Communications technology, radio and television equipment, agricultural engineering, aviation and space technology and textile technology, and the construction, land and sea creatures and mechanical engineering, in particular as support particles, the support materials or proppants, construction materials, insulation, fabrics, absorbents, adsorbents, membranes, separation materials, barrier layers, controlled release materials, catalysts, cultivation media, catalysts, as well as coloring, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame-retardant materials or used for their preparation.

In particular, materials as well as the present invention, the solid, porous materials produced by the novel method can be used on the basis of biopolymers (A) in the oil and gas handling equipment.

In the framework of this use according to the invention, the solid materials are preferably used as a powder, especially powder having spherical particles such as spheres or beads. They are preferably used as deformable, pressure-resistant support particles, the support materials or proppants in liquid media for fracturing or well stimulation. In this case, liquid media may be used on the basis of water or oil. The resulting liquid media for fracturing invention - in short, "fracturing media" - can further customary and known constituents in addition to the inventive proppants, such as proppants, protective coatings, materials for weight modifier described in the American patent application US 2006/0151 170 A1 , gelling agents, cross-linking agent, yellow computing means, curable resins, hardening agents, surface-active compounds, foaming agents, means for separating emulsions, clay stabilizers and / or acids.

The inventive fracturing medium with the inventive proppants is pumped to the breaking of the rock under pressure into the conveyor horizon. Exceeds the hydrostatic pressure of the fracturing fluid to the fracturing gradient of the conveyor horizon, this tearing at defects, and inventive fracturing medium which penetrates into the aufreißenden or already-open columns, cracks and channels. After the reduction of the hydrostatic pressure of the fracturing medium of the invention proppants of the present invention effectively prevent and for a long time, the sealing of the gaps formed, cracks and channels through the overlying rock. There also is no or only a very low formation of particulate abrasion of rock and / or crumbs of proppants. Overall, a better long-term exploitation of the conveyor horizon results.

This all reinforces the extraordinary advantageousness of the materials of the invention and of the method according to the invention and the hereby produced, solid, porous materials based on polymer (A).

Example and comparative experiments

Comparative tests V1 and V2

The preparation of cellulose beads without a core-shell structure

A one percent solution of cellulose in 1-ethyl-3-methylimidazolium acetate (EMIM Ac) was added dropwise with stirring in a water-filled beaker (comparative experiment C1) or in a filled with ethanol beaker (Comparative Example C2). When using water (Example C1) it was necessary to add a drop of wetting agent to lower the surface tension of water and allow the formation of beads. During the period in which the resulting beads reached the bottom of the beakers, they had stabilized to the point that there is no risk of deformation was more. After the addition of the cellulose solution was allowed to attack the beads during each hour. The contents of the beakers were stirred uniformly to prevent deformation of the beads. Subsequently, the beads from the water-EM IN Ac-solution (Comparative Example C1) and the ethanol-EMIM Ac-solution (Comparative Example C2) were separated by filtration and dried for 2 hours in a forced air oven at 80 0 C.

In two comparative experiments dried beads of a diameter of about 1 mm resulted with a compact and uniform structure without a core-shell structure.

example 1

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

A one percent solution of cellulose in EMIM Ac was added dropwise with stirring in a water-filled beaker. The water had been added to lower the surface tension of water and allow the formation of beads, a drop of a wetting agent. During the period in which the resulting beads reached the bottom of the beaker, they had stabilized to the point that there is no risk of deformation was more. After the addition of the cellulose solution was allowed to attack the beads during each hour. 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 20 minutes rinsing with water. Subsequently, the water-wet beads were dried in a forced air oven for 2 hours at 80 0 C.

The result was dried beads having a diameter of about 1 mm with a strong and uniform core-shell structure. The trays had a uniform thickness in the range of 30 to 50 microns. They were clear and transparent and slightly softer than the cores. The cores were opaque and harder than the shells and exhibited a substantially uniform porous structure having pore diameters in the range of 1 to 5 microns on.

Example 2 and Comparative Example C3 The absorbency of the cellulose beads 1 of Example 1 (Example 2) and the cellulose beads V1 of Comparative Example C1 (Comparative Example C3)

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

For Comparative Experiment V4, the cellulose beads C1 of example C1 were used.

The cellulose beads 1 (Example 2) and V1 (Comparative Example C3) were swollen separated from each other in a one percent aqueous solution of a dye (trisodium salt of pyrene trisulfonic acid) for one hour. Subsequently, the cellulose swollen beads were dried for 1 and C1 for 2 hours in a forced air oven at 80 0 C. 5 each of the dried, laden with dye cellulose beads 1 and C1 were added separately from one another in each case a water-filled cuvette. Subsequently, the leaching behavior of the dye-loaded cellulose beads 1 and V1 by UVA / IS-spectroscopy the intensity of the absorption of the dye at 207 nm on the basis of change was measured in the water. In this case, it was found that the dye was leached with essentially the same speed from the cellulose beads 1 and V1, but that the cellulose beads had one significant added more dye than the cellulose beads V1, so that it took significantly longer for the dye completely from the cellulose beads 1 was exhausted. This underscored the fact that the cellulose beads 1 showed a much higher absorption capacity than the cellulose beads V1.

Example 3 and comparative experiments C4 and C5

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

Example 1 was repeated, so that the cellulose beads resulted having particle sizes of 800 microns to 1, 6 mm. Subsequently, the application properties that are essential for use as a proppant were measured (Example 3). For purposes of comparison, the corresponding performance properties were measured by commercially available proppants. It was in the comparative experiment V4 sintered bauxite (high pressure-resistant, ceramic material) and uses an uncoated fracturing sand in the comparative experiment V5. There were obtained the following results.

Compressive strength:

The compressive strength of cellulose beads 3 was determined to ISO 13502-2. For this purpose, in each case 40 g of the proppants were (5.02 cm) packed into a steel cell with 2 inch diameter and loaded with the indicated in Table 1 pressure. Then, the amount of the resulting fine particles was determined.

Table 1: Measurement of compressive strength

Figure imgf000027_0001

The results in Table 1 established that the powder on the basis of cellulose (A) was clearly superior in compressive strength to conventional proppants.

Roundness and sphericity:

As is known, the proppants of the fill introduced into the rock channels. What is important here is that the permeability of the channels is retained and is as little as possible reduced by the proppants. This is mainly achieved in that round, spherical particles are used as possible. Therefore, roundness and sphericity of the proppant according to ISO 13502-2 were determined.

The results are shown in Table 2. The results underlined the fact that the cellulose beads 3 of Example 3 had a significantly better sphericity and a significantly better roundness than the standard fracturing sand (comparative experiment V5) and (in this respect the sintered bauxite Comparative Experiment V4 ) were equal.

Table 2: Measurement of sphericity and roundness

Figure imgf000028_0001

Apparent specific density and bulk density:

and the apparent specific density and bulk density are essential for the effectiveness of the proppants used. A low density prevents the settlement of

Proppants once the fracturing medium penetrates into the rock formed channel.

Penetrates the material is not deep enough into the channel or gap a, it can be in the

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

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

The results are shown in Table 3. They underscored the fact that the cellulose beads 3 of Example 3 was clearly superior to the conventional proppants in this regard.

Table 3: Measurement of bulk density and apparent specific gravity

Figure imgf000028_0002

Conductivity and permeability: Ultimately, it is crucial for the use of the cellulose beads 3 of Example 3 as proppants whether the conductivity and permeability of the rock columns are maintained over a longer period. Therefore, the conductivity and the permeability of a model gap in Ohio Sandstone at a loading of 2 lb / ft2 (95.76 Pa) with a two percent potassium chloride solution according to API RP 61 were determined. The results are shown in Table 4. established that at moderate pressures and temperatures even after 10 hours still remained a significant residual conductivity, which meant that the cellulose beads were 3 of Example 3 useful as proppants.

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

Figure imgf000029_0001

Claims

claims
1. Solid, porous materials having a core-shell structure on the basis of synthetic polymers and biopolymers (A), which in chaotropic liquids (C) and soluble in polar protic inorganic liquids (D1) and protic polar organic liquids (D2) insoluble 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 nuclei are coarsely porous or finely porous.
4. solid porous materials according to claim 3, characterized in that their nuclei are pored.
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 nuclei 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 nuclei.
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, irregularly or regularly shaped, non-spherical particles, plates, rods, cylinders, needles, flakes, filaments, woven 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 form 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 average particle size of 0.1 to 10 mm.
14. Fixed porous materials according to one of claims 1 to 13, characterized in that the biopolymers (A) 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 it comprises 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 and microscopic and macroscopic particles and moldings, biomolecules, cell compartments, cells and cell contained.
17, solid porous materials according to one of claims 1 to 16, characterized in that the chaotropic liquid is liquid (C) in a temperature range from -100 0 C to +150 0 C.
18, solid, porous materials treated claims 1 to 17, characterized in that the chaotropic liquid (C) is an ionic liquid.
19, solid porous materials according to one of claims 1 to 18, characterized in that the inorganic protic polar 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 polymers and / or biopolymers (A) or at least one synthetic polymers and / or biopolymers (A) and at least one additive (B) in at least one entirely or substantially anhydrous chaotropic liquid (C),
(2) contacting the in process step (1) the resulting solution or dispersion (AC) or (ABC) with a protic polar inorganic liquid (D1) which is miscible with the chaotropic liquid (C), but wherein at least the polymer (A) completely insoluble or substantially, 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 of, and a liquid phase (F), the chaotropic liquid (C) and liquid (D1) contains or consists result,
(3) separation of the phase (E) of the phase (F),
(4) removing the chaotropic liquid (C) from the phase (E) using the liquid (D1), whereby a wet gel (G) results on the basis of synthetic polymer and / or biopolymer (A),
(5) treating the (D1) containing wet gel (G) with a protic polar organic liquid (D2) which is miscible with both the chaotropic liquid (C) and with the liquid (D1), but wherein at least the polymer ( A) is substantially or completely insoluble, containing (6) treating the fluid (D2) wet gel (G) with the liquid (D1) and
(7) separating the resulting wet, solid, porous material (A) or
(AB) on the basis of synthetic polymers and / or biopolymers (A)
23. The method according to claim 22, characterized, in that
(8) the moist, solid, porous material (A) or (AB) is dried.
24. The method of claim 22 or 23, characterized in that
(9a) to the wet or dried, solid, porous material (A) at least one additive (B) or
(9b) has at least one further additive (B) is added to the wet or dried, solid, porous material (AB).
22 to 24, characterized in that they see in the process rode (2) solution obtained in process step (1) or dispersion (AC) or (ABC) with the liquid (D1) contacted 25. The method according to any one of claims by the solution or dispersion (AC) or (ABC) in the liquid (D1) pouring, is added dropwise, einsprüht or extruded, or in the form of a film with the liquid (D1) or the vapor of the liquid (D1) brought into contact.
26. The method according to claim 25, characterized in that one see in the process rode (2) in process step (1) obtained solution or dispersion (AC) or (ABC) in the liquid (D1) is added dropwise in the form of droplets or einsprüht ,
27. The method according to any one of claims 22 to 26, characterized in that is separated in step (3) the phase (E) of the phase (F) by decantation, centrifugation and / or filtration.
28. The method according to any one of claims 22 to 27, characterized in that the phase (E) at least once with the liquid (D1) are washed out in step (4), after which the washing liquid from phase (E) is separated off and the resulting wet 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 the polymer (A) 0.1 to 10 wt .-%, based on (AC) or ( ABC) is.
30. The method according to any one of claims 22 to 29, characterized in that the solid, porous materials having a core-shell structure on the basis of synthetic polymers and / or biopolymers (A) as defined in any one of claims 1 to 29 resulting, ,
31. Use of the solid, porous materials having a core-shell structure on the basis of synthetic polymers and / or biopolymers (A) according to any one of claims 1 to 21 as well as the use of the process 22 to 30 produced according to any one of claims solid, porous materials based on synthetic polymers and / or biopolymers (A) in synthetic and analytical chemistry, biochemistry and genetic engineering, biology,
Pharmacology, medical diagnostics, cosmetics, oil and gas handling equipment, process technology, paper technology, packaging, electrical, magnetic equipment, communications equipment, radio and television technology, agricultural technology, aviation and space technology and textile technology, as well as construction, land and sea transport system 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 the support particles, the support materials or proppants,
Construction materials, insulation, fabrics, absorbents, adsorbents, membranes, separation materials, barrier layers, controlled release materials, catalysts, cultivation media, catalysts, as well as coloring, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame-retardant materials or used for the preparation thereof ,
33. Use according to claim 32, characterized in that the support particles, the support materials or proppants are used in liquid fracturing media for well stimulation in which natural gas and crude oil production.
PCT/EP2009/051791 2008-02-22 2009-02-16 Solid, porous materials with a core-shell structure on the basis of synthetic polymers and biopolymers, method for their production and use thereof WO2009103680A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08101892.1 2008-02-22
EP08101892 2008-02-22

Publications (1)

Publication Number Publication Date
WO2009103680A1 true WO2009103680A1 (en) 2009-08-27

Family

ID=40636740

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/051791 WO2009103680A1 (en) 2008-02-22 2009-02-16 Solid, porous materials with a core-shell structure on the basis of synthetic polymers and biopolymers, method for their production and use thereof

Country Status (1)

Country Link
WO (1) WO2009103680A1 (en)

Cited By (2)

* 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
AT515180A1 (en) * 2013-10-15 2015-06-15 Chemiefaser Lenzing Ag Three-dimensional cellulosic molded body, method for its preparation and its use

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (en) * 2000-06-28 2002-01-10 Leder Kunstledertech Forsch Particulate gel material with mobile phase of controlled permeation useful in production of plastics for permeable roads and tracks is obtained by two-stage precipitation polymerization
US6492006B1 (en) * 2000-06-30 2002-12-10 Eastman Kodak Company Ink jet recording element
DE102004002206A1 (en) * 2004-01-15 2005-08-11 Filk Forschungsinstitut für Leder und Kunstledertechnologie GmbH Core-shell type gel particles for controllable release of water-organic solvent mixtures comprise a hydrogel core from a lower critical solution temperature (LCST) polymer and a permeable shell from a precipitation copolymer
WO2007085624A1 (en) * 2006-01-24 2007-08-02 Basf Se Polymer backbone for producing artificial tissue
US20070287760A1 (en) * 2006-06-08 2007-12-13 James Charles Bohling Process for macroporous acrylic resins
WO2008003623A1 (en) * 2006-07-06 2008-01-10 Basf Se Method for producing nanoporous molded parts
WO2009048514A1 (en) * 2007-10-11 2009-04-16 Eastman Kodak Company Manufacturing porous particles with non-porous shell

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (en) * 2000-06-28 2002-01-10 Leder Kunstledertech Forsch Particulate gel material with mobile phase of controlled permeation useful in production of plastics for permeable roads and tracks is obtained by two-stage precipitation polymerization
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 (en) * 2004-01-15 2005-08-11 Filk Forschungsinstitut für Leder und Kunstledertechnologie GmbH Core-shell type gel particles for controllable release of water-organic solvent mixtures comprise a hydrogel core from a lower critical solution temperature (LCST) polymer and a permeable shell from a precipitation copolymer
WO2007085624A1 (en) * 2006-01-24 2007-08-02 Basf Se Polymer backbone for producing artificial tissue
US20070287760A1 (en) * 2006-06-08 2007-12-13 James Charles Bohling Process for macroporous acrylic resins
WO2008003623A1 (en) * 2006-07-06 2008-01-10 Basf Se Method for producing nanoporous molded parts
WO2009048514A1 (en) * 2007-10-11 2009-04-16 Eastman Kodak Company Manufacturing porous particles with non-porous shell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
COUTINHO F M B ET AL: "Pellicular ion exchange resins based on divinylbenzene and 2-vinylpyridine" POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, Bd. 42, Nr. 1, 1. Januar 2001 (2001-01-01), Seiten 43-48, XP004208393 ISSN: 0032-3861 *

Cited By (4)

* 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 (en) * 2013-10-15 2015-06-15 Chemiefaser Lenzing Ag Three-dimensional cellulosic molded body, method for its preparation and its use
AT515180B1 (en) * 2013-10-15 2016-06-15 Chemiefaser Lenzing Ag Three-dimensional cellulosic molded body, method for its preparation and its use

Similar Documents

Publication Publication Date Title
Tan et al. Temperature dependence of polyelectrolyte multilayer assembly
Skjåk-Bræk et al. Inhomogeneous polysaccharide ionic gels
Fundueanu et al. Physico-chemical characterization of Ca-alginate microparticles produced with different methods
Gåserød et al. Microcapsules of alginate-chitosan–I: A quantitative study of the interaction between alginate and chitosan
CA2415814C (en) Methods of consolidating proppant in subterranean fractures
RU2369736C2 (en) System of stabilisers and enhancers of functional qualities of aqueous liquids, thickened by viscoelastic surfactants
US6742590B1 (en) Methods of treating subterranean formations using solid particles and other larger solid materials
AU2003204793B2 (en) Methods and compositions for consolidating proppant in subterranean fractures
CA2337554C (en) Formation treatment method using deformable particles
US5501274A (en) Control of particulate flowback in subterranean wells
US5370184A (en) Method of treating formations
US6875728B2 (en) Method for fracturing subterranean formations
Thorne et al. Microgel applications and commercial considerations
Chen et al. Aggregation kinetics of alginate-coated hematite nanoparticles in monovalent and divalent electrolytes
CA2552421C (en) Aggregating reagents, modified particulate metal-oxides, and methods for making and using same
Stone-Masui et al. Characterization of surface charge on polystyrene latices
US4919209A (en) Method for treating subterranean formations
EP1398458B1 (en) Reducing particulate flow-back in wells
Zhang et al. Protein interactions studied by SAXS: effect of ionic strength and protein concentration for BSA in aqueous solutions
Sescousse et al. Aerocellulose from cellulose–ionic liquid solutions: preparation, properties and comparison with cellulose–NaOH and cellulose–NMMO routes
CA2346324C (en) Encapsulated breakers and method for use in treating subterranean formations
US5164099A (en) Encapsulations for treating subterranean formations and methods for the use thereof
US20050173116A1 (en) Resin compositions and methods of using resin compositions to control proppant flow-back
Carter et al. Gas storage in “dry water” and “dry gel” clathrates
EP0725206A2 (en) Method of fracturing high permeability subterranean formations

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09712582

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct app. not ent. europ. phase

Ref document number: 09712582

Country of ref document: EP

Kind code of ref document: A1