EP2247652A1

EP2247652A1 - Method for producing solid materials on the basis of synthetic polymers and/or biopolymers and use thereof

Info

Publication number: EP2247652A1
Application number: EP09712072A
Authority: EP
Inventors: Simon Champ; Robert Chapman
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-02-22
Filing date: 2009-02-16
Publication date: 2010-11-10
Also published as: WO2009103681A1; US20100323930A1; US8198219B2; CA2715979A1

Abstract

The invention relates to a method for producing solid materials on the basis of synthetic polymers and biopolymers (A) by: (1) the solubilisation of (A) or of (A) and an additive (B) in a non-aqueous chaotropic liquid (C), (2) contacting of the solution or dispersion obtained (AC) or (ABC) with a liquid (D1), which is miscible with (C), in which however (A) is insoluble, to produce a phase (E) containing (A), (C) and (D1) and optionally (B) and a liquid phase (F) containing (C) and (D1), (3) optional separation of (E) from (F), (4) removal of (C) from (E) with the aid of (D1), to produce a gel (G) on the basis of (A), (5) impregnation of (G) with a liquid (D2) which is miscible with (C) and (D1) and in which at least (A) is insoluble and has a higher volatility than (D1), and (6) removal of (D1) and (D2) from (G) by evaporation. The invention also relates to the use of said materials.

Description

Process for the preparation of solid materials based on synthetic polymers and / or biopolymers and their use

Field of the invention

The present invention relates to a novel process for the preparation of solid materials based on synthetic polymers and / or biopolymers. Moreover, the present invention relates to the use of solid materials based on synthetic polymers and / or biopolymers prepared by the novel process.

State of the art

The preparation of solid materials based on polysaccharides, which may also contain additives, using chaotropic liquids, in particular ionic liquids, is known from international and US patent applications and US Patents WO03 / 029329 A2, US 2003/0157351 A1, WO 2004 No. 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. During drying, however, the regenerated polysaccharide gel shrinks very strongly, which is a serious disadvantage, in particular, in the production of films.

These disadvantages occur not only in the production of films, but also in the production of regenerated polysaccharide in other three-dimensional forms. Thus, they complicate the targeted and reproducible production of powder particles based on regenerated polysaccharide, so that the powder particles for numerous applications for technical and economic reasons are not eligible. International patent application WO 2004/083286 A1 discloses a process for producing films of cellulose and the water-soluble polysaccharide xylan. The films are made using only water. The films may contain plasticizers such as water, sugar, ethylene glycol, propylene glycol, butanediol, glycerine or urea. The International Patent Application gives no suggestion or indication as to how the disadvantages of the known processes using ionic liquids could be avoided.

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 is common with the use of hard proppants such as fracturing sand. The deformable proppants thus effectively have the effect of support pillows.

In the known fracturing method, deformable proppants of shredded natural materials, such as, for example, sliced, ground or broken nut shells, fruit seeds, plant shells or wood parts, are used. However, these must be provided with a protective layer in order to adapt the elastic modulus of the proppants to the respective requirements. In addition, 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

The present invention was therefore based on the object to provide a novel process for the preparation of solid materials based on synthetic polymers and / or biopolymers, in which the synthetic polymers and / or biopolymers optionally dissolved or dispersed together with additives in ionic liquids which regenerates synthetic polymers and / or biopolymers by contacting the resulting solution or dispersion with another liquid which is miscible with the ionic liquid but which is incapable of dissolving the synthetic polymers and / or biopolymers, and the resulting regenerated gels of the synthetic polymers and / or biopolymers are freed of the ionic liquids and the further liquid, resulting in the solid materials based on synthetic polymers and / or biopolymers. The new method should no longer have the disadvantages of the prior art, but should cause the regenerated gels of the synthetic polymers and / or biopolymers no longer or only slightly shrink when they are freed from the further liquid, so that the solid materials based on synthetic polymers and / or biopolymers targeted and very well reproducible can be produced.

In this way, the performance properties of particular film-like and powdery solid materials based on synthetic polymers and / or biopolymers, in particular of polysaccharides, such as homogeneity, mechanical stability, flexibility, strength, barrier effect against gases and liquids, especially oxygen and water , as well as the compressive strength are further improved.

In addition, the solid materials produced on the basis of synthetic polymers and / or biopolymers produced by the new process are particularly broad, especially 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, magnet technology, communication technology, radio and television technology, agricultural technology, aviation and space technology and textile technology as well as the Construction, land and sea transport and mechanical engineering, be used with advantage.

Inventive solution

Accordingly, the novel process for the preparation of solid materials based on synthetic polymers and / or biopolymers (A) has been found, which comprises the following processes:

(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 liquid (D1) which is miscible with the chaotropic liquid (C) but wherein at least the synthetic polymer and the biopolymer (A) are substantially or completely insoluble, whereby a phase (E), the solid synthetic polymer and / or biopolymer (A), chaotropic liquid (C) and liquid (D1) and optionally the at least one

Contains or consists of additive (B) and a liquid phase (F) containing or consisting of chaotropic liquid (C) and liquid (D1),

(3) optionally separating the phase (E) from the phase (F),

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

(5) impregnating the gel (G) with a liquid (D2) which is miscible with both the chaotropic liquid (C) and the liquid (D1), wherein, however, at least the synthetic polymer and biopolymer (A) is substantially or are completely insoluble, and which has a higher volatility than the liquid (D1), and (6) Remove the two liquids (D1) and (D2) from the gel (G) by evaporation to form a solid material based on synthetic polymer and / or biopolymer (A).

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

In addition, the use of solid materials based on synthetic polymers produced by the process according to the invention and / or

Biopolymers (A) in synthetic and analytical chemistry, biochemistry and

Genetic engineering, biology, pharmacology, medical diagnostics, cosmetics, natural gas and oil production technology, process technology, paper technology, electrical engineering, magnetic engineering,

Communication technology, radio and television technology, agricultural technology, aviation and space technology and textile technology and construction, agricultural and

Maritime transport and mechanical engineering found what is hereinafter collectively referred to 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 method according to the invention and the use according to the invention.

In particular, it was surprising that the process according to the invention no longer had the disadvantages of the prior art but caused the regenerated gels produced as intermediates during the process to no longer or only slightly to shrink the synthetic polymers and / or biopolymers if they were freed from liquid.

As a result, the performance properties of the solid materials obtained by the process according to the invention on the basis of

Polysaccharides such as homogeneity, mechanical stability, flexibility, strength, barrier to gases and liquids, especially oxygen and water, as well as compressive strength adjusted very accurately and easily reproducible and further improved.

Therefore, the solid materials produced on the basis of synthetic polymers and / or biopolymers produced by the novel process were particularly broad, especially in synthetic and analytical chemistry, biochemistry and

Gene technology, biology, pharmacology, medical diagnostics, cosmetics, natural gas and oil production technology, 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 the

Construction, land and sea transport and engineering, can be used to great advantage.

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 process according to the invention serves to produce solid materials based on synthetic polymers and / or biopolymers (A).

The solid materials can have a variety of three-dimensional shapes, sizes and morphologies.

Thus, they may be powdered, wherein the powder particles may be in the form of plates, spheres, drops, rods, cylinders, needles, flakes or irregularly shaped particles, in particular spheres. These bodies may be more or less compact or highly porous and have a high inner surface. Your

Particle size can vary very widely. It can range from a few nanometers to 1 mm. The particle size distributions may be monomodal or multimodal, ranging from very broad to very narrow, preferably very narrow, distributions. However, the solid materials may also be macroscopic particles, ie particles with a largest diameter> 1 mm. They may have substantially the same shapes as the powder particles.

The powder particles and the macroscopic particles are hereinafter collectively referred to as "powder".

In addition, the solid materials may be in the form of threads. These may have different lengths, for example from about 5 mm to "endless", and different thicknesses, for example 1 micron to 1 mm. The threads can also be spun into fabrics.

Last but not least, the solid materials can be in the form of films. These may have different thicknesses, for example between 500 nm to 1 mm. The films may be substantially compact, nanoporous, microporous, macroporous or spongy. Preferably, the films are substantially compact.

In particular, the solid materials are powders. The powder particles preferably have an average particle size of from 100 μm to 3 mm, preferably 200 μm to 2.5 mm and in particular 300 μm to 2 mm, measured by sedimentation in a gravitational field.

Essentially all synthetic polymers and / or biopolymers (A) are suitable for carrying out the process according to the invention, insofar as they are soluble in one of the chaotropic liquids (C) described below and are insoluble in the liquids (D1) and (D2) described below.

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

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 sulfates and keratan sulfates, as well as alginic acid and alginates. In particular, cellulose is used.

In the first process step, at least one, in particular one, of the above-described synthetic polymers and / or biopolymers (A) is optionally in the presence of at least one of the additives (B) described below in at least one, in particular one, substantially or completely anhydrous chaotropic liquid ( C) solubilized. In the context of the present invention, the term "solubilized" or the term "solubilization" mean that the polysaccharide (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 also used.

"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 hydrogen bonds, without influencing the intramolecular covalent bonds (cf. Römpp Online 2007, "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) in a temperature range from - 100 ⁰ C to +150 ⁰ C, preferably -50 ° C to +130 ⁰ C, in particular -20 ° C to + 100 ° C liquid. This means that the chaotrope liquids (C) have a melting point of preferably at most 150 ^° C., preferably 130 ^° C. and in particular at most 100 ^° C.

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 to liquid at the ambient temperature, but also all salt compounds, which preferably below 150 ° C, preferably below 130 ° C and especially below 100 ⁰ C melt. In contrast to conventional inorganic salts such as common salt (melting point 808 ° C) lattice energy and symmetry are reduced in ionic liquids by charge delocalization, resulting in Freezing points down to -80 ⁰ C and below. 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-dihydroimidazolinium, 4,5-dihydroimidazolinium, 2,5-dihydroimidazolinium, pyrrolidinium, 1, 2,4-triazolium (quaternary nitrogen atom in 1-position), 1, 2,4-triazolium (quaternary nitrogen at the 4-position), 1, 2,3-triazolium (1-position quaternary nitrogen), 1, 2,3-triazolium (4-position quaternary nitrogen), 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) Melting point above 150 ⁰ 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, and 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 oxygen acids of the halides, sulfur, nitrogen, phosphorus, carbon, silicon, boron and the transition metals chlorate, perchlorate, bromate , iodate, sulfate, hydrogen sulfate, sulfite, bisulfite, thiosulfate, nitrite, nitrate, phosphinate, P phosphonate, phosphate, hydrogen phosphate, dihydrogen phosphate, 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 the ionic liquids (C) whose melting point is above 150 ° C, and which also no undesirable interactions with the organic or inorganic cations, how to undergo 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).

Basically all gaseous, liquid and solid, preferably liquid and solid, materials can be used as additives (B), as long as they are not undesirably mixed with the synthetic polymers and / or biopolymers (A), the chaotropic liquid (C) and / or the liquid media (D1) and / or (D2) react, such as Substances with a strong positive redox potential such as platinum hexafluoride or strong negative redox potential such as metallic potassium, and / or explosively decompose uncontrollably, 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 method according to the invention and thus also the solid materials based on polymers (A), in particular of polysaccharides (A), produced with its aid can be varied almost as desired in the desired manner, which is a very particular advantage of the method according to the invention.

The choice of the additive (B) or the additives (B) depends primarily on what technical, sensory and / or aesthetic effects it wants to achieve in or with the solid materials based on polymers (A).

Thus, the additives (B) may have physical or structural properties such as density, strength, flexibility, nanoporosity, microporosity, macroporosity, absorbency, adsorptivity and / or barrier to gases and liquids, solid materials as such, particularly in the form of films, and vary as appropriate. 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 films based on polymers (A), in particular based on polysaccharides (A), are varied.

However, the additives (B) may also impart properties to the solid materials 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 which absorb such ions, 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 amount of additive (B) or additives (B) which may be added in the first process may vary widely and depends mainly on their physical, chemical and structural properties on the one hand and on the technical, sensory and / or aesthetic aspects Effects that you want to set. 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 temperature at which the above-described polymers (A) and optionally the above-described additives (B) 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 ⁰ 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 the solution or dispersion (AC) or (ABC) of polymers (A) 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 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 liquid (D1).

The liquid (D1) is miscible with the above-described chaotropic liquid (C), preferably without a miscibility gap, that is, in any proportion. In contrast, the polymer (A) in (D1) is substantially or completely insoluble. The optionally present additives (B) may be soluble or insoluble in (D1).

Suitable liquids (D1) are protic polar inorganic liquids, in particular water, and strongly protic and aprotic polar organic liquids.

Preferably, the highly protic and aprotic polar organic solvents (D1) are selected from the group consisting of alcohols, nitriles, ethers, aldehydes, ketones, sulfoxides and amides.

Preferred alcohols (D1) are methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and / or 2-butoxyethanol, nitrile (D1), acetonitrile and / or propionitrile Ether diethyl ether, dipropyl ether, tetrahydrofuran and / or dioxane, as ketone (D1) acetone and / or methyl ethyl ketone, as aldehyde (D1) acetaldehyde and / or propionaldehyde, as sulfoxide (D1) dimethyl sulfoxide and as amide (D1) dimethylformamide, acetamide and / or hexamethylphosphoric triamide.

Strongly protic and aprotic polar organic liquids, which already have a comparatively high vapor pressure or their boiling point below 100 ^° C., are particularly preferably used as liquid (D1).

Very particular preference is given to using ethanol and / or water, but in particular water, as liquid (D1).

The solution or dispersion (AC) or (ABC) can be contacted in different ways with (D1), for example by dissolving the solution or dispersion (AC). or (ABC) is poured into the liquid (D1), dripped or extruded or brought into contact with liquid (D1) or its vapor (D1) in the form of a film. This can be carried out continuously or batchwise in batch mode

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 chosen so that the polymer (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), chaotropic liquid (C) and liquid (D1) and optionally the at least one additive (B) contains or consists thereof, and a liquid phase (F), the contains or consists of chaotropic liquid (C) and liquid (D1).

Optionally, in the third process step, the phase (E) is separated from the phase (F). This can be done in different ways, for example by decantation, centrifugation and / or filtration. This process, too, can 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), resulting in a gel (G) based on the polymer (A). 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 are applied. Preferably, the washing and separation is continued until no more chaotropic liquid (C) can be detected in the gel (G) and / or in the washing liquid (D1).

Preferably, the fourth process step is carried out at temperatures at which the resulting 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 ° C and in particular 20 to 30 ⁰ C applied.

Preferably, the resulting gel (G) already has substantially the three-dimensional shape as the solid material based on polymers (A) to be produced therefrom.

In the further course of the process according to the invention, the gel (G) in the fifth process step is mixed with a liquid (D2) which is miscible both with the chaotropic liquid (C) and with the liquid (D1), but wherein at least the polymer (A) is essentially or completely insoluble, soaked. Suitable liquids (D2) are the liquids (D1) described above. It is important, however, that the liquid (D2) has a higher volatility than the liquid (D1).

If, for example-what is particularly preferred according to the invention-water is used as liquid (D1), all of the above-described strongly protic and aprotic polar organic liquids (D1) which have a higher vapor pressure than water or its boiling point at atmospheric pressure below 100 ° C. can be used as liquids (D2). Examples of suitable liquids (D2) in this case are methanol, ethanol, n-propanol, isopropanol, acetonitrile, propionitrile, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, acetaldehyde and propionaldehyde, in particular acetone. If a liquid (D1) other than water is used, the skilled artisan can easily select the appropriate suitable liquid (D2) because of his general knowledge.

In the further course of the process according to the invention, the two liquids (D1) and (D2) are removed from the gel (G) by evaporation in the sixth process step. Preferably, the evaporation takes place comparatively slowly under mild conditions at normal pressure or a slight negative pressure between 50 and 100 kPa. Preference is given to temperatures between 20 and 50 ⁰ C. applied. In particular, the evaporation takes place at room temperature and under normal pressure.

Apart from the sixth process step, at least one of the process steps of the process according to the invention 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 in the sixth process, the gels (G) rode, if at all, only in a very small amount

Extent shrink, making solid materials based on synthetic

Polymers and / or biopolymers (A), in particular polysaccharides (A), in a wide variety of predetermined three-dimensional forms, such as. the shapes described above can be produced in a targeted and very reproducible manner.

Due to the precise adjustability of their dimensions, the resulting solid materials based on synthetic polymers and / or biopolymers (A), especially polysaccharides (A), can be safely and reliably assembled into even more complex three-dimensional moldings.

By the above-described additives (B), the resulting solid materials based on synthetic polymers and / or biopolymers, particularly polysaccharides (A), can be modified in a variety of ways for use in the present invention.

The additives (B) can be more or less homogeneously distributed in the polymer (A) matrix of the solid materials produced by the process according to the invention. 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 polymer (A) matrix can be improved by an inhomogeneous distribution. In the many cases, on the other hand, the most homogeneous possible distribution in the polymer (A) matrix is advantageous, for example if softening additives (B) are used. The additives (B) may be more or less firmly bonded to the polymer (A) matrix of the solid materials produced by the process of the invention. Thus, in particular polymeric or particulate additives (B) can be permanently connected to the polymer (A) matrix. In contrast, it may be particularly advantageous for the low molecular weight additives (B) if they are not permanently bound to the polymer (A) matrix but are released again in the sense of a "slow release" or "controlled release".

The solid materials based on synthetic polymers and / or biopolymers (A), in particular of polysaccharides (A), which are produced 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 oil extraction technology, process engineering, paper technology, packaging technology, electrical engineering, magnet technology, communications technology, radio and television technology, agricultural technology, aviation and space technology and textile technology, as well as construction, land and sea transport and mechanical engineering, in particular as construction materials, insulation, fabrics, absorbents, adsorbents, membranes, release materials, barrier layers, controlled release materials, catalysts, culture media, catalysts and colorant, fluorescent, phosphorescent Electrically conductive, magnetic, microwave radiation absorbing and flame retardant materials or used for their preparation.

In particular, solid materials based on synthetic polymers and / or biopolymers (A) prepared in the process according to the invention are used in natural gas and petroleum extraction technology.

In the context of this use according to the invention, the solid materials are preferably used as powder. 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. In addition to the proppants to be used according to the invention, these liquid media for fracturing-in short: "fracturing media" -may also contain other customary and known constituents, such as those in the American Proppants, protective layers, weight-modifying agents, gelling agents, crosslinking agents, yellowing agents, curable resins, curing agents, surface-active compounds, foaming agents, emulsifying agents, clay stabilizers and / or acids are described in patent application US 2006/0151170 A1.

The fracturing medium with the proppants to be used 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 will crack at defects and the fracturing medium will penetrate into the ruptured or cracked fissures, cracks and channels. After reduction of the hydrostatic pressure of the fracturing medium, the proppants to be used 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 advantageousness of the process according to the invention and of the solid materials based thereon produced on the basis of synthetic polymers and / or biopolymers (A), in particular of polysaccharides (A).

Example and comparative experiments

Comparative Experiment V1

The Preparation of Cellulose (A) Films Using an Ionic Liquid (C) and Liquid (D)

For Comparative Experiment V1, a 1% by weight solution of bleached pine pulp (A) in 1-ethyl-3-methylimidazolium acetate (EMIMAc) (C) was used. The cellulose solution (AC) was made into film-like gels by extrusion in a water bath (D) or alternatively by sizing on screens, glass, aluminum foil or paraffin wax or by pouring into Petri dishes and then contacting the liquid films with water vapor (D) at room temperature for 48 hours (G) processed. The film gels (G) were washed with water until no EMIMAc in them more could be detected. Subsequently, the film gels (G) were dried at normal pressure and room temperature to the corresponding solid films (V1). The film gels (G) shrank by more than 50% of their original volume, causing the solid films (V1) to wrinkle and tear. This could not be prevented by the use of different substrates.

Examples 1 to 9

The preparation of cellulose-based solid films 1 to 9 using an ionic liquid (C) and a liquid (D1) and a liquid (D2) and their mechanical properties

For Examples 1 to 9, EMIMAc was used as ionic liquid (C) and acetone as liquid (D2).

For Examples 1 to 4 and 7 to 9, water was used as the liquid (D1).

For Examples 5 and 6, ethanol was used as liquid (D1).

Films 1 to 9 of Examples 1 to 9 were prepared in the following manner:

In each case 10 g of 2% strength by weight solutions (AC) and (ABC), corresponding in each case to 0.2 g of dry solid material, of

Cellulose (Example 1),

Cellulose / keratin in a weight ratio of 70:30 (Example 2), cellulose / urea in a weight ratio of 70:30 (Example 3), cellulose / glucose in a weight ratio of 70:30 (Example 4), cellulose / xylan in a weight ratio of 97: 3 (Example 5) ), - cellulose / xylan in the weight ratio 97: 3 plus 4.5 wt .-% urea (example

6)

Cellulose / alpha-cyclodextrin in a weight ratio of 99: 1 (Example 7), cellulose / alpha-cyclodextrin in a weight ratio of 90:10 (Example 8) and cellulose / beta-cyclodextrin in a weight ratio of 90:10 (Example 9), EMIMAc in an area of 70 cm ² were poured into petri dishes. The resulting film-form solutions were exposed at room temperature for 48 hours to a water vapor-containing atmosphere (Examples 1 to 4 and 7 to 9) or an atmosphere containing ethanol vapor (Examples 5 and 6). The resulting phases (E) were washed with water (Examples 1 to 4 and 7 to 9) or ethanol (Examples 5 and 6) until no EMIMAc was detectable. The resulting gels (G) of Examples 1 to 9 were soaked in acetone. Then, acetone and water (Examples 1 to 4 and 7 to 9) and acetone and ethanol (Examples 5 and 6) were slowly evaporated from the gels (G) at room temperature and normal pressure to give the dry solid films 1 to 9.

Films 1 to 9 were compact and showed no cracks or ripples.

The mechanical properties of films 1 to 9 were assessed by qualitative comparison of the films with each other. Table 1 gives an overview of the results.

Table 1: The mechanical properties of films 1 to 9 of Examples 1 to 9

Example / cohesion of the film flexibility

Movie no.

1 not very flexible - brittle

2 weaker flexible

3 very flexible

4 very flexible

5 highly flexible

6 very flexible 7 very flexible

8 highly flexible - but less than 7

9 very flexible - but less than 7

The results of Table 1 show that the additives (B) of Examples 3 to 9 urea, glucose, xylan, alpha-cyclodextrin and beta-cyclodextrin did not change the strong cohesion of the films 3 to 9 as compared with the film 1 of pure cellulose , Only the keratin of Example 2 caused a certain weakening of the cohesion of the film 2 as compared to the film 1 of pure cellulose.

However, all the additives (B) of Examples 2 to 9 were softening and significantly increased the flexibility of the films 2 to 9 as compared with the brittle film 1 of pure cellulose.

Examples 10 to 18

The preparation of cellulose-based solid films 10 to 18 using an ionic liquid (C) and a liquid (D1) and a liquid (D2) and their permeability

Examples 1 to 9 were repeated, except that instead of the 2 wt .-% - solutions 1 wt .-% - solutions were used. The examples correlated as follows:

Example 1 - Example 10,

Example 2 - Example 11,

Example 3 - Example 12, Example 4 - Example 13,

Example 5 - Example 14,

Example 6 - Example 15,

Example 7 - Example 16,

Example 8 - Example 17 and Example 9 - Example 18. The permeability of the resulting films 10 to 18 of Examples 10 to 18 to oxygen was determined according to ASTM D 3985 at 23 ° C and a relative humidity of 60%. The permeability of the resulting films 10 to 18 of Examples 10 to 18 to water was determined according to ASTM F 1249. The results are shown in Tables 2 and 3.

Table 2: Permeability of the films 10 to 18 of Examples 10 to 18 to oxygen according to ASTM D 3985 at 23 ° C and a relative humidity of 60%

Example film thickness / passage speed / permeability / No. μm cm ³ / m ² .d cm ³ .1 μm / m ² .d.kPa

10 37.2 2.9 x 10 ³ 788

1 1 37.8 1, 1 x 10 ⁴ 421

12 25.6 4.05 x 10 ⁴ 10.050

13 33.6 1, 47 x 10 ⁴ 5,000

14 46.8 7.86 x 10 ³ 3.730

15 38 1, 15 x 10 ³ 443

16 36.2 3.75 x 10 ² 138

17 34.6 3.45 x 10 ² 121

18 53.4 2.38 x 10 ² 129

The results of Table 2 substantiate that the oxygen permeability of cellulose based films can be varied widely by additives (B). Table 3: Permeability of the resulting films 10 to 18 of Examples 10 to 18 to water according to ASTM F 1249 at 23 ° C

Example Fs ^a> / Lf ^b> / transmission rate / permeability / No. μm% g / m ² .d g.1μm / m ² .d.kPa measured calculated * ⁰ c

10 37.2 81.3 7.24 x 10 ² 7.05 x10 ² 189

11 37.8 78.9 2.87 x10 ³ 3.09 x10 ³ 1,170

12 25.6 83.1 1.64 x 10 ³ 1.68 x 10 ³ 430 13 33.6 83.5 1.7 x 10 ³ 1.73 x 10 ³ 581

14 46.8 76.3 2.34 x 10 ³ 2.61 x 10 ³ 1,220

15 38 78.3 2.51 x10 ³ 2.73x10 ³ 1,040

16 36.1 81 1.8 x 10 ³ 1.89 x10 ³ 683

17 34.6 77.6 1.91 x 10 ³ 2.1 x 10 ³ 725 18 53.4 84.8 8.61 x10 ² 8.62x10 ² 460

a) film thickness; b) relative humidity; c) calculated for a relative humidity of 85%

The results of Table 3 support that also the water permeability of cellulose based films can be varied widely by additives (B).

Examples 19 and 20 and Comparative Experiment V2 Use of Films 10 and 12 of Examples 10 and 12 for sizing paper (Examples 19 and 20) and comparison with unsized paper (Comparative Experiment V2)

Example 19: The surface of a wet unsized paper having a water content of 20% by weight was covered with a dry film 12 according to Example 12 to give a coating. The laminate was dried at 100 ^° C. for 10 minutes. The water absorption of the laminate was determined according to the Cobb test according to ISO 535 (TAPPI T 441). This resulted in a water absorption of 44 g / m ² within 60 seconds.

Example 20:

The surface of a dry unsized paper was covered with a wet film 10 according to Example 10 (water content: 20% by weight) to give a coating. The laminate was dried at 100 ^° C. for 10 minutes. The water absorption of the laminate was determined according to the Cobb test according to ISO 535 (TAPPI T 441). This resulted in a water absorption of 42 g / m ² within 60 seconds.

Comparative experiment V2:

The Cobb test was performed on the dry unsized paper. This resulted in a water absorption of 105 g / m ² within 60 seconds.

Examples 19 and 20 under comparative experiment V2 substantiate that the cellulose-based films produced by the process according to the invention have a good barrier effect with respect to water and can therefore be used as a paper sizing agent.

Example 21 and Comparative Experiments V3 and V4

The preparation of a cellulose-based powder (A) using an ionic liquid (C) and a liquid (D1) and a liquid (D2) and its performance properties

Films according to Example 1 were prepared and comminuted, so that a powder with spherical particles with particle sizes of 800 .mu.m to 1.6 mm resulted. Subsequently, application properties were identified for use as

Proppant are essential, measured (Example 21). For purposes of comparison were measured the corresponding performance properties of commercial proppants. In the comparative experiment V3 sintered bauxite (high-pressure-resistant, ceramic material) was used and in the comparative experiment V4 an uncoated fracturing sand was used. The following results were obtained.

Compressive strength:

The compressive strength of the powder particles 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-based powder (A) (Example 21) had significantly better sphericity and significantly better roundness than the commercial fracturing sand (Comparative Experiment V4) and In this respect, it was equal to sintered bauxite (comparative experiment V3).

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 close again in 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".

The results are shown in Table 3. They supported that the cellulose-based powder (A) was clearly superior to the commercial proppants in this regard.

Table 3: Measurement of bulk density and apparent specific gravity

Conductivity and permeability:

Ultimately, it is for the use of the powder based on cellulose (A) of the

Example 21 as a proppant, whether the conductivity and the permeability of the rock fissures over a longer period remain. That's why the

Conductivity and permeability of a model gap in Ohio sandstone at a

Loading of 2 lb / ft 2 (95.76 Pa) with a 2% potassium chloride solution

API RP 61 determined. The results are shown in Table 4. They supported that at moderate pressures and temperatures, even after 10 hours, there was still significant residual conductivity, which meant that the powder of Example 21 was considered to be a residual

Proppant was suitable.

Table 4: Measurement of conductivity and permeability (Example 21)

Claims

claims

1. Process for the preparation of solid materials based on synthetic polymers and / or biopolymers (A), characterized by the following processes:

(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 step (1) with a liquid (D1) which is miscible with the chaotropic liquid (C) but wherein at least the synthetic one is present

Polymer and the biopolymer (A) are substantially or completely insoluble, whereby a phase (E), the solid synthetic polymer and / or biopolymer (A), chaotropic liquid (C) and liquid (D1) and optionally the at least one additive ( B), or a liquid phase (F), the chaotropic liquid (C) and

Contains or consists of liquid (D1),

(3) optionally separating the phase (E) from the phase (F),

(4) Remove the chaotropic liquid (C) from the phase (E) using the

Liquid (D1), resulting in a gel (G) based on synthetic polymer and / or biopolymer (A),

(5) impregnating the gel (G) with a liquid (D2) which is miscible with both the chaotropic liquid (C) and the liquid (D1), but wherein at least the synthetic polymer and biopolymer (A) are present in the

Are substantially or completely insoluble, and which has a higher volatility than the liquid (D1), and (6) Remove the two liquids (D1) and (D2) from the gel (G) by evaporation to form a solid material based on synthetic polymer and / or biopolymer (A).

2. The method according to claim 1, characterized in that the synthetic polymers (A) 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, and that the biopolymers (A) are selected from the group consisting of nucleic acids composed essentially or exclusively of nucleotides, proteins which are composed essentially or exclusively of amino acids, and polysaccharides which are substantially or exclusively from monosaccharides are selected.

3. The method according to claim 2, characterized in that polysaccharides (A) are used.

4. The method according to claim 3, characterized in that as polysaccharide (A) a structural polysaccharide is used.

A method according to claim 4, characterized in that the structural polysaccharide (A) is selected from the group consisting of cellulose, chitin and chitosan, glucosaminoglycans, alginic acid and alginates.

6. The method according to claim 5, characterized in that cellulose (A) is used.

7. The method according to any one of claims 1 to 6, characterized in that the additive (B) 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.

8. The method according to claim 7, characterized in that the additive (B) has softening effect.

9. The method according to any one of claims 1 to 8, characterized in that the chaotrope liquid (C) in a temperature range from -100 ⁰ C to +150 ⁰ C is liquid.

10. The method according to claim 9, characterized in that the chaotrope liquid (C) has a melting point of at most 150 ⁰ C.

1 1. A method according to claim 9 or 10, characterized in that the chaotrope liquid (C) is an ionic liquid.

12. The method according to claim 11, characterized in that the ionic liquid (C) consists exclusively of organic cations and organic or inorganic anions or of inorganic cations and organic anions.

13. The method according to claim 11, characterized in that the organic cations from the group of non-cyclic or heterocyclic

Oniumverbindungen and the inorganic cations are selected from the group of Lanthanidionen.

14. The method according to claim 13, characterized in that the noncyclic and heterocyclic onium compounds from the group consisting of quaternary ammonium, oxonium, sulfonium and phosphonium cations and of uronium, thiouronium and guanidinium cations, wherein the single positive charge delocalized over several heteroatoms can be selected.

15. The method according to any one of claims 1 to 14, characterized in that the chaotrope liquid (C) has a water content <5 wt .-%.

16. The method according to any one of claims 1 to 15, characterized in that the content of the solution or dispersion (AC) or (ABC) of synthetic polymer and / or biopolymer (A) 0.1 to 10 wt .-%, based on (AC) or (ABC).

17. The method according to any one of claims 1 to 16, characterized in that the liquid (D1) and the liquid (D2) are selected from the group consisting of water, alcohols, nitriles, ethers, aldehydes, ketones, sulfoxides and amides ,

18. The method according to claim 17, characterized in that the alcohol is methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and / or 2-butoxyethanol, as nitrile acetonitrile and / or Propionitrile, as ether diethyl ether, dipropyl ether,

Tetrahydrofuran and / or dioxane, acetone and / or methyl ethyl ketone as the ketone, acetaldehyde and / or propionaldehyde as the aldehyde, dimethyl sulfoxide as the sulfoxide, and dimethylformamide, acetamide and / or hexamethylphosphoramide as the amide.

19. The method according to claim 17 or 18, characterized in that as liquid (D1) water and / or ethanol is used.

20. The method according to any one of claims 17 to 19, characterized in that as the liquid (D2) acetone is used.

21. The method according to any one of claims 1 to 20, characterized in that in the process seh rode (2) in step (1) obtained solution or dispersion (AC) or (ABC) with the liquid (D1) contacted by pouring, dropping 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 its vapor (D1).

22. The method according to any one of claims 1 to 21, characterized in that in step (3) the phase (E) before the phase (F) by decantation,

Centrifuging and / or filtration separates.

23. The method according to any one of claims 1 to 22, characterized in that in step (4) the phase (E) at least once with the liquid (D1) was washed, after which the washing liquid from the phase (E) and the resulting Gel (G) isolated.

24. The method according to any one of claims 1 to 23, characterized in that in the process step (6) the liquids (D1) and (D2) from the gel (G) by evaporation at 10 to 50 ⁰ C removed.

25. The method according to claim 24, characterized in that evaporating at room temperature.

26. The method according to any one of claims 1 to 25, characterized in that the solid material based on synthetic polymers and / or biopolymers

(A) has the form of powders, threads or films.

27. The method according to claim 26, characterized in that the powder has a measured by sedimentation in a gravitational field average particle size of 100 microns to 3 mm.

28. Use of the solid materials based on synthetic polymers and / or biopolymers (A) in synthetic and analytical chemistry, biochemistry and genetic engineering, biology, pharmacology, medical, produced by the method according to one of claims 1 to 27

Diagnostics, cosmetics, natural gas and oil production technology, process technology, paper technology, packaging technology, electrical engineering, magnetic engineering, communications technology, radio and television technology, agricultural technology, aviation and space technology and textile technology as well as construction, land and sea transport and mechanical engineering.

29. Use according to claim 28, characterized in that the solid materials based on synthetic polymers and / or biopolymers (A) as supporting particles, supporting materials or proppants, construction materials, insulations, tissues, absorbents, adsorbents, membranes, separating materials,

Barrier layers, controlled release materials, catalysts,

Cultivation media, catalysts and coloring, fluorescent, phosphorescent, electrically conductive, magnetic, microwave radiation absorbing and flame retardant materials or used for their preparation.

30. Use according to claim 29, 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.