CN107020025A - A kind of preparation method of alkaline anion-exchange membrane - Google Patents

A kind of preparation method of alkaline anion-exchange membrane Download PDF

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CN107020025A
CN107020025A CN201710328718.7A CN201710328718A CN107020025A CN 107020025 A CN107020025 A CN 107020025A CN 201710328718 A CN201710328718 A CN 201710328718A CN 107020025 A CN107020025 A CN 107020025A
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shell particles
mass
exchange membrane
class core
film
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CN107020025B (en
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姜忠义
黄彤
何光伟
李宗雨
尹永恒
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes

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Abstract

The invention discloses a kind of preparation method of alkaline anion-exchange membrane, first, synthesize the nm-class core-and-shell particles being made up of chloromethylated polystyrene molecular brush and silicon ball, then the nm-class core-and-shell particles are filled into the conductive polysulfones membrane matrix of nonionic, wherein, the mass fraction of nm-class core-and-shell particles is 20 70%, and alkaline anion-exchange membrane is made by quaternized, alkalization in composite membrane.By the way that the nm-class core-and-shell particles being made up of the polystyrene molecular brush and silicon ball that highly ionize are introduced into polysulfones in the present invention, these nano particles can build continuous high-effect ionic transmission channels in film, make hydroxide ion conductivity of the film when loading is 50 70% at 80 DEG C up to 88.4 188.1mS/cm.Have benefited from the silica inorganic composition in nano particle simultaneously, hybridized film possesses good mechanical performance and stability.

Description

A kind of preparation method of alkaline anion-exchange membrane
Technical field
The invention belongs to functional high molecule material preparation field, and in particular to a kind of preparation side of alkaline anion-exchange membrane Method.
Background technology
Alkaline anion-exchange membrane (AEM) is because it is in new energy and field of Environment Protection such as fuel cell, flow battery, electric osmose The application value of analysis, electron ion water etc. and enjoy researcher to pay close attention to.Alkaline anion-exchange membrane fuel cell is considered as to substitute The next-generation technology of Proton Exchange Membrane Fuel Cells, this is due to that it has faster electrode reaction speed, can use non-noble The advantages such as metallic catalyst is to significantly reduce cost, lower material corrosive properties, more effective water management.But it is relatively low at present Hydroxide ion conductivity significantly constrain the industrialization development of alkaline anion-exchange membrane.
In order to improve ionic conductance, by using for reference the research experience of PEM, microphase-separated technology is applied to Among the exploitation of anion-exchange membrane.Its principle is when segment hydrophilic and hydrophobic difference is strong, it may occur that is separated, but is due to The prevention of covalent bond, the microphase-separated that can only occur nanoscale.Anion can be realized by the structure for regulating and controlling microphase-separated Exchange membrane has continuous nanoscale ion cluster, it is possible to increase ionic conductance.Chinese patent CN102451620A is disclosed A kind of preparation method of microphase-separated film, is the polymer film forming for containing many single heterocyclic onium cations with side chain, be made film have compared with High electrical conductivity and stability.《Energy and Environment Science》(J.Pan, et al., 2012,7,354- 360) a kind of quaternized polysulfones anion-exchange membrane containing hydrophobic side chain of magazine ran, can form good micro- of continuity Phase separation structure, with good ionic conductance and stability.But the shortcoming of microphase-separated film is its microphase-separated knot Structure is by hydrophobe segment rigidity, polarity, quantity, and many factors influence such as polymer molecular structure regulates and controls relatively difficult.
It is a kind of Research Thinking being widely used with the structure of adjusting film that filler is added into membrane matrix.Chinese patent CN201210545444.4 discloses a kind of method that modified carbon nano-tube prepares anion-exchange membrane with PVDF hydridization, utilizes carbon The excellent structure of nanotube, mechanics, chemical property, the ionic conducting property of obtained film, chemical stability, mechanical performance are obtained Improve.Chinese patent CN201010139148.5 discloses a kind of hybrid anion exchange membrane based on brominated polyphenylether blending Preparation method, is made in film while have inorganic silicon oxide composition and organic principle, obtained film ion by sol-gel process Exchange capacity is high, good mechanical property, with excellent heat endurance, inoxidizability and alkali resistance.The work of current inorganic filler With the interfacial effect that mainly uses between filler and ionomeric polymer and improve the mechanical performance and stability of film, but It is that the filling rate of filler is often difficult to do big, the lifting to performances such as ionic conductances is limited.
The content of the invention
For above-mentioned prior art, the present invention provides a kind of technology of preparing of anion-exchange membrane to overcome inorganic fill The not high shortcoming of thing loading, while playing the advantage of hybridized film, using for reference the valuable experience of micro phase separation structure.It is prepared by the technology The core-shell type nano ion that the polymer molecule brush of height ionization is constituted with silicon ball, shell be polymer can be substantially improved with The compatibility of membrane matrix, so as to prepare loading 20%-70% hybridized film；Core is that silicon ball can provide excellent machine Tool performance and stability, while hold onto the ionomeric polymer in molecular brush by covalent bond, can be formed it is nano level from Sub- cluster, so as to lift the ionic conductivity of film, loading is reachable at 80 DEG C for the ionic conductance of 70% hybridized film 188.1mS/cm.Such hybridized film has good mechanical performance and stability simultaneously.
In order to solve the above-mentioned technical problem, the preparation method of a kind of alkaline anion-exchange membrane proposed by the present invention, first, The nm-class core-and-shell particles being made up of chloromethylated polystyrene molecular brush and silicon ball are synthesized, then by the core-shell type nano Grain is filled into the conductive polysulfones membrane matrix of nonionic, wherein, the mass fraction of nm-class core-and-shell particles is 20-70%, multiple Close film and alkaline anion-exchange membrane is made by quaternized, alkalization.Comprise the following steps that：
Step 1: being 50 by volume ratio:5:1 ethanol, water and ammoniacal liquor is well mixed, adds tetraethyl orthosilicate, positive silicic acid The volume ratio of ethyl ester and ammoniacal liquor is 1.5:1,24h is stirred vigorously, the suspension of Nano particles of silicon dioxide is obtained, is subsequently added first Base acrylic acid propyl trimethoxy silicane stirs 24h, and the silicon ball nano particle of the active double bond of surface grafting is obtained after centrifugation；
Step 2: silicon ball nano particle made from step one is scattered in solvent orange 2 A, wherein, silicon ball nano particle with it is molten Agent A mass-volume concentration is 2~4g/L, then, adds methacrylic acid, p-chloromethyl styrene, divinylbenzene, azo Bis-isobutyronitrile, wherein, solvent orange 2 A and methacrylic acid, p-chloromethyl styrene, the volume ratio of divinylbenzene is 100:0.4~ 0.9:0.2~0.4:0.1~0.3, the mass-volume concentration of azodiisobutyronitrile and solvent orange 2 A is 0.14~0.16g/L；Backflow 60 ~90min, obtains the nano particle that active chloromethyl is contained on top layer；
Step 3: nano particle made from step 2 is scattered in toluene, the quality volume of nano particle and toluene is dense Spend for 0.15~0.25g/mL, then, add styrene, pentamethyl-diethylenetriamine, stannous chloride, wherein, styrene and first The volume ratio of benzene is 1:1, the mass-volume concentration of stannous chloride and toluene is 0.25~1g/L, pentamethyl-diethylenetriamine and chlorine It is 1 to change cuprous mass ratio:13~30,80~120 DEG C of 1~3h of heating response under nitrogen protection, by product tetrahydrofuran Washing, has been grafted the nm-class core-and-shell particles A of polystyrene molecular brush；
Step 4: nm-class core-and-shell particles A made from step 3 is scattered in solvent B, nm-class core-and-shell particles A with it is molten Agent B mass-volume concentration is 0.025~0.035g/mL, adds anhydrous zinc chloride and chloromethyl methyl ether, anhydrous zinc chloride with it is molten Agent B mass-volume concentration is 15~22mg/mL, and chloromethyl methyl ether and solvent B volume ratio are 0.625~1:1, reaction temperature For 40~70 DEG C, the reaction time is 24~48h, obtain by the polystyrene molecular brush and silicon ball of chloromethylation constitute it is hud typed Nano particle B；
Step 5: nm-class core-and-shell particles B made from step 4 is scattered in DMF, it is hud typed to receive The mass-volume concentration of rice grain B and DMF is 15~35g/L, and polysulfones macromolecule is dissolved afterwards and obtains casting film Liquid, polysulfones and nm-class core-and-shell particles B mass ratio are 0.43~4, and 12~24h film forming, gained are dried using 60 DEG C of stream method is prolonged Film soaks trimethylamine aqueous solution 48h that mass fraction is 30% with quaternized at 30 DEG C, and quaternized film is immersed into sodium hydroxide 48h is alkalized in solution, is washed with deionized water to neutrality, obtains the ionic conductivity that loading is 20%~70% hud typed The alkaline anion-exchange membrane of nano particle B insertions.
Further, in step one, the volume ratio of the tetraethyl orthosilicate and methacrylic acid propyl trimethoxy silicane For 100:15~20.In step 2, any one of the solvent orange 2 A in dichloroethanes, acetonitrile, toluene.In step 4, institute State solvent B and be selected from least one of chloroform, dichloromethane, tetrachloroethanes, acetone.
Compared with prior art, the beneficial effects of the invention are as follows：
In preparation method of the present invention, by by by the polystyrene molecular brush and silicon ball that highly ionize constitute it is hud typed Nano particle is introduced into polysulfones, and these nano particles can build continuous high-effect ionic transmission channels in film, fill out film Hydroxide ion conductivity when charge is 50-70% at 80 DEG C is up to 88.4-188.1mS/cm.Have benefited from nano particle simultaneously In silica inorganic composition, hybridized film possesses good mechanical performance and stability.
Brief description of the drawings
Fig. 1 is modified with the transmission electricity of the silicon ball of double bond, chloromethylation silicon ball and chloromethylated polystyrene molecular brush silicon ball Sub- microscope figure；
Fig. 2 is the SEM of nuclear shell type nano meter particle/polysulfones hybridized film of different loadings in each embodiment Figure；
Fig. 3 is each embodiment hydroxide ion conductivity profile.
Embodiment
It is that synthesis is divided by chloromethylated polystyrene first in a kind of preparation method of alkaline anion-exchange membrane of the present invention Then the nm-class core-and-shell particles are 20-70% according to mass fraction by the nm-class core-and-shell particles that son brush and silicon ball are constituted Filling is into the conductive polysulfones membrane matrix of nonionic, and alkaline anion-exchange membrane is made by quaternized, alkalization in composite membrane.
Technical solution of the present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, described is specific Only the present invention is explained for embodiment, is not intended to limit the invention.
Embodiment 1：A kind of preparation of alkaline anion-exchange membrane, step is as follows：
Step 1: mixing and being stirred vigorously 150mL ethanol, 15mL water and 3mL ammoniacal liquor, the positive silicon of 4.5mL is added afterwards Acetoacetic ester, 24h is stirred under 30 DEG C of water-baths, obtains the suspension of Nano particles of silicon dioxide, is subsequently added 1mL3- metering systems Sour propyl trimethoxy silicane (MPS) stirring reaction 24h obtains suspension, centrifuges the silicon ball that above-mentioned suspension obtains MPS modifications Nano particle (SiO2- MPS), as shown in fig. 1A, the SiO2The active double bond of-MPS surface graftings；By consolidating that centrifugation is obtained Body (the i.e. SiO of the active double bond of surface grafting2- MPS) with water and ethanol respectively washing three times, place and 24h is dried in 60 DEG C of baking ovens, It is standby.
Step 2: taking SiO made from 0.5g steps one2- MPS is scattered in 200mL toluene, ultrasonic disperse 1h.Afterwards plus Enter 0.8mL methacrylic acids, 0.5mL p-chloromethyl styrenes, 0.3mL divinylbenzenes, 0.032g azodiisobutyronitriles, ultrasound It is transferred to after 30min in distilling apparatus, flow back 70min.Contain on the silicon ball i.e. top layer that product centrifugation is obtained into chloromethylation modification Nano particle (the SiO of active chloromethyl2- CM), as shown in fig. ib, centrifuge obtained SiO2- CM is respectively washed with water, ethanol Three times, place and 24h is dried in 60 DEG C of vacuum drying ovens, it is standby.
Step 3: taking SiO made from 1.0g step 22- CM, 5.85mL toluene, 0.2mg pentamethyl-diethylenetriamines and 5.85mL styrene, is added in reaction eggplant bottle, is passed through nitrogen degassing 30min.5.85mg CuCl is added afterwards, in 110 DEG C of oil 1h is heated in bath, by the silicon ball (SiO of obtained grafted polystyrene molecular brush2- PSt) wash three with tetrahydrofuran and ethanol It is secondary, place and 48h is dried in 60 DEG C of baking ovens.
Step 4: taking SiO made from 1.0g step 32- PSt is scattered in 40mL chloroforms, 0.73g is added afterwards anhydrous ZnCl2, 25mL chloromethyl methyl ethers, the heating stirring 48h in 60 DEG C of water-baths.Centrifugation obtains the polystyrene molecular brush of chloromethylation Silicon ball (SiO2- CMPSt), shown in the c in Fig. 1, washed with water, ethanol three times, place and 24h is dried in 60 DEG C of vacuum drying ovens, it is standby With.
Step 5: weighing SiO made from 0.06g step 42- CMPSt ultrasonic disperses are in 4ml N,N-dimethylformamides (DMF) in, 0.24g polysulfones macromolecule (PSU) is dissolved in afterwards and obtains casting solution.It is poured on 5*5cm glass plates and is cast, is put into 12h film forming is dried in 60 DEG C of baking ovens.Gained film soaks mass fraction at 30 DEG C and is 30% trimethylamine aqueous solution 48 hours with season Ammonium.Quaternized film room temperature is immersed into 48h in 1MNaOH solution afterwards and carries out ion exchange, and is washed till repeatedly with deionized water Property.Nanometer in the anion-exchange membrane being embedded in nuclear shell structure nano ionic conduction particle, the present embodiment is obtained after drying Grain loading is 20%wt, is designated as PSU/SiO2- QPSt-20, as shown in a in Fig. 2.
Embodiment 2：A kind of preparation of alkaline anion-exchange membrane, step is as follows：
Step 1: mixing and being stirred vigorously 200mL ethanol, 20mL water and 4mL ammoniacal liquor, the positive silicic acid of 6mL is added afterwards Ethyl ester, 24h is stirred under 30 DEG C of water-baths.The suspension of Nano particles of silicon dioxide is obtained, the MPS stirrings for being subsequently added 1mL are anti- Answer 24h to obtain suspension, centrifuge above-mentioned suspension and obtain SiO2- MPS, centrifuges the respectively washing three of obtained solid water and ethanol It is secondary, place and 24h is dried in 60 DEG C of baking ovens.
Step 2: be the same as Example step 2, prepares the silicon ball (SiO of chloromethylation modification2-CM)。
Step 3: taking SiO made from 1.0g step 22- CM, 0.2mg pentamethyl-diethylenetriamine, 5.85mL styrene and 5.85mL toluene, is added in reaction eggplant bottle, is passed through nitrogen degassing 30min.5.85mg CuCl is added afterwards, in 110 DEG C of oil baths Middle heating 1h, by obtained SiO2- PSt is washed three times with tetrahydrofuran and ethanol, places and 48h is dried in 60 DEG C of baking ovens.
Step 4: taking SiO made from 1.0g step 32- PSt is scattered in 30mL tetrachloroethanes, 0.66g is added afterwards anhydrous ZnCl2, 30mL chloromethyl methyl ethers, the heating stirring 48h in 60 DEG C of water-baths.Centrifugation obtains SiO2Shown in c in-CMPSt, Fig. 1, Washed with water, ethanol three times, place and 24h is dried in 60 DEG C of vacuum drying ovens, it is standby.
In 4ml DMF, dissolved in afterwards Step 5: weighing SiO2-CMPSt ultrasonic disperses made from 0.09g step 4 0.21g polysulfones macromolecule (PSU) obtains casting solution.It is poured on 5*5cm glass plates and is cast, is put into 60 DEG C of baking ovens and dries 12h film forming.Gained film soaks mass fraction at 30 DEG C and is 30% trimethylamine aqueous solution 48 hours with quaternized.Afterwards by quaternary ammonium Change 48h in film room temperature immersion 1M NaOH solutions and carry out ion exchange, and neutrality is washed till repeatedly with deionized water.Obtained after drying The anion-exchange membrane being embedded in nuclear shell structure nano ionic conduction particle, nano particle loading is 30%wt, is designated as PSU/SiO2- QPSt-30, as shown in the b in Fig. 2.
Embodiment 3：A kind of preparation of alkaline anion-exchange membrane, step is as follows：
Step 1: mixing and being stirred vigorously 200mL ethanol, 20mL water and 4mL ammoniacal liquor, the positive silicic acid of 6mL is added afterwards Ethyl ester, 24h is stirred under 30 DEG C of water-baths.It is subsequently added 1mL MPS stirring reactions 24h.Centrifuge above-mentioned suspension and obtain SiO2- MPS.Respectively washing three times of obtained solid water and ethanol are centrifuged, places and 24h is dried in 60 DEG C of baking ovens.
Step 2: by SiO made from step one2- MPS nano particles take 0.5g to be scattered in 150mL acetonitriles, ultrasonic disperse 1h.0.6mL methacrylic acids, 0.4mL p-chloromethyl styrenes, 0.25mL divinylbenzenes, 0.022g azos two are added afterwards It is transferred to after isobutyronitrile, ultrasonic 30min in distilling apparatus, flow back 70min.Product centrifugation is obtained into SiO2-CM.What centrifugation was obtained Solid is respectively washed three times with water, ethanol, places and 24h is dried in 60 DEG C of vacuum drying ovens.
Step 3: taking SiO made from 1.0g step 22- CM, 0.2mg pentamethyl-diethylenetriamine, 5.85mL styrene and 5.85mL toluene, is added in reaction eggplant bottle, is passed through nitrogen degassing 30min.5.85mgCuCl is added afterwards, in 110 DEG C of oil baths 1h is heated, by obtained SiO2- PSt is washed three times with tetrahydrofuran and ethanol, places and 48h is dried in 60 DEG C of baking ovens.
Step 4: taking SiO made from 1.0g step 32- PSt is scattered in 30mL tetrachloroethanes, 0.66g is added afterwards anhydrous ZnCl2, 30mL chloromethyl methyl ethers, the heating stirring 48h in 60 DEG C of water-baths.Centrifugation obtains SiO2- CMPSt, is washed with water, ethanol Three times, place and 24h is dried in 60 DEG C of vacuum drying ovens.
Step 5: weighing SiO made from 0.12g step 42- CMPSt ultrasonic disperses dissolve in afterwards in 5ml DMF 0.18g polysulfones macromolecule (PSU) obtains casting solution.It is poured on 5*5cm glass plates and is cast, is put into 60 DEG C of baking ovens and dries 12h film forming.Gained film soaks mass fraction at 30 DEG C and is 30% trimethylamine aqueous solution 48 hours with quaternized.Afterwards by quaternary ammonium Change 48h in film room temperature immersion 1MNaOH solution and carry out ion exchange, and neutrality is washed till repeatedly with deionized water.Had after drying There is the anion-exchange membrane that nuclear shell structure nano ionic conduction particle is embedded in, nano particle loading is 40%wt, is designated as PSU/ SiO2- QPSt-40, as shown in the c in Fig. 2.
Embodiment 4：A kind of preparation of alkaline anion-exchange membrane, step is as follows：
Step 1: mixing and being stirred vigorously 150mL ethanol, 15mL water and 3mL ammoniacal liquor, the positive silicon of 4.5mL is added afterwards Acetoacetic ester, 24h is stirred under 30 DEG C of water-baths.It is subsequently added 1mLMPS, stirring reaction 24h.Centrifuge above-mentioned suspension and obtain SiO2- MPS.Respectively washing three times of obtained solid water and ethanol are centrifuged, places and 24h is dried in 60 DEG C of baking ovens.
Step 2: by SiO made from step one2- MPS nano particles take 0.5g to be scattered in 200mL dichloroethanes, ultrasound Scattered 1h.0.8mL methacrylic acids, 0.5mL p-chloromethyl styrenes, 0.3mL divinylbenzenes, 0.032g azos are added afterwards It is transferred to after bis-isobutyronitrile, ultrasonic 30min in distilling apparatus, flow back 90min.Product centrifugation is obtained into SiO2-CM.Centrifugation is obtained Solid respectively washed with water, ethanol three times, place 60 DEG C of vacuum drying ovens in dry 24h.
Step 3: taking SiO made from 1.0g step 22- CM, 0.15mg pentamethyl-diethylenetriamine, 4.39mL styrene With 4.39mL toluene, add in reaction eggplant bottle, be passed through nitrogen degassing 30min.4.39mgCuCl is added afterwards, in 105 DEG C of oil baths Middle heating 1h, by obtained SiO2- PSt is washed three times with tetrahydrofuran and ethanol, places and 48h is dried in 60 DEG C of baking ovens.
Step 4: taking SiO made from 1.0g step 32- PSt is scattered in 30mL tetrachloroethanes, 0.66g is added afterwards anhydrous ZnCl2, 30mL chloromethyl methyl ethers, the heating stirring 48h in 60 DEG C of water-baths.Centrifugation obtains SiO2- CMPSt, is washed with water, ethanol Three times, place and 24h is dried in 60 DEG C of vacuum drying ovens.
Step 5: weighing SiO made from 0.15g step 42- CMPSt ultrasonic disperses dissolve in afterwards in 5mlDMF 0.15g polysulfones macromolecule (PSU) obtains casting solution.It is poured on 5*5cm glass plates and is cast, is put into 60 DEG C of baking ovens and dries 12h film forming.Gained film soaks mass fraction at 30 DEG C and is 30% trimethylamine aqueous solution 48 hours with quaternized.Afterwards by quaternary ammonium Change 48h in film room temperature immersion 1MNaOH solution and carry out ion exchange, and neutrality is washed till repeatedly with deionized water.Had after drying There is the anion-exchange membrane that nuclear shell structure nano ionic conduction particle is embedded in, nano particle loading is 50%wt, is designated as PSU/ SiO2- QPSt-50, as shown in the d in Fig. 2.
Embodiment 5：A kind of preparation of alkaline anion-exchange membrane, step is as follows：
Step 1: mixing and being stirred vigorously 200mL ethanol, 20mL water and 4mL ammoniacal liquor, the positive silicic acid of 6mL is added afterwards Ethyl ester, 24h is stirred under 30 DEG C of water-baths.It is subsequently added 1mL MPS, stirring reaction 24h.Centrifuge above-mentioned suspension and obtain SiO2- MPS.Respectively washing three times of obtained solid water and ethanol are centrifuged, places and 24h is dried in 60 DEG C of baking ovens.
Step 2: by SiO made from step one2- MPS nano particles take 0.5g to be scattered in 150mL acetonitriles, ultrasonic disperse 1h.0.6mL methacrylic acids, 0.4mL p-chloromethyl styrenes, 0.25mL divinylbenzenes, 0.022g azos two are added afterwards It is transferred to after isobutyronitrile, ultrasonic 30min in distilling apparatus, flow back 70min.Product centrifugation is obtained into SiO2-CM.What centrifugation was obtained Solid is respectively washed three times with water, ethanol, places and 24h is dried in 60 DEG C of vacuum drying ovens.
Step 3: taking SiO made from 1.0g step 22- CM, 0.2mg pentamethyl-diethylenetriamine, 5.85mL styrene and 5.85mL toluene, is added in reaction eggplant bottle, is passed through nitrogen degassing 30min.5.85mgCuCl is added afterwards, in 110 DEG C of oil baths 1h is heated, by obtained SiO2- PSt is washed three times with tetrahydrofuran and ethanol, places and 48h is dried in 60 DEG C of baking ovens.
Step 4: taking SiO made from 1.0g step 32- PSt is scattered in 40mL acetone, 0.66g is added afterwards anhydrous ZnCl2, 30mL chloromethyl methyl ethers, the heating stirring 48h in 60 DEG C of water-baths.Centrifugation obtains SiO2- CMPSt, is washed with water, ethanol Three times, place and 24h is dried in 60 DEG C of vacuum drying ovens.
Step 5: weighing SiO made from 0.18g step 42- CMPSt ultrasonic disperses dissolve in afterwards in 6mlDMF 0.12g polysulfones macromolecule (PSU) obtains casting solution.It is poured on 5*5cm glass plates and is cast, is put into 60 DEG C of baking ovens and dries 24h film forming.Gained film soaks mass fraction at 30 DEG C and is 30% trimethylamine aqueous solution 48 hours with quaternized.Afterwards by quaternary ammonium Change 48h in film room temperature immersion 1MNaOH solution and carry out ion exchange, and neutrality is washed till repeatedly with deionized water.Had after drying There is the anion-exchange membrane that nuclear shell structure nano ionic conduction particle is embedded in, nano particle loading is 60%wt, is designated as PSU/ SiO2- QPSt-60, as shown in the e in Fig. 2.
Embodiment 6：A kind of preparation of alkaline anion-exchange membrane, step is as follows：
Difference with embodiment 5 is only：The SiO added in step 52- CMPSt is 0.21g, and polysulfones macromolecule is 0.09g, remaining condition is constant, and the film finally prepared is designated as PSU/SiO2- QPSt-70, as shown in the f in Fig. 2.
The property indices of film are as shown in Fig. 3, Tables 1 and 2 made from the various embodiments described above of the present invention.
The ionic conduction performance and water absorption and swelling performance of the quaternized molecular brush silicon ball/polysulfones hybridized film of table 1
Ionic conductance in table 1 is the measured value of hydroxide ion at 30 DEG C.
The mechanical performance of the quaternized molecular brush silicon ball/polysulfones hybridized film of table 2
To sum up, it is to synthesize the core being made up of chloromethylated polystyrene molecular brush and silicon ball first in preparation method of the present invention Then the nm-class core-and-shell particles are that 20-70% is filled to nonionic conductibility according to mass fraction by core-shell type nanometer particle Polysulfones membrane matrix in, composite membrane by it is quaternized, alkalization be made alkaline anion-exchange membrane.
Invention has been described with accompanying drawing by above-mentioned in conjunction with the embodiments, but specific implementation case is only portion above Divide experiment, be not the practical range for limiting the present invention.The person skilled of this area is according to the present invention or does not depart from In the case of present inventive concept, the equivalent deformation and relevant modifications carried out, these are all within the protection of the present invention.

Claims (5)

1. a kind of preparation method of alkaline anion-exchange membrane, it is characterised in that first, synthesis is by chloromethylated polystyrene point Then the nm-class core-and-shell particles are filled conductive poly- to nonionic by the nm-class core-and-shell particles that son brush and silicon ball are constituted In sulfone membrane matrix, wherein, the mass fraction of nm-class core-and-shell particles is 20-70%, and alkali is made by quaternized, alkalization in composite membrane Property anion-exchange membrane.
2. the preparation method of alkaline anion-exchange membrane according to claim 1, it is characterised in that step is as follows：
Step 1: being 50 by volume ratio:5:1 ethanol, water and ammoniacal liquor is well mixed, adds tetraethyl orthosilicate, tetraethyl orthosilicate Volume ratio with ammoniacal liquor is 1.5:1,24h is stirred vigorously, the suspension of Nano particles of silicon dioxide is obtained, is subsequently added methyl-prop Olefin(e) acid propyl trimethoxy silicane stirs 24h, and the silicon ball nano particle of the active double bond of surface grafting is obtained after centrifugation；
Step 2: silicon ball nano particle made from step one is scattered in solvent orange 2 A, wherein, silicon ball nano particle and solvent orange 2 A Mass-volume concentration is 2~4g/L, then, adds methacrylic acid, p-chloromethyl styrene, divinylbenzene, azo two different Butyronitrile, wherein, solvent orange 2 A and methacrylic acid, p-chloromethyl styrene, the volume ratio of divinylbenzene is 100:0.4~0.9: 0.2~0.4:0.1~0.3, the mass-volume concentration of azodiisobutyronitrile and solvent orange 2 A is 0.14~0.16g/L；Backflow 60~ 90min, obtains the nano particle that active chloromethyl is contained on top layer；
Step 3: nano particle made from step 2 is scattered in toluene, the mass-volume concentration of nano particle and toluene is 0.15~0.25g/mL, then, adds styrene, pentamethyl-diethylenetriamine, stannous chloride, wherein, styrene and toluene Volume ratio is 1:1, the mass-volume concentration of stannous chloride and toluene is 0.25~0.5g/L, pentamethyl-diethylenetriamine and chlorination Cuprous mass ratio is 1:13~30,80~120 DEG C of 1~3h of heating response, are washed with tetrahydrofuran under nitrogen protection, are obtained It has been grafted the nm-class core-and-shell particles A of polystyrene molecular brush；
Step 4: nm-class core-and-shell particles A made from step 3 is scattered in solvent B, nm-class core-and-shell particles A and solvent B Mass-volume concentration be 0.025~0.035g/mL, add anhydrous zinc chloride and chloromethyl methyl ether, anhydrous zinc chloride and solvent B Mass-volume concentration be 15~22mg/mL, chloromethyl methyl ether and solvent B volume ratio are 0.625~1:1, reaction temperature is 40~70 DEG C, the reaction time is 24~48h, obtains hud typed being received by what the polystyrene molecular brush and silicon ball of chloromethylation were constituted Rice grain B；
Step 5: nm-class core-and-shell particles B made from step 4 is scattered in DMF, core-shell type nano The mass-volume concentration of grain B and DMF is 15~35g/L, and polysulfones macromolecule is dissolved afterwards and obtains casting solution, Polysulfones and nm-class core-and-shell particles B mass ratio are 0.43~4, and using 60 DEG C of drying 12~24h film forming of stream method are prolonged, gained film exists It is 30% trimethylamine aqueous solution 48h with quaternized that mass fraction is soaked at 30 DEG C, and quaternized film is immersed into sodium hydroxide solution Middle 48h is alkalized, and is washed with deionized water to neutrality, obtains the ionic conductivity core-shell type nano that loading is 20%~70% The alkaline anion-exchange membrane of particle B insertions.
3. the preparation method of alkaline anionic membrane according to claim 2, it is characterised in that in step one, the positive silicic acid The volume ratio of ethyl ester and methacrylic acid propyl trimethoxy silicane is 100:15~20.
4. the preparation method of alkaline anionic membrane according to claim 2, it is characterised in that in step 2, the solvent orange 2 A choosing From any one in dichloroethanes, acetonitrile, toluene.
5. the preparation method of alkaline anionic membrane according to claim 2, it is characterised in that in step 4, the solvent B choosings From at least one of chloroform, dichloromethane, tetrachloroethanes, acetone.
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CN109585888A (en) * 2018-11-07 2019-04-05 大连理工大学 A kind of blending type anion-exchange membrane and preparation method thereof
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