WO2015074739A1 - Polymères contenant des liquides ioniques polymérisés et utilisation desdits polymères dans des membranes - Google Patents

Polymères contenant des liquides ioniques polymérisés et utilisation desdits polymères dans des membranes Download PDF

Info

Publication number
WO2015074739A1
WO2015074739A1 PCT/EP2014/002888 EP2014002888W WO2015074739A1 WO 2015074739 A1 WO2015074739 A1 WO 2015074739A1 EP 2014002888 W EP2014002888 W EP 2014002888W WO 2015074739 A1 WO2015074739 A1 WO 2015074739A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
monomeric units
membrane
methyl
linear
Prior art date
Application number
PCT/EP2014/002888
Other languages
German (de)
English (en)
Inventor
Matthias Koch
Uwe KAETZEL
Angela Lennert
Benjamin MIANO
Jens Eichhorn
Original Assignee
Merck Patent Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Publication of WO2015074739A1 publication Critical patent/WO2015074739A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • 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
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/10—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/14—Membrane materials having negatively charged functional groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to polymers comprising monomeric units of the formula (I), as described below, or in other words containing specific polymerized ionic liquids (PILs), their preparation, the monomers of the formula (I) and a membrane comprising
  • PILs polymerized ionic liquids
  • Support material and the polymers according to the invention in particular for gas separation, as well as modules with such a membrane.
  • the selectivity which indicates the ratio in which those gases which are to be separated (permeate), to those gases which are to be retained (retentate), diffuse through the membrane, determines the separation quality of the membrane and determines whether, if that Permeate the desired product represents, further purification steps are necessary or if, if the retentate is the desired product, is slightly lost from the desired product through the membrane.
  • the highest possible selectivity is desirable for a high separation quality.
  • the durability of the membrane and of the membrane material under real process conditions are further important performance parameters. The influence of these three parameters on the total process costs depends very much on the process conditions, the composition of the gas mixture and the required separation quality.
  • Membranes for the separation of gas mixtures such as CO 2 / N 2 or CO 2 / CH 4 .
  • gas mixtures such as CO 2 / N 2 or CO 2 / CH 4 .
  • membranes for separating gases which have both high selectivity for the gas to be separated and high permeability.
  • Theoretically desirable would be technically usable membranes with a selectivity of about 40 during operation of the membrane and a permeance of 200 gpu.
  • Permeanz corresponds to the permeability based on the thickness of
  • the object of the present invention is therefore to develop alternative polymers which are suitable for the production of alternative or improved membranes.
  • a first subject of the invention are accordingly polymers comprising monomeric units of the formula (I)
  • A are each independently a linear or branched
  • a 1 each independently a linear or branched
  • Alkyl group having 1 to 8 C atoms or H means
  • Each X is independently F or H
  • each n is independently 0 or 1 and wherein the monomeric units of formula (I) may be the same or different.
  • the monomeric units of formula (I) are also ionic
  • Ionic liquids or liquid salts are ionic species consisting of an organic cation and a generally inorganic anion. They contain no neutral molecules and usually have melting points less than 373 K.
  • TCB anions tetracyano borate anions
  • X F in formula (I)
  • WO 2012/072218 describes polymer particles which are suitable for
  • polymerizable compounds of the formula (I) are to be regarded as a selection with regard to this prior art.
  • polymers containing imidazolium cations are disclosed as part of the main rod, which may, inter alia, also possess tetracyanoborate anions as counterions, for example the compound
  • Another object of the invention are also the compounds of formula (I)
  • A is a linear or branched alkyl group having 1 to 8 carbon atoms
  • a 1 denotes a linear or branched alkyl group having 1 to 8 C atoms or H
  • Sp is an alkylene group having 2 to 6 C atoms
  • X is F or H
  • n 0 or 1.
  • the polymers of the invention are in a preferred
  • This preferred embodiment of the invention accordingly relates to polymers consisting of linear or crosslinked monomeric units of the formula (I
  • A are each independently a linear or branched
  • A are each independently a linear or branched
  • Alkyl group having 1 to 8 C atoms or H means
  • Each X is independently F or H and
  • each n is independently 0 or 1
  • crosslinking agent or crosslinking agent is not limited here. Suitable crosslinking agents are known to those skilled in the art of polymer chemistry and are described below.
  • a linear or branched alkyl group having 1 to 8 C atoms is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, ferf-butyl, pentyl, 1-, 2- or 3-methylbutyl, 1, 1, 1 , 2- or 2,2-dimethylpropyl,
  • alkylene group having 2 to 6 C atoms is, for example, ethylene
  • monomeric units or in compounds of the formula (I) is ethylene, propylene or butylene. Irrespective of whether the monomeric units of the formula (I) are identical or different, it is particularly preferred if the spacer Sp in all monomeric units or in compounds of the formula (I) is ethylene (-CH 2 -CH 2 -) , Another object of the invention are therefore polymers comprising monomeric units of the formula (I) or consisting of linear or crosslinked monomeric units of the formula (I), as described above, wherein in the monomeric units of the formula (I) Sp ethylene, propylene or butylene means.
  • Another object of the invention are therefore polymers comprising monomeric units of the formula (I) or consisting of linear or crosslinked monomeric units of the formula (I), as described above, wherein in the monomeric units of the formula (I) Sp is ethylene.
  • a 1 in the monomeric units of the formula (I) is methyl and / or H.
  • polymer according to the invention or consists of the polymer according to the invention of a mixture of monomeric units of the formula (I) in which A 1 is methyl and H, all other variables of the formula (I) each independently have a meaning given above.
  • the polymer of the invention contains or consists of linear or crosslinked monomeric units of the formula (I) in which A is methyl, all other variables of the formula (I) each independently of one another having the meaning given above to have.
  • a further subject of the invention is therefore a polymer comprising monomeric units of the formula (Ia) or consisting of linear or crosslinked monomeric units of the formula (Ia),
  • A are each independently a linear or branched
  • Each X is independently F or H and
  • each n is independently 0 or 1
  • the polymer according to the invention or contains the polymer according to the invention of linear or crosslinked monomeric units of the formula (I), in which A is H, wherein all other variables of the formula (I) each independently have a previously given meaning ,
  • a further subject of the invention is therefore a polymer comprising monomeric units of the formula (Ib) or consisting of linear or crosslinked monomeric units of the formula (Ib),
  • A are each independently a linear or branched
  • Each X is independently F or H and
  • each n is independently 0 or 1
  • monomeric units of formula (Ib) may be the same or different.
  • A is preferably methyl, ethyl or n- Butyl, more preferably methyl or ethyl, and most preferably methyl.
  • the anions of the monomers of the formula (I), (Ia) or (Ib) are selected from the group consisting of tetracyano boronate, monofluorotricyanoborate or monohydridotricyanoborate.
  • polymers according to the invention contain only one particular anion selected from the group mentioned.
  • a further subject of the invention is therefore a polymer comprising monomeric units of the formula (I), (Ia) or (Ib) or consisting of linear or crosslinked monomeric units of the formula (I), (Ia) or (Ib), where the anions of the formula (I), (Ia) or (Ib) are selected from the group tetracyanoborate, monofluorotricyanoborate or
  • Tetracyanoborate or Monofluortricyanoborat selected.
  • tetracyanoborate or monohydridotricyanoborate is selected.
  • Tetracyanoborate is particularly preferably selected.
  • the anions of the monomers of the formula (I), (Ia) or (Ib) are selected from at least two anions of the group tetracyanoborate, monofluorotricyanoborate or monohydridotricyanoborate.
  • a further subject of the invention is therefore a polymer containing monomeric units of the formula (I), (Ia) or (Ib) or consisting of linear or crosslinked monomeric units of the formula (I), (Ia) or (Ib), where the anions of the monomeric units of the formula (I), (Ia) or (Ib) are selected from at least two anions of the group tetracyano borate,
  • Monofluorovicyanoborat or Monohydridotricyanoborat be selected.
  • Tetracyanoborate Monohydridotricyanoborat and Monofluordtncyanoborat.
  • Another object of the invention is a process for the preparation of the polymers according to the invention, as described above or described as preferred, characterized in that monomers of formula (I), (la) or (Ib), as described above or described as preferred, optionally in the presence of a crosslinking agent.
  • the type of polymerization is not limited. It can be polymerized anionic, cationic or free-radical. Also a living
  • Polymerization is suitable.
  • Preference is radically polymerized according to the invention.
  • the free-radical polymerization is preferably carried out with exclusion of oxygen. Radical polymerization can be achieved by a radical initiator,
  • the polymers according to the invention are preferably free-radically polymerized as described above or as described in which the polymerization is initiated by a photoinitiator.
  • a photopolymerization initiator the polymerization process is started by irradiation of the initiator-monomer mixture, for which purpose energy rays of light, electrons or ⁇ -rays can be used.
  • Photopolimerization usually leads to a rapidly cross-linked end product.
  • Preference is given to irradiation with UV light.
  • photoinitiator is not limited.
  • Suitable photoinitiators for the irradiation with UV light are
  • 2-hydroxy-2-methyl-1-phenyl-propan-1-one marketed under the trade name Darocur® 1173 BASF
  • 1-Hydroxycylohexylphenylketon marketed for example under the
  • the photoinitiator is used, for example, in 0.1 to 5% by weight, based on the total of monomers of the formula (I), (Ia) or (Ib).
  • the photoinitiator is preferably used in 1% by weight.
  • the monomers of the formula (I), (Ia) or (Ib) or the monomer mixture of the monomers of the formula (I), (Ia) or (Ib) are radically polymerized in the presence of a crosslinking agent.
  • Suitable crosslinking agents are, for example, hexadioldiacrylate, divinylbenzene, tripropylene glycol diacrylate, butanediol diacrylate, Trimethylolpropane triacrylate, dipropylene glycol diacrylate or mixtures thereof.
  • the crosslinking agent used is preferably tripropylene glycol diacrylate (TPGDA).
  • TPGDA tripropylene glycol diacrylate
  • the crosslinking agent or crosslinking agent is preferably used in an amount of from 3 to 10 mol%, more preferably in 5 mol%, based on the total of monomers of the formula (I), (Ia) or (Ib).
  • the radical polymerization is preferably carried out at temperatures of 10 ° C to 30 ° C. Particularly preferred is at
  • Preferred compounds of the formula (I) are compounds of the formula (Ia) and / or of the formula (Ib).
  • A is preferably methyl, ethyl or n-butyl, more preferably methyl or ethyl and most preferably methyl.
  • An object of the invention is furthermore a process for the preparation of a compound of the formula (I) as described above, preferably described or described as a single compound
  • A is a linear or branched alkyl group having 1 to 8 carbon atoms
  • Sp is an alkylene group having 2 to 6 C atoms
  • Y is Br or Cl
  • A is a linear or branched alkyl group having 1 to 8 carbon atoms
  • XF or H means n is 0 or 1 and
  • Me means an alkali metal.
  • Suitable solvents are, for example, acetonitrile, propionitrile, ethyl acetate, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide,
  • Tetrahydrofuran, dimethylformamide or alcohol for example methanol, ethanol or isopropanol, diethyl ether or mixtures of said solvents.
  • the starting materials of the formula (II) and formula (III) are preferably mixed at temperatures between 10.degree. C. and 40.degree. C., more preferably mixed at room temperature, and then reacted at temperatures between 40.degree. C. and 150.degree.
  • the starting materials of the formula (II) and formula (III) are preferably mixed at temperatures between 10.degree. C. and 40.degree. C., more preferably mixed at room temperature, and then reacted at temperatures between 40.degree. C. and 150.degree.
  • the starting materials of the formula (II) and formula (III) are preferably mixed at temperatures between 10.degree. C. and 40.degree. C., more preferably mixed at room temperature, and then reacted at temperatures between 40.degree. C. and 150.degree.
  • the starting materials of the formula (II) and formula (III) are preferably mixed at temperatures between 10.degree. C. and 40.degree. C., more preferably mixed at room temperature, and then reacted at temperatures between 40.degree. C. and 150.degree.
  • Reaction temperature after mixing the starting materials at 70 ° C to 100 ° C, more preferably at 80 ° C to 90 ° C.
  • resulting compounds of formula (IV), as described above, may for example be purified and / or isolated as solvates or in bulk, but they may also be used directly in the
  • Salination reaction can be used. Suitable purification steps include the separation of volatile components by distillation or condensation, extraction with an organic solvent, or a combination of these methods. Any known separation method can be used or combined for this purpose.
  • [Me] + is a lithium, sodium or potassium cation. More preferably, [Me] + is a sodium or potassium cation, most preferably a potassium cation.
  • Another object of the invention is the use of
  • PIL polymerized ionic liquid
  • Another object of the invention is the use of the
  • Another object of the invention is a membrane comprising a support material and a polymer according to the invention, as before
  • Carrier material a MWCO (Engl., For molecular weight cut off, limit of the molecular weight of a probe molecule, which is pressed into the membrane for the determination of this limit) of 1000 to 500000 Da, preferably 4000 to 100000 Da, more preferably 6000 to 30,000 Da ,
  • Probes molecule polyethylene glycol determined.
  • an RO permeate (RO for the English term reversed osmosis) consisting of water and 2000 ppm of the probe molecule at a pressure of 2.068 bar and brought to a temperature of 25 ° C on the substrate and measured the retention of the support material.
  • Suitable carrier materials are polysulfones, polyethersulfones,
  • Polyphenylsulfones polyimides, polyamides, polyvinylidene fluoride (PVDF), polyacrylonitriles, polyaniline, polyetherimides or cellulose acetate.
  • PVDF polyvinylidene fluoride
  • asymmetric polysulfone having a MWCO of 20 kDa is preferably used as support material.
  • carrier materials are well known to those skilled in the art and are commercially available, for example from the company Sepro.
  • Particularly suitable is a polysulfone having a MWCO of 20 kDa, which is commercially available from the company Septro under the name M-PS20-GPP.
  • a membrane of the invention comprising a carrier material selected from the group of polysulfones, polyethersulfones, polyphenylsulfones, polyimides, polyamides, polyvinylidene fluoride (PVDF), polyacrylonitriles, polyaniline, polyetherimides or cellulose acetate and a polymer containing monomeric units of the formula (I), (Ia) and / or (Ib) or consisting of linear or crosslinked monomeric units of the formula (I), (Ia) and / or (Ib), wherein the anions of the formula (I), (Ia) and or (Ib) are selected from the group tetracyanoborate, monofluorotricyanoborate or
  • a membrane of the invention comprising a support material selected from the group of polysulfones, polyethersulfones,
  • Polyphenylsulfones polyimides, polyamides, polyvinylidene fluoride (PVDF), polyacrylonitriles, polyaniline, polyetherimides or cellulose acetate and a polymer containing monomeric units of the formula (I), (Ia) and / or (Ib) or consisting of linear or crosslinked monomeric units of the formula (I), (Ia) and / or (Ib), where the anions of the monomeric units of the formula (I), (Ia) and / or (Ib) are prepared from at least two anions of Tetracyanoborate, Monofluortricyanoborat or Monohydridotricyanoborat be selected.
  • a process for producing the membrane as described above, the invention, characterized in that a formulation solution containing monomers of formula (I), (la) and / or (Ib), as described above, with an initiator and optionally a crosslinking agent is applied to the support material and
  • the corresponding polymerization preferably the free-radical polymerization takes place.
  • the formulation solution contains the monomers of the formula (I), (Ia) or (Ib) or the mixture of monomers of the formula (I), (Ia) or (Ib) as described above, and the initiator and the crosslinking agent in the previously stated quantities.
  • the ratio of the monomers of formula (I), (Ia) and (Ib), if different, is not limited.
  • a formulation solution is used in which the monomer corresponds to the formula (I), the formula (Ia) or the formula (Ib) and the monomer of the formula (I), (Ia) or (Ib) is identical.
  • the molar ratio of three different monomers is preferably 10: 1: 1 to 2: 1: 1.
  • the monomers of the mixture preferably differ by the anions, as described above or preferably described.
  • the formulation solution can be applied to the substrate manually or by means of a device.
  • the manual application is done for example by means of a doctor with different
  • wet film thickness Suitable wet film thicknesses are 6, 12, 24, 50 or 150 ⁇ m. A preferred wet film thickness is 24 ⁇ .
  • the application of the formulation solution is as even as possible and without pressure.
  • the formulation solution may contain or consist of the specified ingredients.
  • the formulation solution may also contain an organic solvent which should be removed prior to polymerization.
  • Solvents are, for example, dialkyl ethers, such as diethyl ether.
  • the proportion of the organic solvent should be between 5 and 50% by weight.
  • Formulation solutions are preferred which contain no organic solvent.
  • the radical polymerization preferably takes place with the aid of a
  • the formulation solution preferably contains no organic solvent.
  • a plurality of membranes according to the invention can be interconnected to form a membrane module, wherein in one respective membrane unit channels are provided to facilitate the introduction of the gas mixture to be separated, which is to be separated.
  • Another object of the invention is also a module with at least one membrane according to the invention, as described above.
  • the shape of the module is not limited in this case, i. it may be a tubular module (hollow fiber), a spiral winding module, a
  • the membrane according to the invention or a corresponding module is to be used in particular for gas separation.
  • a membrane according to the invention or a
  • FIG. 1 describes a C0 2 / N 2 -Robeson plot of the prepared membranes according to Example A in comparison with the data from the literature, as described above.
  • the membranes according to the invention indicate a better ratio of selectivity to permeability, ie they are closer to the trade-off line of the Robeson plot with regard to the economy of a membrane than hitherto known membranes of polymerized ionic liquids.
  • FIG. 2 describes a C0 2 / N 2 -Robeson plot of the prepared one
  • Example 1 Synthesis of 3-methyl-1- [2- (2-methyl-acryloyloxy) -ethyl] -imidazolium tetracyanoborate [EMAMIM TCB] Step 1: Synthesis of 3-methyl-1- [2- (2-methyl-acryloyloxy) -ethyl] -imidazolium bromide:
  • the reaction mixture is cooled to RT and added to 1 L diethyl ether. It forms a very viscous second phase at the bottom of the piston.
  • the supernatant diethyl ether is carefully decanted off and the yellowish, highly viscous product is mixed with 300 ml of water and then washed with 3 ⁇ 300 ml of ethyl acetate.
  • the aqueous phase is then present as a clear and yellow solution, which is stored in the refrigerator.
  • the water is removed on a rotary evaporator in vacuo and determines the yield.
  • the product precipitates as a yellow-orange liquid.
  • the measurement was carried out on a Bruker Avance 300 with a frequency of 300 MHz for 1 H.
  • Measurement of 11 B was carried out on a Bruker Avance 400 at a frequency of 128 MHz.
  • the phases are separated and the aqueous phase extracted 3 times with 100 ml of dichloromethane.
  • the combined organic phases are washed 6 times with 150 ml of cold water each time. It is then filtered and the solvent on a rotary evaporator in vacuo quickly removed (40 ° C bath temperature). The viscous product is on
  • Example 2 Analogously to Example 1, the stage 1 is performed. Subsequently, the aqueous solution of 3-methyl-1- [2- (2-methyl-acryloyloxy) -ethyl] -imidazolium presented bromide (13.9 g, 0.051 mol) and slowly and carefully with stirring potassium monofluorotricyanoborate (8.167 g, 0.056 mol) was added and worked up analogously to Example 1 on.
  • Example 2 Analogously to Example 1, the stage 1 is performed. Subsequently, the aqueous solution of 3-methyl-1- [2- (2-methyl-acryloyloxy) ethyl] imidazolium bromide (17.56 g, 0.063 mol) is added and slowly and carefully while stirring potassium monohydridotricyanoborate (8.14 g , 0.063 mol) was added and worked up analogously to Example 1 on.
  • Example 2 Analogously to Example 1, the stage 1 is performed. Subsequently, the aqueous solution of 3-methyl-1- [2- (2-methyl-acryloyloxy) -ethyl] -imidazolium bromide (40 g, 0.145 mol) and slowly and cautiously added with stirring lithium bis (trifluoromethanesulfonyl) imide (45.91 g, 0.16 mol) _ and worked up analogously to Example 1 on.
  • 3-methyl-1- [2- (2-methyl-acryloyloxy) -ethyl] -imidazolium bromide 40 g, 0.145 mol
  • lithium bis (trifluoromethanesulfonyl) imide 45.91 g, 0.16 mol
  • the membranes are produced by applying a membrane
  • Formulation solution as indicated in the following Table 1 on a porous polysulfone carrier having a MWCO of 20 kDa (Sepro, M-PS20-GPP).
  • the formulation solution is applied manually to the membrane support by means of a doctor blade (24 ⁇ m).
  • the doctor blade is pulled as evenly as possible and without pressure in about 2 s over the 21 cm long carrier.
  • the curing of the polymer is then carried out with a UV illuminator AKTIPRINT Mini from Technigraf with a maximum
  • TCB HDDA hexadioldiacrylate
  • TPGD tripropylene glycol diacrylate
  • the membranes were analyzed by the Time Lag method as described in SW Rutherford et al., Adsorption 3, 2007, 283-312. For this purpose, measurements were carried out with pure gases at different pressures (from 1 to 2.5 bar) and at a temperature of 35 ° C. As pure gases CO 2 and N 2 were used and the respective gas flow was 3-4 L / min. The pressure on the permeate side was ⁇ 1 mbar. The permeabilities of the pure gases were determined experimentally. The selectivity for CO 2 is calculated from the permeabilities of the pure gases, as in the literature by SW Rutherford et al or in JE Bara et al, Ind. Eng. Chem. Res. 2007, 46, 5397-5404.
  • Figure 1 is a graph of the results of Table 2 containing comparative data from the literature JE Bara et al, Ind. Eng.
  • the membranes are produced by applying a membrane
  • Formulation solution as indicated in the following Table 1 on a porous Polysulfon vicinity with a MWCO of 20 kDa (Sepro, M-PS20-GPP).
  • the formulation solution is manually applied to the membrane support by means of a doctor blade (24 ⁇ ).
  • the doctor blade is pulled as evenly as possible and without pressure in about 2 s over the 21 cm long carrier.
  • the curing of the polymer is then carried out with a UV illuminator AKTIPRINT Mini from Technigraf with a maximum
  • HDDA hexadioldiacrylate
  • TPGD tripropylene glycol diacrylate
  • the membranes were analyzed by the Time Lag method as described in SW Rutherford et al., Adsorption 3, 2007, 283-312. For this purpose, measurements were carried out with pure gases at different pressures (from 1 to 2.5 bar) and at a temperature of 35 ° C. As pure gases CO 2 and N 2 were used and the respective gas flow was 3-4 L / min. The pressure on the permeate side was ⁇ 1 mbar. The permeabilities of the pure gases were determined experimentally. The selectivity for CO 2 is calculated from the permeabilities of the pure gases, as in the literature by SW Rutherford et al or JE Bara et al, Ind. Eng. Chem. Res. 2007, 46, 5397-5404. Table 4 summarizes the results:
  • Figure 2 is a graph of the results of Table 4 containing comparative data from J.E. Bara et al, Ind. Eng.
  • Figure 1 graphic listing of the results of Example A containing comparative data from the literature J.E. Bara et al, Ind. Eng. Chem. Res. 2007, 46, 5397-5404.
  • FIG. 2 graphical representation of the results of example B containing comparative data from the literature J.E. Bara et al, Ind. Eng. Chem. Res. 2007, 46, 5397-5404.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des polymères contenant des unités monomères de la formule (I), ou en d'autres termes contenant des liquides ioniques polymérisés spéciaux (PIL), la production desdits polymères, les monomères de la formule (I), une membrane comprenant un matériau de support approprié et les polymères selon l'invention, en particulier pour la séparation de gaz, ainsi qu'un module muni de ladite membrane.
PCT/EP2014/002888 2013-11-25 2014-10-27 Polymères contenant des liquides ioniques polymérisés et utilisation desdits polymères dans des membranes WO2015074739A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13005485.1 2013-11-25
EP13005485 2013-11-25

Publications (1)

Publication Number Publication Date
WO2015074739A1 true WO2015074739A1 (fr) 2015-05-28

Family

ID=49679275

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/002888 WO2015074739A1 (fr) 2013-11-25 2014-10-27 Polymères contenant des liquides ioniques polymérisés et utilisation desdits polymères dans des membranes

Country Status (1)

Country Link
WO (1) WO2015074739A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107694358A (zh) * 2017-09-22 2018-02-16 同济大学 一种基于表面接枝的抗菌抗污染聚合物分离膜的制备方法
CN112261977A (zh) * 2018-06-08 2021-01-22 可泰克斯公司 控制金属矿渣的流变性
US11548784B1 (en) 2021-10-26 2023-01-10 Saudi Arabian Oil Company Treating sulfur dioxide containing stream by acid aqueous absorption
WO2023091369A1 (fr) * 2021-11-19 2023-05-25 W. L. Gore & Associates, Inc. Composite de poly(liquides ioniques) à des fins d'absorption et de séparation
US11759766B1 (en) 2022-08-26 2023-09-19 Saudi Arabian Oil Company Reducing sulfur emissions of sulfur recovery plant by a sorption based SO2 selective crosslinked polyionic liquid system
US11926799B2 (en) 2021-12-14 2024-03-12 Saudi Arabian Oil Company 2-iso-alkyl-2-(4-hydroxyphenyl)propane derivatives used as emulsion breakers for crude oil

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006026064A2 (fr) * 2004-08-05 2006-03-09 University Of Wyoming Nouveaux liquides ioniques et liquides polyioniques utilises en tant que nouveaux materiaux pour separer des gaz et servant egalement dans d'autres applications
WO2006053083A2 (fr) * 2004-11-10 2006-05-18 University Of Wyoming Polymeres et copolymeres de liquides ioniques en tant que matieres absorbant les radiofrequences

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006026064A2 (fr) * 2004-08-05 2006-03-09 University Of Wyoming Nouveaux liquides ioniques et liquides polyioniques utilises en tant que nouveaux materiaux pour separer des gaz et servant egalement dans d'autres applications
WO2006053083A2 (fr) * 2004-11-10 2006-05-18 University Of Wyoming Polymeres et copolymeres de liquides ioniques en tant que matieres absorbant les radiofrequences

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANBIN TANG ET AL: "Enhanced CO 2 Absorption of Poly(ionic liquid)s", MACROMOLECULES, vol. 38, no. 6, 1 March 2005 (2005-03-01), pages 2037 - 2039, XP055169558, ISSN: 0024-9297, DOI: 10.1021/ma047574z *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107694358A (zh) * 2017-09-22 2018-02-16 同济大学 一种基于表面接枝的抗菌抗污染聚合物分离膜的制备方法
CN112261977A (zh) * 2018-06-08 2021-01-22 可泰克斯公司 控制金属矿渣的流变性
CN112261977B (zh) * 2018-06-08 2022-09-23 可泰克斯公司 控制金属矿渣的流变性
US11548784B1 (en) 2021-10-26 2023-01-10 Saudi Arabian Oil Company Treating sulfur dioxide containing stream by acid aqueous absorption
WO2023091369A1 (fr) * 2021-11-19 2023-05-25 W. L. Gore & Associates, Inc. Composite de poly(liquides ioniques) à des fins d'absorption et de séparation
US11926799B2 (en) 2021-12-14 2024-03-12 Saudi Arabian Oil Company 2-iso-alkyl-2-(4-hydroxyphenyl)propane derivatives used as emulsion breakers for crude oil
US11759766B1 (en) 2022-08-26 2023-09-19 Saudi Arabian Oil Company Reducing sulfur emissions of sulfur recovery plant by a sorption based SO2 selective crosslinked polyionic liquid system

Similar Documents

Publication Publication Date Title
WO2015074739A1 (fr) Polymères contenant des liquides ioniques polymérisés et utilisation desdits polymères dans des membranes
EP2965803B1 (fr) Membrane polymère fonctionnelle et son procédé de fabrication
EP3112401B1 (fr) Membrane échangeuse d'ions et son procédé de production
EP2032239B1 (fr) Procédé de fabrication d'une membrane composite et utilisations
EP1866320B1 (fr) Derives pontes azotes d'oxydes de 6h-dibenz(e,e)(1,2)-oxaphosphorine-6-oxides, procede pour leur production et leur utilisation comme agents ignifuges
EP2531282B1 (fr) Procédé de fabrication de corps moulés poreux en silicone
EP2979748A1 (fr) Film fonctionnel de polymère et son procédé de production
DE2040983B2 (de) Acrylsäurederivate des 2,2,6,6-Tetramethylpiperidins und Verfahren zu deren Herstellung
DE4140086C2 (de) Verfahren zur Herstellung hochreiner N-Vinylpyrrolidon-Polymerisate
EP1706197A1 (fr) Membrane composite
WO2014111363A1 (fr) Procédé de préparation de l'acide acrylique
DE1913280C3 (de) Aromatische Polyimide
EP2881163A1 (fr) Membrane composite
EP3697830A1 (fr) Membranes polymères conductrices d'anions
EP2882783B1 (fr) Procédé de fabrication de solutions aqueuses à partir de polymères de lactame vinylique et leur poudre
EP0338004B1 (fr) Polymere a structure betainique, membrane de diffusion de solution, procede pour leur fabrication et leur emploi
DE60304824T2 (de) Verwendung einer Kompositmembran zur Trennung von Kohlenwasserstoffen mit einer Übergangsmetall-Polymer-Trennschicht
EP3402847B1 (fr) Composition réticulable et procédé pour produire un article revêtu
DE102015006493A1 (de) Polymere enthaltend polymerisierte ionische Flüssigkeiten und deren Anwendung in Membranen
EP1512460A1 (fr) Preparation et utilisation des liquides ioniques contenant anions de thiocyanate
EP3490695B1 (fr) Membrane en hydrate de cellulose réticulée non renforcée, procédé pour la produire et utilisation de ladite membrane
DE2950236C2 (fr)
DE102011079778A1 (de) Membran umfassend mindestens ein photochemisch vernetztes Polyimid
EP0004287B1 (fr) Disulfimides contenant des groupes maléimides polymérisables, procédé pour leur préparation et leur utilisation
DE10154209A1 (de) Verfahren zur Abtrennung von Substanzen aus Lösungen mit ionischen Flüssigkeiten unter Verwendung einer Membran

Legal Events

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

Ref document number: 14792743

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14792743

Country of ref document: EP

Kind code of ref document: A1