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WO2015003880A1 - Membranes à porosité asymétrique en élastomère de silicone thermoplastique réticulé au moyen d'un aldéhyde - Google Patents

Membranes à porosité asymétrique en élastomère de silicone thermoplastique réticulé au moyen d'un aldéhyde Download PDF

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Publication number
WO2015003880A1
WO2015003880A1 PCT/EP2014/062808 EP2014062808W WO2015003880A1 WO 2015003880 A1 WO2015003880 A1 WO 2015003880A1 EP 2014062808 W EP2014062808 W EP 2014062808W WO 2015003880 A1 WO2015003880 A1 WO 2015003880A1
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Prior art keywords
membrane
aldehyde
membranes
silicone elastomer
solution
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German (de)
English (en)
Inventor
Tobias Halbach
Peter Ball
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Wacker Chemie AG
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Wacker Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B01D71/701—Polydimethylsiloxane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the invention relates to a process for producing porous membranes having an asymmetric pore structure of a thermoplastic silicone elastomer, which are crosslinked by means of aldehyde, and to their use.
  • the thin cover layer is responsible for the separation performance, while the porous substructure leads to a mechanical stability of the membranes.
  • This type of membranes is used in plants for reverse osmosis for drinking water or ultrapure water production from sea or brackish water use.
  • silicones are rubbery polymers with a low glass transition point (Tg ⁇ -50 ° C) and a high proportion of free volume in the polymer structure.
  • Tg ⁇ -50 ° C glass transition point
  • the release-selective silicone layer is always prepared by methods such as e.g. Spraying or dissolution coating on a porous carrier substrate
  • Membranes are state of the art.
  • US2004 / 254325 describes the preparation and use of thermoplastically processable organopolysiloxane / polyurea copolymers.
  • JP-6277438 also claims silicone-polyimide copolymers as material for the production of compact membranes.
  • the applications listed there are aimed at the separation of gases.
  • porous membranes of silicone carbonate JP59225703
  • silicone polyimide copolymers JP2008 / 86903
  • membranes with an asymmetric pore structure of silicone copolymers are described, which are produced via a phase inversion process and which are characterized by high gas permeability.
  • membranes of this material are disadvantageous in that an undesirable so-called "cold flow” occurs, whereby the porous membranes can change their membrane structure under continuous load, to prevent this, the membranes can be crosslinked after the formation of the porous structure.
  • crosslinking of membranes can be achieved by the addition of
  • crosslinkers and possibly catalysts or initiators take place.
  • a disadvantage of this method is that the crosslinker must be added during the membrane production and thus influence the manufacturing process or the
  • N-methylol crosslinking Another crosslinking mechanism which is already known in the field of purely organic polymers is the so-called N-methylol crosslinking.
  • polymers which carry N-methylolamide groups are produced by copolymerization with suitable monomers.
  • suitable monomers Of these it is known that in the absence of water at elevated temperature or in the presence of acidic catalysts already at lower
  • EP0143175A exploits, which generates polymer emulsions via radical emulsion polymerization, which are nachvernetzbar via the methylol mechanism.
  • Amine group-containing silicones can also be crosslinked via the methylol mechanism, as described in DE102008054679A1
  • the invention relates to an asymmetrically porous membrane M made of at least two amino NH groups per molecule thermoplastic silicone elastomer Sl, which is crosslinked by means of aldehyde.
  • the invention also provides a first process for preparing the aldehyde-crosslinked asymmetrically porous membrane M, in which
  • thermoplastic resin in a first step, a solution of thermoplastic resin
  • Silicone elastomer Sl which has at least two amino-NH groups per molecule, an aldehyde-containing aldehyde reagent AR and solvent L is prepared,
  • the solution in a second step, the solution is brought into a mold, in a third step, the solution brought into contact with a precipitating medium F is brought into contact, forming a membrane,
  • solvent L and precipitation medium F are removed from the membrane and
  • the invention also provides a second method for
  • thermoplastic resin in a first step, a solution of thermoplastic resin
  • Silicone elastomer Sl which has at least two amino NH groups per molecule, and solvent L is prepared,
  • the solution in a second step, the solution is brought into a mold, in a third step, the solution brought into contact with a precipitating medium F is brought into contact, forming a membrane,
  • solvent L and precipitation medium F are removed from the membrane and
  • Aldehyde-containing aldehyde reagent AR is introduced and the membrane is then crosslinked, wherein the covalent
  • crosslinked membrane M is formed.
  • thermoplastic silicone elastomer Sl still fillers FS and / or additives Z.
  • Thermoplastic elastomers are usually not covalently postcrosslinked, but crosslink purely by physical
  • the crosslinked membranes M are also distinguished by the fact that their shrinkage in moisture atmosphere compared to uncrosslinked membranes is significantly reduced.
  • silicone copolymers are preferably used.
  • silicone copolymers include the groups of silicone carbonate, silicone imide, silicone imidazole, silicone urethane, silicone amide, silicone polysulfone, silicone polyether sulfone, silicone polyurea, and the like Silicone polyoxalyldiamine copolymers. Particularly preferred is the use of
  • structural element E is selected from the general formulas (Ia-f) R H OR H R H OR H
  • R H is hydrogen, or the meaning of R ⁇ has,
  • X is an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O-, or an arylene radical having 6 to 22
  • Y is a bivalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20
  • D is optionally substituted by fluorine, chlorine, C ⁇ -Cg alkyl or
  • Methylene units by groups -O-, -COO-, -OCO-, or - OCOO may be replaced, or arylene radical with 6 to 22
  • B, B x is a reactive or non-reactive end group
  • n 1 to 4000
  • n is an integer from 1 to 4000
  • g is an integer of at least 1
  • h is an integer from 0 to 40
  • i is an integer from 0 to 30 and
  • j is an integer greater than 0.
  • the radicals R 1 are monovalent or divalent hydrocarbon radicals having 1 to 18 carbon atoms, which are optionally substituted by halogen atoms, amino groups, ether groups, ester groups, epoxy groups, mercapto groups, cyano groups or (poly) glycol radicals, the latter being
  • Oxyethylene and / or oxypropylene units are constructed, particularly preferably to alkyl radicals having 1 to 12
  • Carbon atoms in particular the methyl radical.
  • radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical and iso-
  • Octyl radicals such as the 2, 2, 4-trimethylpentyl radical
  • Nonyl radicals such as the n-nonyl radical
  • Decyl radicals such as the n-decyl radical
  • Dodecyl radicals such as the n-dodecyl radical
  • Octadecyl radicals such as the n-octadecyl radical
  • Cycloalkyl radicals such as cyclopentyl, cyclohexyl,
  • substituted radicals are methoxyethyl,
  • divalent radicals R 1 are the ethylene radical
  • radical R H is preferably hydrogen or the radicals indicated above for R 1. It is preferable that radical Y is optionally substituted by halogen atoms such as fluorine or chlorine substituted hydrocarbon ⁇ hydrocarbon radicals having 3 to 13 carbon atoms, particularly preferably a hydrocarbon radical having 3 to 13 carbon atoms, in particular the 1, 6-hexamethylene, the 1.4 - Cyclohexylenrest, the methylene-bis (4-cyclohexylene) rest, the 3-methylene-3, 5, 5-trimethylcyclohexylenrest, the phenylene and the naphthylene radical, the m-Tetramethylxylylenrest and the
  • Methylene bis (4-phenylene) radical examples of divalent hydrocarbon radicals Y are alkylene radicals, such as the methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert. Butylene, n-pentylene, iso-pentylene, neo-pentylene, tert.
  • Pentylene radical hexylene radicals, such as the n-hexylene radical, heptylene radicals, such as the n-heptylene radical, octylene radicals, such as the n-octylene radical and iso-octylene radicals, such as the 2, 2, 4-trimethylpentylene radical,
  • Nonylene radicals such as the n-nonylene radical, decylene radicals, such as the n-decylene radical, dodecylene radicals, such as the n-dodecylene radical; Cycloalkylene radicals, such as cyclopentylene, cyclohexylene, cycloheptylene radicals, and methylcyclohexylene radicals, such as
  • Arylene radicals such as the phenylene and the naphthylene radical;
  • Alkarylene radicals such as o-, m-, p-tolylene radicals, xylylene radicals, such as the m-tetramethylxylylene radical, and
  • Ethylphenylenreste such as the benzylene radical, the a- and the ß-phenylethylene radical and the methylene bis (4-phenylene) radical.
  • radical X is ethylene radicals having 1 to 20 carbon atoms which may be interrupted by oxygen atoms, particularly preferably ethylene radicals having 1 to 10 carbon atoms which may be interrupted by oxygen atoms, particularly preferably n-propylene, isobutylene, 2-0xabutylene and methylene residues.
  • radicals X are the examples given for radical Y as well as optionally substituted ⁇ lkylenreste in which the carbon chain may be interrupted by oxygen atoms, such. 2-Oxabutylenrest.
  • radical B is preferably a hydrogen atom, a radical OCN-Y-NH-CO-, a radical H 2 NY-NH-C0-, a radical R 3 3Si- (0-SiR 3 2) n - or a radical R 3 3 Si (0-SiR 3 2 ) n -XE-.
  • the radical B ' is preferably the radicals indicated for B.
  • the radicals D are preferably divalent polyether radicals and ethylene radicals, particularly preferably divalent polypropylene glycol radicals and also ethylene radicals having at least 2 and at most 20 carbon atoms, such as the ethylene radical, Methylpentylene and the butylene radical, in particular are polypropylene glycol radicals having 2 to 600 carbon atoms and the ethylene and 2-methylpentylene.
  • n is preferably a number of at least 3, in particular at least 10 and preferably at most 800, in particular at most 400.
  • m is preferably the ranges specified for n.
  • g is a number of at most 100, more preferably from 10 to 60.
  • H is preferably a number of at most 10, more preferably of 0 or 1, in particular 0.
  • j is preferably a number of at most 400, particularly preferably 1 to 100, in particular 1 to 20.
  • i preferably has a number of at most 10, particularly preferably from 0 or 1, in particular 0.
  • E Ia
  • R H H
  • Y 75 mol% of m-tetramethylxylylene and 25 mol% of methylenebis (4-cyclohexylene)
  • R 3 CH 3
  • X n-propylene
  • D 2-methylpentylene
  • B, B ' H 2 NY-NH-CO-
  • the aldehyde reagents AR can be gases, liquids or solids.
  • the aldehyde present in the aldehyde reagents AR preferably has the general formula (III) (III), where
  • R is a hydrogen atom, a hydrocarbon radical with 1 to
  • the aldehyde reagents AR used according to the invention may be gases, liquids or solids. If the aldehyde reagents AR are gaseous, these are preferably pure gases, such as formaldehyde gas, or mixed with inert gases, such as argon or
  • a gas mixture AR preferably contains more than 5% by weight of aldehyde mixed with an inert gas.
  • the gas mixture AR preferably contains 0 to 0.01% by weight of oxygen and more preferably none
  • aldehyde reagents AR used are solids, they are preferably used as a solution
  • Preferred solvents are liquids which dissolve 1 to 50% by weight of aldehyde reagent at 20 ° C. and 1013 hPa, and which are compatible with the process conditions. Examples of particularly preferred solvents for the preparation of
  • Aldehyde solutions AR are water, alcohols, such as isopropanol or methanol, ethers, such as THF, polar aprotic solvents, such as N, N-dimethylacetamide, dimethylformamide, dimethylsulfoxide and N-dimethylacetamide. Methyl pyrrolidone.
  • Aqueous aldehyde solutions AR can be used as
  • Stabilizer alcohols such as methanol
  • Particularly preferred aqueous aldehyde solutions AR are formalin solutions which preferably contain 10 to 50% by weight of formaldehyde, 3 to 20% by weight of methanol and 30 to 87% by weight of water.
  • R is preferably a hydrogen atom or
  • Alkyl or aryl radicals each having 1 to 10 carbon atoms each having 1 to 10 carbon atoms.
  • the aldehyde reagent AR is particularly preferably formaldehyde, paraformaldehyde or glyoxal, if appropriate in a mixture with inert gas or a solvent.
  • thermoplastic silicone elastomer Sl has at least two amino NH groups per molecule.
  • a primary H2 group formally two amino NH groups are included, therefore, for the cross-linking one primary amino group per polymer
  • a secondary amino group only one amino NH group is included, therefore at least two secondary amino groups per polymer are required for crosslinking.
  • thermoplastic silicone elastomer Sl has at least three amino NH groups per molecule.
  • the silicone thermoplastic elastomer Sl has amino groups selected from primary and secondary amino groups. Secondary amino groups are e.g.
  • Aldehyde reagent AR is preferably used in an amount such that the molar ratio of aldehyde groups in AR to primary or secondary amino groups of the thermoplastic silicone elastomer Sl is between 0.01 and 10, more preferably between 0.1 and 8, in particular between 0.5 and 5 ,
  • thermoplastic silicone elastomer Sl can be used as additive A contain at least one filler FS.
  • Fillers FS with a BET surface area of up to 50 m 2 / g are, for example, quartz, diatomaceous earth, calcium silicate,
  • Zirkoniumsilikat zeolites
  • metal oxide powder such as aluminum, titanium, iron or zinc oxides or their mixed oxides
  • Fillers Silicon carbide, boron nitride, glass and plastic powder.
  • a list of further fillers in particulate form can be found in EP 1940940.
  • Reinforcing fillers ie fillers having a BET surface area of at least 50 nm / g, in particular 100 to 400 m2 / g, are, for example, fumed silica, precipitated silica, aluminum hydroxide, carbon black, such as furnace and acetylene black and silicon-aluminum mixed oxides of large BET surface area.
  • the mentioned fillers FS can be hydrophobic
  • Organosilazanes or siloxanes or by etherification of hydroxyl groups to alkoxy groups can be a kind of
  • Filler FS it can also be used a mixture of at least two fillers FS.
  • the solution prepared in the first step preferably contains at least 3, more preferably at least 5, in particular at least 10 and at most 40 parts by weight of filler FS per 100 parts by weight of thermoplastic silicone elastomer S1.
  • the solution or suspension prepared in the first step may optionally contain 0 to 150 parts by weight, more preferably 0.0001 to 80 parts by weight of additives, as further constituent Z per 100 parts by weight of thermoplastic silicone elastomer S1.
  • additives can be resinous, for example
  • Crosslinking aids flow control agents, surface-active substances, adhesion promoters, light stabilizers such as UV absorbers and / or radical scavengers, thixotropic agents.
  • thermoplastic silicone elastomers Sl cause a
  • Pervaporation plants require membranes that can withstand very high mechanical loads.
  • thermoplastic silicone elastomers Sl affect the diffusion and solubility of the to be separated Molecules, which leads in most cases to an improvement in the selectivity of the membranes M over pure silicones.
  • the membranes M have opposite membranes of the state
  • the pore structure of the membranes M can be easily varied over a wide range. This can also be done
  • hydrophobic media are also easy to separate.
  • the crosslinked, porous membranes M thus have a significantly improved property profile compared to pure silicone or other silicone copolymer membranes
  • the membranes M are further characterized by having excellent storage stability. This means that the membranes M after a storage period of 4 months no
  • Phase inversion process also referred to as Loeb-Souriraj an-process
  • Loeb-Souriraj an-process is their asymmetric construction with a thin, selective layer and a porous one Substructure that provides mechanical stability. Such membranes are particularly preferred.
  • thermoplastic silicone elastomer Sl is dissolved in an organic or inorganic solvent L or mixtures thereof.
  • Preferred organic solvents L are hydrocarbons, halogenated hydrocarbons, ethers, alcohols, aldehydes,
  • Ketones acids, anhydrides, esters, N-containing solvents and S-containing solvents.
  • hydrocarbons examples include pentane, hexane, dimethyl butane, heptane, hex-1-ene, hexa-1, 5-diene, cyclohexane,
  • Turpentine benzene, isopropylbenzene, xylene, toluene, naphthalene, and tetrahydronaphthalene.
  • common halogenated hydrocarbons are fluoroform, perfluoroheptane,
  • Ethylene oxide tetrahydrofuran, furan and 1,4-dioxane.
  • Examples of common alcohols are methanol, ethanol, propanol, butanol, octanol, cyclohexanol, benzyl alcohol, ethylene glycol,
  • Examples of common aldehydes are acetaldehyde and butyraldehyde.
  • Examples of common ketones are acetone, diisobutyl ketone, butan-2-one, cyclohexanone and
  • Acetophenone Common examples of acids are formic acid and acetic acid. Common examples of anhydrides are
  • esters are acetic acid methyl ester, ethyl acetate, butyl acetate, phenyl acetate, glycerol triacetate, diethyl oxalate, dioctyl sebacate, methyl benzoate, dibutyl phthalate and tricresyl phosphate.
  • inorganic solvents are water, ammonia, hydrazine, sulfur dioxide, silicon tetrachloride and titanium tetrachloride.
  • thermoplastic silicone elastomer Sl is dissolved in solvent mixtures L.
  • solvent mixtures L Common examples of binary solvent mixtures L are isopropanol-N-ethylpiperazine, isopropanol-aminoethanol,
  • thermoplastic silicone elastomer Sl is dissolved in tertiary solvent mixtures L.
  • tertiary solvent mixtures are isopropanol-N-methylpiperazine-aminoethanol, isopropanol-N-methylpiperazine-dimethylformamide, Isopropanol-N-methylpiperazine-tetrahydrofuran, isopropanol-N-methylpiperazine-dimethylsulfoxide, isopropanol-aminoethanol-dimethylacetamide, isopropanol-N-methylpiperazine-N, - diethylaminoethanol, isopropanol-dimethylformamide-N, N-diethylaminoethanol, isopropanol-aminoethanol-tetrahydrofuran, isopropanol -Aminoethanol-dimethyl sulfoxide and isopropanol-dimethylformamide
  • Silicone elastomer Sl dissolve in the precipitation medium F at 20 ° C and 1 bar to at least 20 wt .-%, in particular to
  • Suitable solvent pairs L are asser-isopropanol, water-tetrahydrofuran, water-dimethylformamide, water-N-methylpiperazine, water-dimethylsulfoxide, water-aminoethanol, water-N, -diethylaminoethanol, THF-dimethylformamide,
  • thermoplastic silicone elastomer Sl submitted thermoplastic silicone elastomer Sl
  • the thermoplastic silicone elastomer Sl is initially charged, mixed with N-methyl-2-pyrrolidone and then completely dissolved with isopropanol.
  • the concentration of silicone elastomer Sl is preferably in a range of 5 to 60 wt .-%, based on the weight of the solution of the thermoplastic silicone elastomer Sl.
  • the concentration of silicone elastomer Sl is in a range from 12 to 33 wt .-%.
  • thermoplastic silicone elastomer Sl are preferably prepared by conventional methods, e.g. Stirring, shaking or mixing, more preferably by shaking in the solvent L or solvent mixture L.
  • thermoplastic silicone elastomer Sl By heating the solutions, the solution process can sometimes be considerably accelerated. Preference is given to temperatures of 10 to 160 ° C. Further preferred is the temperature range of 22 to 40 ° C. Particularly preferred is the preparation of the solution of thermoplastic silicone elastomer Sl at
  • thermoplastic silicone elastomer Sl is completely dissolved.
  • the time for this dissolving process is e.g. between 5 min and 48 h.
  • the dissolution process lasts between 1 h and 24 h, more preferably between 2 h and 8 h.
  • the dissolution process lasts between 1 h and 24 h, more preferably between 2 h and 8 h.
  • the dissolution process lasts between 1 h and 24 h, more preferably between 2 h and 8 h.
  • thermoplastic silicone elastomer S1 further additives Z
  • Typical additives Z are inorganic salts and polymers soluble in the precipitation medium F.
  • Common inorganic salts are LiF, NaF, KF, LiCl, NaCl, KCl, MgCl 2 , CaCl 2 , ZnCl 2 and CdCl 2 .
  • Common water-soluble polymers are polyethylene glycols), poly (propylene glycols), poly (propylene ethylene glycols), poly (vinyl pyrrolidones), poly (vinyl alcohols),
  • Silicone-alkylene oxide copolymers and sulfonated polystyrenes A large part of the additives Z dissolves in the precipitation medium F in the phase inversion and is no longer contained in the membrane M. Residues of the additives Z, which still remain in the membrane M after production, can make the membrane M more hydrophilic overall.
  • thermoplastic silicone elastomer Sl mixtures of different additives Z can be incorporated into the solution of the thermoplastic silicone elastomer Sl.
  • thermoplastic silicone elastomer Sl is between 0.01 wt .-% and up to 50 wt .-%. In a preferred
  • the concentration is 0, 1 wt .-% to 15 wt .-%.
  • the concentration is 0, 1 wt .-% to 15 wt .-%.
  • the concentration of the additives Z is 1 to 5 wt .-%.
  • thermoplastic silicone elastomer Sl still the aldehyde reagent AR added.
  • the aldehyde reagent AR may be added as a solution, solid or gaseous. It is preferably added as a solution or solid.
  • thermoplastic silicone elastomer Sl in a mold, preferably a film or a fiber.
  • a mold preferably a film or a fiber.
  • Solutions of the thermoplastic silicone elastomer Sl preferably applied to a substrate or spun.
  • the solutions applied to substrates are preferably further processed into flat membranes, while the spun solutions are preferably processed into hollow fiber membranes.
  • thermoplastic silicone elastomer Sl are applied to a substrate by means of a doctor blade application. It has been found to be particularly advantageous, the
  • Filter filter cartridges This step removes large particles that are used in membrane fabrication
  • the pore size of the filter is preferably 0.2 pm to 100 ⁇ . Preferred pore sizes are from 0.2 pm to 50 pm. Particularly preferred pore sizes are from 0.2 to 10 ⁇ m.
  • thermoplastic silicone elastomer S1 prior to the doctor blade application.
  • the height of the polymer film is thereby substantially of the
  • the gap height of the doctor blade used influences.
  • the gap height of the doctor blade is preferably at least 1 pm, especially
  • the doctor height should not be set too high.
  • the width of the squeegee job is basically not limited. Typical widths are in the range of 5 cm to 2 m. In a preferred embodiment of the invention, the doctor blade width is at least 10 cm and at most 1 m, in particular at most 50 cm. Another way to make the wet polymer film is through the meniscus coating of a suitable one
  • Silicone elastomers Sl Other ways of making the polymer films include all conventional methods, e.g.
  • the film thickness is adjusted by the viscosity of the solution and by the film-forming speed.
  • the speed of the job must always be chosen so that the solution can still wet the substrate, so that no flow disturbances occur during film production. Typical speeds are thereby
  • the order takes place at temperatures above 20 ° C.
  • the application takes place in a temperature range of 25 to 50 ° C.
  • Both the prepared solutions and the substrates used can be adjusted to the temperature. In some cases, it may be advantageous to heat both the solutions of the thermoplastic silicone elastomer Sl and the substrate to the desired temperature. In a preferred embodiment of the invention, the solution is heated to 40 ° C to 60 ° C and applied to the tempered to 20 ° C to 25 ° C substrate. The temperatures should be chosen so that the crosslinking reaction is not or only delayed takes place.
  • Substrate material is particularly suitable metals, polymers, fabrics, polymer-coated fabrics and glasses.
  • Suitable metals consist of titanium, iron, copper, aluminum and their alloys.
  • polymers which can be processed into films or nonwovens.
  • examples of such polymers are cellulose, polyamides, polyimides, polyetherimides,
  • Polycarbonates polybenzimidazoles, polyethersulfones, polyesters, polysulfones, polytetrafluoroethylenes, polyurethanes,
  • Polyvinyl chlorides polyether glycols, polyethylene terephthalate (PET), polyaryl ether ketones, polyacrylonitrile,
  • Polymethyl methacrylates Polyphenylene oxides, polycarbonates,
  • Glass substrates all common glasses can be used. Examples are e.g. Quartz glass, leaded glass, float glass or soda-lime glass.
  • the materials described can be present as plates, films, nets, woven and nonwoven, as well as nonwovens.
  • the spacer is already connected to the membrane.
  • the film on a PET film with a layer thickness of 100 ⁇ to 50 ⁇ applied In a preferred embodiment of the invention, the film on a PET film with a layer thickness of 100 ⁇ to 50 ⁇ applied. In a likewise preferred
  • the film is on a
  • the film is produced on a PTFE-coated fabric.
  • the film is applied to nonwovens, so that forms a membrane-nonwoven composite material after the precipitation process, whereby in the subsequent production of the membrane modules
  • Nonwovens is divided into the application of the still wet polymer film on the nonwoven with subsequent phase inversion with the precipitation medium F in the third step.
  • nonwoven fabrics which do not have defects on the surface such as e.g. Holes or perpendicular fibers.
  • the porous membrane can be applied both to non-woven and woven nonwovens.
  • the porous membrane is applied to a nonwoven web.
  • Preferred materials for the nonwoven fabrics used are cellulose, polyesters, polyethylenes, polypropylenes,
  • the porous membrane is applied to a nonwoven polyester nonwoven.
  • the porous membrane is applied to a glass fiber fleece, carbon fiber or aramid fiber fleece.
  • the layer thickness of the substrates for the porous membrane depends on the technical conditions of the
  • Coating plant is preferably at least 10 pm, more preferably at least 50 pm, in particular at least 100 ⁇ and preferably at most 2 mm, more preferably at most 600 m, in particular at most 400 pm.
  • the substrates used for the preparation of the membranes can be treated on the surface with additional substances.
  • additional substances to call here would be u.a.
  • the films are additionally treated with ozone or UV light.
  • additives are preferred.
  • the outer diameter of the fiber is preferably at least 10 ⁇ m, particularly preferably at least 100 ⁇ m, in particular at least 200 ⁇ m, more preferably at least 300 ⁇ m and preferably at most 5 mm, particularly preferably at most 3 mm,
  • the maximum inner diameter of the hollow fiber is limited by the maximum outer diameter and is preferably at least 8 ⁇ , more preferably at least 80 pm, in particular at least 180 pm, more preferably at least 280 .um and preferably at most 4.5 mm, more preferably at most 1.9 mm, in particular at most 900 pm.
  • the medium is either gas or um
  • Examples of typical gaseous media are air, compressed air,
  • Nitrogen, oxygen or carbon dioxide Nitrogen, oxygen or carbon dioxide.
  • Examples of typical liquid media are water or
  • organic solvents are hydrocarbons, halogenated hydrocarbons, ethers,
  • Hollow fiber membrane forming the separation-selective layer on the outside, inside or in the hollow fiber wall.
  • water is used as the precipitation medium F and toluene is injected inside the hollow fiber.
  • a second polymer layer may also be co-spun.
  • Production of hollow fibers can be increased. Typical temperatures are above 20 ° C. Spinning is particularly preferred at temperatures of from 20 ° C to 150 ° C. In a particularly preferred embodiment of the invention, the hollow fibers are prepared at 25 to 55 ° C. The temperatures should be chosen so that the crosslinking reaction is not or only delayed takes place.
  • Hollow fibers are pre-dried before immersion in the precipitation bath for a defined time.
  • the predrying can take place under ambient conditions. In some cases, it may be advantageous to pre-dry at defined environmental conditions, i. Temperature and relative humidity. The temperature is included
  • the length of the pre-drying time depends on the ambient conditions. Typically, the predrying time is longer than 5 seconds.
  • the predrying time is 7 seconds to 10 minutes. In a particularly preferred embodiment of the invention, the predrying time is 10 to 30 seconds.
  • the predrying time is 30 seconds to 1 minute.
  • the molded solutions in particular the polymer films or hollow fibers with a
  • Precipitated medium F brought into contact, especially in a with
  • the third step represents a phase inversion process.
  • the precipitation medium F is a liquid in which the
  • thermoplastic silicone elastomer Sl preferably at most 2 wt .-% at 20 ° C is soluble.
  • Embodiment of the invention solves the solvent L or solvent mixture L, which is used for the preparation of the solution in the first step, in the precipitation medium F at the prevailing pressure and temperature in the third step to at least 10 wt .-%, in particular at least 30 wt. -%.
  • the most common precipitation medium F is water, in particular
  • water is also the preferred precipitation medium F.
  • Further preferred precipitation media F are alcohols, e.g. Methanol, ethanol, isopropanol and longer chain alcohols, or N-containing solvents, e.g. Acetonitrile.
  • the solvents and solvent mixtures which are described for the preparation of the polymer solution are basically suitable as precipitation medium F.
  • Felling medium F dissolves.
  • the temperature of the precipitation medium F can thereby exert great influence on the structure of the membrane M.
  • the temperature of the precipitation medium F can thereby exert great influence on the structure of the membrane M.
  • Filling medium F for the preparation of uncrosslinked membranes M is between the melting temperature and the boiling point of the precipitation medium F used.
  • the temperature is preferably in a range of 0 ° C to 80 ° C. More preferably, the temperature is in a range of 10 ° C to 60 ° C.
  • Crosslinking reaction is not yet or only delayed takes place.
  • the precipitation medium F may also contain additives that affect the precipitation of the thermoplastic
  • Additives of the precipitation medium F are inorganic salts and polymers soluble in the precipitation medium F.
  • Common inorganic salts are LiF, NaF, KF, LiCl, NaCl, KCl, MgCl 2 , CaCl 2 , ZnCl 2 and CdCl 2 .
  • water-soluble polymers are added to the precipitation medium F.
  • Common water-soluble polymers are polyethylene glycols),
  • Poly (vinyl pyrrolidones), poly (vinyl alcohols), silicone-alkylene oxide copolymers and sulfonated polystyrenes are examples of polystyrenes.
  • the precipitation medium F may also contain the customary in solutions additives and additives. Examples are u.a. Flow control agents, surface-active substances, adhesion promoters, light stabilizers such as UV absorbers and / or radical scavengers.
  • mixtures of different additives in the precipitation medium F can be incorporated with. So will be in one Particularly preferred embodiment of the invention 0.3 to 0.8 wt .-% dodecyl sulfate and 0.3 to 0.8 wt .-% LiF added to the precipitation bath .
  • the concentration of the additives in the precipitation medium F is preferably at least 0.01 wt .-%, particularly preferably at least 0.1 wt .-%, in particular at least 1 wt .-% and preferably at most 30 wt .-%, particularly preferably at most 15 Wt .-%, in particular at most 5 wt .-%.
  • Falling medium F is immersed, must in principle be chosen so that the necessary for membrane production
  • Solvent exchange can take place.
  • Immersion speeds are preferably at least 1 cm / s, more preferably at least 2 cm / s, in particular at least 5 cm / s, more preferably at least 10 cm / s and preferably at most 1 m / s, more preferably at most 50 cm / s, in particular at most 30 cm / s.
  • the speed is preferably adjusted so that the uncrosslinked membranes M are produced continuously.
  • the production of the wet shaped solution is preferably carried out with the same
  • Typical angles are preferably at least 1 °, particularly preferably at least 10 °, in particular at least 15 ° and preferably at most 90 °, particularly preferably at most 70 °, in particular at most 45 °.
  • Hollow fibers are preferably immersed in the precipitation medium F at an angle of 85 ° to 90 °.
  • the preparation of the hollow fibers can be done with or without an air gap between the nozzle and precipitation bath.
  • Solution in the precipitation medium F must always be chosen so that there is sufficient time until the solvent exchange has taken place.
  • Typical times are preferably at least 10 s, more preferably at least 30 s,
  • Silicone Elastomer Sl existing, covalently uncrosslinked membrane subjected to crosslinking.
  • the time sequence is arbitrary, both steps can be sequential or
  • the removal of residues of solvent L preferably takes place first in the fourth step and / or precipitation medium F and then the crosslinking of the thermoplastic silicone elastomer Sl in the fifth step.
  • the membrane is crosslinked in the fifth step.
  • the crosslinking takes place by increasing the temperature.
  • the crosslinking is preferably carried out at temperatures of 40 ° C to 250 ° C, more preferably at 60 ° C to 200 ° C, in particular at 80 ° C to 150 ° C.
  • the fifth step the first method, the membrane is crosslinked in the fifth step.
  • Aldehyde reagent AR introduced into the membrane, for example by immersion, spraying or by gassing of the membrane. Subsequently, the crosslinking reaction by a
  • the membrane is immersed in a bath containing an aldehyde reagent AR, or the membrane is stored in a formaldehyde gas-containing atmosphere.
  • a bath preferably contains an aqueous solution with 10 to 50 wt .-% aldehyde, the
  • an aqueous solution with 10 to 50 wt .-% of formaldehyde or glyoxal, optionally with alcohol, preferred
  • the formaldehyde gas-containing atmosphere preferably consists of more than 5 wt .-% formaldehyde in an inert gas, such as argon or nitrogen, and preferably contains 0 wt .-% to 0.01 wt .-% oxygen and more preferably no oxygen.
  • Aldehyde reagents AR is determined by the rate of diffusion of the aldehyde reagent into the membrane and can not be generalized. The optimum duration can be determined experimentally depending on the temperature, the concentration of the aldehyde in the bath or the atmosphere and the material composition and the membrane thickness.
  • the duration is preferably 5 minutes to 24 hours, more preferably 10 minutes to 12 hours.
  • the duration is preferably 5 s to 24 h
  • thermoplastic silicone elastomer S1 it may also be advantageous to add a catalyst for the crosslinking reaction.
  • a catalyst for the crosslinking reaction In principle, all Lewis and Bronsted acids are suitable as catalyst. These can be added directly to the thermoplastic silicone elastomer S1 or to a solution of the thermoplastic silicone elastomer S or as a separate component
  • the crosslinked membranes M are characterized by the degree of crosslinking> 50%, preferably> 70%.
  • Degree of crosslinking is defined as the proportion of polymer which no longer dissolves in organic solvents which normally dissolve the thermoplastic silicone elastomers S1.
  • solvents examples include THF or iso-propanol.
  • Silicone elastomer Sl be between the N atoms of the
  • thermoplastic silicone elastomers Sl crosslinking units of the general formula N-CHR 4 -N obtained.
  • modify or functionalize is the treatment of the membranes M with high or low pressure plasma or with corona discharges.
  • the membranes M By the removal of the membranes M into a plasma, the membranes can e.g. be subsequently sterilized, cleaned or etched with masks.
  • the surface hydrophobized or hydrophilized the surface hydrophobized or hydrophilized.
  • the membranes M produced according to the above-described phase inversion process and crosslinking, in particular flat and hollow-fiber membranes M have a layer thickness of
  • At least 0.1 ⁇ m particularly preferably at least 1 ⁇ m, in particular at least 10 ⁇ m, more preferably at least 50 ⁇ m and preferably at most 2000 ⁇ m, particularly preferably
  • the membranes M have a porous after production
  • the free volume is at least 5% by volume and at most up to 99% by volume, based on the volume of the crosslinked material Silicone elastomers Sl.
  • the membranes M basically have an anisotropic
  • a more compact cover layer is followed by an increasingly porous polymer skeleton.
  • the polymer backbone is covalently crosslinked.
  • the selective cover layer may be closed, i. there are no pores> 1000 ⁇ , which is used as a gas separation membrane, with a pore size smaller than 100 ⁇ , as membrane M for nanofiltration, with a pore size smaller than 20 ⁇ , as membrane M for reverse osmosis, with a
  • Pore size smaller 10 ⁇ , or as membrane M is necessary for pervaporation.
  • the thickness is preferably at least 10 nm, more preferably at least 100 nm, in particular at least 200 nm and preferably
  • Preferred polymers have a high gas permeability.
  • preferred polymers are polydimethylsiloxanes. Another way to spot defects on the surface
  • Closing consists of a thermal treatment of
  • Another object of the invention is the use of the porous cross-linked membranes M for the separation of
  • compositions of the mixtures to be separated include solid-solid, liquid-liquid, gas-gaseous, solid-liquid, solid-gaseous, and liquid-gas mixtures. Tertiary mixtures can also be used with the
  • gaseous-gas, liquid-solid and liquid-liquid mixtures are separated.
  • the separation is preferably carried out in a one-step process or in so-called hybrid processes, i. two or more
  • liquid-liquid mixtures are first purified by distillation and then further separated using the porous membranes M.
  • the membranes M can be used in all membrane processes. Typical membrane processes are e.g. Reverse osmosis, gas separation, pervaporation, resin infusion in the manufacture of composites, nanofiltration, ultrafiltration and microfiltration.
  • the membranes M are produced by selecting the appropriate production parameters in such a way that the pore structure necessary for the respective application is produced.
  • the pore sizes are preferably in a range of 1-10 ⁇ , which are particularly suitable for the separation of gas mixtures. Due to the anisotropic structure of the membranes M, the flow and thus the performance compared to compact, non-porous silicone membranes can be significantly increased. For the separation of the gas mixtures are so Significantly small amounts of energy necessary. The membranes M can be produced significantly faster and cheaper, which is absolutely necessary for the technical use of such membranes M.
  • the covalent crosslinking increases the mechanical stability.
  • the stability is compared
  • Solvents or gases that can dissolve the membrane increases and thus prevents the membrane is damaged or destroyed in the separation process.
  • Gaseous-gaseous mixtures which can be separated with the membranes M are e.g. O2 / 2, air, H2 / 2, H20-steam / air,
  • H 2 / CO H2 / C0 2, CO / C0 2, N 2 / C0 2, 0 2 / C0 2, H 2 / CH 4, CH 4 / C0 2, CH / H 2 S,
  • VOC volatile organic compounds
  • Impurities which can be separated from the effluents with the membranes M are e.g. Benzene, acetone,
  • the membrane M has pores in a range of 1 nm to 100 nm.
  • the ultrafiltration membranes M are the purification of
  • the membrane M has pores in a range of 100 nm to 10 pm. These membranes M are particularly preferred for use in microfiltration systems.
  • microfiltration membranes M are e.g. The removal of bacteria or viruses from water, the sterile filtration of pharmaceutical products, the sterilization of wine and beer and the production of particulate ultrapure water for the electrical industry.
  • porous membranes M are coated with an additional polymer on the surface.
  • the additional polymer coating is preferably a compact film.
  • the thickness of the additional layer depends on the intended application of the end membrane. The thicknesses of
  • Coatings are in a range of preferably at least 10 nm, particularly preferably at least 50 nm, in particular at least 100 nm and preferably at most 500 .mu.m, particularly preferably at most 50 .mu.m, in particular at most 10 .mu.m.
  • Suitable materials for the coating are all polymers processable into films.
  • typical polymers are cellulose acetate, polyamides, polyimides, polyetherimides, Polycarbonates, polybenzimidazoles, polyethersulfones, polyesters, polysulfones, polytetrafluoroethylenes, polyurethanes, silicones, polydimethylsilicones, polymethylphenylsilicones,
  • Polymethylaryl silicones polyvinyl chlorides, polyvinyl alcohols, polyether glycols, polyethylene terephthalate (PET),
  • Polyaryletherketones polyacrylonitrile, polymethylmethacrylates, polyphenylene oxides, polycarbonates, polyethylenes, polypropylenes and their possible copolymers.
  • the polymers can by conventional methods on the
  • Membranes M are applied. Examples of common
  • Coating processes include lamination, spraying, knife coating or gluing.
  • the membrane M must have a surface structure that allows compact and dense
  • closed films can be applied. This can be adjusted inter alia by the pore structure of the membrane M.
  • the additional coating is applied to membranes M having pores in a range of 100 nm-1 pm.
  • the high permeability and good film formation on the surface of the membranes M membranes can be achieved with better overall performance. It can both the
  • Membrane flow and the selectivity of the membranes M can be further improved.
  • the covalent crosslinking increases the stability of the membrane.
  • Another application of the membranes M is the
  • the membranes M can be incorporated, for example, in garments, such as jackets. Further examples of applications of membranes M can be found, inter alia, in Membrane Technology and Applications, Second Edition, RW Baker, New York, Wiley, 2004.
  • the membranes next to the compact and thin selective layer have a porous, crosslinked substructure, which gives the membranes M sufficient mechanical stability.
  • the membranes M can be easily
  • the membranes M can also be applied to porous structures. This can be done either directly on the support, ie, the polymer film is applied to the substrate and so immersed in the precipitation medium F, or the membrane M is prepared and in a further step laminated to the support structure.
  • adhesives z As silicone, acrylate, epoxy, poly (urethane) or poly (olefin) based adhesives are used.
  • adhesion promoters such. B. silanes
  • Carrier structures continue to improve.
  • the composite material can also be produced by thermally welding the membrane M to the support structure.
  • the membranes M can easily be installed in membrane modules. Basically, the structure of
  • Hollow fiber modules spiral wound winding modules, plate modules, cross-flow modules or dead-end modules, depending on the shape of the membrane M as a flat or hollow fiber membrane, possible.
  • the membranes M can be easily integrated into the processes of the currently common methods and with the components that are required in addition to the membrane for the construction of the modules. All the above symbols of the above formulas each have their meanings independently of each other. In all
  • Formulas is the silicon atom tetravalent.
  • the membrane piece is dried at 100 ° C, weighed and at 82 ° C and 1.013 bar (abs.) In iso-propanol for one hour
  • Non-crosslinked membranes completely dissolve under these conditions. After one hour, the membrane is again dried at 100 ° C and then weighed.
  • a doctor blade applicator (Coatmaster 509 MC-I, Erichson) is used to prepare a membrane from a doctoring solution.
  • the film-drawing frame used is a chambered doctor blade having a film width of 11 cm and a gap height of 300 ⁇ m.
  • the glass plate used as a substrate is fixed by means of a vacuum suction plate.
  • the glass plate is in front of the
  • the Filmziehrahmen is filled with the solution and pulled with a constant film drawing speed of 25 mm / s over the glass plate.
  • Example 1 Production of a Non-Crosslinked, Asymmetric, Porous Silicone Membrane (Not According to the Invention)
  • Organopolysiloxane-polyurea copolymers (SLM TPSE 100, Wacker Chemie AG) given. Subsequently, 12.9 g of NMP (N-methyl-pyrrolidone) are added to the mixture and the entire mixture is dissolved for 16 h at room temperature.
  • NMP N-methyl-pyrrolidone
  • Solids content of 14 wt .-% which is hereinafter referred to as squeegee solution.
  • the compact cover layer is followed by an open-pore and porous substructure.
  • the total porosity of the membrane thus produced is 80% by volume.
  • Solubility test is 0% by weight.
  • Example 2 Crosslinking of a membrane by insertion into
  • a membrane from Example 1 is placed in a membrane in an aqueous methanol-stabilized formalin solution (37% by weight of formaldehyde, 12% by weight of methanol, 51% by weight of water) for 18 h.
  • aqueous methanol-stabilized formalin solution (37% by weight of formaldehyde, 12% by weight of methanol, 51% by weight of water) for 18 h.
  • Example 3 Crosslinking of a membrane by placing in glyoxal solution
  • a membrane from example 1 is placed in an aqueous glyoxal solution (40% by weight glyoxal) for 18 h. Subsequently, the membrane is annealed at 120 ° C for 60 min. The degree of crosslinking of the membrane according to the solubility test described above was 71%.
  • Example 1 It is a 10 cm * 10 cm large membrane piece of Example 1 a dense chamber, which is heated to 110 ° C, treated with a continuous stream of gaseous formaldehyde and N 2 .
  • the gas stream of formaldehyde and N 2 is through
  • Formaldehyde in the supply pipes to the chamber is through
  • the degree of crosslinking is determined according to the solubility test described above:
  • the membrane is still present as an opaque membrane, which is also the
  • the tensile tests are carried out in accordance with EN ISO 527-3.
  • 5 rectangular specimens (6 cm * 1 cm) are punched out of the produced membranes.
  • the test pieces thus produced are pulled apart at a speed of 0.5 cm / s. From the determined stress-strain curves, the modulus of elasticity becomes
  • Example 6 Testing of Thermal Stability
  • Example 1 and a 7.5 cm * 7.8 cm large piece of membrane from Example 4 (# 1) at 80 ° C in water and determines the shrinkage of the two materials, in which after 24 h
  • the crosslinked membrane of Example 4 shows a much lower shrinkage than the uncrosslinked membrane of Example 1.

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Abstract

L'invention concerne une membrane à porosité asymétrique M constituée d'un élastomère de silicone thermoplastique S1, contenant au moins deux groupes amino NH par molécule, qui est réticulé au moyen d'un aldéhyde. Elle concerne également deux procédés de fabrication de la membrane à porosité asymétrique M réticulée au moyen d'un aldéhyde. Dans une première étape, on prépare une solution d'un élastomère de silicone thermoplastique S1 contenant au moins deux groupes amino NH par molécule dans un solvant L. Dans une deuxième étape, on introduit la solution dans un moule. Dans une troisième étape, on met la solution introduite dans le moule en contact avec un agent de précipitation F afin de former une membrane. Dans une quatrième étape, on élimine le solvant L et l'agent de précipitation F de la membrane et, dans une cinquième étape, on soumet la membrane à une réticulation pour obtenir une membrane M réticulée de manière covalente. Dans la première étape dans le cas du premier procédé et dans la cinquième étape dans le cas du deuxième procédé, on ajoute un réactif aldéhydique AR contenant un aldéhyde. L'invention concerne en outre l'utilisation de la membrane M pour séparer des mélanges de substances.
PCT/EP2014/062808 2013-07-08 2014-06-18 Membranes à porosité asymétrique en élastomère de silicone thermoplastique réticulé au moyen d'un aldéhyde Ceased WO2015003880A1 (fr)

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CN114144253A (zh) * 2019-06-12 2022-03-04 新南创新私人有限公司 过滤膜以及其生产方法

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