CN101775202B - Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes - Google Patents
Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes Download PDFInfo
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Abstract
The invention discloses a method based on sulfonated polyphenylene oxide (SPPO) for preparing organic-inorganic hybrid cation-exchange membranes. The method comprises the following steps: (1) preparing poly-silicon copolymers containing both alkoxy silicon groups and cation-exchange groups or functional groups which can be converted into the cation-exchange groups; (2) dissolving Na+ type SPPO in methanol or N,N-dimethylformamide to obtain SPPO solution, adding water, catalysts and the poly-silicon copolymers to the SPPO solution, and stirring and reacting to obtain membrane-coating liquid; and (3) coating a substrate with the membrane-coating liquid, so that the membrane-coating liquid can be dried into a gel layer, i.e., a membrane; and then, carrying out the heat treatment on the membrane to obtain the organic-inorganic hybrid cation-exchange membrane. The invention has the advantages of anti-swelling capacity, high thermal stability, good mechanical properties and stable electrical performance.
Description
Technical field
The present invention relates to a kind of method based on the sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation exchange membrane.
Background technology
" membrane science magazine " (Journal of Membrane Science, 272 (2006) 116-124) have reported business-like
1100EW solution and tetraethoxysilane mix, and carry out sol gel reaction then, obtain organic-inorganic hybrid cation-exchange membranes after the thermal treatment.Owing to select for use
1100EW costs an arm and a leg, loading capacity is not high, and the film electric property that obtains descends, practical is not high.
" energy magazine " (Journal of Power Sources 186 (2009) 286-292) have reported sulfonated poly (phenylene oxide) (SPPO) and the blend of (3-amine propyl group) triethoxyl silane (A-1100), after the sol gel reaction, form acid-alkali to system, obtain hybrid cation-exchange membranes after the thermal treatment.The prepared hybrid cation-exchange membranes consistency of this method is good, mechanical property is high, electric property is good, and film is fit to be applied to fuel cell field; But because film loses the part ion cation exchange groups in heat treatment process, the hybrid cation-exchange membranes carrying capacity that obtains is not high, has limited the separation performance of film.
The preparation method of Chinese patent application number 03131571.2 a kind of organic-inorganic hybrid cation-exchange membranes of announcing, utilize the organoalkoxysilane or the halosilanes that contain sulfydryl in the molecular chain to be raw material, be prepared into colloidal sol and on inorganic matrix, film, after the thermal treatment sulfydryl is carried out oxidation.This method steps is simple, and inorganic in the film-organic composition consistency is good, but owing to adopted inorganic matrix to make supporter, makes that the carrying capacity of film is not high, lacks snappiness, has limited the application of film at aspects such as diffusion dialysis, electrodialysis.
The preparation method of the Chinese patent application number hybrid cation-exchange membranes that 200810064727.0 a kind of nano particles of announcing are filled, utilize polyvinylidene difluoride (PVDF), divinylbenzene, inorganic nanoparticles, glycidyl methacrylate to be raw material, the blend post polymerization, the film that obtains is handled through NaOH.This method preparation cost is low, preparation time is short, but the carrying capacity of film is low, lack the covalent linkage effect between the organic and inorganic component, makes the homogeneity of film and stability be restricted.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of organic-inorganic hybrid cation-exchange membranes is to overcome the above-mentioned defective of prior art.
The present invention adopts the preparation method who comprises following steps to reach purpose of the present invention:
(1) preparation of multipolymer: prepare and a kind ofly not only contained the alkoxyl silicone group, but also contain many siliceous copolymers that cation exchange group maybe can change into the functional group of cation exchange group;
(2) preparation of coating liquid: with Na
+The type sulfonated poly (phenylene oxide) is dissolved in methyl alcohol or N, forming concentration in the dinethylformamide is the solution of 0.1-0.3g/mL, with the mass ratio is water: catalyzer: many siliceous copolymers: sulfonated poly (phenylene oxide)=0.10-0.50: 0-0.02: 0.05-0.35: 1 proportion relation, in above-mentioned solution, add entry, catalyzer and many siliceous copolymers, under 20-60 ℃ of temperature condition, made coating liquid in stirring reaction 12-48 hour;
(3) preparation of cationic exchange membrane: the coating liquid that step (2) makes is filmed on matrix, coating liquid being dried on matrix forming uniform and stable gel coat is diaphragm, diaphragm is heat-treated can obtain described organic-inorganic hybrid cation-exchange membranes then;
Catalyzer described in the step (2) comprises hydrochloric acid, sulfuric acid, acetate or ammoniacal liquor.
The preparation process of described many siliceous copolymers is: select a kind of monomer A that cation exchange group maybe can be converted into the functional group of cation exchange group that contains for use, a kind of monomers B that contains the alkoxyl silicone group, it is monomer A in molar ratio: monomers B: solvent C: the proportion relation of initiator D=1: 0.42-2.33: 20.2-47.2: 0.004-0.027, with monomer A, monomers B, solvent C and initiator D mix, 60-80 ℃ of temperature condition reacted 2-48 hour down, obtain polymeric solution, then polymeric solution is carried out following operation: (1) is Resorcinol by mass ratio: initiator D=0.3-0.5: 1 proportion relation adds Resorcinol in polymeric solution, remove solvent C, remaining monomer A and B obtain many siliceous copolymers liquid; Or after (2) removed the solvent C of 0-66%, to generate throw out be the method purification multipolymer of multipolymer by add normal hexane or sherwood oil to polymeric solution, and the multipolymer after purifying is dissolved in the solvent C, makes many siliceous copolymers solution; Monomer A comprises vinylformic acid, methacrylic acid, maleic anhydride or sodium vinyl sulfonate; Monomers B comprises methacrylic acid trimethoxy silicon propyl ester, vinyltriethoxysilane, vinyltrimethoxy silane, allyltrimethoxysilanis or triethoxysilicane vinylbenzene; Solvent C comprises toluene, methyl alcohol, ethanol, N, dinethylformamide or methyl-sulphoxide; Initiator D is dibenzoyl peroxide or Diisopropyl azodicarboxylate.
Described matrix comprises sheet glass, aluminium foil, polyfluortetraethylene plate, polyvinyl chloride panel, porous polyethylene membrane or non-woven fabrics.
Described method of filming comprises knifing, hydrostomia, dipping or coating.
Described heat-treating methods is: (1) places the diaphragm of ribbon matrix under 50 ℃ of conditions of temperature and is warming up to temperature 105-135 ℃ with 5-20 ℃/hour speed, is incubated 1-8 hour, promptly obtains organic-inorganic hybrid cation-exchange membranes of the present invention; Or (2) scrape diaphragm from matrix, diaphragm is placed under 50 ℃ of conditions of temperature and is warming up to temperature 105-135 ℃ with 5-20 ℃/hour speed, is incubated 1-8 hour, promptly obtains organic-inorganic hybrid cation-exchange membranes of the present invention; Or (3) scrape diaphragm from matrix, diaphragm placed under 50 ℃ of conditions of temperature and be warming up to temperature 75-95 ℃ with 5-20 ℃/hour speed, be incubated 1-4 hour, it is that 0.5-1mol/L NaCl solution or concentration are in the 0.1-0.5mol/L NaOH solution after 2-12 hour that diaphragm is immersed in concentration, again diaphragm is immersed in the water 4-12 hour, change water 3-6 time between soak period, take out diaphragm and place the speed that continues with 5-20 ℃/hour under the temperature 75-95 ℃ condition to be warming up to 105-135 ℃, be incubated 1-8 hour, promptly obtain organic-inorganic hybrid cation-exchange membranes of the present invention.
Method of the present invention is to contain cation exchange group and maybe can be converted into the monomer of functional group of cation exchange group and the monomer that contains the alkoxyl silicone group is a raw material, prepare many siliceous copolymers by copolyreaction, after many siliceous copolymers and the SPPO blend, carry out sol gel reaction, heat-treat after filming, promptly obtain organic-inorganic hybrid cation-exchange membranes.Wherein the use of many siliceous copolymers has kept the balance of the carrying capacity of film, can improve anti-swelling ability, thermostability and the electric property of film simultaneously.Method of the present invention and " membrane science magazine " (Journal of Membrane Science, 272 (2006) 116-124) and " energy magazine " (Journal of Power Sources 186 (2009) 286-292) report carry out sol gel reaction with the small molecules organoalkoxysilane in cation exchange polymer inside, the method for preparing hybrid cation-exchange membranes is compared, because the present invention has adopted many siliceous copolymers to carry out sol gel reaction, thereby the carrying capacity of film is higher, mechanical property is better, thereby application prospect is wider; With application number be that the disclosed organoalkoxysilane or the halosilanes that contain sulfydryl in the molecular chain of utilizing is raw material in 03131571.2 the Chinese patent file, after being prepared into colloidal sol, through filming, the method for thermal treatment and oxidation compares, do not use inorganic supporting body in the inventive method, the mechanical property of film is better, can be applied in fields such as diffusion dialysis, electrodialysis; With number of patent application be disclosed blend polyvinylidene fluoride, divinylbenzene, inorganic nanoparticles and glycidyl methacrylate etc. in 200810064727.0 the Chinese patent file, after the polymerization, handle through NaOH again, the method that makes the hybrid cation-exchange membranes of nano particle filling is compared, the film that the present invention makes has better homogeneity and stability, and more excellent electric property is arranged.
The invention has the advantages that: utilize sulfonated poly (phenylene oxide) and many siliceous copolymers to prepare that the anti-swelling ability of a class is good, thermostability is high, mechanical property is good, the hybrid cation-exchange membranes of stable electrical properties; Wherein the use of many siliceous copolymers has broken through the limitation of traditional hybrid cation-exchange membranes preparation method, can improve the stability and the electric property of hybrid cation-exchange membranes simultaneously.
Embodiment
Embodiment 1
The preparation of raw material: (1) toluene is immersed in the molecular sieve two days; (2) be Resorcinol by mass ratio: vinylformic acid=to vinylformic acid in add Resorcinol at 0.002: 1, the cut of about 80 ℃ of temperature is collected in underpressure distillation, obtains the liquid acrylic of purifying; (3) recrystallization of Diisopropyl azodicarboxylate (AIBN): under 35 ℃ of conditions of temperature, in the 10 100mL methyl alcohol that are dissolved in of gram Diisopropyl azodicarboxylates, cryosel is bathed crystallisation by cooling, obtains crystallized product behind the suction filtration, crystallized product under room temperature, vacuum environment dry two days.Carry out following steps then:
(1) preparation of multipolymer: in the round-bottomed flask that reflux condensing tube and drying tube are housed, add 6.9mL vinylformic acid, 23.7mL methacrylic acid trimethoxy silicon propyl ester (KH-570) and 300mL toluene, be warming up to 70 ℃ of temperature, add 0.262 gram Diisopropyl azodicarboxylate, stirring reaction 2 hours, obtain polymeric solution, in polymeric solution, add 0.131 gram Resorcinol, remove vinylformic acid and the KH-570 of toluene, remnants by rotary evaporation, drip until no cut, obtain many siliceous copolymers liquid.
(2) preparation of coating liquid: with 4 gram Na
+Type sulfonated poly (phenylene oxide) (sky, Shandong dimension film company produces) is dissolved in and forms concentration in the 20mL methyl alcohol is the sulfonated polyphenyl ethereal solution of 0.18g/mL, many siliceous copolymers liquid that adding 0.8mL step (1) makes in the sulfonated polyphenyl ethereal solution, hydrochloric acid and the 1mL water that 0.2mL concentration is 1mol/L, stirring reaction is 12 hours under 40 ℃ of temperature condition, the coating liquid 24mL of system.
(3) preparation of cationic exchange membrane: above-mentioned coating liquid is coated on the sheet glass, air seasoning is 1 day under the room temperature physical environment, making coating liquid form uniform and stable gel coat on sheet glass is diaphragm, scrape diaphragm from sheet glass, diaphragm is placed under 50 ℃ of conditions of temperature, be warming up to 90 ℃ of temperature with 10 ℃/hour speed then, and under 90 ℃ of conditions of temperature, be incubated 2 hours, diaphragm is immersed in the NaCl aqueous solution that concentration is 1mol/L 24 hours, the taking-up diaphragm is placed in the water and soaked 12 hours from the NaCl aqueous solution, change water 4 times during the water logging bubble, from water, take out diaphragm and diaphragm is placed under 90 ℃ of conditions of temperature, continuation is warming up to 130 ℃ with 10 ℃/hour speed from 90 ℃, and insulation 4 hours under 130 ℃ of conditions of temperature, promptly gets organic-inorganic hybrid cation-exchange membranes of the present invention.
The above-mentioned cationic exchange membrane that makes is carried out following test:
(1) water-content: operation is all at room temperature carried out, and weight of clip is m
1Diaphragm, m
1Scope restrain at 0.10-0.30, be immersed in the water after 2 days, take out diaphragm, dry the water of membrane surface with filter paper, the gravimetric value that obtains after the weighing is designated as m
2Diaphragm-operated water-content=(m
2-m
1) * 100%/m1.
(2) loading capacity (IEC): operation is all at room temperature carried out, and weight of clip is m
3Diaphragm, m
3Scope restrain at 0.15-0.40, after concentration is to soak 2 days among the HCl of 1mol/L, take out diaphragm, with distilled water immersion 16 hours and in soak period, change water 4 times, again diaphragm is immersed in the KOH solution that 80mL concentration is 0.04mol/L two days, making indicator with phenolphthalein, is that the HCl of 0.04mol/L carries out back titration to colourless to the KOH solution after soaking with concentration.IEC=(concentration is that mole number-concentration of the KOH of 0.04mol/L is the mole number of the HCl of 0.04mol/L)/m
3
(3) anti-swelling test: weight of clip is m
4Diaphragm, m
4Scope restrain at 0.15-0.30, be immersed in the 80mL temperature and be in 65 ℃ the water, took out diaphragm every 6 hours, dry the water on surface, after the weighing diaphragm is put into 65 ℃ of water again and continues to soak.Make changes in weight per-cent curve over time, the time when weight increase per-cent reaches maximum value is designated as the swelling time.
(4) chemically stable property testing: the diaphragm that area of clip is 6cm * 6cm, the Fenton reagent that immerses 65 ℃ (is 4ppm FeCl
2And 3%H
2O
2Mixing solutions) in, changed a Fenton reagent every 3 hours, took out diaphragm every 3 hours simultaneously, diaphragm dried and weighed.Investigate the variation tendency of the weight in wet base of film along with the time.
Exchange membrane is carried out physical strength, scanning electron microscope and proton conductivity test, and testing method is with reference to " membrane science magazine " (Journal of Membrane Science 307 (2008) 28-36) and " energy magazine " (Journal of Power Sources 186 (2009) 286-292).
Test result:
The water-content of the exchange membrane that present embodiment is prepared is 60.3%; IEC is 2.47mmol/g, illustrates that exchange membrane has suitable wetting ability and high carrying capacity.(water-content is 88% to the SPPO character of reporting with " energy magazine " (Journal of Power Sources 186 (2009) 286-292), IEC is 2.52mmol/g) to compare, the prepared exchange membrane of present embodiment has similar carrying capacity but the ability of higher anti-swelling is arranged.
Anti-swelling test: the swelling time of exchange membrane is 36 hours, compares (24 hours) with SPPO, and the prepared exchange membrane of present embodiment has better anti-swelling ability.
The chemically stable property testing: the duration of the exchange membrane that present embodiment is prepared is about 5 hours, compares (about 3 hours) with SPPO, and the prepared exchange membrane of present embodiment has better oxidation-resistance.
Mechanical strength test: the elongation at break of the exchange membrane for preparing in the present embodiment is 19%, and tensile strength is 45.8MPa.
Scanning electron microscope observation shows, the prepared exchange membrane homogeneous of present embodiment is smooth, no noted phase separation phenomena.
The specific conductivity test: the specific conductivity of the exchange membrane that present embodiment is prepared is 0.13S/cm, illustrates that film has good electric property.
Comprehensive above test result, present embodiment has obtained the homogeneous organic-inorganic hybrid cation-exchange membranes as can be known, and film has favorable mechanical performance and excellent electric property.With respect to the SPPO film, the prepared film of present embodiment has higher anti-swelling ability and chemical stability.
Embodiment 2
The set-up procedure of raw material is identical with embodiment 1, carries out following steps then:
(1) preparation of multipolymer: in the round-bottomed flask that reflux condensing tube and drying tube are housed, add 4.1mL vinylformic acid, 33.1mL methacrylic acid trimethoxy silicon propyl ester (KH-570) and 300mL toluene, be warming up to 70 ℃ of temperature, add 0.262 gram Diisopropyl azodicarboxylate, stirring reaction 6 hours, obtain polymeric solution, in polymeric solution, add 0.079 gram Resorcinol, remove toluene and remaining vinylformic acid by air distillation, carry out underpressure distillation again and remove remaining KH-570, obtain many siliceous copolymers liquid.
(2) preparation of coating liquid: with the step among the embodiment 1 (2).
(3) preparation of cationic exchange membrane: with the step among the embodiment 1 (3).
The cationic exchange membrane that the method for employing embodiment 1 makes present embodiment carries out water-content, IEC and the test of anti-swelling, and test result is as follows:
The water-content of cationic exchange membrane is 45.7%, and IEC is 2.11mmol/g, and the swelling time is 66 hours.With respect to embodiment 1, the prepared cationic exchange membrane of present embodiment has lower carrying capacity, but better stability is arranged.
Embodiment 3
Raw material is prepared: toluene is immersed in the molecular sieve two days; Diisopropyl azodicarboxylate (AIBN) carries out recrystallization, and method is with embodiment 1.Carry out following steps then:
(1) preparation of multipolymer: in the round-bottomed flask that serpentine condenser and drying tube are housed, add 5.11mL methacrylic acid, 33.2mL methacrylic acid trimethoxy silicon propyl ester (KH-570) and 280mL toluene, be warming up to 80 ℃, add 0.131 gram Diisopropyl azodicarboxylate (AIBN), stirring reaction 12 hours obtains polymeric solution.After rotary evaporation is removed the interior 184mL toluene of polymeric solution, in polymeric solution, add normal hexane, until the heavy-gravity precipitation is arranged is that multipolymer is separated out, in the multipolymer dissolving toluene that is settled out, and then the adding normal hexane is that multipolymer is separated out until precipitation is arranged, to be dissolved among the DMF through the multipolymer that secondary is purified at last, making concentration is many siliceous copolymers solution 50mL of 0.3g/mL.
(2) preparation of coating liquid: with 4 gram Na
+Type sulfonated poly (phenylene oxide) (SPPO, the production of sky, Shandong dimension film company) be dissolved in 36mL N, forming concentration in the dinethylformamide (DMF) is the solution of 0.1g/mL, and adding 0.67mL above-mentioned steps (1) makes in solution many siliceous copolymers solution and 2mL concentration are the ammonia soln of 2mol/L; Stirring reaction is 12 hours under 60 ℃ of temperature condition, the coating liquid 40mL of system.
(3) preparation of cationic exchange membrane: the coating liquid hydrostomia that step (2) is made is on polyfluortetraethylene plate, room temperature ventilated environment dry 2 days down, making coating liquid form uniform and stable gel coat on polyfluortetraethylene plate is diaphragm, scrape diaphragm from polyfluortetraethylene plate, diaphragm is placed under 50 ℃ of conditions of temperature, be warmed up to 105 ℃ of temperature with 5 ℃/hour speed from 50 ℃ of temperature then, be incubated 8 hours, promptly obtain organic-inorganic hybrid cation-exchange membranes.
The above-mentioned cationic exchange membrane that makes is carried out water-content, IEC, anti-swelling, chemical stability, physical strength analysis, proton conductivity and methanol crossover test, and testing method is with reference to " membrane science magazine " (Journal of Membrane Science 310 (2008) 522-530).
Test result: water-content is 42.6%; The swelling time is 84 hours, and IEC is 2.06mmol/g; Duration reaches 7 hours (anti-and so on duration); The elongation at break of film is 25%, and tensile strength can reach 52.3MPa; Methanol permeability is 1.1 * 10
-6Cm
2s
-1The proton conductivity of film is 0.15S/cm.SPPO character (1.7 * 10 with " energy magazine " (Journal of Power Sources 186 (2009) 286-292) report
-6Cm
2s
-1, 0.14S/cm) to compare, the prepared cationic exchange membrane of present embodiment has similar specific conductivity, but the pure ability of better resistance is arranged.
Analyze above test result, present embodiment has successfully prepared hybrid cation-exchange membranes as can be known.Cationic exchange membrane has good physical stability and electric property, and the resistance that improves alcohol ability.
Embodiment 4
The pre-treatment of raw material: N, dinethylformamide (DMF) are immersed in the molecular sieve two days; The 10 thick dibenzoyl peroxide of gram (BPO) are dissolved in the 40mL chloroform, the elimination insolubles, and filtrate is poured 100mL into and is bathed in the refrigerative methyl alcohol with cryosel in advance, promptly has crystallization to separate out, and obtains crystallized product after the filtration, and room temperature vacuum-drying is one day in the presence of calcium chloride.Carry out following steps then:
(1) preparation of multipolymer: in the round-bottomed flask of reflux condensing tube is housed, under the protection of inert gas; mix 18.2 gram vinyl semi-annular jade pendant acid sodium, 12.6mL vinyltriethoxysilane (VTES) and 220mL N; dinethylformamide (DMF); be warming up to 60 ℃ of temperature; add 0.097 gram dibenzoyl peroxide (BPO); stirring reaction 48 hours obtains polymeric solution.Rotary evaporation is removed the 176mL N in the polymeric solution, behind the dinethylformamide (DMF), in polymeric solution, add the 180mL petroleum ether precipitation and go out multipolymer, the multipolymer that is settled out is dissolved among the 40mL DMF again, adding the 160mL sherwood oil then is settled out multipolymer, at last multipolymer is dissolved among the DMF, making concentration is many siliceous copolymers solution 75mL of 0.2g/mL.
(2) preparation of coating liquid: with 4 gram Na
+Type sulfonated poly (phenylene oxide) (SPPO, the production of sky, Shandong dimension film company) be dissolved in 9.3mL N, forming concentration in the dinethylformamide (DMF) is the solution of 0.3g/mL, and adding 7mL step (1) makes in solution many siliceous copolymers solution, 0.2mL concentration are 1mol/LHCl and 0.3mL water; Stirring reaction is 48 hours under 20 ℃ of temperature condition, makes coating liquid 20mL.
(3) preparation of cationic exchange membrane: the coating liquid knifing that step (2) is made is on non-woven fabrics, room temperature ventilated environment dry 1 day down, making coating liquid form uniform and stable gel coat on non-woven fabrics is diaphragm, place diaphragm under the condition of 50 ℃ of temperature together with non-woven fabrics, be raised to 135 ℃ of temperature with 20 ℃/hour speed from 50 ℃ of temperature then, be incubated 1 hour, promptly obtain organic-inorganic hybrid cation-exchange membranes.
The above-mentioned cationic exchange membrane that makes is carried out water-content, IEC, chemical stability, proton conductivity and mechanical strength test, testing method reference example 1; Scrape from non-woven fabrics and to be coated with rete and to carry out thermogravimetric analysis, the method for thermogravimetric analysis is with reference to " membrane science magazine " (Journal of Membrane Science 307 (2008) 28-36).
Test result: the water-content of the exchange membrane for preparing in the present embodiment is 75.6%, and IEC is 2.78mmol/g, illustrates that prepared exchange membrane has high carrying capacity and higher wetting ability; The duration of exchange membrane is 6 hours, and proton conductivity is 0.12S/cm, and the tensile strength of exchange membrane is 39.7MPa, and elongation at break is 14%; The thermogravimetric analysis test shows, the initial heat decomposition temperature of exchange membrane is 262 ℃, illustrates that exchange membrane has good thermostability.
By above test result, present embodiment has obtained the cationic exchange membrane of highly charged amount as can be known, and cationic exchange membrane has higher wetting ability and good thermostability.
Embodiment 5
The pre-treatment of raw material: methyl-sulphoxide and normal hexane are immersed in the molecular sieve two days; Purification dibenzoyl peroxide (BPO), purification step are carried out following steps then with embodiment 4:
(1) preparation of multipolymer: under the nitrogen protection; in the 250mL three-necked round bottom flask, add 0.04mol methacrylic acid, 0.06mol triethoxysilicane vinylbenzene and 120mL methyl-sulphoxide; oil bath heat temperature raising to 75 ℃; add 0.145 gram BPO; stirring reaction is 18 hours under nitrogen protection and the 75 ℃ of temperature condition, obtains polymeric solution.In polymeric solution, add the 400mL normal hexane and be settled out multipolymer, the multipolymer that is settled out is dissolved among the 20mLDMF again, add the 80mL normal hexane then multipolymer is settled out, at last multipolymer is dissolved among the DMF, making concentration is many siliceous copolymers solution 90mL of 0.1g/mL.
(2) preparation of coating liquid: with 4 gram Na
+Type sulfonated poly (phenylene oxide) (SPPO, sky, Shandong dimension film company produces) be dissolved among the DMF, obtain the solution that 13.5mL concentration is 0.30g/mL, add many siliceous copolymers solution and 1.2mL water that 6mL step (1) makes subsequently, stirring reaction is 1 day under 40 ℃ of temperature condition, the coating liquid 20mL of system.
(3) preparation of cationic exchange membrane: the coating liquid hydrostomia that step (2) is made is on the tetrafluoroethylene plate, room temperature ventilated environment dry 3 days down, making coating liquid form uniform and stable gel coat on the tetrafluoroethylene plate is diaphragm, scrape diaphragm from the tetrafluoroethylene plate, diaphragm is placed under 50 ℃ of conditions of temperature, be raised to 75 ℃ of temperature with 20 ℃/hour speed from 50 ℃ of temperature, and under 75 ℃ of conditions of temperature, be incubated 4 hours; Diaphragm is immersed among the NaOH that concentration is 0.1mol/L 12 hours, from NaOH, take out and in water, soaked 4 hours, change water 6 times during the water logging bubble, then diaphragm is taken out from water and place under 75 temperature condition, continuation is warmed up to 135 ℃ with 20 ℃/hour speed from 75 ℃, and under 135 ℃ of temperature condition, be incubated 1 hour, promptly obtain organic-inorganic hybrid cation-exchange membranes.
The above-mentioned cationic exchange membrane that makes is carried out water-content, IEC, chemically stable property testing; Scanning electron microscopic observation; Measuring mechanical property, testing method adopts the method described in the embodiment 1.
Test result: the water-content of the cationic exchange membrane of present embodiment preparation is 48.7%, and IEC is 2.33mmol/g, and tensile strength is 28.5MPa, and elongation at break is 11%; Scanning electron microscope observation shows, the smooth densification of exchange membrane, and consistency is good between the organic and inorganic phase; The chemical stability test shows, the duration of exchange membrane is 6 hours, illustrates that exchange membrane has certain resistance of oxidation.
Embodiment 6
The pre-treatment of raw material is with embodiment 5.
(1) preparation of multipolymer: with the step (1) of embodiment 5.
(2) preparation of coating liquid: with the step (2) of embodiment 5.
(3) preparation of cationic exchange membrane: the coating liquid that step (2) is made is coated on the aluminium foil, room temperature ventilated environment dry 2 days down, making coating liquid form uniform and stable gel coat on aluminium foil is diaphragm, scrape diaphragm from aluminium foil, diaphragm is placed under 50 ℃ of conditions of temperature, 5 ℃/hour speed is warmed up to 95 ℃ from 50 ℃ then, and insulation 1 hour under 95 ℃ of temperature condition; It is among the 0.5mol/L NaOH 2 hours that diaphragm is immersed in concentration, from NaOH, take out and in water, soaked 12 hours, change water in 12 hours 3 times, taking out diaphragm from water is placed under 95 ℃ of temperature condition, continuation is warmed up to 105 ℃ with 5 ℃/hour speed from 95 ℃, and under 105 ℃ of temperature condition, be incubated 8 hours, promptly obtain organic-inorganic hybrid cation-exchange membranes.
The above-mentioned cationic exchange membrane that makes is carried out water-content, IEC, measuring mechanical property, and testing method is with embodiment 1.
Test result: the water-content of the cationic exchange membrane that present embodiment makes is 52.5%, and IEC is 2.46mmol/g; The tensile strength of film is 32.5MPa, and elongation at break is 19%, and with respect to embodiment 5, the prepared cationic exchange membrane of present embodiment has the mechanical property of improvement.
Claims (4)
1. method based on the sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation exchange membrane is characterized in that may further comprise the steps:
(1) preparation of multipolymer: prepare and a kind ofly not only contained the alkoxyl silicone group, but also contain many siliceous copolymers that cation exchange group maybe can change into the functional group of cation exchange group;
(2) preparation of coating liquid: with Na
+The type sulfonated poly (phenylene oxide) is dissolved in methyl alcohol or N, forming concentration in the dinethylformamide is the solution of 0.1-0.3g/mL, with the mass ratio is water: catalyzer: many siliceous copolymers: sulfonated poly (phenylene oxide)=0.10-0.50: 0-0.02: 0.05-0.35: 1 proportion relation, in above-mentioned solution, add entry, catalyzer and many siliceous copolymers, under 20-60 ℃ of temperature condition, made coating liquid in stirring reaction 12-48 hour;
(3) preparation of cationic exchange membrane: the coating liquid that step (2) makes is filmed on matrix, coating liquid on the matrix being dried to forming uniform and stable gel coat is diaphragm, diaphragm is heat-treated can obtain described organic-inorganic hybrid cation-exchange membranes then;
Catalyzer described in the step (2) comprises hydrochloric acid, sulfuric acid, acetate or ammoniacal liquor;
The preparation process of described many siliceous copolymers is: select a kind of monomer A that cation exchange group maybe can be converted into the functional group of cation exchange group that contains for use, a kind of monomers B that contains the alkoxyl silicone group, it is monomer A in molar ratio: monomers B: solvent C: the proportion relation of initiator D=1: 0.42-2.33: 20.2-47.2: 0.004-0.027, with monomer A, monomers B, solvent C and initiator D mix, 60-80 ℃ of temperature condition reacted 2-48 hour down, obtain polymeric solution, then polymeric solution is carried out following operation: (1) is Resorcinol by mass ratio: initiator D=0.3-0.5: 1 proportion relation adds Resorcinol in polymeric solution, remove solvent C, remaining monomer A and monomers B obtain many siliceous copolymers liquid; Or after (2) removed the solvent C of 0-80%, to generate throw out be the method purification multipolymer of multipolymer by add normal hexane or sherwood oil in polymeric solution, and the multipolymer after purifying is dissolved in the solvent C, makes many siliceous copolymers solution;
Described monomer A comprises vinylformic acid, methacrylic acid, maleic anhydride or sodium vinyl sulfonate;
Described monomers B comprises methacrylic acid trimethoxy silicon propyl ester, vinyltriethoxysilane, vinyltrimethoxy silane, allyltrimethoxysilanis or triethoxysilicane vinylbenzene;
Described solvent C comprises toluene, methyl alcohol, ethanol, N, dinethylformamide or methyl-sulphoxide;
Described initiator D is dibenzoyl peroxide or Diisopropyl azodicarboxylate.
2. the method based on the sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation exchange membrane according to claim 1 is characterized in that described matrix comprises sheet glass, aluminium foil, polyfluortetraethylene plate, polyvinyl chloride panel, porous polyethylene membrane or non-woven fabrics.
3. the method based on the sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation exchange membrane according to claim 1 is characterized in that described method of filming comprises knifing, hydrostomia, dipping or coating.
4. the method based on the sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation exchange membrane according to claim 1 is characterized in that described heat-treating methods is:
(1) diaphragm of ribbon matrix is placed under 50 ℃ of conditions of temperature and be warming up to temperature 105-135 ℃, be incubated 1-8 hour, promptly obtain described organic-inorganic hybrid cation-exchange membranes with 5-20 ℃/hour speed; Or
(2) scrape diaphragm from matrix, diaphragm is placed under 50 ℃ of conditions of temperature and be warming up to temperature 105-135 ℃, be incubated 1-8 hour, promptly obtain described organic-inorganic hybrid cation-exchange membranes with 5-20 ℃/hour speed; Or
(3) scrape diaphragm from matrix, diaphragm placed under 50 ℃ of conditions of temperature and be warming up to temperature 75-95 ℃ with 5-20 ℃/hour speed, be incubated 1-4 hour, diaphragm was immersed in the NaOH solution that NaCl solution that concentration is 0.5-1mol/L or concentration is 0.1-0.5mol/L after 2-12 hour, again diaphragm is immersed in the water 4-12 hour, change water 3-6 time between soak period, take out diaphragm and place the speed that continues with 5-20 ℃/hour under the temperature 75-95 ℃ condition to be warming up to 105-135 ℃, be incubated 1-8 hour, promptly obtain described organic-inorganic hybrid cation-exchange membranes.
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| CN102658036A (en) * | 2012-03-06 | 2012-09-12 | 中国科学技术大学 | Coating liquid, organic-inorganic hybrid cation exchange membrane and preparation method thereof |
| CN102780020B (en) * | 2012-08-03 | 2016-08-31 | 上海锦众信息科技有限公司 | A kind of preparation method of fuel cell composite proton exchange membrane |
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| CN1772796A (en) * | 2004-11-13 | 2006-05-17 | 中国科学技术大学 | Prepn process of positively charged hybrid organic-inorganic film |
| CN101220169A (en) * | 2007-09-14 | 2008-07-16 | 中国科学技术大学 | Production method for organic-inorganic hybridisation anion exchange membrane |
| CN101234307A (en) * | 2008-01-08 | 2008-08-06 | 中国科学技术大学 | Method for preparing organic-inorganic hybridization anion exchange membrane based on co-polymer |
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| CN1772796A (en) * | 2004-11-13 | 2006-05-17 | 中国科学技术大学 | Prepn process of positively charged hybrid organic-inorganic film |
| CN101220169A (en) * | 2007-09-14 | 2008-07-16 | 中国科学技术大学 | Production method for organic-inorganic hybridisation anion exchange membrane |
| CN101234307A (en) * | 2008-01-08 | 2008-08-06 | 中国科学技术大学 | Method for preparing organic-inorganic hybridization anion exchange membrane based on co-polymer |
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