CN100577271C - Method for preparing organic-inorganic hybridization anion exchange membrane based on co-polymer - Google Patents
Method for preparing organic-inorganic hybridization anion exchange membrane based on co-polymer Download PDFInfo
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- CN100577271C CN100577271C CN200810019008A CN200810019008A CN100577271C CN 100577271 C CN100577271 C CN 100577271C CN 200810019008 A CN200810019008 A CN 200810019008A CN 200810019008 A CN200810019008 A CN 200810019008A CN 100577271 C CN100577271 C CN 100577271C
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Abstract
The invention discloses a preparation method for preparing the exchange membrane based on copolymer organic-inorganic hybrid anion. The preparation method is that a polymer that contains halogen methyl and alkoxy silicon group is firstly synthesized, the polymer is dissolved into the mixed solvent to form the solution, and is added or not added with small molecule alkoxy silane crosslinking agent to obtain the sol-gel precursor body which is added with tertiary amine, catalyst, water and ethanol for reacting under the magnetic stirring to obtain the sol-gel solution; the sol-gel solution after being concentrated is coated on the base to form the membrane; the membrane is dried and solidified to obtain the exchange membrane of organic-inorganic hybrid anion. The exchange membrane of organic-inorganic hybrid anion prepared by adopting the method of the invention has the advantages of high exchange capacity of ion, good mechanical property, excellent compatibility between inorganic silicon oxide component and organic component in the membrane, excellent heat stability, oxidation resistance, alkali resistance and high application potential to the battery of alkaline fuel.
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:
The preparation method of Chinese patent application number 200410065737.8 a kind of organic-inorganic hybridisation anion exchange membranes of announcing, benzyl bromide a-bromotoluene for the benzyl bromine group on polyphenylene oxide (BPPO) chain in grafting in the amino-alkyl silicane, also generate quaternary ammonium group with reactive tertiary amine, obtain the sol gel reaction precursor of lotus positive electricity, together carry out sol gel reaction with unreacted amino-alkyl silicane again, make hybrid anion exchange membrane.The hybrid anion exchange membrane organic and inorganic component compatibility that this method obtains is good, and 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.
The preparation method of the Chinese patent application number 200610097187.7 a kind of organic-inorganic hybridisation anion exchange membranes that propose, the big molecular precursor and the little molecule alkoxy silane of a kind of lotus positive electricity that mix a kind of lotus positive electricity alkoxyl functionalization by certain mol proportion, add one or both little molecule alkoxy silanes again, obtain sol-gel mixing presoma, mix presoma and carry out sol gel reaction, promptly obtain hybrid anion exchange membrane behind the dried coating film.Because the preparation raw material that the big molecular precursor of lotus positive electricity alkoxyl functionalization adopts is an aliphatic polymer, stability is not as good as aromatic polymer; The ion exchange capacity of film is not high yet, and the anion in the film is by Cl
-Type is converted into OH
-Behind the type, the bad stability of film has limited the application aspect alkaline fuel cell.
" membrane science magazine " (Journal of Membrane Science, 218 (2003) 147-163) have reported by full fluorine copolymer is carried out irradiation, and 1-chloro-4-methyl-benzene in the grafting carries out quaternizedly then to chloromethyl, obtain anion-exchange membrane.The membrane stability that this method obtains is good, the OH of film
-The electrical conductivity height, but selected full fluorine copolymer costs an arm and a leg, radiation parameter is wayward, and the film ion exchange capacity that obtains is low.
" using polymer magazine " (Journal of Applied Polymer Science, 100 (2006) 2248-2251) first preparation 4-vinylpyridine and cinnamic copolymer have been reported, after copolymer and 1-bromooctane carry out quaterisation, be coated on the nonwoven, obtain anion-exchange membrane after the drying.Because the pyridine type quaternary ammonium salt is unstable under alkaline environment, the easier degraded of back pyridine type quaternary ammonium salt heats up, so the membrane stability that obtains is not good, find in electrochemical Characterization that simultaneously the methanol crossover of film is also comparatively serious, so feasibility is not high on DMFC is used.
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.
Technical scheme of the present invention is as follows: earlier synthetic a kind of polymer that contains halomethyl and alkoxyl silicone group, being dissolved in and forming concentration in the mixed solvent is the solution of 0.04-0.13 grams per milliliter (g/ml), selects for use one or both little molecule alkoxy silanes as crosslinking agent again; It is characterized in that: in described polymer solution, add/do not add described crosslinking agent, obtain the sol-gel presoma; In the sol-gel presoma, add tertiary amine again, catalyst and water, react under the magnetic agitation 12-64h (hour), before reaction or in the 4h of reaction back, in solution, add ethanol, finish to obtain sol-gel solution after the reaction; Sol-gel solution evaporates into volume and reduces to original 40%-64%, is applied to film forming on the matrix, promptly obtains organic-inorganic hybridisation anion exchange membrane behind the diaphragm dry solidification;
Described mixed solvent is made up of category-A solvent and category-B solvent, and the category-A solvent is toluene, chloroform or chlorobenzene, and the category-B solvent is N, dinethylformamide (DMF) or N-methyl pyrrolidone; Category-A solvent shared volume fraction in mixed solvent is 17%-52%;
The chemical formula of described little molecule alkoxy silane can be expressed as [R]
4-qSi (R3)
q, wherein R3 represents to contain the alkyl or aryl of 0-1 nitrogen and 1-7 carbon, and the value of q is 0 or 1;
The mass ratio of described polymer and crosslinking agent is 1: 0-0.63;
The mass ratio of contained polymer and tertiary amine, catalyst, water is 1 in the described sol-gel presoma: 0.16-1.77: 0-0.015: 0.37-1.73, and the volume ratio of sol-gel presoma and ethanol is 1: 0.14-0.53;
Described tertiary amine is selected from trimethylamine, triethylamine or tripropyl amine (TPA);
Described catalyst is selected from ammoniacal liquor, sodium formate, sodium acetate, NaOH, potassium hydroxide;
Described matrix is meant inorganic matrix Al
2O
3Porous ceramics, Al
2O
3Micro-filtration or milipore filter, glass plate, aluminium sheet or corrosion resistant plate, or organic matrix woven dacron, polyamide fabric, glass fabric, nylon cloth, nonwoven, polyfluortetraethylene plate or polyvinyl chloride panel;
Described method of filming comprises knifing, sprinkling, dipping, hydrostomia or coating;
The diaphragm dry solidification is: diaphragm at room temperature is dried to film solidifies fully; Continued again at room temperature dry 8-14 days or be warmed up to 75-105 ℃ from room temperature, insulation 2.5-7h with the speed of 2.5-6 ℃/h.
The described preparation process that contains the polymer of halomethyl and alkoxyl silicone group is: select a kind of monomer M that contains two keys and alkoxyl silicone group for use, a kind of monomer N that contains two keys and halomethyl is that M: N=1: 0.42-2.34 mixes two kinds of monomers in molar ratio; Be solvent by volume: the volume of two kinds of monomers and=3.7-8.3 adds the category-A solvent in two kinds of monomer mixtures; Under inert gas shielding; be radical initiator in molar ratio: two kinds of monomer sum=0.4%-1.2% add dibenzoyl peroxide (BPO) or azodiisobutyronitrile (AIBN) in two kinds of monomer solutions; 60-80 ℃ of reaction 12-48h; after the polymer solution that obtains concentrates by reducing pressure and removes the 0-66%A kind solvent, by purify polymer solution 2-6 time after concentrating of the method for n-hexane or petroleum ether precipitation-category-A dissolution with solvents.
The described monomer M that contains two keys and alkoxyl silicone group, its chemical formula can be expressed as XR1Si (R)
3Wherein R1 represents to contain the alkyl or aryl of 1-7 carbon atom, and R represents to contain the alkoxyl of 1 or 2 carbon, and X represents vinyl or methacrylic acid group.
The described monomer N that contains two keys and halomethyl, its chemical formula can be expressed as YZR2; Wherein Y represents halomethyl, and Z represents vinyl or styryl, and R2 represents to contain the alkyl of 0-4 carbon.
The inventive method has been taked first synthetic a kind of polymer that contains halomethyl and alkoxyl silicone group, polymer is with after little molecule alkoxy silane mixes, the halomethyl that contains in the polymer carries out quaterisation, and the alkoxyl silicone group that contains can carry out sol gel reaction with little molecule alkoxy silane, obtains sol-gel solution; Sol-gel solution can self film forming, also can be prepared into the film of supporter.The grafting amino-alkyl silicane on macromolecular compound BPPO chain of the inventive method and Chinese patent application number 200410065737.8 reports, carry out quaternized subsequently, last and unreacted amino-alkyl silicane together carries out sol gel reaction, the method that makes hybrid anion exchange membrane is compared, the raw material sources that the present invention adopts are extensive, by changing the kind and the quaternization degree of copolymer, can obtain the film of different performance; Mix a kind of big molecular precursor and the little molecule alkoxy silane of a kind of lotus positive electricity of lotus positive electricity alkoxyl functionalization with Chinese patent application numbers 200610097187.7 proposes by certain mol proportion, add one or both little molecule alkoxy silanes again, carrying out obtaining after the sol gel reaction method of hybrid anion exchange membrane compares, the present invention can utilize the aromatic copolymer that contains functional group, prepare the higher film of stability, by improving the content of halomethyl in quaternization degree and the copolymer, can prepare the film of high ion exchange volume; With " membrane science magazine " (Journal of Membrane Science, 218 (2003) 147-163) report carries out irradiation with full fluorine copolymer, carry out quaterisation in the grafting behind the 1-chloro-4-methyl-benzene again, the method that obtains anion-exchange membrane is compared, can adopt widely in the inventive method, cheap raw material, the preparation method is simple, and the film that obtains has higher ion exchange capacity; With " using polymer magazine " (Journal of Applied PolymerScience, 100 (2006) 2248-2251) the preparation 4-vinylpyridine and the cinnamic copolymer earlier of report, copolymer is carried out being coated on the nonwoven again after quaternized, the method that obtains anion-exchange membrane after the drying is compared, can prepare densification, film that alkaline-resisting ability is high in the inventive method, film has high non-oxidizability, has higher application potential on alkaline fuel cell.
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: copolymer (VBC/KH-570)-SiO
2The preparation of hybrid anion exchange membrane
The preparation of raw material: (1) dewaters: toluene, n-hexane are immersed in the molecular sieve two days; (2) recrystallization of azodiisobutyronitrile (AIBN): under 35 ℃ of conditions, in the 10 100ml methyl alcohol that are dissolved in of gram AIBN, cryosel is bathed crystallisation by cooling, obtains crystallized product behind the suction filtration, crystallized product under room temperature, vacuum environment dry two days; (3) collection of trimethylamine: in a single neck round-bottomed flask, add the saturated trimethylamine aqueous solution of 100ml, from 30 ℃ with the programming rate heated solution of 10 ℃/h up to 80 ℃ and at 80 ℃ of insulation 2h, use 130ml N, dinethylformamide (DMF) is collected the trimethylamine gas of overflowing in the trimethylamine aqueous solution, and obtaining concentration is the trimethylamine DMF solution of 3.27 mol (mol/L).Carry out following steps then:
1, the preparation of p-chloromethyl styrene (VBC)/methacrylic acid trimethoxy silicon propyl ester (KH-570) copolymer: the 250ml round-bottomed flask that adopts reflux condensing tube is housed, has nitrogen inlet and outlet; add 6.9ml VBC, 11.8mlKH-570 and 70ml toluene; be warming up to 70 ℃ under the logical nitrogen protection; add 0.131 gram AIBN; stirring reaction 24h under the same environment obtains polymer solution.With the method for n-hexane precipitation-toluene dissolving purifying polymer four times repeatedly, the polymer dissolution after purifying is become the solution of 0.21g/ml in toluene.Get the 2ml polymer solution and be coated on the tetrafluoroethene plate, place a week under the room temperature vacuum environment, scrape polymer with scalpel, carry out the nuclear-magnetism test, the result shows that the mole percent that VBC occupies in the copolymer is 54.7%.
2, the preparation of sol-gel solution: pipette the 7.20ml polymer solution and go in the conical flask, add 13.92ml DMF, mix the back and add 0.38ml phenyl triethoxysilane (EPh), stir and add 1.73ml trimethylamine and 0.82ml water down, behind the room temperature reaction 0.5h, add 11ml ethanol, continue under the room temperature to stir 48h, obtain sol-gel solution.
3, the preparation of hybridized film: sol-gel solution is transferred in the culture dish, and free evaporating solution reduces to 14ml until volume under the magnetic agitation.Keep 7ml solution, remaining 7ml solution hydrostomia is on polyfluortetraethylene plate, and after air dry under the room temperature ventilated environment was solidified extremely fully, same environment continued drying 8 days down, promptly obtained not having the hybrid material of supporter after taking off.Area of clip is 160cm
2Nonwoven be tiled on the projection film, projection film with glass plate as supporting layer, form the three-decker of nonwoven-projection film-glass plate from top to bottom, the 7.0ml solution of reservation is coated on the nonwoven of the superiors, scrapes solution with glass bar and obtains uniform sol-gel layer.Under the room temperature ventilated environment, be dried to film equally and solidify fully, continued down dry 8 days, take nonwoven off, obtain hybridized film from projection film with environment.
Because what hybrid material and hybridized film adopted is same sol-gel solution and similar last handling process, so the character of hybrid material can be represented the character of hybridized film.Hybrid material is carried out following test:
(1) water content: operation is all at room temperature carried out, and gets the material of a weight range at 0.15-0.60 gram, is immersed in the distilled water after 2 days, takes out material from water.Dry the water of material surface with filter paper, the gravimetric value that obtains after the weighing is designated as m.Again material is put into baking oven, 105 ℃ of baking 6h, the material of weighing oven dry, weight is designated as m
1The water content of material=(m-m
1) * 100%/m
1
(2) ion exchange capacity (IEC) comprises Cl
-Type IEC (IEC
Cl) and OH
-Type IEC (IEC
OH), test is all at room temperature carried out.
IEC
ClMethod of testing is as follows: get the material of a 0.40-0.55 gram, soak in 1mol/L sodium chloride after 2 days, take out material, soak and change water four times with deionized water, change water every 4h at every turn, material is immersed in the 200mL 0.5mol/L sodium sulphate two days again.Keep the sodium sulphate soak, take out material and be immersed in the 1mol/L sodium chloride two days again, again material is immersed in the deionized water, at last material is taken out with above same mode, 105 ℃ of baking 6h, the material that weighing is dried, weight is designated as m
2As indicator, use the sodium sulphate soak of the AgNO3 titration reservation of 0.1mol/L with potassium chromate.IEC
ClSilver nitrate molal quantity/the m of=consumption
2
IEC
OHMethod of testing is as follows: the material of a 0.40-0.55 gram of weighing, be immersed in 2.5-4h among the 0.5mol/L KOH, and take out material, soak and change water four times with deionized water, change water every 4h at every turn, again material is immersed in the 160ml 0.04mol/L hydrochloric acid one day.Keep the hydrochloric acid soak, again material is immersed in the deionized water, at last material is taken out with above same mode, 105 ℃ of baking 6h, the material of weighing oven dry, weight is designated as m
3With 0.04mol/L KOH the hydrochloric acid soak that keeps is carried out titration.IEC
OH=(0.04mol/L hydrochloric acid molal quantity-0.04mol/L potassium hydroxide molal quantity)/m
3
(3) thermogravimetric analysis test: material is immersed in 12h in the methyl alcohol in advance, takes out the final vacuum room temperature and places 3h.Employed instrument model is a Shimadzu TGA-50H analyzer, under air atmosphere, rises to 800 ℃ with 10 ℃/minute heating rates from room temperature.
Hybridized film is carried out mechanical strength, ESEM (SEM) and OH
-The electrical conductivity test, method of testing is with reference to " membrane science magazine " (Journal of Membrane Science 307 (2008) 28-36).Just in the SEM test, because the sample pliability is fine, it is disconnected to quench by liquid nitrogen, and directly sample is cut off.Also hybridized film is carried out the chemically stable property testing in addition, operating procedure is as follows: the diaphragm that area of clip is 6cm * 6cm, the Fenton reagent that immerses 80 ℃ (is 4ppm FeCl
2And 3%H
2O
2Mixed solution), change a Fenton reagent every 6h, take out diaphragm every 6h simultaneously, dry the solution on film surface and weigh.Investigate the variation tendency of the weight in wet base of film along with the time.
Test result shows that the water content of the film for preparing in the present embodiment is 30.6%; IEC
ClBe 1.73mmol/g, IEC
OHBe 1.26mmol/g, illustrate that prepared film is a hybrid anion exchange membrane.Compare the IEC of the film for preparing in the present embodiment with the organic-inorganic hybridisation anion exchange membrane in the Chinese patent application numbers 200610097187.7
ClPeak (1.50mmol/g) than its report is wanted high 0.23mmol/g.IEC
OHWith IEC
ClRatio be 72.8%, with comparing of " using polymer magazine " (Journal of Applied Polymer Science 107 (2008) 1865-1871) report, present embodiment wants high by 20.8% than the peak (52%) of its report, and the film of this explanation present embodiment preparation has better alkaline-resisting ability.
The thermogravimetric analysis result shows that the initial degradation temperature of the hybridized film for preparing in the present embodiment is 249.2 ℃; Thermal degradation temperature is 286.6 ℃.With comparing that Chinese patent application numbers 200610097187.7 is reported, its initial degradation temperature and thermal degradation temperature all exceed the numerical value of report, illustrate that the hybrid material that present embodiment obtains has higher heat endurance.
The chemical stability test shows, the film duration for preparing in the present embodiment can reach 12h, with comparing of " energy magazine " (Journalof Power Sources 165 (2007) 16-23) report, present embodiment is wanted high 6.8h than the maximum (5.2h) of its report, illustrates that the hybridized film of present embodiment preparation has good non-oxidizability.
The mechanical strength analysis result shows that the elongation at break of the film for preparing in the present embodiment is 41%, and hot strength is 65.8MPa.With comparing of " European polymer magazine " (European Polymer Journal 42 (2006) 1696-1704) report, though the extension at break rate score in the scope of report (16.7%-42.6%), hot strength is six times of report.The film that the present embodiment preparation is described has better mechanical performance.
SEM observation shows, prepared film uniform surface in the present embodiment, no noted phase separation phenomena; Can observe non-woven fabrics fiber from section is wrapped in the polymer.
OH
-The electrical conductivity test shows, the electrical conductivity of prepared film is 4.33 * 10 in the present embodiment
-4S/cm.
Because the character of hybrid material can be represented the character of hybridized film, for the ease of expressing, the character of material can be belonged to the character of film, adopt same inductive method among the embodiment afterwards.Comprehensive above analysis result, present embodiment has obtained the organic-inorganic hybridisation anion exchange membrane of homogeneous phase as can be known, film has lower water content and higher carrying capacity, and has good alkaline-resisting ability, heat endurance, non-oxidizability and mechanical performance, also has certain electrical conductivity.
Embodiment 2: the copolymer of high inorganic phase content (VBC/KH-570)-SiO
2The preparation of hybrid anion exchange membrane
Adopt similarly to Example 1 device, preparation process and proportion relation, just in the preparation process of step 2 sol-gel solution, replace 0.38ml EPh with 0.95ml EPh, replace 0.82ml water with 1.20ml water.The hybrid material that obtains carries out water content, IEC and thermogravimetric analysis test; Hybridized film is carried out SEM and measuring mechanical property.
Test result shows that the water content of the film for preparing in the present embodiment is 16.3%; IEC
ClBe 1.74mmol/g, IEC
OHBe 1.11mmol/g.
SEM observation shows, the prepared coarse slightly inequality in film surface in the present embodiment, and very a spot of fine crack is arranged; Illustrate that too high inorganic phase content can cause the phase-splitting problem.
The thermogravimetric analysis result shows that the initial degradation temperature of the hybridized film for preparing in the present embodiment is 237.7 ℃; Thermal degradation temperature is 257.8 ℃.This result is lower than the respective value that embodiment 1 obtains, and has further proved the phase-splitting problem that exists in the film to a certain degree.
The mechanical strength analysis result shows that the elongation at break of the film for preparing in the present embodiment is 33%, and hot strength is 59.3MPa.
Comprehensive above analysis result, the hybrid anion exchange membrane that obtains of present embodiment has stronger hydrophobicity as can be known, and film contains the too high inorganic slightly phase-splitting problem of film that caused mutually; But film still has heat endurance preferably.
Embodiment 3: copolymer (the VBC/KH-570)-SiO of low inorganic phase content
2The preparation of hybrid anion exchange membrane
Adopt similarly to Example 1 device, preparation process and proportion relation, just in the preparation process of step 2 sol-gel solution, do not add any little molecule silane (promptly not adding 0.38ml EPh) in the polymer solution, replace 0.82ml water with 0.57ml water.The hybrid material that obtains carries out water content and IEC test; The hybridized film that obtains is carried out OH
-The electrical conductivity test.
Test result shows that the water content of the film for preparing in the present embodiment is 35.0%; IEC
ClBe 2.17mmol/g, IEC
OHBe 1.47mmol/g.The OH of film
-Electrical conductivity is 4.16 * 10
-4S/cm.
Embodiment 4: the copolymer of highly charged amount (VBC/KH-570)-SiO
2The preparation of hybrid anion exchange membrane
The preparation of raw material: chloroform, benzinum are immersed in the molecular sieve two days; AIBN recrystallization method and trimethylamine are collected step with embodiment 1.Carry out following three steps subsequently:
1, the preparation of VBC/KH-570 copolymer: the 250ml round bottom three-necked bottle that adopts reflux condensing tube is housed, has nitrogen inlet and outlet; add 9.6ml VBC, 7.1ml KH-570 and 100ml chlorobenzene; be warming up to 80 ℃ under the logical argon shield; add 0.196g AIBN; stirring reaction 12h under the same environment obtains polymer solution.Remove 60ml chlorobenzene in the polymer solution with the rotary evaporation method, with the method for petroleum ether precipitation-chloroform dissolving purifying polymer five times repeatedly.Polymer dissolution after purifying is become the solution of 0.22g/ml in chloroform, get the 1ml polymer solution and be coated on the tetrafluoroethene plate, placed 2 days under the room temperature vacuum environment, carry out nuclear-magnetism subsequently and test.The result shows that the mole percent that VBC occupies in the copolymer is 69.0%.
2, the preparation of sol-gel solution: pipette the 6.88ml polymer solution and go in the conical flask, add 25.0ml DMF, mix the back and add 0.20ml tetraethoxysilane (TEOS) and 0.19ml EPh, stirring the DMF solution, the 0.73ml concentration that add the 5.48ml trimethylamine down is the ammoniacal liquor of 0.1mol/L, add 11ml ethanol subsequently, stirring at room reaction 16h obtains sol-gel solution.
3, the preparation of hybridized film: sol-gel solution is transferred in the culture dish, and under magnetic agitation, sol-gel solution freely evaporates into volume and reduces to 28ml, and hydrostomia is on polyfluortetraethylene plate.In room temperature, humidity is aeration-drying 2 days under 45% environment, and the speed with 5 ℃/h is warmed up to 105 ℃ from room temperature again, and at 105 ℃ of insulation 2.5h.Promptly obtain hybrid organic-inorganic film after scraping with scalpel.
Hybridized film is in carrying out the water content test process, because the hydrophily of film is strong excessively, the overall method that still adopts embodiment 1 to propose, but film is immersed in the beaker that fills distilled water two days later, and the film of swelling has been full of beaker bottom, inclines to the free water in beaker upper strata, weigh wet film weight with minusing, again wet film is put into baking oven, 105 ℃ of baking 10h, the water content of calculating film is 2100%.The IEC of IEC test shows film
ClBe 3.03mmol/g.
SEM observation shows that all smooth homogeneous in the section of film and surface illustrates that the film that present embodiment obtains is a homogeneous membrane.
Comprehensive above analysis result, present embodiment has obtained the hybrid anion exchange membrane of homogeneous phase, highly charged amount as can be known, and the characteristic strip of highly charged amount is to the very high swelling performance of film.
Embodiment 5: the copolymer of ceramic supporting body (3-bromopropene/allyltrimethoxysilanis)-SiO
2The preparation of hybrid anion exchange membrane
The preparation of raw material: (1) chloroform, n-hexane are immersed in a week in the molecular sieve; (2) AIBN recrystallization method and trimethylamine are collected step with embodiment 1.Carry out following three steps subsequently:
1, the preparation of 3-bromopropene (BPE)/allyltrimethoxysilanis (ALLMO) copolymer solution: adopt reflux condensing tube is housed, have the 250ml three-necked round bottom flask of nitrogen inlet and outlet; add 4.33ml BPE, 8.20mlALLMO and 100ml chloroform; be warming up to 60 ℃ under the logical nitrogen protection; add 0.066g AIBN; stirring reaction 48h under the same environment obtains polymer solution.Remove 50ml chloroform in the polymer solution with the rotary evaporation method.With the method for n-hexane precipitation-chloroform dissolving purifying polymer three times repeatedly.In 14ml chloroform and 13ml N-methyl pyrrolidone, solution concentration is 0.13g/ml with the polymer dissolution after purifying.
2, the preparation of sol-gel solution: pipette the 11.6ml polymer solution and go in the conical flask, add 0.67ml anilinomethyl triethoxysilane (ND-42), stirring down, adding 1.83ml triethylamine, 1.92ml concentration are the NaOH solution of 0.03mol/L, behind 40 ℃ of stirring reaction 1h, add 4.4ml ethanol, 40 ℃ are continued stirring reaction 24h, obtain sol-gel solution.
3, the preparation of hybridized film: sol-gel solution is transferred in the culture dish, freely evaporates into volume under the magnetic agitation and reduces to 12ml.Keep the 5ml sol-gel solution, get 7ml solution hydrostomia on aluminium sheet, air dry is 1 day under the room temperature ventilated environment, puts into baking oven again and is warmed up to 95 ℃ with the speed of 2.5 ℃/h from room temperature, and, promptly obtain hybrid material after scraping with scalpel at 95 ℃ of insulation 7h.Get a porous Alpha-alumina potsherd asymmetric, that top layer average pore size scope is the 0.4-0.5 micron, the potsherd top layer is immersed in the sol-gel solution of reservation 25 seconds, take out back air dry 1 day in the room temperature ventilated environment, speed with 2.5 ℃/h is warmed up to 95 ℃ from room temperature again, and at 95 ℃ of insulation 7h.The Alpha-alumina potsherd is carried out above dipping-air dry-heat treatment process once more,, obtain the hybrid organic-inorganic film of supporter to eliminate the big hole defect that may exist.
Hybrid material is carried out water content, IEC test; Hybridized film is carried out SEM and film potential test.
Test result shows that the water content of the hybrid material for preparing in the present embodiment is 96.6%; IEC
ClBe 1.67mmol/g, IEC
OHBe 1.03mmol/g, illustrate that prepared film is an anion-exchange membrane.
Utilize the surface and the section of SEM observation hybridized film, the result shows: prepared hybridized film surfacing homogeneous in the present embodiment; Section is divided into three-decker, is one deck compacted zone topmost, and the centre is the alundum (Al layer, bottom correspondence be porous ceramic support.
Film potential test shows, the film potential of the hybridized film that present embodiment is prepared are 4.6mv.
Comprehensive above analysis result, to have prepared a kind of be the hybrid anion exchange membrane of supporter with the porous alumina ceramic sheet to present embodiment as can be known, film has suitable water content and carrying capacity, the top layer homogeneous phase densification of film.
Embodiment 6: based on the preparation of the hybrid anion exchange membrane of copolymer (BPE/ALLMO)
Chloroform and n-hexane are immersed in the molecular sieve two days, and the recrystallization method of AIBN carries out following operation subsequently with embodiment 1:
1, the preparation of BPE/ALLMO copolymer solution and embodiment 5 steps 1 are identical.
2, the preparation of sol-gel solution: pipette the 11.6ml polymer solution and go in the conical flask, add 0.67ml amine propyl-triethoxysilicane (A-1100), stirring down, adding 3.55ml tripropyl amine (TPA), 2.60ml concentration are the sodium acetate solution of 0.1mol/L, behind 10 ℃ of stirring reaction 4h, add 5.2ml ethanol, 10 ℃ are continued stirring reaction 60h, obtain sol-gel solution.
3, the preparation of hybridized film: sol-gel solution is under 65% environment in room temperature, relative humidity, stirring evaporates into volume and reduces to 15ml, be coated on the aluminium sheet, after air dry under the room temperature ventilated environment to film solidifies fully, same environment continues dry fortnight down, promptly obtains hybridized film after scraping with scalpel.
Test result shows that the water content of the hybridized film for preparing in the present embodiment is 62.7%; IEC
ClBe 1.15mmol/g, IEC
OHBe 0.80mmol/g.Illustrate that the prepared film of present embodiment is a hybrid anion exchange membrane.
Embodiment 7: the copolymer of high stability (VBC/4-triethoxysilicane styrene)-SiO
2The preparation of hybrid anion exchange membrane
The preparation of raw material: toluene, n-hexane are immersed in the molecular sieve two days; The collection process of trimethylamine is with embodiment 1, and obtaining concentration is the trimethylamine DMF solution of 3.27mol/L; (BPO) purifies to dibenzoyl peroxide: thick BPO is dissolved in the 40ml chloroform with 10 grams, elimination insoluble matter, filtrate are poured 100ml in advance with in the salt-cooled methyl alcohol of ice, promptly have crystallization to separate out, obtain crystallized product after the filtration, the room temperature vacuum drying is one day in the presence of calcium chloride.Carry out following three steps subsequently:
1, the preparation of VBC/4-triethoxysilicane styrol copolymer: under the argon shield; in 250ml round bottom three-necked bottle, add 0.03mol VBC, 0.07mol 4-triethoxysilicane styrene and 180ml toluene; oil bath heat temperature raising to 75 ℃; add 0.145g BPO; stirring reaction 18h under the same environment obtains polymer solution.Rotary evaporation polymer solution in 60-75 ℃ of scope reduces to original 2/5 up to liquor capacity.With the method purifying polymer secondary of n-hexane precipitation-toluene dissolving, in 32ml toluene and 60ml DMF, forming concentration is the solution of 0.06g/ml with the polymer dissolution after purifying.
2, the preparation of sol-gel solution: pipette the 20.0ml polymer solution and go in the boiling flask, add the 0.34ml MTES, stir the DMF solution and the 0.95ml water that add the 1.04ml trimethylamine down, at 40 ℃ of stirring reaction 1h, add 3ml ethanol subsequently, 40 ℃ are continued reaction 12h, obtain sol-gel solution.
3, the preparation of hybridized film: sol-gel solution is transferred in the culture dish, under the magnetic agitation, evaporates into volume and reduce to 15ml in room temperature, relative humidity are 30% environment, and hydrostomia is on polyfluortetraethylene plate.In room temperature, humidity is aeration-drying 2 days in 45% environment, puts into baking oven again, is warmed up to 75 ℃ with the speed of 6 ℃/h from room temperature, and at 75 ℃ of insulation 4h.Promptly obtain hybrid organic-inorganic film after scraping with scalpel.
The hybridized film that obtains is carried out water content, IEC
ClAnd IEC
OHTest; The chemically stable property testing; Also carry out the alkali resistance test, operate as follows: getting a quality is m
4Film (0.40 gram≤m
4≤ 0.55 gram), soak in 100ml concentration is the sodium hydroxide solution of 2mol/L, the temperature of regulating sodium hydroxide solution is 40 ℃, takes out film behind the 25h, soaks 16h with deionized water, and changes water one time every 4h.Film is transferred in the hydrochloric acid of 160ml 0.04mol/L again, soaks and uses 0.04mol/L potassium hydroxide back titration after one day, calculates IEC
(OH)=(0.04mol/L hydrochloric acid molal quantity-0.04mol/L potassium hydroxide molal quantity)/m
4
The water content of test shows film is 28.4%; IEC
ClBe 1.13mmol/g, IEC
OHBe 0.91mmol/g.
The chemical stability test shows: the duration scope of film is 20-24h, illustrates that the hybridized film that present embodiment obtains has high non-oxidizability.
Alkali resistance test shows IEC
(OH)With IEC
OHRatio be 96.7%, with comparing of " membrane science magazine " (Journal ofMembrane Science 244 (2004) 25-34) report, the alkaline-resisting optimal value that can its report of force rate of film wants high, illustrates that the film that present embodiment obtains has strong alkali resistant ability.
Comprehensive above analysis result, present embodiment has obtained the hybrid anion exchange membrane of high stability as can be known.
Claims (2)
1, a kind of preparation method of organic-inorganic hybridisation anion exchange membrane, earlier synthetic a kind of polymer that contains halomethyl and alkoxyl silicone group, being dissolved in and forming concentration in the mixed solvent is the solution of 0.04-0.13 grams per milliliter, selects for use one or both little molecule alkoxy silanes as crosslinking agent again; It is characterized in that: in described solution, add/do not add described crosslinking agent, obtain the sol-gel presoma; In the sol-gel presoma, add tertiary amine again, catalyst and water, react under the magnetic agitation 12-64h (hour), before reaction or in the 4h of reaction back, in solution, add ethanol, finish to obtain sol-gel solution after the reaction; Sol-gel solution evaporates into volume and reduces to original 40%-64%, is applied to film forming on the matrix, promptly obtains organic-inorganic hybridisation anion exchange membrane behind the diaphragm dry solidification;
Described mixed solvent is made up of category-A solvent and category-B solvent, and the category-A solvent is toluene, chloroform or chlorobenzene, and the category-B solvent is N, dinethylformamide or N-methyl pyrrolidone; Category-A solvent shared volume fraction in mixed solvent is 17%-52%;
The mass ratio of described polymer and crosslinking agent is 1: 0-0.63;
The mass ratio of contained polymer and tertiary amine, catalyst, water is 1 in the described sol-gel presoma: 0.16-1.77: 0-0.015: 0.37-1.73, and the volume ratio of sol-gel presoma and ethanol is 1: 0.14-0.53;
Described tertiary amine is selected from trimethylamine, triethylamine or tripropyl amine (TPA);
Described catalyst is selected from ammoniacal liquor, sodium formate, sodium acetate, NaOH, potassium hydroxide;
Described matrix is meant inorganic matrix Al
2O
3Porous ceramics, Al
2O
3Micro-filtration or milipore filter, glass plate, aluminium sheet or corrosion resistant plate, or organic matrix woven dacron, polyamide fabric, glass fabric, nylon cloth, nonwoven, polyfluortetraethylene plate or polyvinyl chloride panel;
The method of described film forming is knifing, sprinkling, dipping, hydrostomia or coating;
Described diaphragm dry solidification is: diaphragm at room temperature is dried to film solidifies fully; Continued again at room temperature dry 8-14 days or be warmed up to 75-105 ℃ from room temperature, insulation 2.5-7h with the speed of 2.5-6 ℃/h.
2, the preparation method of a kind of organic-inorganic hybridisation anion exchange membrane according to claim 1, it is characterized in that the described preparation process that contains the polymer of halomethyl and alkoxyl silicone group is: select a kind of monomer M that contains two keys and alkoxyl silicone group for use, a kind of monomer N that contains two keys and halomethyl is that M: N=1: 0.42-2.34 mixes two kinds of monomers in molar ratio; By the volume of solvent and two kinds of monomers and volume ratio be that 3.7-8.3 adds the category-A solvent in two kinds of monomer mixtures; Under inert gas shielding, mol ratio by radical initiator and two kinds of monomer sums is that 0.4%-1.2% adds dibenzoyl peroxide or azodiisobutyronitrile in two kinds of monomer solutions, 60-80 ℃ of reaction 12-48h, after the polymer solution that obtains concentrates by reducing pressure and removes the 0-66%A kind solvent, by purify polymer solution 2-6 time after concentrating of the method for n-hexane or petroleum ether precipitation-category-A dissolution with solvents;
The described monomer M that contains two keys and alkoxyl silicone group, its chemical formulation is XR1Si (R)
3Wherein R1 represents to contain the alkyl or aryl of 1-7 carbon atom, and R represents to contain the alkoxyl of 1 or 2 carbon, and X represents vinyl or methacrylic acid group;
The described monomer N that contains two keys and halomethyl, its chemical formulation is YZR2; Wherein Y represents halomethyl, and Z represents vinyl or styryl, and R2 represents to contain the alkyl of 0-4 carbon.
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| CN101845215B (en) * | 2010-04-02 | 2011-12-14 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
| CN102476477B (en) * | 2011-06-29 | 2013-07-03 | 深圳光启高等理工研究院 | Preparation method of metamaterial medium substrate |
| SG10201701647SA (en) * | 2012-10-04 | 2017-04-27 | Evoqua Water Technologies Llc | High-performance anion exchange membranes and methods of making same |
| CN115286784B (en) * | 2022-08-23 | 2023-05-02 | 浙江工业大学 | Preparation method of solvent-resistant anion exchange membrane with cross-linked structure |
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| US5121029A (en) * | 1987-12-11 | 1992-06-09 | Idemitsu Kosan Co., Ltd. | Electroluminescence device having an organic electroluminescent element |
| US20050087491A1 (en) * | 2002-02-26 | 2005-04-28 | Creavis Gesellschaft F. Techn. U. Innovation Mbh | Hybrid membrane, method for producing the same and use of said membrane |
| US20060230926A1 (en) * | 2005-04-13 | 2006-10-19 | Gkss-Forschungszentrum Geesthacht Gmbh | Composite material, in particular composite membrane, and process for the production of the same |
| CN1970136A (en) * | 2006-10-27 | 2007-05-30 | 中国科学技术大学 | Organic-inorganic hybridized anion exchange membrane preparation method |
| CN101091878A (en) * | 2007-04-15 | 2007-12-26 | 合肥学院 | Membrane material of inorganic - organic hybrid pair of amphoteric ion, and preparation method |
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| US5121029A (en) * | 1987-12-11 | 1992-06-09 | Idemitsu Kosan Co., Ltd. | Electroluminescence device having an organic electroluminescent element |
| US20050087491A1 (en) * | 2002-02-26 | 2005-04-28 | Creavis Gesellschaft F. Techn. U. Innovation Mbh | Hybrid membrane, method for producing the same and use of said membrane |
| US20060230926A1 (en) * | 2005-04-13 | 2006-10-19 | Gkss-Forschungszentrum Geesthacht Gmbh | Composite material, in particular composite membrane, and process for the production of the same |
| CN1970136A (en) * | 2006-10-27 | 2007-05-30 | 中国科学技术大学 | Organic-inorganic hybridized anion exchange membrane preparation method |
| CN101091878A (en) * | 2007-04-15 | 2007-12-26 | 合肥学院 | Membrane material of inorganic - organic hybrid pair of amphoteric ion, and preparation method |
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