CN1440438A - Polymers and polymer membranes covalently cross-linked sulphinate alkylation - Google Patents
Polymers and polymer membranes covalently cross-linked sulphinate alkylation Download PDFInfo
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- CN1440438A CN1440438A CN01801863A CN01801863A CN1440438A CN 1440438 A CN1440438 A CN 1440438A CN 01801863 A CN01801863 A CN 01801863A CN 01801863 A CN01801863 A CN 01801863A CN 1440438 A CN1440438 A CN 1440438A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 229920005597 polymer membrane Polymers 0.000 title claims abstract 12
- 230000029936 alkylation Effects 0.000 title description 8
- 238000005804 alkylation reaction Methods 0.000 title description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- 238000005341 cation exchange Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 10
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- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- -1 ammonium ions Chemical class 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 4
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- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229920002959 polymer blend Polymers 0.000 claims abstract 8
- 229910052792 caesium Inorganic materials 0.000 claims abstract 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract 3
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- 239000000126 substance Substances 0.000 claims description 52
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims description 3
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- 238000007348 radical reaction Methods 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000004696 Poly ether ether ketone Substances 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 claims 1
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- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 claims 1
- 238000000502 dialysis Methods 0.000 claims 1
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- 238000000909 electrodialysis Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 2
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- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 abstract 3
- 101100275854 Arabidopsis thaliana CSI1 gene Proteins 0.000 abstract 1
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- 230000015572 biosynthetic process Effects 0.000 description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 2
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- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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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
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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Abstract
The invention relates to a covalently cross-linked polymer or polymer membrane consisting of one or more polymers, which can bear the following functional groups (M=Hal (F, Cl, Br, I), OR, NR2; R=alkyl, hydroxyalkyl, aryl; (Me=H, Li, Na, K, Cs, or other metal cations or ammonium ions); a) precursors of cation exchange groups: SO2M and/or POM2 and/or COM b) sulphinate groups SO2Me and which can be covalently cross-linked using the following organic compounds: a) di, tri or oligofunctional haloalkanes or haloaromatics, which have been reacted with sulphinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane (Y=cross-linking bridges, X=Hal (F, Cl, Br, I), OR, Y=(CH2)x-; -arylene-; -(CH2)x-arylene-; CH2arylene-CH2-, x=3-12): polymer-SO2Y-SO2-polymer and/or b) compounds containing the following groups: Hal-(CH2)x-NHR, one side of which (Hal-) has been reacted with sulphinate groups SO2ME and the other side (-NHR) with SO2M groups, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane: polymer-SO2-(CH2)x-NR-SO2-polymer and/or c) compounds containing the following groups: NHR-(CH2)x)-NHR, which have been reacted with sulphinate groups SO2Me, whereby the following cross-linking bridges are present in the polymer/in the polymer blend/in the polymer membrane: polymer-SO2-NR-(CH2)x-NR-SO2-polymer.
Description
Prior art
The contriver of present patent application has succeeded in developing a kind of novel method that is used to prepare covalently cross-linked iolon film, this method is based on the polymkeric substance that contains the-sulfinate group, alkylated reaction (the J.Kerres of blend polymer and polymkeric substance (blend) film, W.Cui, W.Schnurnberger: " Vernetzung von moditizierten Engineering Thermoplasten; the German Patent 196 22 337.7 (applying date: June 4; 1996); German Patent office (1997); " Reticulation de Materiaux Thermoplastiques Industriels Modifies "; French Patent, F 97 06706, authorize day: May 30,1997).The advantage of covalent is a hydrolysis, even under comparatively high temps.In the ionic conductivity described in the foregoing invention, with covalently cross-linked polymkeric substance and blend polymer, be to form a kind of hydrophobicity network, this hydrophobicity network and ionic conductive polymers (blend) component such as sulfonate polymer (polymkeric substance-SO when the alkylation of-sulfinate group in film forming process
3Me) be that part is compatible, thereby can produce a kind of heteropolymer (blend) form, this can reduce mechanical stability (dry time embrittlement) and also can overslaugh crosslinked fully, and this is because-sulfinic acid salt face and sulfonic acid salt face generating unit are divided isolating result.
Summary of the invention
Therefore, the purpose of this invention is to provide that some are new for covalently cross-linked polymkeric substance/film, wherein the polymkeric substance of this covalent cross-linking (blend) component and ionic conductive polymers (blend) component are good compatible.
This purpose is by providing films more as claimed in claim 1 to reach.Further, the object of the present invention is to provide a kind of preparation method.
In addition, preparation includes the polymers soln of some polymkeric substance, and they have following functional group:
-sulfinate group-SO
2Me
The precursor species of SULPHURYL CHLORIDE group and/or other cation exchange group,
In addition, in polymers soln, also add alkylation linking agent a kind of bifunctional or few functional group (being typically α, ω-saturated dihalide), and optional add a kind of secondary diamine linking agent NHR-(CH
2)
x-NHR.Alkylation by the-sulfinate group and optional reaction by the sulfuryl halide group that will exist in the polymkeric substance and the secondary amino group of two amine crosslinkers form sulphonamide, during when solvent evaporation, just form covalently cross-linked bridged bond in the formation thin-film process.After film forms, film is being carried out in the last handling process of acidity and/or alkalescence and/or neutral aqueous solution the just hydrolysis and form cation exchange group of the precursor of cation exchange group.
Fig. 1 signal is to be illustrated in the situation that has formed the covalent cross-linking bridged bond in the blend of sulfonating chlorinating polymkeric substance and-sulfinate polymkeric substance, and Fig. 2 is illustrated in the situation that forms the covalent cross-linking bridged bond in the polymkeric substance that contains-sulfinate group and SULPHURYL CHLORIDE group.
Composite of the present invention is comprised of the polymer with following functional group:
·-SO
2M and/or-POM2And/or-COM (M=halogen (F, Cl, Br, I), OR, NR2 The R=alkyl, hydroxyalkyl, aryl),
Crosslinked bridged bond:
A) polymer-SO2-Y-SO
2-polymer
Optional:
B) polymer-SO2-Y’-NR-SO
2-polymer
C) polymer-SO2-NR-Y”-NR-SO
2-polymer
After hydrolysis:
-SO
3M-,-PO
3M
2-,-COOM-group,
Above-mentioned crosslinked bridged bond.
Compare with the covalently cross-linked polymkeric substance of making by cation exchange polymer and polymkeric substance-sulfinate (blend),-sulfinate polymkeric substance in mixture can produce each better mixing mutually of blend with the covalently cross-linked of cation exchange polymer precursor, thereby the crosslinked of higher degree arranged, resulting like this polymeric film can reach higher mechanical stability.Can further improve mechanical characteristics by the controlled crosslinked composition (it and cation exchange group precursors reaction) of in polymer network, introducing amido-containing group.
Embodiment
To carefully be described as follows in the ocean more by two embodiment the present invention.The weight/volume of employed each component is shown in the table 1.
1. be used for the guidance of membrane prepare
PSU Udel with sulfonating chlorinating
(ion exchange capacity=1.8meq SO
2Cl/g) and PSUSO
2Li (ion exchange capacity=1.95meq SO
2Li/g) (be used for the structure of polymkeric substance, see Fig. 2) being dissolved in the N-Methyl pyrrolidone (NMP).In the solution of this linking agent, add α then, ω-two butyl iodide.After stirring 15 minutes, solution is filtered and the degassing.The film of polymers soln is applied on the sheet glass with scraper.This sheet glass is put into vacuum drying oven and under the low pressure of 80-130 ℃ temperature and 700 to final 15mbar, remove and desolvate.Film is taken out from loft drier and cool off.Polymeric film is stripped down and at first is hydrolyzed 10% hydrochloric acid respectively/aftertreatment from sheet glass under water, in the water of sloughing salt fully, handled 24 hours then at 60-90 ℃.
2. employed each amounts of reactants and characterization result
Table 1: employed each amounts of reactants and characterization result
*2 SO are arranged on each PSU repeating unit
2Cl group the application's part 2
| Film | NMP (gram) | PSU-SO 2Cl (gram) | ??PSU-SO 2Li (gram) | Linking agent (milliliter) | Loading capacity (meq/g) | Swelling (%) | ??R sp H+??(Ωcm) |
| ??wz?10 | ????10 | ????1 | ????1 | ????0.3 | ????0.2 | ??19.3 | ??337.6 |
| ??wz?13 | ????10 | ????1 | ????0.4 | ????0.12 | ????0.85 | ??18.3 | ??15.2 |
| ??wz?14 | ????10 | ????1 | ????0.3 | ????0.09 | ????0.56 | ??8.6 | ??62.6 |
| ??wz?15 | ????10 | ????1 | ????0.2 | ????0.06 | ????0.7 | ??13 | ??36.14 |
| ??wz?16 | ????10 | ????1 * | ????1 * | ????0.3 | ????0.75 | ??11.7 | ??31.6 |
Covalently cross-linked composite material film
Prior art
Relate to the continuation of German parent patent application DE 100 24 575.7 (the covalently cross-linked polymkeric substance and the polymeric film that obtain by the-sulfinate alkylation) or different content in addition based on of the present invention replacement demand.The content of this previous German patent application DE 1 00 24 575.7 is incorporated herein with reference with explaining property.
The product of above-mentioned parent patent application and method for making have following shortcoming:
For some films that make with aforesaid method, the operation in hydrogen fuel cell still needs moistening gas.If gas is not by moistening, then film meeting drying and proton conductive have the reduction of quite big degree.
In order to address this problem, present patent application proposes to introduce mesh silicate (tectosilicates) and page or leaf layered silicate (phyllosilicates) especially in covalent, and they are applied for by optional featureization according to mother.
The parent patent application is just described polymkeric substance is introduced in the covalent.During when the page or leaf layered silicate of functions of useization and/or with mesh silicate, can be surprised to find, have low molecule functional group and the compound that is bonded on page layered silicate and/or the mesh silicate, in the use of film, especially under the situation of using hydrogen fuel cell, do not discharge or just discharge lenitively.This just might increase the concentration of ionic conduction group in covalent, and does not have the extreme common effect that worsens of film mechanical characteristics (embrittlement or strong swelling).Under extreme case, thereby might in covalent, avoid using the ionic conductive polymer of inclosure fully.By the silicate that has functional group just ionic conduction can take place uniquely.
Therefore, the invention solves the dry problem of film and be limited to the problem of non-edge degree at the number of film intermediate ion conduction group.
Thereby, the purpose of this invention is to provide some novel covalently cross-linked polymkeric substance/films, it can demonstrate proton conductive, does not promptly use moistening or has only moistening slightly gas.And further purpose is to introduce the compound of the low molecular functionization that is connected with silicate in covalent, and they were retained in the film in the industrial effective time cycle.
Method for making of the present invention also further helps the solution of this purpose.The description of content of the present invention:
Hereinafter mention to the property explained parent patent application DE 100 24 575.7:
Made a kind ofly in appropriate solvent, the preferred mixture in aprotic solvent, this mixture contain network-like silicate and/or page or leaf layered silicate and more optional low molecular compounds of polymkeric substance and functionalization.
This mixture contains polymkeric substance and following functional group:
-sulfinate group SO
2Me (Me is monovalence or multivalent metal cation)
The precursor of SULPHURYL CHLORIDE group and/or other cation exchange group.
Also replenish in mixture, preferably in polymers soln, add alkylation linking agent a kind of bifunctional or few functional group (being typically α, ω-saturated dihalide), and optionally add a kind of secondary diamine linking agent NHR-(CH
2)
x-NHR.Alkylation by the-sulfinate group and optional reaction by the sulfuryl halide group that will exist in the polymkeric substance and the secondary amino group of two amine crosslinkers form sulphonamide, just generate the covalent cross-linking bridged bond when desolvating when evaporating in forming thin-film process.In the last handling process of the acidity of film and/or alkalescence and/or neutral aqueous solution, the precursor of ion-exchange group is hydrolyzed respectively with oxidation and forms ion-exchange group after forming film.
Fig. 1 signal is to be illustrated in the situation that forms covalent crosslink in the blend of sulfonating chlorinating polymkeric substance and-sulfinate polymkeric substance, and Fig. 2 is illustrated in the situation that forms covalent crosslink in the polymkeric substance that contains-sulfinate group and SULPHURYL CHLORIDE group.
Mixture of the present invention is made up of some polymkeric substance with following functional group: after membrane prepare, before the hydrolysis:
SO
2M and/or POM
2And/or COM (the M=halogen (F, Cl, Br, I), OR, NR
2The R=alkyl, hydroxyalkyl, aryl),
Crosslinked bridged bond:
A) polymkeric substance-SO
2-Y-SO
2-polymkeric substance
Optional:
B) polymkeric substance-SO
2-Y '-NR-SO
2-polymkeric substance
C) polymkeric substance-SO
2-NR-Y "-NR-SO
2-polymkeric substance is after hydrolysis:
-SO
3M ,-PO
3M
2-,-COOM group,
Above-mentioned crosslinked bridged bond.
Compare with covalently cross-linked polymkeric substance (blend) film of making by cation exchange polymer and polymkeric substance-sulfinate, the present invention is by covalently cross-linked and ion-exchange polymer, especially the precursor phase blended-sulfinate polymkeric substance of cation exchange polymer, in the presence of functionalization page or leaf layered silicate and/or mesh silicate, can obtain the better mixing of blend phase, thereby reach higher degree of crosslinking, make resulting polymeric film produce better mechanical stability.Introduce the linking agent component (precursors reaction of this component and cation exchange group) that has amino group by control and enter polymer network, can further improve mechanical characteristics.
In film formation process, mesh silicate by introducing functionalization and/or page or leaf layered silicate are in covalent, and the water of film keeps capacity just to increase.These functional groups from stretch out on the mesh silicate or the page or leaf layered silicate surface of functionalization can replenish the characteristic that changes film, and this decides according to functional group's character.
The description of mineral filler
Active Filler White Carbon is a kind of page or leaf layered silicate based on following material: the mixture of polynite, terre verte, illite, sepiolite, polygorskite, white mica, rectorite, amesite, hectorite, talcum, fluorine hectorite, talcum powder, beidellite, nontronite (nontronite), Si Diwen saponite, wilkinite, mica, vermiculite, fluorine-containing vermiculite, halloysite (dust trachelospermum jasminoide), fluorine-containing altacite type or above-mentioned two or more pages layer silicates.The page or leaf layered silicate can be a leafing, or column.Preferred especially person is polynite.
The weight ratio of page or leaf layered silicate is preferably 1-80 weight %, more preferably 2-30 weight %, most preferably 5-20 weight %.
If the member in the filler of functionalization, particularly zeolite and beidellite series and the wilkinite only is the ionic conduction component, its weight ratio is generally 5-80 weight %, preferred 20-70 weight %, most preferably 30-60 weight %.
The explanation of the page or leaf layered silicate of functionalization:
Term " page or leaf layered silicate " generally is meant a kind of silicate, SiO therein
4Tetrahedron (tetraeders) is connected with the bidimensional infinite network.(anionic empirical formula is (Si
2O
5 2-)
n).Each simple layer is interconnective by some positively charged ions between them, and these positively charged ions in the page or leaf layered silicate that nature exists are generally Na, K, and Mg, Al is or/and Ca.
We mean some pages layered silicate like this with term " the functionalization page or leaf layer silicate of leafing ", and the distance of each interlayer is at first by having increased with so-called functionalizers reaction therein.The layer thickness of this silicate was preferably the 5-100 dust before leafing, more preferably 5-50 dust, most preferably 8-20 dust.In order to increase interfloor distance (hydrophobic interaction), be with page or leaf layered silicate and so-called functionalization hydrophobizing agent (also often being called ion or salt) reaction (is to carry out before matrix material production according to the present invention).
Some positively charged ions of page or leaf layered silicate are replaced by the hydrophobizing agent of organic functional, can be regulated by the kind of organic residue with this needed interfloor distance, interfloor distance depends on the functionalization molecule that is introduced in page layered silicate or the kind of polymkeric substance.
The exchange of metal ion or proton can be whole or part.Be preferably the exchange fully of metal ion or proton.The amount of tradable metal ion or proton is typically expressed as milligramequivalent (meq)/every gram page or leaf layered silicate or mesh silicate, and is called loading capacity.
Preferred person is at least 0.5 for having cation exchange capacity, is preferably page or leaf layered silicate or the mesh silicate of 0.8-1.3meq/g.
The organic functional hydrophobizing agent that is suitable for is derived from oxygen, ammonium, phosphorus and sulfonium ion, and they have one or more organic residues.
As the functionalization hydrophobizing agent that is suitable for, should mention some compounds of general formula I and/or general formula I I:
Some substituting groups in the formula have following implication: R1, R2, R3, R4 are hydrogen independent of each other, straight chain, side chain, saturated or unsaturated have a 1-40, and the hydro carbons group of preferred 1-20 carbon atom is chosen wantonly and is loaded with at least one functional group or two groups connected to one another, the heterocyclic group that preferably has 5-10 carbon atom more preferably has the heterocyclic group of one or more N atoms.
X represents phosphorus, nitrogen or carbon,
Y represents oxygen or sulphur,
N is the integer of 1-5, the integer of preferred 1-3, and
Z is a negatively charged ion.
The functional group that is fit to is a hydroxyl, nitro or sulfo group, and preferred especially person is carboxyl or sulfonic acid group.Equally, SULPHURYL CHLORIDE and carboxylic acid chloride also are particularly preferred.
The negatively charged ion Z that is fit to supplies with acids derived from proton, inorganic acids particularly, and wherein halogen such as chlorine, bromine, fluorine, iodine, vitriol, sulfonate, phosphoric acid salt, phosphonate, phosphite and carboxylate salt, especially acetate are preferred person.Page or leaf layered silicate as raw material normally reacts with suspension.Preferred suspension agent is a water, chooses wantonly with alcohols, especially mixes mutually with the lower alcohol with 1-3 carbon atom.If the hydrophobizing agent of functionalization is not water miscible, then preferred this hydrophobizing agent dissolves in solvent wherein.In these cases, aprotic solvent is especially suitable.Further example as suspension agent is ketone and hydro carbons.Suspension agent that preferably can be miscible normally with water.When in the page or leaf layered silicate, adding hydrophobizing agent, ion-exchange just takes place, thereby the page or leaf layered silicate is precipitated out from solution just usually.Be preferably water miscible as the resulting metal-salt of ion-exchange by product, like this, hydrophobic page or leaf layered silicate for example just can be separated with crystalline solid forms by filtering.
The ion-exchange great majority are irrelevant with temperature of reaction.Temperature preferably is higher than the ctystallizing point of medium and is lower than the boiling point of medium.Concerning aqueous systems, temperature is 0-100 ℃, preferred 40-80 ℃.
For positively charged ion and anion exchange polymer, answer the preferred alkyl ammonium ion, if particularly as functional group, in a part, exist additional carboxylic acid chloride or sulfonic acid muriate then more like this.Alkyl phosphate ion can make by common methylating reagent such as methyl iodide.The acid that is suitable for is the omega-amino-carboxylic-acid, and especially preferred person is omega-amino-aryl sulfonic acid class and ω-alkylamino sulfonic acid class.Omega-amino-aryl sulfonic acid class and ω-alkylamino sulfonic acid class can make with common mineral acid example hydrochloric acid, sulfuric acid or phosphoric acid, or makes by methylating reagent such as methyl iodide.
In addition, preferred ammonium ion is pyridine and dodecyl ammonium ion.After hydrophobization, the interfloor distance of page or leaf layered silicate is generally the 10-50 dust, preferred 13-40 dust.
Page or leaf layered silicate hydrophobization and functionalization is dewatered through super-dry.General such page or leaf layered silicate of handling still contains the water that quantity of residual is 0-5 weight %.Page or leaf layered silicate with hydrophobization is mixed together with form of suspension in suspension agent (suspension agent as much as possible remove anhydrate) and above-mentioned polymkeric substance subsequently, and further processing treatment and obtain a kind of film.
The particularly preferred functionalization effect of mesh silicate and/or page or leaf layered silicate generally is dyestuff or its precursor with modification, especially realizes with triphenylmethane dye.These dyestuffs can be represented with following general formula:
R in the formula
1=alkyl (CH especially
3C
2H
5)
Be to use in the present invention by following some dyestuffs of basic framework deutero-:
R contains C in the formula
1-C
20And 0-4 N atom, and 0-3 S atom, the R positively chargeable.
In order to make page layered silicate produce a functionalization effect, should (tetrahydrofuran (THF) for example, DMAC fully stir in NMP) at aprotic solvent with silicate in container with dyestuff or its reduction precursor.After 24 hours, dyestuff and precursor are embedded in the hole of page layered silicate respectively.Must embed like this, the ionic conduction group is positioned on the surface of silicate particles.
Figure below is this telescopiny of illustrative:
Carried out the page or leaf layered silicate of functionalization effect like this,, be added in the polymers soln as a kind of additive, described as German patent DE 100 24 575.7.Found once that it was particularly preferred using dyestuff former.Only in acid last handling process, form dyestuff itself by the division water outlet:
Under the triphenhlmethane dye situation, can be surprised to find thus, these dyestuffs can be supported the electroconductibility of proton in prepared film.Whether this is a kind of anhydrous proton conductive, also not fully according to foretelling.If dyestuff is not incorporated on the silicate, if promptly dyestuff exists with free form in film, then they can be discharged from fuel cell with reaction water after short cycle.
According to the present invention, be to contain the blend polymer of the-sulfinic acid alkali of above-mentioned parent patent application, most preferably the person is the polymkeric substance (ionomer) of thermoplasticity functionalization, adds in the suspension of page or leaf laminar silicic acid salt of hydrophobization.Its practice is, use the polymkeric substance of solubilized form or with polymer dissolution in suspension.Preferably, the consumption of page or leaf layered silicate is 1-70 weight %, and more preferably 2-40 weight % most preferably is 5-15 weight %.
Further improvement to the parent patent application is, with zirconyl chloride (ZrOCl
2) replenish to be blended in this membrane polymer solution and to make it and be embedded in the hole of page layered silicate and/or mesh silicate.If the aftertreatment of film is to carry out in phosphoric acid, just be difficult to the contiguous place that the dissolved zirconium phosphate is deposited in film mesosilicic acid salt particle.When operation of fuel cells, zirconium phosphate shows self proton conductive.Proton conductive is by forming hydrophosphate as asking in some that step works, and is the part of the present state of the art.Contiguous the wrapping into that stores agent (silicate) at water is novel with locating Be Controlled.1. the embodiment that is used for membrane prepare
PSU Udel with sulfonating chlorinating
(loading capacity=1.8meq SO
2Cl/g) and PSUSO
2Li (loading capacity=1.95meq SO
2Li/g) (can be referring to Fig. 2) to the structure of polymkeric substance and with the triphenhlmethane dye functionalization polynite be dissolved in the N-Methyl pyrrolidone (NMP).Add α then in this solution, ω-two butyl iodide is as linking agent.After stirring 15 minutes, solution is filtered and the degassing.The film of polymers soln is applied on the sheet glass with scraper.Sheet glass is put into vacuum drying oven, and be 80-130 ℃ and under 700 to final 15mbar low pressure, remove and desolvate in temperature.From loft drier, take out film and cooling.Under water polymeric film is stripped down from sheet glass, and at first hydrolysis/aftertreatment in 10% hydrochloric acid respectively, in the water of desalination fully, be 60-90 ℃ then and handled 24 hours in temperature.2. embodiment
PSU Udel with sulfonating chlorinating
(loading capacity=1.2meq SO
2Cl/g) and PSUSO
2Li (loading capacity=1.95meq SO
2Li/g) and use α, to be dissolved in N-Methyl pyrrolidone (NMP) little in the polynite (the SULPHURYL CHLORIDE group is towards the outside) that the omega-amino-alkyl sulfonyl chloride is handled.In this solution, add linking agent α, ω-two butyl iodide then.After stirring 15 minutes, solution filtered and outgas and be processed into film, as described in embodiment 1.
Compare with the control sample of the page or leaf layered silicate that does not have functionalization, this film has higher loading capacity value after curing.3. embodiment
PSU Udel with sulfonating chlorinating
(loading capacity=1.8meq SO
2Cl/g) and PSUSO
2Li (loading capacity=1.95meq SO
2Li/g) (structure of polymkeric substance can referring to Fig. 2) and be dissolved in the dimethyl sulfoxide (DMSO) (DMSO) with the polynite that zirconyl chloride was handled.
Dissolve according to following order: elder generation is suspended in polynite K10 among the DMSO and adds the zirconyl chloride (based on the total weight of film) of 10 weight %.Add other polymeric constituent then.In this solution, add linking agent α, ω-two butyl iodide then.After stirring 15 minutes, solution is filtered and the degassing.The film of polymers soln is applied on the sheet glass with scraper.Sheet glass is put into vacuum drying oven, and be 80-130 ℃ and under 700 to final 15mbar low pressure, remove and desolvate in temperature.From loft drier, take out film and cooling.In phosphoric acid, polymeric film is stripped down and store about 10 hours temperature 30-90 ℃ phosphoric acid from sheet glass, then randomly respectively 10% hydrochloric acid neutralization then in the water of desalination fully in temperature 60-90 ℃ of further hydrolysis/aftertreatment 24 hours.
Claims (14)
1. with covalently cross-linked polymkeric substance or with covalently cross-linked polymeric membrane, it contains one or more polymkeric substance, these polymkeric substance are optional have following functional group (the M=halogen (and F, Cl, Br, I), OR, NR
2The R=alkyl, hydroxyalkyl, aryl; Me=H, Li, Na, K, Cs or other metallic cation or ammonium ion):
A) precursor of cation exchange group: SO
2M and/or POM
2And/or COM,
B)-sulfinate group SO
2Me,
And can be covalently cross-linked by following organic compound deposits yields:
A) bifunctional, trifunctional or few functional group halo alkanes or halogenated aromatic thing, it with-sulfinate group SO
2Me reaction, thus in polymer/polymer blend/polymeric film, exist following crosslinked bridged bond (the crosslinked bridged bond of Y=, the X=halogen (F, Cl, Br, I), OR, Y=-(CH
2)
x-;-arylidene-;-(CH
2)
x-arylidene-;-CH
2-arylidene-CH
2-, x=3-12): polymkeric substance-SO
2-Y-SO
2-polymkeric substance, and/or
B) contain the compound of following groups: halogen-(CH
2)
x-NHR, it is (halogen-) and-sulfinate group SO at one end
2Me reaction and (NHR) and SO at the other end
2The M-radical reaction, thus in polymer/polymer blend/polymeric film, there is following crosslinked bridged bond: polymkeric substance-SO
2-(CH
2)
x-NR-SO
2-polymkeric substance, and/or
C) contain the compound of following group: NHR-(CH
2)
x-NHR, it and SO
2The Me radical reaction, thus in polymer/polymer blend/polymeric film, there is following crosslinked bridged bond: polymkeric substance-SO
2-NR-(CH
2)
x-NR-SO
2-polymkeric substance.
2. as claimed in claim 1 with covalently cross-linked blend polymer or blend polymer membranes, it is characterized in that it is made up of following polymkeric substance:
A) a kind of have SO at least
2The polymkeric substance of M group,
B) a kind of have SO at least
2The polymkeric substance of Me group.
3. as claim 1 and 2 described, it is characterized in that it is to be made of the polymkeric substance that contains following group: SO with covalently cross-linked blend polymer or blend polymer membranes
2M group and SO
2The Me group.
4. as any one is described with covalently cross-linked blend polymer or blend polymer membranes among the claim 1-3, it is characterized in that some basic polymkeric substance that have the basic polymkeric substance of functional group or have functional group are selected from: polyethersulfone, polysulfones, polyphenylsulphine, polyether ethersulfone, polyetherketone, polyether-ether-ketone, polyphenylene oxide, poly biphenyl ether, polyphenylene sulfide or contain the multipolymer of one of these components at least.
5. as any one described blend polymer or blend polymer membranes among the claim 1-4 with covalent linkage and ionic crosslinking, it is characterized in that following polymkeric substance is preferred as some basic polymkeric substance: some polymkeric substance that polysulfones, polyphenylene oxide or other can lithiumations.
6. as any one is described with covalently cross-linked blend polymer or blend polymer membranes among the claim 1-5, it is characterized in that as linking agent preferred: halogen-(CH
2)
x-halogen or halogen-CH
2-phenylene-CH
2-halogen (x=3-12, halogen=F, Cl, Br, I).
7. as any one is described with covalently cross-linked blend polymer or blend polymer membranes among the claim 1-6, it is characterized in that the SO of polymer/polymer (blend) film
2M group and/or POM
2Group and/or COM group are to be hydrolyzed into cation exchange group SO by following aftertreatment (curing)
3Me and/or PO
3Me
2And/or COOMe (Me=H, Li, Na, K, Cs or other metallic cation or ammonium ion):
A) in the buck of 1-50 weight % in T=room temperature-95 ℃,
B) in the water of fully desalination in T=room temperature-95 ℃,
C) in the inorganic acid aqueous solution of 1-50 weight % in T=room temperature-95 ℃,
D) in the water of fully desalination in T=room temperature-95 ℃,
Wherein can choose wantonly and save one or more curing schedules.
8. as any one is described with covalently cross-linked polymkeric substance among the claim 1-7, the preparation method of blend polymer or blend polymer membranes, it is characterized in that polymkeric substance is to be dissolved in simultaneously or sequentially in the dipolar aprotic solvent that is selected from down group: N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) or tetramethylene sulfone, after this add linking agent, by stirring linking agent is evenly dispersed in the polymers soln then, after this polymers soln is filtered and the degassing, then polymers soln is coated on matrix (sheet glass, metal sheet, Woven fabric, supatex fabric or other) go up as film, by being heated to 80-130 ℃ and/or by using low pressure or in the drying by circulating air device, remove and desolvate, optional then polymeric film is stripped down from matrix, be cured polymeric film is following then:
A) in the buck of 1-50 weight % in temperature=room temperature-95 ℃,
B) in the water of fully desalination in temperature=room temperature-95 ℃,
C) in the inorganic acid aqueous solution of 1-50 weight % in temperature=room temperature-95 ℃,
D) in the water of fully desalination in temperature=room temperature-95 ℃,
Wherein can choose wantonly and save one or more curing schedules.
9. be used for the application of the energy of production electrochemistry route as any one described film among the claim 1-8.
As any one described film among the claim 1-8 temperature be 0-180 ℃ as membrane fuel cell (H
2Or direct methanol fuel cell) a kind of application of composition.
11. as any one described film application in electrochemical cell among the claim 1-8.
12. as any one described film application in secondary battery among the claim 1-8.
13. as any one described film application in electrolytic cell among the claim 1-8.
14. as any one described film among the claim 1-8 in the film sepn process such as the application in gas delivery, pervaporation, full extraction, inverse osmosis, electrodialysis and the diffusion dialysis.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10024575A DE10024575A1 (en) | 2000-11-02 | 2000-05-19 | Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane |
| DE10024575.7 | 2000-05-19 | ||
| DE10054233.6 | 2000-11-02 | ||
| DE10054233A DE10054233A1 (en) | 2000-05-19 | 2000-11-02 | Covalently cross-linked composite membranes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1440438A true CN1440438A (en) | 2003-09-03 |
| CN100354344C CN100354344C (en) | 2007-12-12 |
Family
ID=26005738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018018637A Expired - Fee Related CN100354344C (en) | 2000-05-19 | 2001-05-21 | Covalently cross-linked polymers and polymer membranes by sulfinate alkylation |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1290069A2 (en) |
| JP (1) | JP2004502008A (en) |
| CN (1) | CN100354344C (en) |
| AU (2) | AU784360B2 (en) |
| BR (1) | BR0106652A (en) |
| CA (1) | CA2379962C (en) |
| DE (1) | DE10054233A1 (en) |
| IL (1) | IL147726A0 (en) |
| WO (1) | WO2002000773A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258170A (en) * | 2017-12-05 | 2018-07-06 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm |
| CN115646223A (en) * | 2022-10-19 | 2023-01-31 | 安徽省海徽化工有限公司 | Stain-resistant polyethersulfone ultrafiltration membrane |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10024575A1 (en) * | 2000-11-02 | 2001-11-22 | Univ Stuttgart | Covalently crosslinked polymer or membrane, used e.g. in fuel cells, batteries or separation processes, comprises reacting polymers with chlorosulphonyl or sulfinate groups with bifunctional crosslinker, e.g. dihalo-alkane |
| WO2003050169A2 (en) * | 2001-05-21 | 2003-06-19 | Haering Thomas | Covalently cross-linked composite membranes |
| KR100403754B1 (en) * | 2001-06-19 | 2003-10-30 | 송민규 | Composite Polymeric Electrolyte Membrane, Preparation Method Thereof and Fuel Cell Containing the Same |
| DE10209784A1 (en) * | 2001-09-01 | 2003-12-04 | Univ Stuttgart Inst Fuer Chemi | Oligomers and polymers containing sulfinate groups and process for their preparation |
| JP4827044B2 (en) * | 2002-02-28 | 2011-11-30 | ウニヴェルズィテート シュトゥットガルト | Oligomer and polymer containing sulfinate group, and method for producing the same |
| AU2003229264A1 (en) * | 2002-02-28 | 2003-09-09 | Universitat Stuttgart | Oligomers and polymers containing sulfinate groups, and methods for producing the same |
| CN100593259C (en) * | 2002-02-28 | 2010-03-03 | 托马斯·翰翎 | Layered structure producing method, membrane electrode unit and combined plane setting structure thereof |
| KR100486728B1 (en) | 2002-12-12 | 2005-05-03 | 삼성에스디아이 주식회사 | Nanocomposite electrolyte membrane and fuel cell employing the same |
| WO2005090480A1 (en) * | 2004-03-23 | 2005-09-29 | Mitsubishi Gas Chemical Co., Inc. | Solid polyelectrolyte, solid-polymer gel film, solid polyelectrolyte film, and fuel cell |
| JP6016019B2 (en) * | 2012-10-30 | 2016-10-26 | 独立行政法人国立高等専門学校機構 | ELECTROLYTE MEMBRANE FOR FUEL CELL, METHOD FOR PRODUCING ELECTROLYTE MEMBRANE FOR FUEL CELL, AND FUEL CELL |
| CN109659601B (en) * | 2018-12-12 | 2021-09-28 | 南京师范大学 | Application of polyacid/high-molecular polymer hybrid nanowire material as solid electrolyte |
| EP3772129B1 (en) | 2019-07-31 | 2021-06-30 | Innolith Technology AG | So2-based electrolyte for rechargeable battery cell and rechargeable battery cell comprising the same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG73410A1 (en) * | 1992-06-13 | 2000-06-20 | Hoechst Ag | Polymer electrolyte membrane and process for the production thereof |
| FR2695131B1 (en) * | 1992-09-01 | 1994-09-30 | Alsthom Cge Alcatel | Solid proton conducting polymer electrolyte. |
| DE19622337C1 (en) * | 1996-06-04 | 1998-03-12 | Dlr Deutsche Forschungsanstalt | Networking of modified engineering thermoplastics |
| WO1999028292A1 (en) * | 1997-12-01 | 1999-06-10 | Acep Inc. | Perfluorynated sulphone salts, and their uses as ionic conduction materials |
| DE69934170T2 (en) * | 1998-02-03 | 2007-09-27 | Acep Inc., Montreal | NEW MATERIALS SUITABLE AS ELECTROLYTIC SOLUBILISTS |
| DE19836514A1 (en) * | 1998-08-12 | 2000-02-17 | Univ Stuttgart | Modification of engineering polymers with N-basic groups and ion exchange groups in the side chain gives membranes of good thermal and mechanical stability useful for fuel cells, diffusion dialysis, electrodialysis, and reverse osmosis |
| ATE338785T1 (en) * | 1998-09-11 | 2006-09-15 | Victrex Mfg Ltd | ION EXCHANGE POLYMERS |
| DE19919708A1 (en) * | 1999-04-30 | 2001-03-01 | Univ Stuttgart | Gradual alkylation of polymeric amines |
| DE10024576A1 (en) * | 2000-05-19 | 2001-11-22 | Univ Stuttgart | Covalently and ionically crosslinked polymer preparation, for use as electrochemical and separating membranes, comprises crosslinking acid-, sulfinate- and amine-functional polymers |
-
2000
- 2000-11-02 DE DE10054233A patent/DE10054233A1/en not_active Withdrawn
-
2001
- 2001-05-21 CA CA2379962A patent/CA2379962C/en not_active Expired - Lifetime
- 2001-05-21 BR BR0106652-8A patent/BR0106652A/en not_active IP Right Cessation
- 2001-05-21 AU AU93695/01A patent/AU784360B2/en not_active Ceased
- 2001-05-21 IL IL14772601A patent/IL147726A0/en unknown
- 2001-05-21 JP JP2002505894A patent/JP2004502008A/en active Pending
- 2001-05-21 WO PCT/EP2001/005826 patent/WO2002000773A2/en active Application Filing
- 2001-05-21 EP EP01974075A patent/EP1290069A2/en not_active Withdrawn
- 2001-05-21 CN CNB018018637A patent/CN100354344C/en not_active Expired - Fee Related
-
2006
- 2006-06-17 AU AU2006202592A patent/AU2006202592A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258170A (en) * | 2017-12-05 | 2018-07-06 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm |
| CN108258170B (en) * | 2017-12-05 | 2021-07-16 | 宜宾天原集团股份有限公司 | Preparation method of polyether-ether-ketone-based lithium battery diaphragm |
| CN115646223A (en) * | 2022-10-19 | 2023-01-31 | 安徽省海徽化工有限公司 | Stain-resistant polyethersulfone ultrafiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002000773A9 (en) | 2003-02-13 |
| JP2004502008A (en) | 2004-01-22 |
| CN100354344C (en) | 2007-12-12 |
| CA2379962C (en) | 2016-10-18 |
| AU9369501A (en) | 2002-01-08 |
| CA2379962A1 (en) | 2002-01-03 |
| DE10054233A1 (en) | 2002-05-08 |
| WO2002000773A2 (en) | 2002-01-03 |
| IL147726A0 (en) | 2002-08-14 |
| AU784360B2 (en) | 2006-03-16 |
| WO2002000773A3 (en) | 2002-07-18 |
| EP1290069A2 (en) | 2003-03-12 |
| BR0106652A (en) | 2002-04-09 |
| AU2006202592A1 (en) | 2006-07-13 |
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