CN1970136A - Organic-inorganic hybridized anion exchange membrane preparation method - Google Patents
Organic-inorganic hybridized anion exchange membrane preparation method Download PDFInfo
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Abstract
The organic and inorganic mixed anion exchange membrane features in the silicon content, with the molecule rates of 1:0.4-4:0.5-4 of positive alkoxylation catalyst functional macromolecule forerunner: positive micromolecule alkoxy silane and one or more kinds of mixed positive micromolecule alkoxy silane, getting the sol-gal mixture forerunner, adding solvent, water and catalyst, achieving organic and inorganic mixed anion exchange membrane after drying of the coating. It chooses positive alkoxylation catalyst functional macromolecule forerunner, positive micromolecule alkoxy silane, and micromolecule alkoxy silane lead the flexibility, charging performance and stability of the film. With different material matching, it will get organic and inorganic mixed anion exchange membrane of varied features. The film has fine mechanical feature, high anion exchange capacity, and fine compatibility of inorganic silicone oxide compound and organic components.
Description
Technical field:
The invention belongs to the membrane technology field, particularly adopt sol-gel process to prepare the method for organic-inorganic hybridisation anion exchange membrane.
Background technology:
Holland " membrane science magazine " (Journal of Membrane Science, 1997,126,161-169) and U.S.'s " chemical material " (Chemistry of Materials, 2001,13,1124-1130) reported and utilize the little molecule alkoxy silane sol gel reaction of lotus positive electricity behind the inorganic matrix face coat, to make organic-inorganic hybridisation anion exchange membrane.Because this preparation method is a raw material with little molecule alkoxy silane, sol-gel product organic component content is less, and pliability is not high, so must be supporter with the inorganic matrix, this have limited the application of prepared film.
The preparation method of Chinese patent application number 03132271.9 a kind of organic-inorganic hybridisation anion exchange membrane of announcing, multiple functional radical alkoxy silane and the macromolecular compound that contains ester group or epoxy side group or end group are carried out aminolysis, alcoholysis or ring-opening reaction, then product is carried out quaterisation, obtain lotus positive electricity sol gel reaction precursor; Again this precursor is carried out sol gel reaction, obtain hybrid anion exchange membrane.Compatibility between organic facies and the inorganic phase is poor though the prepared hybrid anion exchange membrane of this method has overcome, the not high defective of pliability of film, and raw material sources are extensive relatively, but because aminolysis, alcoholysis or ring-opening reaction are not easy to carry out fully, the hybrid anion exchange membrane ion exchange capacity that obtains is not high, has limited the separating property of film.
The preparation method of Chinese patent application number 2004100657378 a kind of organic-inorganic hybridisation anion exchange membranes of announcing, utilize the benzyl bromine group on the macromolecular chain and the primary amine group of amino-alkyl silicane to react, the macromolecular compound benzyl bromide a-bromotoluene for polyphenylene oxide (BPPO) chain in the grafting amino-alkyl silicane benzyl bromine group on the macromolecular chain also generate the method for quaternized ammonium groups with reactive tertiary amine, obtain the sol gel reaction precursor of lotus positive electricity, the hybrid anion exchange membrane organic and inorganic component compatibility that this method obtains is good, method is easy, but raw material sources are single, and the film character after the modification is subjected to the influence of former macromolecular material BPPO character to a great extent.
" membrane science magazine " (Journal of Membrane Science, 2003,216 (1-2), 269-278) reported that the alkoxy silane that contains primary amine and secondary amine group is linked on the peg molecule chain of isocyanide ester base end-blocking by hydrogen transfer reaction, then product is carried out sol gel reaction, quaternized again after filming, obtain organic-inorganic hybridisation anion exchange membrane.Because the molecular weight polyethylene glycol of selecting for use is less than normal, precursor is coated in film forming on the supporter, and the film pliability that obtains is limited.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of organic-inorganic hybridisation anion exchange membrane is to overcome the above-mentioned defective of prior art.
The preparation method of organic-inorganic hybridisation anion exchange membrane of the present invention, the big molecular precursor and the little molecule alkoxy silane of a kind of lotus positive electricity of earlier synthetic a kind of lotus positive electricity alkoxyl functionalization; Select for use one or both little molecule alkoxy silanes as crosslinking agent again; It is characterized in that: calculate with silicone content, be the big molecular precursor of lotus positive electricity alkoxyl functionalization in molar ratio: the little molecule alkoxy silane of lotus positive electricity: one or both little molecule alkoxy silane sum=1: 0.4-4: 0.5-4 obtains sol-gel mixing presoma after mixing; Be sol-gel mixing presoma in molar ratio: solvent: water with siliceous calculation of total: catalyst=1: 0-10: 2-8: 0.0-0.1, in this mixing presoma, add solvent, add entry and catalyst again; At 20-60 ℃ of stirring reaction 1-4 days, under being the environment of 30-80%, room temperature, relative humidity freely volatilized 1-2 days again, on matrix, film;
Described solvent comprises methyl alcohol, ethanol, N, dinethylformamide, N, N-dimethylacetylamide, methyl-sulfoxide, benzene or toluene;
Described catalyst comprises hydrochloric acid, sulfuric acid, acetate, NaOH, potassium hydroxide or ammonium chloride; Described matrix comprises inorganic matrix glass plate, aluminium foil or iron plate, or organic matrix polyethylene film, polyfluortetraethylene plate or polyvinyl chloride panel;
Described method of filming comprises knifing, hydrostomia or coating;
Be to be dried under the environment of 30-80% to form uniform and stable gel layer with diaphragm in room temperature, relative humidity; Be warmed up to 95-135 ℃ with 2.5-10 ℃/hour speed from room temperature again, be incubated 1-8 hour, formed film is scraped from matrix, be organic-inorganic hybridisation anion exchange membrane.
The preparation process of the big molecule precursor of described lotus positive electricity alkoxyl functionalization is: select for use end to contain the aliphatic polymer of hydroxyl, amido or carboxyl, under inert gas shielding, with diisocyanate terminated, obtain terminated polymer; React with the alkoxy silane that contains primary amine and secondary amine group again, obtain big molecular precursor; Be the big molecular precursor with the aliphatic polymer cubage in molar ratio: halogenated hydrocarbons=1: 6-12 is added drop-wise to the speed of halogenated hydrocarbons with 0.5-3.5ml/min in the big molecular precursor solution, 20-58 ℃ of reaction 8-30 hour, excessive halogenated hydrocarbons was reclaimed in distillation; Described halogenated hydrocarbons comprises iodomethane, bromoethane or 1,2-Bromofume.
The aliphatic polymer that described end contains hydroxyl, amido or carboxyl is polyester polyols alcohols, polyamide-based or polyalcohols, and its chemical formula can be expressed as ARB, and wherein R represents aliphatic chain, and molecular weight is at 800-2500; A or B are hydroxyl, amido or carboxyl.
Described diisocyanate comprises 2,4-toluene diisocyanate (TDI), TDI and 2,6-toluene diisocyanate mixture or to the benzene diisocyanate.
Described usefulness is diisocyanate terminated, is meant in molar ratio to be diisocyanate: aliphatic polymer=2: 1 is added drop-wise to the speed of aliphatic polymer ARB solution with 0.5-3.5ml/min in the vulcabond solution; After dropwising, continue reaction 12-34 hour at 0-60 ℃; Selected solvent is the good solvent of aliphatic polymer in described aliphatic polymer solution and the vulcabond solution, simultaneously can and vulcabond, to contain the alkoxy silane of primary amine groups and secondary amine compatible and do not react, comprise methyl-sulfoxide, oxolane, acetone, benzinum, N, dinethylformamide (DMF), N, N-dimethylacetylamide, methyl-sulfoxide, benzene or toluene; Employing is an aliphatic polymer by mass ratio: solvent=1: 1-3 is a vulcabond: solvent=1: 0.5-2.5 by volume.
The described alkoxy silane that contains primary amine and secondary amine group, chemical formula can be expressed as X[R
1Y]
nR
2Si (R1)
3Or X[R
1Y]
nR
2Si (R1)
2R
3R wherein
1, R
2And R
3Expression contains the alkyl of 1-3 carbon, and R1 represents to contain the alkoxy grp of 1 or 2 carbon, and X represents primary amine groups; Y represents secondary amine, and the value of n is 1 or 2.
Described with contain the alkoxy silane X[R of primary amine and secondary amine group
1Y] nR
2Si (R1)
3Or X[R
1Y] nR
2Si (R1)
2R
3React, be meant the terminated polymer for calculating in molar ratio: alkoxy silane=1: 2 with polymer content, the volume proportion that contains the alkoxy silane solution of primary amine and secondary amine is an alkoxy silane: solvent=1: 1-3.5, the speed of aliphatic polymer behind the end-blocking with 0.5-4.5ml/min is added dropwise in the alkoxy silane solution that contains primary amine and secondary amine, continues reaction 16-48 hour at 20-65 ℃; Described solvent types scope is with solvent used in the diisocyanate terminated course of reaction.
The preparation process of the little molecule alkoxy silane of described lotus positive electricity is: in molar ratio for containing the alkoxy silane of primary amine or secondary amine: halogenated hydrocarbons total amount=1: 3-9, the alkoxy silane that will contain primary amine or secondary amine was added drop-wise in the halogenated hydrocarbons with the speed of 0.5-2.5ml/min, 20-65 ℃ of reaction 6-24 hour; Adopt the excessive halogenated hydrocarbons of common distillation recovery or adopt decompression distillation to remove excessive halogenated hydrocarbons; Described halogenated hydrocarbons comprises iodomethane, bromoethane or/and 1, the 2-Bromofume.
The described alkoxy silane that contains primary amine or secondary amine, its chemical formula can be expressed as R
4X ' R
5Si (R1)
3, R wherein
4Expression contains the alkyl or aryl of 0-6 carbon; R
5Expression contains the alkyl of 1-4 carbon; R1 represents to contain the alkoxyl of 1 or 2 carbon; X ' expression primary amine or secondary amine.
The chemical formula of described little molecule alkoxy silane can be expressed as [R1]
4-qSi (R
6)
q, wherein R1 represents to contain the alkoxyl of 1 or 2 carbon; R
6For containing the alkyl or aryl of 1-6 carbon; The value of q is 0 or 1.
The inventive method has taked elder generation to contain the aliphatic polymer of hydroxyl, amido or carboxyl and contain primary amine or the alkoxy silane of secondary amine is an initial feed with end, the big molecular precursor and the little molecule alkoxy silane of a kind of lotus positive electricity of synthetic a kind of lotus positive electricity alkoxyl functionalization, again with one or both little molecule alkoxy silanes as crosslinking agent, obtain sol-gel mixing presoma after above each component mixed by certain mole proportioning; Again this presoma is carried out sol gel reaction, promptly obtain organic-inorganic hybridisation anion exchange membrane.Wherein regulate the pliability of film by the big molecular precursor of lotus positive electricity alkoxyl functionalization; Regulate the charging performance of film by the little molecule alkoxy silane of lotus positive electricity; Little molecule alkoxy silane can strengthening membrane crosslinking degree, thereby strengthen the stability of film.The inventive method and " membrane science magazine " (Journal of MembraneScience, 1997,126,161-169) with " chemical material " (Chemistry of Materials, 2001,13,1124-1130) report is that raw material carries out the method that sol gel reaction prepares hybrid anion exchange membrane and compares with little molecule alkoxy silane, because one of sol gel reaction precursor among the present invention is a macromolecular compound, thereby organic content can be higher, thereby pliability can be better, and the film form and the structure that obtain also have more diversity; With Chinese patent application number 03132271.9 report multiple functional radical alkoxy silane and the macromolecular compound that contains ester group or epoxy side group or end group are carried out aminolysis, alcoholysis or ring-opening reaction, then product is carried out quaterisation, the method that obtains lotus positive electricity sol gel reaction precursor is compared, the various constituent contents of film are more prone to regulate in the inventive method, ion exchange capacity can be higher, and mechanical performance is better; Grafting amino-alkyl silicane on macromolecular compound BPPO chain with Chinese patent application number 2004100657378 reports, benzyl bromine group on the macromolecular chain carries out quaternized simultaneously, the sol gel reaction precursor of the lotus positive electricity that obtains carries out sol gel reaction with amino-alkyl silicane again, the method that makes hybrid anion exchange membrane is compared, the hybridized film that the present invention makes has higher ion exchange capacity, the mechanical performance of film is better, and raw material sources are extensive simultaneously; With " membrane science magazine " (Journal ofMembrane Science, 2003,216 (1-2), 269-278) report is alkoxy silane cross linked to the peg molecule chain of isocyanide ester base end-blocking with little molecule, carry out sol gel reaction again, the quaternized method that obtains hybrid anion exchange membrane in back of filming is compared, because the present invention adopts the aliphatic polymer of macromolecule to replace the polyethylene glycol of small-molecular weight, and adopted plurality of raw materials, so the mechanical performance of the film of preparation is better, need not to use supporter, and can be by regulating the film that various proportion of raw materials obtain different performance, resulting hybrid anion exchange membrane has application prospect widely.
The specific embodiment:
Further describe the preparation method of organic-inorganic hybridisation anion exchange membrane of the present invention by the following examples.
Embodiment 1: polyethylene glycol (PEO) (1000)-SiO
2The preparation of hybrid anion exchange membrane
Carry out the preliminary treatment of raw material earlier: with N, dinethylformamide (DMF) is immersed in the molecular sieve two days; With molecular weight is 80 ℃ of vacuum drying of polyethylene glycol (PEO) of 1,000 6 hours.Carry out following steps then:
1, the preparation of the PEO presoma of lotus positive electricity alkoxyl functionalization: the 100ml round bottom three-necked bottle that adopts reflux condensing tube is housed, has nitrogen inlet and dropping funel, add 2.9 milliliter 2,4-toluene diisocyanate (TDI) and 3.5 milliliters of DMF under agitation drip the solution that contains 10 gram PEO and 10.6 milliliters of DMF from dropping funel with the speed of 2.0ml/min; Behind the room temperature reaction 12 hours, be warming up to 40 ℃ of reactions 6 hours.Infrared test is carried out in sampling ,～1100cm
-1The C-O-C absworption peak appears in the place;～2270cm
-1The place has-absworption peak of NCO, shows that end capping reaction carries out smoothly, and product is also keeping part-NCO, so can confirm that resulting is end-blocking PEO.
Reacted solution is transferred in the dropping funel, it is end-blocking PEO in molar ratio: N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (A-1120)=1: 2 with the PEO cubage, volume ratio is A-1120: DMF=1: 3, be added drop-wise in the DMF solution of A-1120 with the speed of 1.5ml/min; Be warmed up to 30 ℃ after dropwising, under nitrogen protection, continue reaction 2 days.Take a morsel and carry out infrared test after product is purified with precipitation with alcohol ,～1100cm
-1The place is owing to Si-O-CH occurs
3Absworption peak, intensity increases; And～2270cm
-1Place-NCO absworption peak disappears, and the alkoxy silane that connects of PEO molecular end success is described, what obtain is the PEO presoma.
Be PEO presoma in molar ratio with the PEO cubage: iodomethane=1: 8, the speed with 1.5ml/min in the PEO precursor solution drips iodomethane; After dropwising, 58 ℃ of back flow reaction 8h adopt common distillation to reclaim iodomethane.Reference membrane science magazine (Journal of Membrane Science, 2003,216 (1-2), 269-278) report on as can be known, the end product that makes is the PEO presoma of lotus positive electricity alkoxyl functionalization.
2, the preparation of the little molecule alkoxy silane of lotus positive electricity: adopting the two neck bottles that dropping funel and reflux condensing tube are housed, is aminopropyl triethoxysilane (A-1100): CH in molar ratio
3I=1: 6 add iodomethane, and under agitation the speed with 1ml/min drips A-1100 from dropping funel, behind the room temperature reaction 6h, and 58 ℃ of heating reflux reaction 12h; Adopt common distillation to reclaim iodomethane.
3, the preparation of organic-inorganic hybridisation anion exchange membrane: calculate with silicon content, be the PEO presoma of lotus positive electricity alkoxyl functionalization in molar ratio: the little molecule alkoxy silane of lotus positive electricity: phenyl triethoxysilane=mix three kind raw materials at 1: 1: 1 obtains sol-gel mixing presoma.Be the mixing presoma with siliceous calculation of total: H in molar ratio
2O=1: 6, in mixing presoma, add entry; 40 ℃ of stirring reactions 1 day, room temperature and relative humidity were freely to volatilize under 80% condition two days, and the hydrostomia film forming is on polyfluortetraethylene plate.After room temperature, relative humidity are continue to place 24 hours under 80% condition, be warmed up to 135 ℃ from room temperature with 5 ℃/hour speed, normal pressure insulation 2 hours down.
4, formed film is scraped from the tetrafluoroethene plate with scalpel, carry out water content, ion exchange capacity test; Mechanical strength is analyzed; The thermogravimetric analysis test; Scanning electron microscope observation is also measured film potential.
Test result shows that the water content of the film for preparing in the present embodiment is 99%; Ion exchange capacity is 1.30mmol/g, compare with the ion exchange capacity of organic-inorganic hybridisation anion exchange membrane in the Chinese patent application number 03132271.9, the ion exchange capacity of the film for preparing in the present embodiment be approximately its more than four times or four times, illustrate that the film of present embodiment preparation has higher carrying capacity.
The mechanical strength analysis result shows that the elongation at break of the film for preparing in the present embodiment can reach 120%, and hot strength is 5.2MPa.(that 269-278) reports compares for Journal of Membrane Science, 2003,216 (1-2), and the film of present embodiment preparation need not to adopt supporter with " membrane science magazine "; With comparing of " European polymer magazine " (European PolymerJournal 42 (2006) 1696-1704) report, its elongation at break is three times of report approximately.The film that the present embodiment preparation is described has good pliability.
The thermogravimetric analysis result shows that the initial degradation temperature of the hybridized film for preparing in the present embodiment is 180 ℃; Thermal degradation temperature is 239 ℃.
Scanning electron microscope observation shows, prepared film surface and all smooth homogeneous of section in the present embodiment, no noted phase separation phenomena.This shows in the present embodiment that the oxide component microcosmic of organic component and inorganic silicon is uniformly dispersed in the prepared hybridized film.
The film potential test shows, the film potential value of prepared film is 12.1mv in the present embodiment, calculates thus, the transport number of film is 0.840; Illustrate that film prepared in the present embodiment is an anion-exchange membrane.
Comprehensive above analysis result, the film that obtains of present embodiment is the organic-inorganic hybridisation anion exchange membrane of homogeneous phase as can be known.Film has the favorable mechanical performance, appropriate water content and higher carrying capacity.
Embodiment 2: the PEO of high-crosslinking-degree (1000)-SiO
2The preparation of hybrid anion exchange membrane
Adopt similarly to Example 1 device and operating process, just in proportioning sol-gel mixing presoma, calculate with silicone content in each raw material, be the PEO presoma of lotus positive electricity alkoxyl functionalization by the mole proportioning: the little molecule alkoxy silane of lotus positive electricity: phenyl triethoxysilane: tetraethoxysilane=1: 3: 2: 2 have added another kind of little molecule alkoxy silane TEOS.The organic-inorganic hybridisation anion exchange membrane that obtains carries out thermogravimetric analysis, and water content and ion exchange capacity are measured.
Test result shows that the initial weightless peak of film is at 240 ℃; The water content of film is 77%; The ion exchange capacity of film is 1.105mmol/g.
Embodiment 3:PEO (1000)-SiO
2The preparation of hybrid anion exchange membrane
Adopt similarly to Example 1 device and operating process and identical proportion relation, in the big molecular precursor process of preparation lotus positive electricity alkoxyl functionalization, replace N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (A-1120) with N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane (KH-602).In the little molecule alkoxy silane of preparation lotus positive electricity process, replace gamma-aminopropyl-triethoxy-silane with γ-An Bingjisanjiayangjiguiwan.
The water content test result shows that the water content of film is 104%; The anion-exchange capacity of ion exchange capacity test shows film is 1.25mmol/g.
Embodiment 4:PEO (2000)-SiO
2The preparation of hybrid anion exchange membrane
The preliminary treatment of the raw material that is adopted in the present embodiment: with N, the N-dimethylacetylamide is immersed in the molecular sieve two days; With molecular weight is 95 ℃ of vacuum drying of polyethylene glycol (PEO) of 2,000 8 hours.Carry out following steps then:
1, the preparation of the PEO presoma of lotus positive electricity alkoxyl functionalization: the 100ml round bottom three-necked bottle that adopts reflux condensing tube is housed, has nitrogen inlet and dropping funel, add 2.1ml TDI and 5.3ml N, the N-dimethylacetylamide, the N that under agitation contains 15 gram PEO and 31.8ml then with the speed dropping of 1.2ml/min from dropping funel, N-dimethylacetamide solution (mass ratio is 1: 2), earlier under ice-water bath, react 8h, room temperature reaction 8 hours, be warming up to 55 ℃ of reactions 18 hours at last again.Infrared test is carried out in sampling ,～1100cm
-1There is the C-O-C absworption peak at the place;～2270cm
-1The place has-absworption peak of NCO, shows that end capping reaction carries out smoothly, and product is also keeping remaining-NCO, so can confirm that resulting is end-blocking PEO.
Reacted solution is transferred in the dropping funel, be the end-blocking PEO with the PEO cubage: A-1120=1: 2 in molar ratio, volume ratio is A-1120: DMF=1: 3.5, be added drop-wise to the N of N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (A-1120) with the speed of 1.5ml/min, in the N-dimethylacetamide solution; Be warmed up to 40 ℃ after dropwising, under nitrogen protection, continue reaction 2 days.Take a morsel and carry out infrared test after product is purified with precipitation with alcohol ,～1100cm
-1The place is owing to Si-O-CH occurs
3Absworption peak, intensity increases; And～2270cm
-1Place-NCO absworption peak disappears, and the alkoxy silane that connects of PEO molecular end success is described, what obtain is the PEO presoma.
Be PEO presoma in molar ratio with the PEO cubage: bromoethane=1: 8, in the PEO precursor solution with the speed dripping bromine ethane of 3.5ml/min; After dropwising, 45 ℃ of back flow reaction 18h adopt common distillation to reclaim bromoethane, and the end product that obtains is the PEO presoma of lotus positive electricity alkoxyl functionalization.
2, the preparation of the little molecule alkoxy silane of lotus positive electricity: adopt the two neck bottles that dropping funel and reflux condensing tube are housed, it is N-methyl aminopropyl trimethoxysilane in molar ratio: bromoethane=1: 4 adding bromoethane, under agitation the speed with 0.5ml/min drips N-methyl aminopropyl trimethoxysilane from dropping funel, behind the room temperature reaction 6h, 40 ℃ of heating reflux reaction 12h adopt common distillation to reclaim Celfume.
3, the preparation of organic-inorganic hybridisation anion exchange membrane: calculate with silicon content, be the PEO presoma of lotus positive electricity alkoxyl functionalization in molar ratio: the little molecule alkoxy silane of lotus positive electricity: phenyltrimethoxysila,e=mix three kind raw materials at 1: 3: 2 obtains sol-gel mixing presoma.Be mixing presoma in molar ratio: ethanol: water: NaOH=1: 4: 8: 0.1 with siliceous calculation of total, in mixing presoma, add ethanol, water and sodium hydroxide solution, stirring at room solution 4 days, in room temperature and relative humidity is freely to volatilize under 30% condition two days, is coated on the polyfluortetraethylene plate; After room temperature, relative humidity are continue to place 24 hours under 30% condition, be warmed up to 135 ℃ from room temperature with 2.5 ℃/hour speed, normal pressure insulation 1 hour down.
4, formed film is scraped from the tetrafluoroethene plate with scalpel, carry out water content, ion exchange capacity test; Scanning electron microscope observation.
Test result shows that the water content of the film for preparing in the present embodiment is 114%; Ion exchange capacity is 1.27mmol/g, illustrates that the film of preparation has good hydrophilicity and carrying capacity.
Scanning electron microscope observation shows, the film plesiomorphism of the different proportionings that prepare in the present embodiment, surface and all smooth homogeneous of section, no noted phase separation phenomena.This shows that the oxide component microcosmic of organic component and inorganic silicon is uniformly dispersed in the prepared hybridized film of present embodiment.
By above analysis result, the film that obtains of present embodiment is the organic-inorganic hybridisation anion exchange membrane of homogeneous phase as can be known.Film has higher water content and carrying capacity.
Embodiment 5: the PEO of highly charged amount (2000)-SiO
2The preparation of hybrid anion exchange membrane
Adopt similarly to Example 4 device and operating process, just in proportioning sol-gel mixing presoma process, replace phenyltrimethoxysila,e with methyl silicate, be the PEO presoma of lotus positive electricity alkoxyl functionalization in molar ratio: the little molecule alkoxy silane of lotus positive electricity: methyl silicate=mix three kind raw materials at 1: 4: 3 obtains sol-gel mixing presoma.Resulting film carries out film potential and ion exchange capacity is measured, and measurement result shows that the film potential of film is 12.5mv, and the anion-exchange capacity of film is 1.50mmol/g, illustrates that the film that present embodiment obtains has highly charged amount.
Embodiment 6: polypropylene glycol (800)-SiO
2The preparation of hybrid anion exchange membrane
The preliminary treatment of the raw material that is adopted in the present embodiment: DMF is immersed in the molecular sieve two days; Molecular weight is 95 ℃ of vacuum drying of polypropylene glycol (PPG) of 800 8 hours.Carry out following steps then:
1, the preparation of the PPG presoma of lotus positive electricity alkoxyl functionalization: the 100ml three-necked bottle that adopts reflux condensing tube is housed, has nitrogen inlet and dropping funel, add 2.9ml TDI and 2, the mixture of 6-toluene diisocyanate, wherein the TDI mass percent is 65%, adds 1.7ml DMF again; The solution that under agitation contains 8 gram PPG and 25.4ml DMF with the speed dropping of 3.5ml/min from dropping funel; Behind the room temperature reaction 4 hours, be warming up to 60 ℃ of reactions 8 hours.Infrared test is carried out in sampling ,～1100cm
-1There is the C-O-C absworption peak at the place;～2270cm
-1The place has-absworption peak of NCO, illustrate the polymer success with 2,6-toluene diisocyanate generation end capping reaction and remaining with-NCO is so can confirm that resulting is end-blocking PPG.
Reacted solution is transferred in the dropping funel, is the end-blocking PPG with the polypropylene glycol cubage in molar ratio: (Y-7162, molecular formula is NH to N-β-aminoethyl-N '-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan
2CH
2CH
2NHCH
2CH
2NHC
3H
6Si (OCH
3)
3)=1: 2, volume ratio are Y-7162: DMF=1: 1, be added drop-wise in the DMF solution of Y-7162 with the speed of 0.5ml/min; Be warmed up to 65 ℃ after dropwising, under nitrogen protection, continue reaction 16 hours.Take a morsel and carry out infrared test after product is purified with precipitation with alcohol ,～1100cm
-1The place is owing to Si-O-CH occurs
3Absworption peak, intensity increases; And～2270cm
-1Place-NCO absworption peak disappears, and the alkoxy silane that connects of PPG molecular end success is described, what obtain is the PPG presoma.
It is PPG precursor in molar ratio: bromoethane=1: 12 with the PPG cubage, in the PPG precursor solution with the speed dripping bromine ethane of 0.5ml/min, 50 ℃ of back flow reaction 30h, adopt common distillation to reclaim bromoethane, the end product that obtains is the PPG presoma of lotus positive electricity alkoxyl functionalization.
2, the preparation of the little molecule alkoxy silane of lotus positive electricity: adopt the two neck bottles that dropping funel and reflux condensing tube are housed, be 1 in molar ratio, 2-Bromofume: bromoethane: N-methyl-aminopropyl trimethoxysilane=add 1 at 1.5: 1.5: 1,2-Bromofume and bromoethane, under agitation the speed with 2.5ml/min drips N-methyl-aminopropyl trimethoxysilane from dropping funel; After dropwising, under agitation be warming up to 65 ℃ of reaction 24h, it is unreacted 1 to adopt decompression distillation to remove, the accessory substance of 2-Bromofume and bromoethane and generation.
3, the preparation of organic-inorganic hybridisation anion exchange membrane: calculate with silicon content, be the polypropylene glycol presoma of lotus positive electricity alkoxyl functionalization in molar ratio: the little molecule alkoxy silane of lotus positive electricity: MTES=mix three kind raw materials at 1: 0.4: 0.5 obtains sol-gel mixing presoma.Be mixing presoma in molar ratio: ethanol: water: hydrochloric acid=1: 10: 2 with siliceous calculation of total: 0.05, in mixing presoma, add ethanol, water and hydrochloric acid; 60 ℃ of stirring reactions 2 days, room temperature, relative humidity 60% time, the resulting colloidal sol one day of freely volatilizing, with the glass bar knifing on smooth aluminium foil; Same environment continues down to place after 36 hours, is warmed up to 95 ℃ from room temperature with 10 ℃/hour speed, normal pressure insulation 8 hours down.
4, formed film is scraped from aluminium foil with scalpel, carry out the ion exchange capacity test; Scanning electron microscope observation.
Test result shows that the ion exchange capacity of the film for preparing in the present embodiment is 0.95mmol/g, illustrates that it is quaternary ammonium group that this film contains a certain amount of ion-exchange group.
Scanning electron microscope observation shows, the film surfacing homogeneous for preparing in the present embodiment, and this shows that the oxide component microcosmic of organic component and inorganic silicon is uniformly dispersed in this hybridized film.
The film that above analysis result explanation present embodiment obtains is the organic-inorganic hybridisation anion exchange membrane of homogeneous phase.
Embodiment 7: polyethylene glycol adipate (2000)-SiO
2The preparation of hybrid anion exchange membrane
Adopting similarly to Example 6 device, operating process and proportion relation, in the big molecular precursor process of preparation lotus positive electricity alkoxyl functionalization, is the DMF solution of the acetone soln replacement polypropylene glycol of 2000 polyethylene glycol adipate with molecular weight; In the little molecule alkoxy silane of preparation lotus positive electricity process, replace N-methyl-aminopropyl trimethoxysilane with anilinomethyl triethoxysilane, obtain organic-inorganic hybridisation anion exchange membrane.The water content of water content test shows film is 79%; The anion-exchange capacity of ion exchange capacity test shows film is 1.0mmol/g.
Embodiment 8: polyhexamethylene adipamide (2500)-SiO
2The preparation of hybrid anion exchange membrane
1, the preparation of the polyhexamethylene adipamide presoma of lotus positive electricity alkoxyl functionalization: the 100ml three-necked bottle that adopts magneton agitator, reflux condensing tube are housed, has nitrogen inlet and dropping funel, add 1.6ml to benzene diisocyanate and 3.3mlDMF, drip with the speed of 0.5ml/min from dropping funel under agitation that to contain 15 gram-molecular weights be 2500 polyhexamethylene adipamide and the solution of 47.6ml DMF; Behind the room temperature reaction 8 hours, be warming up to 60 ℃ of reactions 16 hours.Infrared test is carried out in sampling ,～3400cm
-1Amido peak, place disappears;～2270cm
-1The place has-absworption peak of NCO, illustrate the polymer success with 2, the 6-toluene diisocyanate reacts and remains with-NCO, so can confirm that resulting is the end-blocking polyhexamethylene adipamide.
Reacted solution is transferred in the dropping funel, is the end-blocking polyhexamethylene adipamide with the polyhexamethylene adipamide cubage: A-1120=1 in molar ratio: 2, and volume ratio is A-1120: DMF=1: 4; Speed with 4.5ml/min is added drop-wise in the DMF solution of A-1120; After dropwising, under nitrogen protection, be warmed up to 50 ℃ and continue reaction 28 hours.Take a morsel and carry out infrared test after product is purified with ether sedimentation ,～1100cm
-1The place is owing to Si-O-CH occurs
3Absworption peak, intensity increases; And～2270cm
-1Place-NCO absworption peak disappears, and the alkoxy silane that connects of polyhexamethylene adipamide molecular end success is described, what obtain is the polyhexamethylene adipamide precursor.
Be the polyhexamethylene adipamide precursor with the polyhexamethylene adipamide cubage: CH in molar ratio
3I=1: 6, speed with 1.5ml/min in the polyhexamethylene adipamide precursor solution adds iodomethane, after dropwising, and 48 ℃ of back flow reaction 16h, adopt common distillation to reclaim iodomethane, the end product that makes is the polyhexamethylene adipamide presoma of lotus positive electricity alkoxyl functionalization.
2, the preparation of the little molecule alkoxy silane of lotus positive electricity: adopt the two neck bottles that dropping funel and reflux condensing tube are housed, be bromoethane in molar ratio: aminomethyl triethoxysilane=add bromoethane at 9: 1, under agitation the speed with 1.2ml/min drips the aminomethyl triethoxysilane from dropping funel; After dropwising, be warming up to 50 ℃ of reaction 6h, adopt common distillation to reclaim unreacted bromoethane.
3, the preparation of organic-inorganic hybridisation anion exchange membrane: calculate with silicon content, be the polyhexamethylene adipamide presoma of lotus positive electricity alkoxyl functionalization in molar ratio: the little molecule alkoxy silane of lotus positive electricity: MTES=mix three kind raw materials at 1: 2: 2 obtains sol-gel mixing presoma.Be mixing presoma in molar ratio: ethanol: water: hydrochloric acid=1: 6: 4.5: 0.05 with siliceous calculation of total, in mixing presoma, add ethanol, water and hydrochloric acid, 60 ℃ of stirring reactions 2 days, be freely to volatilize two days under 35% the environment in room temperature, relative humidity, the hydrostomia film forming is on glass plate; Same environment was placed down after 24 hours, was warmed up to 115 ℃ from room temperature with 8 ℃/hour speed, normal pressure insulation 4 hours down.
4, formed film is scraped from glass plate with scalpel, carry out the ion exchange capacity test; Scanning electron microscope observation is also measured film potential.
The ion exchange capacity that records this film is 1.20mmol/g, illustrates that the film of present embodiment preparation contains a certain amount of quaternary ammonium group.
Scanning electron microscope observation shows, this film surfacing homogeneous, and this shows that the oxide component microcosmic of organic component and inorganic silicon is uniformly dispersed in the hybridized film that present embodiment makes.
The film potential test shows, the film potential value of this film is 11.8mv, illustrates that the film of present embodiment preparation is an anion-exchange membrane.
Comprehensive above analysis result, the film that obtains of present embodiment is the organic-inorganic hybridisation anion exchange membrane of homogeneous phase as can be known.
9: four component sol gel reaction of embodiment prepare polyhexamethylene adipamide (2500)-SiO
2Hybrid anion exchange membrane
Adopt similarly to Example 8 device and operating process, in proportioning sol-gel mixing presoma process, adopt butyl trimethoxy silane and phenyltrimethoxysila,e to replace MTES; Calculate with silicon content, by the mole proportioning is the polyhexamethylene adipamide presoma of lotus positive electricity alkoxyl functionalization: the little molecule alkoxy silane of lotus positive electricity: butyl trimethoxy silane: phenyltrimethoxysila,e=1: 2: 1: 1, obtain organic-inorganic hybridisation anion exchange membrane and carry out water content and ion exchange capacity test, the result shows that the water content of prepared film in the present embodiment is 74%, and the ion exchange capacity of film is 1.15mmol/g.
Embodiment 10: polyhexamethylene adipamide (2500)-SiO that carrying capacity is higher
2The preparation of hybrid anion exchange membrane
Adopt similarly to Example 8 device and operating process, in the little molecule alkoxy silane of preparation lotus positive electricity process, replace the aminomethyl triethoxysilane with ammonia butyl triethoxysilane; In proportioning sol-gel mixing presoma process, replace MTES with phenyltrimethoxysila,e.Calculate with silicone content, the mol ratio of three kinds of raw materials is the polyhexamethylene adipamide presoma of lotus positive electricity alkoxyl functionalization: the little molecule alkoxy silane of lotus positive electricity: phenyltrimethoxysila,e=1: 3: 1, obtain organic-inorganic hybridisation anion exchange membrane, the water content of water content test shows film is 103%; The anion-exchange capacity of this film of ion exchange capacity test shows is 1.35mmol/g.
Claims (7)
1, a kind of preparation method of organic-inorganic hybridisation anion exchange membrane, the big molecular precursor and the little molecule alkoxy silane of a kind of lotus positive electricity of earlier synthetic a kind of lotus positive electricity alkoxyl functionalization; Select for use one or both little molecule alkoxy silanes as crosslinking agent again; It is characterized in that: calculate with silicone content, be the big molecular precursor of lotus positive electricity alkoxyl functionalization in molar ratio: the little molecule alkoxy silane of lotus positive electricity: one or both little molecule alkoxy silane sum=1: 0.4-4: 0.5-4 obtains sol-gel mixing presoma after mixing; Be sol-gel mixing presoma in molar ratio: solvent: water with siliceous calculation of total: catalyst=1: 0-10: 2-8: 0.0-0.1, in this mixing presoma, add solvent, add entry and catalyst again; At 20-60 ℃ of stirring reaction 1-4 days, under being the environment of 30-80%, room temperature, relative humidity freely volatilized 1-2 days again, on matrix, film;
Described solvent comprises methyl alcohol, ethanol, N, dinethylformamide, N, N-dimethylacetylamide, methyl-sulfoxide, benzene or toluene;
Described catalyst comprises hydrochloric acid, sulfuric acid, acetate, NaOH, potassium hydroxide or ammonium chloride; Described matrix comprises inorganic matrix glass plate, aluminium foil or iron plate, or organic matrix polyethylene film, polyfluortetraethylene plate or polyvinyl chloride panel;
Described method of filming comprises knifing, hydrostomia or coating;
Be to be dried under the environment of 30-80% to form uniform and stable gel layer with diaphragm in room temperature, relative humidity; Be warmed up to 95-135 ℃ with 2.5-10 ℃/hour speed from room temperature again, be incubated 1-8 hour, formed film is scraped from matrix, be organic-inorganic hybridisation anion exchange membrane.
2, the preparation method of organic-inorganic hybridisation anion exchange membrane according to claim 1, feature is that the preparation process of the big molecule precursor of described lotus positive electricity alkoxyl functionalization is: select for use end to contain the aliphatic polymer of hydroxyl, amido or carboxyl, under inert gas shielding, with diisocyanate terminated, obtain terminated polymer; React with the alkoxy silane that contains primary amine and secondary amine group again, obtain big molecular precursor; Be the big molecular precursor with the aliphatic polymer cubage in molar ratio: halogenated hydrocarbons=1: 6-12 is added drop-wise to the speed of halogenated hydrocarbons with 0.5-3.5ml/min in the big molecular precursor solution, 20-58 ℃ of reaction 8-30 hour, excessive halogenated hydrocarbons was reclaimed in distillation; Described halogenated hydrocarbons comprises iodomethane, bromoethane or 1,2-Bromofume.
3, as the preparation method of organic-inorganic hybridisation anion exchange membrane as described in the claim 2, feature is that the aliphatic polymer that described end contains hydroxyl, amido or carboxyl is polyester polyols alcohols, polyamide-based or polyalcohols, its chemical formula can be expressed as ARB, wherein R represents aliphatic chain, and molecular weight is at 800-2500; A or B are hydroxyl, amido or carboxyl.
4, as the preparation method of organic-inorganic hybridisation anion exchange membrane as described in the claim 2, feature is that described usefulness is diisocyanate terminated, is meant in molar ratio to be diisocyanate: aliphatic polymer=2: 1 is added drop-wise to the speed of aliphatic polymer ARB solution with 0.5-3.5ml/min in the vulcabond solution; After dropwising, continue reaction 12-34 hour at 0-60 ℃; Selected solvent is the good solvent of aliphatic polymer in described aliphatic polymer solution and the vulcabond solution, simultaneously can and vulcabond, to contain the alkoxy silane of primary amine groups and secondary amine compatible and do not react, comprise methyl-sulfoxide, oxolane, acetone, benzinum, N, dinethylformamide (DMF), N, N-dimethylacetylamide, methyl-sulfoxide, benzene or toluene; Employing is an aliphatic polymer by mass ratio: solvent=1: 1-3 is a vulcabond: solvent=1: 0.5-2.5 by volume; Described diisocyanate comprises 2,4-toluene diisocyanate (TDI), TDI and 2,6-toluene diisocyanate mixture or to the benzene diisocyanate.
5, preparation method as organic-inorganic hybridisation anion exchange membrane as described in the claim 2, feature is that the described terminated polymer that will obtain reacts with the alkoxy silane that contains primary amine and secondary amine group again, be meant the terminated polymer for calculating in molar ratio: alkoxy silane=1: 2 with polymer content, the volume proportion that contains the alkoxy silane solution of primary amine and secondary amine is an alkoxy silane: solvent=1: 1-3.5, the speed of aliphatic polymer behind the end-blocking with 0.5-4.5ml/min is added dropwise in the alkoxy silane solution that contains primary amine and secondary amine, continues reaction 16-48 hour at 20-65 ℃; Described solvent types scope is with solvent used in the diisocyanate terminated course of reaction; The described alkoxy silane that contains primary amine and secondary amine group, chemical formulation are X[R
1Y]
nR
2Si (R1)
3Or X[R
1Y]
nR
2Si (R1)
2R
3R wherein
1, R
2And R
3Expression contains the alkyl of 1-3 carbon, and R1 represents to contain the alkoxy grp of 1 or 2 carbon, and X represents primary amine groups; Y represents secondary amine, and the value of n is 1 or 2.
6, the preparation method of organic-inorganic hybridisation anion exchange membrane according to claim 1, feature is that the preparation process of the little molecule alkoxy silane of described lotus positive electricity is: in molar ratio for containing the alkoxy silane of primary amine or secondary amine: halogenated hydrocarbons total amount=1: 3-9, the alkoxy silane that will contain primary amine or secondary amine was added drop-wise in the halogenated hydrocarbons with the speed of 0.5-2.5ml/min, 20-65 ℃ of reaction 6-24 hour; Adopt the excessive halogenated hydrocarbons of common distillation recovery or adopt decompression distillation to remove excessive halogenated hydrocarbons; Described halogenated hydrocarbons comprises iodomethane, bromoethane or/and 1, the 2-Bromofume; The described alkoxy silane that contains primary amine or secondary amine, its chemical formulation are R
4X ' R
5Si (R1)
3, R wherein
4Expression contains the alkyl or aryl of 0-6 carbon; R
5Expression contains the alkyl of 1-4 carbon; R1 represents to contain the alkoxyl of 1 or 2 carbon; X ' expression primary amine or secondary amine.
7, the preparation method of organic-inorganic hybridisation anion exchange membrane according to claim 1, feature are that the chemical formulation of described little molecule alkoxy silane is [R1]
4-qSi (R
6)
q, wherein R1 represents to contain the alkoxyl of 1 or 2 carbon; R
6For containing the alkyl or aryl of 1-carbon; The value of q is 0 or 1.
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