EP2247652A1 - Procédé de production de matériaux solides à base de polymères et/ou de biopolymères synthétiques et leur utilisation - Google Patents

Procédé de production de matériaux solides à base de polymères et/ou de biopolymères synthétiques et leur utilisation

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Publication number
EP2247652A1
EP2247652A1 EP09712072A EP09712072A EP2247652A1 EP 2247652 A1 EP2247652 A1 EP 2247652A1 EP 09712072 A EP09712072 A EP 09712072A EP 09712072 A EP09712072 A EP 09712072A EP 2247652 A1 EP2247652 A1 EP 2247652A1
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EP
European Patent Office
Prior art keywords
liquid
biopolymers
technology
phase
biopolymer
Prior art date
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Application number
EP09712072A
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German (de)
English (en)
Inventor
Simon Champ
Robert Chapman
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BASF SE
Original Assignee
BASF SE
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Publication date
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Priority to EP09712072A priority Critical patent/EP2247652A1/fr
Publication of EP2247652A1 publication Critical patent/EP2247652A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair

Definitions

  • 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.
  • a polysaccharide in particular cellulose, optionally dissolved together with additives in an ionic liquid.
  • the solution is introduced into a liquid medium which is miscible with the ionic liquid, but which is unable to dissolve the polysaccharide.
  • Suitable liquid media include or consist of water, alcohols, nitriles, ethers or ketones.
  • water is used, because then can be dispensed with the use of volatile organic solvents.
  • the regenerated polysaccharide accumulates in the form of a gel. During drying, however, the regenerated polysaccharide gel shrinks very strongly, which is a serious disadvantage, in particular, in the production of films.
  • US 2006/0151 170 A1 discloses a process for stimulating petroleum and natural gas sources.
  • a thickened liquid medium containing deformable particles in the form of spheres, cylinders, cubes, rods, cones or irregular shapes of a particle diameter of 850 ⁇ m is press-fitted into a wellbore.
  • new cracks and fissures are formed in the oil or natural gas formation, through which the oil or natural gas easily gets back to the borehole.
  • This method for well stimulation is also called “fracturing” in natural gas and oil well technology.
  • the deformable particles serve as support particles or proppants which prevent the newly formed cracks and crevices from being closed again by the pressure of the overlying rock.
  • proppants These supporting particles or supporting materials are also referred to as "proppants" in the natural gas and crude oil extraction technology.
  • the deformability of the proppants to some extent prevents the formation of finely divided material by abrasion of rock material, and / or by breaking the proppants, as is common with the use of hard proppants such as fracturing sand.
  • the deformable proppants thus effectively have the effect of support pillows.
  • deformable proppants of shredded natural materials such as, for example, sliced, ground or broken nut shells, fruit seeds, plant shells or wood parts
  • these must be provided with a protective layer in order to adapt the elastic modulus of the proppants to the respective requirements.
  • the known deformable proppants have the disadvantage that their chemical compositions and mechanical properties vary widely, so that elaborate tests are required to check whether a delivered batch is suitable for a given petroleum or natural gas formation. 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.
  • 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
  • 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.
  • 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
  • Construction, land and sea transport and engineering, can be used to great advantage.
  • the powdery solid materials based on synthetic polymers and / or biopolymers prepared by the process of the invention were outstandingly suitable as abrasion-resistant, pressure-resistant, deformable proppants in liquid media for fracturing for the purpose of highly effective and particularly long-lasting well stimulation in the production of natural gas and petroleum.
  • the flow rates could be significantly increased.
  • the 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.
  • 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.
  • 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.
  • 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.
  • powder particles and the macroscopic particles are hereinafter collectively referred to as "powder”.
  • 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.
  • 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.
  • the solid materials are powders.
  • the powder particles preferably have an average particle size of from 100 ⁇ m to 3 mm, preferably 200 ⁇ m to 2.5 mm and in particular 300 ⁇ m to 2 mm, measured by sedimentation in a gravitational field.
  • polymer (A) 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.
  • the biopolymers (A) are selected from the group consisting of nucleic acids which are composed essentially or exclusively of nucleotides, proteins which are composed essentially or exclusively of amino acids, and polysaccharides which are composed essentially or exclusively of monosaccharides ,
  • "essentially” means that the relevant biopolymers (A) may contain other structural units or building blocks than those mentioned, but that the structures and the essential chemical and physical properties of the relevant biopolymers (A) of the nucleic acids, the amino acids or the Monosaccharides are determined (see Thieme Römpp Online 2008, »Biopolymers«)
  • the synthetic polymers and biopolymers (A) can be prepared in situ in the process according to the invention in the chaotropic liquid (C) described below.
  • Polysaccharides (A) are preferably used.
  • the polysaccharides (A) include homopolysaccharides or heteropolysaccharides as well as proteoglycans, wherein the polysaccharide portion outweighs the protein content.
  • structural polysaccharides (A) are used. They are characterized by largely elongated, unbranched and therefore easily crystallizable chains, which ensure the mechanical strength.
  • suitable structural polysaccharides (A) are cellulose, lignocellulose, chitin, chitosan, glucosaminoglycans, in particular chondroitin sulfates and keratan sulfates, as well as alginic acid and alginates.
  • cellulose is used.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • noncyclic and heterocyclic onium compounds from the group consisting of quaternary ammonium, oxonium, sulfonium and phosphonium cations and of uronium, thiouronium and guanidinium cations, in which the single positive charge is delocalized over several heteroatoms used ,
  • heterocyclic quaternary ammonium cations are selected from the group consisting of pyrrolium, imidazolium, 1H-pyrazolium, 3H-pyrazolium, 4H-pyrazolium, 1-pyrazolinium, 2-pyrazolinium, 3-pyrazolinium , 2,3-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
  • imidazolium cations in particular the 1-ethyl-3-methylimidazolium cation (EMIM) or the 1-butyl-3-methylimidazolium cation (BMIM), in which the quaternary nitrogen in each case in 1 - Position is used.
  • EMIM 1-ethyl-3-methylimidazolium cation
  • BMIM 1-butyl-3-methylimidazolium cation
  • Suitable inorganic cations are all cations which do not form crystalline salts with the organic anions of the ionic liquids (C) Melting point above 150 0 C.
  • suitable inorganic cations are the cations of the lanthanides.
  • inorganic anions are basically all anions into consideration, which do not form crystalline salts with the organic cations of ionic liquids (C) whose melting point is above 150 0 C, and which also no undesirable interactions with the organic cations, such as chemical reactions, received.
  • the inorganic anions are selected from the group consisting of halide, pseudohalide, sulfide, halometalate, cyanometalate, carbonylmetalate, haloborate, halophosphate, haloarsenate, and haloantimonate anions and the anions of the halide, sulfur, of nitrogen, phosphorus, carbon, silicon, boron and transition metals.
  • Fluoride, chloride, bromide and / or iodide ions are preferred as halide anions, cyanide, cyanate, thiocyanate, isothiocyanate and / or azide anions as pseudohalide anions, 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,
  • 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.
  • the organic anions of aliphatic, cycloaliphatic and aromatic acids are derived from the group consisting of carboxylic acids, sulfonic acids, acidic sulfate esters, phosphonic acids, phosphinic acids, acidic phosphate esters, hypodiphosphinic acids, hypodiphosphonic acids, acidic boric acid esters, boronic acids, acidic silicic acid esters and acidic silanes they are selected from the group consisting of aliphatic, cycloaliphatic and aromatic thiolate, alcoholate, phenolate, methide, bis (carbonyl) imide, bis (sulfonyl) imide and
  • Carbonylsulfonylimidanionen selected.
  • EMIM Ac 1-ethyl-3-methylimidazolium acetate
  • 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.
  • a strong positive redox potential such as platinum hexafluoride or strong negative redox potential such as metallic potassium
  • 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).
  • 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.
  • 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.
  • the additives (B) may also impart properties to the solid materials containing them which comprise the additives (B) as such.
  • the additives (B) dyes, catalysts, colorants, fluorescent, phosphorescent, electrically conductive, magnetic or microwave radiation absorbing pigments, light stabilizers, vitamins, provitamins, antioxidants, Peroxidzersetzer, repellent, radioactive and non-radioactive non-metal and / or metal ions containing compounds , Compounds 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.
  • additives (B) are known from international patent application WO
  • 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.
  • the temperature should not be so high that it comes in the solubilization to a thermal decomposition of the substances (A) and (B) and / or undesirable reactions between them.
  • the temperature should not be so low that the speed of solubilization becomes too low for practical needs.
  • the solubilization in the first process step has no special features, but can be carried out batchwise or continuously using the customary and known mixing units, such as stirred tanks, Ultraturrax, inline dissolvers, homogenization units such as homogenizing nozzles, kneaders or extruders.
  • mixing units such as stirred tanks, Ultraturrax, inline dissolvers, homogenization units such as homogenizing nozzles, kneaders or extruders.
  • the content of the solution or dispersion (AC) or (ABC) of polymers (A) resulting in the first process step may likewise vary widely.
  • the upper limit of the content is determined on a case-by-case basis in such a way that the viscosity of the solution or dispersion (AC) or (ABC) in question can not be so high that it can no longer be processed.
  • the content is 0.1 to 10 Wt .-%, preferably 0.25 to 5 wt .-% and in particular 0.5 to 3 wt .-%, each based on (AC) or (ABC).
  • the solution or dispersion (AC) or (ABC) obtained in the first process step is contacted with a liquid (D1).
  • the liquid (D1) is miscible with the above-described chaotropic liquid (C), preferably without a miscibility gap, that is, in any proportion.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • the chaotrope liquid (C) is removed by washing the phase (E) at least once with the liquid (D1), after which the washing liquid (D1) is separated from the phase (E).
  • the above-described continuous or discontinuous methods are applied.
  • 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).
  • 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.
  • the resulting gel (G) already has substantially the three-dimensional shape as the solid material based on polymers (A) to be produced therefrom.
  • 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).
  • 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).
  • 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.
  • a liquid (D1) other than water the skilled artisan can easily select the appropriate suitable liquid (D2) because of his general knowledge.
  • the two liquids (D1) and (D2) are removed from the gel (G) by evaporation in the sixth process step.
  • 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.
  • 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.
  • the process according to the invention is carried out overall at atmospheric pressure.
  • 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.
  • 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.
  • fibrous additives (B) may have an inhomogeneous distribution in order to vary mechanical properties in the desired manner.
  • catalytically active additives (B) whose accessibility in the polymer (A) matrix can be improved by an inhomogeneous distribution.
  • 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.
  • polymeric or particulate additives (B) can be permanently connected to the polymer (A) matrix.
  • low molecular weight additives (B) 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".
  • 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.
  • 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.
  • 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.
  • liquid media for fracturing-in short 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.
  • 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.
  • 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.
  • EMIMAc was used as ionic liquid (C) and acetone as liquid (D2).
  • 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 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 2), cellulose / urea in a weight ratio of 70:30 (Example
  • 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.
  • Table 1 The mechanical properties of films 1 to 9 of Examples 1 to 9
  • Example 3 Example 12, Example 4 - Example 13,
  • 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%
  • Table 2 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 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 10 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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".
  • Example 21 as a proppant, whether the conductivity and the permeability of the rock fissures over a longer period remain. That's why the
  • 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

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Abstract

L'invention concerne un procédé utilisé pour produire des matériaux solides à base de polymères et de biopolymères synthétiques (A): (1) solubilisation de (A) ou de (A) et d'un additif (B) dans un liquide chaotrope exempt d'eau (C); (2) mise en contact de la solution ou dispersion obtenue (AC) ou (ABC) avec un liquide (D1) miscible avec (C), dans lequel (A) est néanmoins insoluble, ce qui permet d'obtenir une phase (E) contenant (A), (C) et (D1), ainsi qu'éventuellement (B), ainsi qu'une phase (F) contenant (C) et (D1); (3) éventuellement séparation de (E) hors de (F); (4) élimination de (C) hors de (E) au moyen de (D1), ce qui permet d'obtenir un gel (G) à base de (A); (5) imprégnation de (G) avec un liquide (D2) miscible avec (C) et (D1), dans lequel au moins (A) est toutefois insoluble, et qui présente une plus grande volatilité que (D1); et (6) éliminer (D1) et (D2) de (G) par évaporation. L'invention concerne également l'utilisation de ces matériaux.
EP09712072A 2008-02-22 2009-02-16 Procédé de production de matériaux solides à base de polymères et/ou de biopolymères synthétiques et leur utilisation Withdrawn EP2247652A1 (fr)

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CN101724096B (zh) * 2009-12-17 2011-12-07 华南理工大学 水相中微波辐射制备壳聚糖季铵盐的方法
US8980050B2 (en) 2012-08-20 2015-03-17 Celanese International Corporation Methods for removing hemicellulose
CN102876309B (zh) * 2011-07-14 2014-10-29 中国石油化工股份有限公司 一种稠油降粘剂
US8986501B2 (en) 2012-08-20 2015-03-24 Celanese International Corporation Methods for removing hemicellulose
CN112316614B (zh) * 2020-09-10 2022-02-08 江苏吉能达环境能源科技有限公司 一种用于可再生能源回收利用的除尘器
US20220080628A1 (en) * 2020-09-17 2022-03-17 Nutech Ventures Method of reinforcement for keratin materials
CN112080248B (zh) * 2020-09-24 2022-05-17 中山沃硅化工科技有限公司 一种复合阻燃绝缘电子密封胶及其制备方法

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