CZ2022238A3 - An anion-exchange material based on block polymer of styrene and olefins - Google Patents
An anion-exchange material based on block polymer of styrene and olefins Download PDFInfo
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- CZ2022238A3 CZ2022238A3 CZ2022-238A CZ2022238A CZ2022238A3 CZ 2022238 A3 CZ2022238 A3 CZ 2022238A3 CZ 2022238 A CZ2022238 A CZ 2022238A CZ 2022238 A3 CZ2022238 A3 CZ 2022238A3
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- styrene
- alkylene
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 22
- 229920000642 polymer Polymers 0.000 title description 8
- 239000000463 material Substances 0.000 title description 6
- 238000005349 anion exchange Methods 0.000 title description 3
- 150000001336 alkenes Chemical class 0.000 title description 2
- 239000012528 membrane Substances 0.000 claims abstract description 38
- 229920001400 block copolymer Polymers 0.000 claims abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- GARJMFRQLMUUDD-UHFFFAOYSA-N 1,1-dimethylpyrrolidin-1-ium Chemical group C[N+]1(C)CCCC1 GARJMFRQLMUUDD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 238000007265 chloromethylation reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 8
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 poly(4-vinylpyridine) Polymers 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical group ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical group 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical group C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D71/80—Block polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
-
- 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
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
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- 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
- B01D71/28—Polymers of vinyl aromatic compounds
- B01D71/281—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Předkládané řešení poskytuje blokový kopolymer poly(styren‑block‑C2‑C4‑alkylen‑stat‑C2‑C4‑alkylen‑block‑styren), v němž benzenová jádra styrenových jednotek nesou kvartérní 1,1‑dimethylpyrrolidiniovou skupinu kovalentně navázanou na benzen prostřednictvím její methylové skupiny, dále anexové membrány jím tvořené nebo jej obsahující, dále způsob přípravy tohoto kopolymeru a těchto membrán, a jejich použití.The presented solution provides a block copolymer poly(styrene-block-C2-C4-alkylene-stat-C2-C4-alkylene-block-styrene), in which the benzene cores of the styrene units carry a quaternary 1,1-dimethylpyrrolidinium group covalently bound to benzene through its methyl groups, then anionic membranes formed by it or containing it, then the method of preparing this copolymer and these membranes, and their use.
Description
Anion-výměnný materiál na bázi blokového polymeru styrenu a olefinůAnion-exchange material based on block polymer of styrene and olefins
Oblast technikyField of technology
Vynález se týká vysoce kapacitního anion-výměnného materiálu na bázi blokového kopolymeru poly(styren-block -C2-C4 alkylen-stat -C2-C4 alkylen-block -styren) nesoucího kvartérní 1,1dimethylpyrrolidiniové skupiny kovalentně navázané na aromatickém jádře prostřednictvím jednoho z methylů uvedené 1,1-dimethylpyrrolidiniové skupiny.The invention relates to a high-capacity anion-exchange material based on the block copolymer poly(styrene-block -C2-C4 alkylene-stat -C2-C4 alkylene-block -styrene) bearing quaternary 1,1dimethylpyrrolidinium groups covalently bound to the aromatic nucleus via one of the methyl said 1,1-dimethylpyrrolidinium groups.
Dosavadní stav technikyCurrent state of the art
Iontovýměnné membrány nacházejí uplatnění v laboratorním i průmyslovém měřítku. K nejvýznamnějším aplikacím patří především elektrochemické odsolování mořských a brakických vod, oddělování elektrolytů od neelektrolytů, čištění farmaceutických preparátů, použití jako tuhé elektrolyty a využití v jiných procesech. Vyrábějí se jednak jako homogenní membrány, které jsou jednofázovým systémem, nebo jako membrány heterogenní, jež jsou tvořeny disperzí iontovýměnných částic v hydrofobním polymerním pojivu (J. Schauer, L. Brožová, Journal of Membrane Science 250 (2005) 151).Ion-exchange membranes find application on a laboratory and industrial scale. The most important applications include mainly electrochemical desalination of sea and brackish waters, separation of electrolytes from non-electrolytes, purification of pharmaceutical preparations, use as solid electrolytes and use in other processes. They are produced either as homogeneous membranes, which are a single-phase system, or as heterogeneous membranes, which are formed by the dispersion of ion-exchange particles in a hydrophobic polymer binder (J. Schauer, L. Brožová, Journal of Membrane Science 250 (2005) 151).
Obvykle se aniogenní (anexové) membrány připravují z chlormethylovaného sesíťovaného polystyrenu, nebo roubováním styrenu či vinylbenzylchloridu na porézní membránu s následnou chlormethylací. Atom chlóru z chloromethylové skupiny je posléze podroben substituční reakci s trialkylaminem za vzniku kvarterní tetraalkylamoniové funkční skupiny. Dalším způsobem přípravy anexových membrán je kvarternizace poly(4-vinylpyridinu) (G. Merle, M. Wessling, K. Nijmeijer, J. Membr. Sci. 377 (2011) 1).Usually, aniogenic (annex) membranes are prepared from chloromethylated cross-linked polystyrene, or by grafting styrene or vinylbenzyl chloride onto a porous membrane with subsequent chloromethylation. The chlorine atom from the chloromethyl group is subsequently subjected to a substitution reaction with a trialkylamine to form a quaternary tetraalkylammonium functional group. Another way of preparing anionic membranes is the quaternization of poly(4-vinylpyridine) (G. Merle, M. Wessling, K. Nijmeijer, J. Membr. Sci. 377 (2011) 1).
Pro chlormethylaci se v průmyslu často používají karcinogenní a toxické chloralkylethery nebo bischloralkylethery (např. (chlormethyl)methylether nebo bis(chlormethyl)ether). Chlormethylaci blokového kopolymeru poly(styren-block-ethylen-stat-propylen-block-styrenu) (PSEBS) o Mw 30 000 g mol-1 reakcí s (chlormethyl)methyletherem za katalýzy ZnCh popisuje dokument EP 2 157 105 A1. Takto připravený prekurzor je následně reagován s roztokem trimethylaminu, čímž vznikne PSEBS nesoucí kvarterní tetramethylamoniové skupiny připojené na benzenové jádro styrenové jednotky kovalentní vazbou přes jeden z methylů. V literatuře je také uvedena chlormethylace blokového kopolymeru PSEBS o Mw 89 000 g mol-1 a obsahu styrenu 28,6 % hmotn. bez použití (chlormethyl)methyletheru (R. Vinodh, A. Ilakkiya, S. Elamathi and D. Sangeetha, Mater. Sci. Eng. B: Solid-State Mater. Adv. Technol. 167 (2010) (1), 43). Pro tuto reakci byl použit paraformaldehyd s chlorovodíkem a jako katalyzátor ZnCl2. Vzniklý chlormethylovaný polymer byl následně podroben kvarternizační reakci s triethylaminem. Membrány připravené z tohoto materiálu vykazovaly malou iontovou vodivost (0,69 mS cm-1) i iontovýměnnou kapacitu (0,578 meq g-1), což odpovídá zhruba 20% chlormethylaci za předpokladu, že následná tvorba kvartérní tetraalkylamoniové soli probíhá v podstatě kvantitativně. Obdobná procedura s kopolymerem PSEBS o Mw 118 000 g mol-1 a obsahu styrenu 29 % hmotn. podle publikace (Q. H. Zeng, Q. L. Liu, I. Broadwell, A. M. Zhu, Y. Xiong and X. P. Tu, J. Membr. Sci. 349 (2010) (1 až 2), 237) vykazovala také stupeň chlormethylace zhruba 20 % s maximálním obsahem chloru 1,75 % a výsledná membrána po reakci s trimethylaminem měla také malou iontovou vodivost. 9,37 mS cm-1 při 80 °C. Chlormethylaci kopolymeru PSEBS (chlormethyl)methyletherem a následnou kvarternizační reakci s trimethylaminem popisují také další publikace (J. Zhou, J. Guo, D. Chu, R. Chen, J. Power Sources 219 (2012) 272); L. Sun, J. Guo, J. Zhou, Q. Xu, D. Chu, R. Chen, J. Power Sources 202 (2012) 70; J. Žitka, J. Peter, B. Galajdová, L. Pavlovec, Z. Pientka, M. Paidar, J. Hnát, K. Bouzek, Desalination Water Treat. 142 (2019) 90). U literatuře je také popsána kvarternizační reakce chlormethylovaného PSEBS s 1,4-bicyklo[2.2.2] oktanem (J. Hnát, M. Plevová, J. Žitka, M. Paidar, K. Bouzek, Electrochim Acta 248 (2017) 547). Při použití chlormethyl(methyl)etheruCarcinogenic and toxic chloroalkyl ethers or bischloroalkyl ethers (e.g. (chloromethyl)methyl ether or bis(chloromethyl)ether) are often used in industry for chloromethylation. The chloromethylation of the block copolymer poly(styrene-block-ethylene-stat-propylene-block-styrene) (PSEBS) with Mw 30,000 g mol -1 by reaction with (chloromethyl)methyl ether catalyzed by ZnCh is described in document EP 2 157 105 A1. The precursor prepared in this way is subsequently reacted with a solution of trimethylamine, resulting in PSEBS bearing quaternary tetramethylammonium groups attached to the benzene nucleus of the styrene unit via a covalent bond through one of the methyls. Chloromethylation of the PSEBS block copolymer with Mw 89,000 g mol -1 and styrene content 28.6% by weight is also reported in the literature. without the use of (chloromethyl)methyl ether (R. Vinodh, A. Ilakkiya, S. Elamathi and D. Sangeetha, Mater. Sci. Eng. B: Solid-State Mater. Adv. Technol. 167 (2010) (1), 43) . Paraformaldehyde with hydrogen chloride and ZnCl2 as a catalyst were used for this reaction. The resulting chloromethylated polymer was subsequently subjected to a quaternization reaction with triethylamine. Membranes prepared from this material showed a low ionic conductivity (0.69 mS cm -1 ) and ion exchange capacity (0.578 meq g -1 ), which corresponds to roughly 20% chloromethylation, assuming that the subsequent formation of the quaternary tetraalkylammonium salt takes place essentially quantitatively. A similar procedure with a PSEBS copolymer with a Mw of 118,000 g mol -1 and a styrene content of 29 wt%. according to the publication (QH Zeng, QL Liu, I. Broadwell, AM Zhu, Y. Xiong and XP Tu, J. Membr. Sci. 349 (2010) (1 to 2), 237) also showed a degree of chloromethylation of about 20% with a maximum with a chlorine content of 1.75% and the resulting membrane after reaction with trimethylamine also had a low ionic conductivity. 9.37 mS cm -1 at 80 °C. Chloromethylation of PSEBS copolymer with (chloromethyl)methyl ether and subsequent quaternization reaction with trimethylamine is also described in other publications (J. Zhou, J. Guo, D. Chu, R. Chen, J. Power Sources 219 (2012) 272); L. Sun, J. Guo, J. Zhou, Q. Xu, D. Chu, R. Chen, J. Power Sources 202 (2012) 70; J. Žitka, J. Peter, B. Galajdová, L. Pavlovec, Z. Pientka, M. Paidar, J. Hnát, K. Bouzek, Desalination Water Treat. 142 (2019) 90). The quaternization reaction of chloromethylated PSEBS with 1,4-bicyclo[2.2.2] octane is also described in the literature (J. Hnát, M. Plevová, J. Žitka, M. Paidar, K. Bouzek, Electrochim Acta 248 (2017) 547) . When using chloromethyl(methyl)ether
- 1 CZ 2022 - 238 A3 jev literatuře zmiňována tendence k vedlejším reakcím, která v případě styrenových polymerů vede k sesíťování (R. C. Fuson, C. H. McKeever, Chloromethylation of Aromatic Compounds, Organic Reactions, John Wiley & Sons, Inc., 2004). Chlormethylaci blokového kopolymeru PSEBS bez použití (chlormethyl)methyletheru s následnou reakcí s trimethylaminem popisuje patent CZ 305 138. Další nedostatek všech těchto membrán spočívá, jak je popsáno ve výše zmíněných publikacích, v jejich omezené stabilitě v alkalickém prostředí.- 1 CZ 2022 - 238 A3 phenomenon mentioned in the literature is the tendency to side reactions, which in the case of styrene polymers leads to cross-linking (R. C. Fuson, C. H. McKeever, Chloromethylation of Aromatic Compounds, Organic Reactions, John Wiley & Sons, Inc., 2004). Chloromethylation of the block copolymer PSEBS without the use of (chloromethyl)methyl ether followed by reaction with trimethylamine is described in patent CZ 305 138. Another shortcoming of all these membranes, as described in the above-mentioned publications, is their limited stability in an alkaline environment.
Podstata vynálezuThe essence of the invention
Předmětem předkládaného vynálezu je anexová membrána tvořená blokovým kopolymerem poly(styren-block-C2-C4-alkylen-stat-C2-C4-alkylen-block-styren)em, v němž benzenová jádra styrenových jednotek nesou kvartérní 1,1-dimetaylpyrrolidiniovou skupinu kovalentně navázanou na benzen přes jeden z jejích methylů, připravitelná postupem popsaným níže.The subject of the present invention is an anion membrane formed by the block copolymer poly(styrene-block-C2-C4-alkylene-stat-C2-C4-alkylene-block-styrene) in which the benzene cores of the styrene units bear the quaternary 1,1-dimethylpyrrolidinium group covalently attached to benzene via one of its methyls, can be prepared by the procedure described below.
Blokový kopolymer lze schematicky vyjádřit vzorcem I.The block copolymer can be represented schematically by formula I.
S výhodou je obsah styrenových jednotek v rozmezí 10 až 70 % hmota., výhodněji 20 až 40 % hmota., a obsah alkylenových jednotek každého typuje v rozmezí 10 až 50 % hmota., vztaženo na hmotnost výchozího poly(styren-block-C2-C4-alkylen-stat-C2-C4-alkylen-block-styrenu) bez navázaných 1,1 -dimetaylpyrrolidiniových skupin.Preferably, the content of styrene units is in the range of 10 to 70% by weight, more preferably 20 to 40% by weight, and the content of alkylene units of each type is in the range of 10 to 50% by weight, based on the weight of the starting poly(styrene-block-C2- C4-alkylene-stat-C2-C4-alkylene-block-styrene) without attached 1,1-dimethylpyrrolidinium groups.
S výhodou je alkylenem butylen a ethylen.Preferably, the alkylene is butylene and ethylene.
S výhodou je obsah 1,1-dimetaylpyrrolidiniových skupin v rozmezí 0,8 až 3,2 mmol.g1, výhodněji 0,9 až 1,9 mmol.g1, vztaženo na hmotnost nezbotaalého blokového kopolymeru s navázanými 1,1 -dimetaylpyrolidiniovými skupinami a chloridovým protiiontem, vzorec I.Advantageously, the content of 1,1-dimethylpyrrolidinium groups is in the range of 0.8 to 3.2 mmol.g 1 , more preferably 0.9 to 1.9 mmol.g 1 , based on the weight of the intact block copolymer with attached 1,1-dimethylpyrrolidinium groups and a chloride counterion, formula I.
Anexové membrány tvořené blokovým kopolymerem - poly(styren-Z?/oc&-C2-C4-alkylen-statC2-C4-alkylen-Z?/ocÁ:-styrenem), v němž benzenová jádra styrenových jednotek nesou kvartérní 1,1-dimetaylpyrrolidiniovou skupinu kovalentně navázanou na benzen přes jeden z jejíchAnnex membranes formed by a block copolymer - poly(styrene-Z?/oc?-C2-C4-alkylene-statC2-C4-alkylene-Z?/oc?:-styrene), in which the benzene cores of the styrene units carry a quaternary 1,1-dimethylpyrrolidinium group covalently bound to benzene through one of its
-2CZ 2022 - 238 A3 methylů (vzorec I), jsou vysoce iontově vodivé, mají dobré mechanické vlastnosti i v suchém stavu, a jsou využitelné například v aplikacích pro iontovýměnné materiály, jako jsou zejména tuhé elektrolyty, iontovýměnné membrány, iontovýměnná pojiva a nosiče katalyzátorů. Vysokou iontovou vodivostí je míněna vodivost alespoň 50 mS cm-1 v hydroxidovém cyklu při teplotě 25 °C.-2CZ 2022 - 238 A3 methyls (formula I), are highly ionically conductive, have good mechanical properties even in the dry state, and are useful, for example, in applications for ion-exchange materials, such as especially solid electrolytes, ion-exchange membranes, ion-exchange binders and catalyst carriers . By high ionic conductivity is meant a conductivity of at least 50 mS cm -1 in the hydroxide cycle at a temperature of 25 °C.
Předmětem předkládaného vynálezu je rovněž způsob přípravy anexových membrán tvořených blokovým kopolymerem - poly(styren-block -C2-C4-alkylen-stat -C2-C4-alkylen-block styrenem), v němž benzenová jádra styrenových jednotek nesou kvartérní 1,1dimethylpyrrolidiniovou skupinu kovalentně navázanou přes jeden z jejích methylů (vzorec I), zahrnující následující kroky:The subject of the present invention is also a method of preparing anionic membranes formed by a block copolymer - poly(styrene-block -C2-C4-alkylene-stat -C2-C4-alkylene-block styrene), in which the benzene cores of the styrene units bear the quaternary 1,1dimethylpyrrolidinium group covalently attached via one of its methyls (formula I), involving the following steps:
- poly(styren-block-C2-C4-alkylen-stat-C2-C4-alkylen-block-styren) se podrobí chlormethylaci na benzenových jádrech v jednotkách styrenu;- poly(styrene-block-C2-C4-alkylene-stat-C2-C4-alkylene-block-styrene) is subjected to chloromethylation on the benzene nuclei in the styrene units;
- chlormethylovaný poly(styren-block-C2-C4-alkylen-stat-C2-C4-alkylen-block-styren) se odlije do formy membrány;- chloromethylated poly(styrene-block-C2-C4-alkylene-stat-C2-C4-alkylene-block-styrene) is cast into a membrane mold;
- chlormethylovaný poly(styren-block -C2-C4-alkylen-stat -C2-C4-alkylen-block-styren) ve formě membrány se podrobí reakci s 1-methylpyrrolidinem za vzniku kvartérní 1,1dimethylpyrrolidiniové soli kovalentně vázané na benzenové jádro styrénových jednotek.- chloromethylated poly(styrene-block -C2-C4-alkylene-stat -C2-C4-alkylene-block-styrene) in the form of a membrane is subjected to a reaction with 1-methylpyrrolidine to form a quaternary 1,1dimethylpyrrolidinium salt covalently bound to the benzene core of the styrene units .
Ve výhodném provedení lze jako vhodné rozpouštědlo pro krok reakce chlormethylované membrány s 1-methylpyrrolidinem použít vodu a/nebo C1-C4 alkohol. Tato rozpouštědla zajistí dobrou rozpustnost reagencií a smáčitelnost membrány bez jejího rozpuštění.In a preferred embodiment, water and/or C1-C4 alcohol can be used as a suitable solvent for the reaction step of the chloromethylated membrane with 1-methylpyrrolidine. These solvents ensure good solubility of the reagents and wettability of the membrane without dissolving it.
Ve výhodném provedení je výchozím kopolymerem kopolymer poly(styren-block-ethylen-statbutylen-block -styren) (PSEBS).In a preferred embodiment, the starting copolymer is a poly(styrene-block-ethylene-statbutylene-block-styrene) copolymer (PSEBS).
Ve výhodném provedení má blokový kopolymer poly(styren-block-C2-C4alkylen-stat-C2C4alkylen-block-styren) použitý pro chlormethylaci početně průměrnou molární hmotnost 10 000 až 1 000 000 g mol-1 a hmotnostní obsah styrenu v rozmezí 10 až 70 %.In a preferred embodiment, the block copolymer poly(styrene-block-C2-C4alkylene-stat-C2C4alkylene-block-styrene) used for chloromethylation has a number average molar mass of 10,000 to 1,000,000 g mol -1 and a mass content of styrene in the range of 10 to 70 %.
Chlormethylaci lze s výhodou provést postupem popsaným v patentu CZ 305138, tedy uvedením výchozího blokového kopolymeru poly(styren-block-C2-C4-alkylen-stat-C2-C4-alkylen-blockstyrenu) do reakce s dimethoxymethanem, s činidlem vybraným ze skupiny PCl3, SOCl2 a SiCl4, a katalyzátorem ZnCl2, při teplotě v rozmezí 10 °C až 65 °C, po dobu alespoň 2 hodin, v některých provedeních 2 až 24 h, v jiných provedeních 24 hodin až 1 měsíc.Chloromethylation can be advantageously carried out by the procedure described in patent CZ 305138, i.e. by introducing the initial block copolymer poly(styrene-block-C2-C4-alkylene-stat-C2-C4-alkylene-blockstyrene) into a reaction with dimethoxymethane, with a reagent selected from the PCl3 group , SOCl2 and SiCl4, and a ZnCl2 catalyst, at a temperature in the range of 10°C to 65°C, for at least 2 hours, in some embodiments 2 to 24 h, in other embodiments 24 hours to 1 month.
S výhodou se reakce s 1-methylpyrrolidinem provede při teplotě v rozmezí 20 °C až 65 °C.Preferably, the reaction with 1-methylpyrrolidine is carried out at a temperature in the range of 20°C to 65°C.
Výhodněji se reakce s 1-methylpyrrolidinem provede při teplotě v rozmezí 20 °C až 65 °C a po dobu alespoň 24 h až 48 hodin.More preferably, the reaction with 1-methylpyrrolidine is carried out at a temperature in the range of 20°C to 65°C and for a period of at least 24 h to 48 h.
Postup přípravy lze ilustrovat následujícím schématem, které však neomezuje rozsah ochrany:The preparation procedure can be illustrated by the following diagram, which, however, does not limit the scope of protection:
- 3 CZ 2022 - 238 A3- 3 CZ 2022 - 238 A3
22
R ,R = H. methyl nabo ethylR , R = H. methyl or ethyl
Příklady uskutečnění vynálezuExamples of implementation of the invention
Příklad 1 g blokového kopolymeru PSEBS s obsahem styrenu 29 % hmotn., Ij. 1,45 g (0,0139 mol), bylo rozpuštěno v 95 g chloroformu a přidáno 10 g (0,131 mol) dimethoxymethanu, 1,8 g (0,0132 mol) ZnCE a 2 g (0,0146 mol) PCI3. ZnCT byl rozdispergován mícháním po dobu lha směs byla následně zahřívána 24 h na 60 °C. Pak byla reakční směs naředěna 100 g chloroformu a vysrážena do 2 1 ethanolu. Vysrážený polymer byl odfiltrován, promyt 2 1 ethanolu a usušen při laboratorní teplotě. Obsah chloru 4,56 % hmotn.. Stupeň chlormethylace 49 %. Produkt byl rozpustný v toluenu a chlorovaných rozpouštědlech.Example 1 g of block copolymer PSEBS with a styrene content of 29% by weight, Ij. 1.45 g (0.0139 mol) was dissolved in 95 g chloroform and 10 g (0.131 mol) dimethoxymethane, 1.8 g (0.0132 mol) ZnCE and 2 g (0.0146 mol) PCI3 were added. ZnCT was dispersed by stirring for 1 h, the mixture was then heated for 24 h at 60 °C. Then the reaction mixture was diluted with 100 g of chloroform and precipitated into 2 L of ethanol. The precipitated polymer was filtered off, washed with 2 L of ethanol and dried at room temperature. Chlorine content 4.56% by weight. Degree of chloromethylation 49%. The product was soluble in toluene and chlorinated solvents.
Příklad 2 g blokového kopolymeru PSEBS s obsahem styrenu 29 % hmotn., tj. 1,45 g (0,0139 mol), bylo rozpuštěno v 95 g chloroformu a přidáno 10 g (0,131 mol) dimethoxymethanu, 1,8 g (0,0132 mol) ZnCE a 2 g (0,0146 mol) PCI3. ZnCT byl rozdispergován mícháním po dobu 1 h. Směs byla následně ponechána za laboratorní teploty 20 °C po dobu 27 dní. Po 27 dnech byla směs naředěna 100 g chloroformu a vysrážena do 2 1 ethanolu. Následně byl polymer odfiltrován a promyt 2 1 ethanolu a usušen při laboratorní teplotě. Obsah chloru 5,38 % hmotn.. Stupeň chlormethylace 59 %. Produkt byl rozpustný v toluenu a chlorovaných rozpouštědlech.Example 2 g of PSEBS block copolymer with a styrene content of 29% by weight, i.e. 1.45 g (0.0139 mol), was dissolved in 95 g of chloroform and 10 g (0.131 mol) of dimethoxymethane, 1.8 g (0. 0132 mol) of ZnCE and 2 g (0.0146 mol) of PCI3. The ZnCT was dispersed by stirring for 1 h. The mixture was then left at a laboratory temperature of 20 °C for 27 days. After 27 days, the mixture was diluted with 100 g of chloroform and precipitated into 2 L of ethanol. Subsequently, the polymer was filtered off and washed with 2 l of ethanol and dried at room temperature. Chlorine content 5.38% by weight. Degree of chloromethylation 59%. The product was soluble in toluene and chlorinated solvents.
Příklad 3Example 3
Chlormethylovaný polymer připravený podle příkladu 2 byl rozpuštěn na 5% roztok v tetrahydrofuranu, odlit na teflonovou podložku a překryt Petriho miskou, aby se zpomalilo odpařování rozpouštědla. Za těchto podmínek se rozpouštědlo při laboratorní teplotě odpařilo po 48 h. Takto připravená membrána o hmotnosti cca 1 g byla vnořena do 100 ml 35% ethanolického roztoku 1-methylpyrrolidinu v reagenční nádobě. Nádoba byla těsně uzavřena a temperována při teplotě 60 °C po 24 h. Poté byla membrána vyjmuta a ponořena do 0,5 1 IM HC1The chloromethylated polymer prepared according to Example 2 was dissolved into a 5% solution in tetrahydrofuran, cast onto a Teflon pad and covered with a petri dish to slow the evaporation of the solvent. Under these conditions, the solvent was evaporated at laboratory temperature after 48 h. The thus prepared membrane weighing about 1 g was embedded in 100 ml of a 35% ethanol solution of 1-methylpyrrolidine in a reagent container. The vessel was tightly closed and heated at 60 °C for 24 h. The membrane was then removed and immersed in 0.5 L HC1
-4CZ 2022 - 238 A3 po dobu 1 h. Následně byla membrána opět vyjmuta, omyta demineralizovanou vodou a sušena za laboratorní teploty. Převedení do OH- fáze bylo provedeno ponořením membrány do 1 l 1M NaOH, po dobu 1 h a následným promytím destilovanou vodou. Iontová vodivost v OH- fázi takto připravené membrány při 30 °C je 42,3 mS cm-1.-4CZ 2022 - 238 A3 for 1 h. Subsequently, the membrane was removed again, washed with demineralized water and dried at laboratory temperature. The conversion to the OH - phase was carried out by immersing the membrane in 1 l of 1M NaOH for 1 h followed by washing with distilled water. The ionic conductivity in the OH - phase of the membrane prepared in this way at 30 °C is 42.3 mS cm -1 .
Příklad 4Example 4
Chlormethylovaný polymer připravený podle příkladu 2 byl rozpuštěn na 5% roztok v tetrahydrofuranu, odlit na teflonovou podložku a překryt Petriho miskou, aby se zpomalilo odpařování rozpouštědla. Za těchto podmínek se rozpouštědlo při laboratorní teplotě odpařilo po 48 h. Takto připravená membrána o hmotnosti cca 1 g byla vnořena do 100 ml 10% ethanolického roztoku 1-methylpyrrolidinu v reagenční nádobě. Nádoba byla těsně uzavřena a ponechána při laboratorní teplotě 25°C po dobu 48 h. Poté byla membrána vyjmuta a ponořena do 0,5 litru 1M HCl po dobu 1 h. Následně byla membrána opět vyjmuta, omyta demineralizovanou vodou a sušena za laboratorní teploty. Převedení do OH- fáze bylo provedeno ponořením membrány do 1 litru 1M NaOH, po dobu 1 h a následným promytím destilovanou vodou. Iontová vodivost v OH- fázi takto připravené membrány při 30 °C je 30,2 mS cm-1.The chloromethylated polymer prepared according to Example 2 was dissolved into a 5% solution in tetrahydrofuran, cast onto a Teflon pad and covered with a petri dish to slow the evaporation of the solvent. Under these conditions, the solvent was evaporated at laboratory temperature after 48 h. The thus prepared membrane weighing about 1 g was embedded in 100 ml of a 10% ethanol solution of 1-methylpyrrolidine in a reagent container. The container was tightly closed and left at a laboratory temperature of 25°C for 48 h. The membrane was then removed and immersed in 0.5 liter of 1M HCl for 1 h. Subsequently, the membrane was again removed, washed with demineralized water and dried at laboratory temperature. Conversion to the OH - phase was carried out by immersing the membrane in 1 liter of 1M NaOH for 1 h followed by washing with distilled water. The ionic conductivity in the OH - phase of the membrane prepared in this way at 30 °C is 30.2 mS cm -1 .
Průmyslová využitelnostIndustrial applicability
Anexové membrány (a iontovýměnné membrány obecně) nacházejí uplatnění v laboratorním i průmyslovém měřítku. K nejvýznamnějším aplikacím patří především elektrochemické odsolování mořských a brakických vod, dělení elektrolytů od neelektrolytů, čištění farmaceutických preparátů, použití jako tuhé elektrolyty a využití v jiných elektrochemických procesech jako je například elektrodialýza, elektrolýza a palivové články. Materiály podle předloženého vynálezu jsou určeny zejména pro přípravu těchto membrán, homogenních i mikroheterogenních, a pro jejich použití v zařízeních využívajících iontovýměnné procesy.Anex membranes (and ion-exchange membranes in general) are used in both laboratory and industrial scale. The most important applications include mainly electrochemical desalination of sea and brackish waters, separation of electrolytes from non-electrolytes, purification of pharmaceutical preparations, use as solid electrolytes and use in other electrochemical processes such as electrodialysis, electrolysis and fuel cells. The materials according to the present invention are intended in particular for the preparation of these membranes, both homogeneous and microheterogeneous, and for their use in devices using ion exchange processes.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| CZ2022-238A CZ2022238A3 (en) | 2022-06-03 | 2022-06-03 | An anion-exchange material based on block polymer of styrene and olefins |
| PCT/CZ2023/050021 WO2023232169A1 (en) | 2022-06-03 | 2023-04-22 | Anion-exchange material based on block polymer of styrene and olefins |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CZ2022-238A CZ2022238A3 (en) | 2022-06-03 | 2022-06-03 | An anion-exchange material based on block polymer of styrene and olefins |
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| Publication Number | Publication Date |
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| CZ309781B6 CZ309781B6 (en) | 2023-10-04 |
| CZ2022238A3 true CZ2022238A3 (en) | 2023-10-04 |
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| CZ2022-238A CZ2022238A3 (en) | 2022-06-03 | 2022-06-03 | An anion-exchange material based on block polymer of styrene and olefins |
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| Country | Link |
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| CZ (1) | CZ2022238A3 (en) |
| WO (1) | WO2023232169A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101475098B1 (en) | 2007-06-05 | 2014-12-22 | 가부시키가이샤 도쿠야마 | Hydrocarbon elastomer capable of oh type anion exchange, use thereof, and process for producing the same |
| CZ201456A3 (en) | 2014-01-24 | 2015-05-13 | Ústav makromolekulární chemie AV ČR, v.v.i. | Process for preparing soluble block copolymer of styrene and olefins as well as use thereof |
| WO2019079513A1 (en) * | 2017-10-17 | 2019-04-25 | Yushan Yan | Polymers having stable cationic pendant groups for use as anion exchange membranes and ionomers |
| CZ309072B6 (en) * | 2020-09-01 | 2022-01-12 | Ústav makromolekulární chemie AV ČR, v. v. i. | Process for preparing a block copolymer |
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| Publication number | Publication date |
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| CZ309781B6 (en) | 2023-10-04 |
| WO2023232169A1 (en) | 2023-12-07 |
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