CN108043254A - A kind of preparation method of cross-linking type anion-selective membrane - Google Patents
A kind of preparation method of cross-linking type anion-selective membrane Download PDFInfo
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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Abstract
The present invention relates to a kind of preparation method of cross-linking type anion-selective membrane, step is：By bromomethylation poly- 2,6 dimethyl 1,4 phenylates are dissolved in organic solvent, then the unsaturated tertiary amine and part bromomethyl for adding in molecular structure carbon-carbon double bonds carry out the 1st step aminating reaction, it then adds saturation tertiary amine and carries out the 2nd step aminating reaction with remaining bromomethyl, reaction solution is obtained after the completion of reaction；Oil-soluble initiator is dissolved in reaction solution, film liquid is made；By film liquid coated on base material, basement membrane is obtained after heating, drying, basement membrane is inserted in the aqueous solution dissolved with water soluble, redox initiator and is fully impregnated, takes out and washes with water after immersion, just obtains cross-linking type anion-selective membrane.Anion-selective membrane prepared by this method has the advantages that production cost is relatively low, the degree of cross linking can be adjusted on demand, and cross-linked structure is hydrophobic, film machinery and thermal stability height, suitable for electrodialysis and diffusion dialysis application process.
Description
Technical field
The present invention relates to a kind of preparation methods of anion-selective membrane, and in particular to and it is a kind of with macromolecule engineering plastics 2,
6- dimethyl -1,4- phenylates（Referred to as polyphenylene oxide, English polyphenylene ether）Contain covalent cross-linking knot for base material
The anion-selective membrane of structure, the film are suitable for diffusion dialysis and electrodialytic process.
Background technology
Ion selective membrane can be divided into anion-selective membrane（Referred to as cavity block）With cation selective film（Anode membrane）；It is cloudy
The macromolecular scaffold of film is positively charged, can select to penetrate anion；The macromolecular scaffold of anode membrane is negatively charged, can select
Cross cation.Based on ion selective membrane to the selective penetrated property of ion, ion selective membrane can realize salinity using process
Removing and concentration, acid and the separation of salt and the separation of alkali and salt, have in the industries such as chemical industry, environmental protection, metallurgy extensive
Using.
Electrodialytic process using ion selective membrane as core is driven by potential gradient, the salinity available for removing aqueous solution
（Desalination）Or the salinity of concentrated aqueous solution（Salt manufacturing）, specifically applying is included in various chemical industry/food/medicine productions
Material desalination, brackish water desalination, natural water purifying, industrial waste water purifying, sea water desalination, seawater or bittern salt manufacturing etc..
Diffusion dialysis process is driven by concentration gradient, including cavity block diffusion dialysis process and anode membrane diffusion dialysis process.It is cloudy
Membrane diffusion dialysis process realizes the preferential permeability of acid using cavity block the separation of acid and salt, so as to fulfill sour recycling reuse；
Anode membrane diffusion dialysis process realizes the preferential permeability of alkali using anode membrane the separation of alkali and salt, is returned so as to fulfill alkali recycling
With.
Ion selective membrane can be prepared by distinct methods.Ion selective membrane can polymerize to prepare by organic monomer.
Document number is that the Japanese document of S39-27861 describes the ion selectivity that a kind of coating method produces styrene-based monomer
Polyvinyl chloride powder is added to by styrene, divinylbenzene by the method for film, this method first（Crosslinking agent）, phthalic acid two it is pungent
Fat（Plasticizer）And dibenzoyl peroxide（Initiator）Slurries are made in the monomer mixture of composition；The slurries pass through special
Film synthesis device is applied on polyvinyl chloride screen cloth, is placed in closed reactor and is carried out polymerisation acquisition basement membrane；By basement membrane
Anion-selective membrane is made in chloromethylation and amination, and basement membrane sulfonation is made cation selective film.Ion selective membrane
It can be prepared by polymers function base.Periodical《Journal of Membrane Science》Volume 22 page 325
Research paper describes one kind in polysulfones（polyethersulfone）Macromolecular chain introduces functional group and prepares cation selective
Property film method, this method first prepares polysulfones solution, then adds in chlorosulfonic acid and carries out sulfonating reaction, solution coated on screen cloth,
Cation selective film is obtained after drying.Periodical《International Journal of Hydrogen Energy》42nd
It rolls up the research paper of page 17229 and describes and a kind of introduce functional group in polysulfones macromolecular chain and prepare anion-selective membrane
Method, this method first prepare polysulfones solution, then carry out chloromethylation and aminating reaction, and solution is done coated on screen cloth
Anion-selective membrane is obtained after dry.
Similar with polysulfones, the functionalizing of polyphenylene oxide strand can equally prepare ion selective membrane.Periodical
《Journal of Membrane Science》In the research paper of page 159 of volume 190, polyphenylene oxide is dissolved in chlorobenzene, adds in bromine
Element occurs bromination reaction and obtains brominated polyphenylether, and bromination is prone on the methyl of macromolecular chain when reaction temperature is higher,
And temperature it is relatively low when be prone on the phenyl ring of macromolecular chain；Addition methanol extraction goes out brominated polyphenylether and consolidates in the solution
Body, solid are dissolved in after organic solvent coated on screen cloth, it is dry after basement membrane；Basement membrane, which is soaked into trimethylamine solution, to be occurred
Anion-selective membrane is obtained after aminating reaction；Basement membrane is soaked into generation aminating reaction in trimethylamine and ethylenediamine mixed solution and obtains
To cross-linking type anion-selective membrane, which realized by the reaction of ethylenediamine and bromomethyl.
In addition to trimethylamine, imidazoles heterocyclic compound containing N also can be as the aminating agent of brominated polyphenylether.Publication No.
Addition N- methylimidazoles, N- ethyl imidazol(e)s etc. in brominated polyphenylene ethereal solution is described in the Chinese patent of CN103372381B to take
For imidazoles, imidazole radicals is reacted with bromomethyl, and subsequent coating materials obtains anion-selective membrane coated on screen cloth after dry, should
Film thermal stability and alkali resistance are good, suitable for fuel cell field.Periodical《Journal of Membrane Science》The
Volume 443 page 193 of research paper uses aminating agent of the N- tolimidazoles as brominated polyphenylether, brominated polyphenylene ethereal solution
Coating materials after being reacted with N- tolimidazoles obtains anion-selective membrane, which possesses coated on screen cloth after dry
Preferable thermal stability and mechanical strength, suitable for fuel cell field.Periodical《Journal of Chemical Industry and Engineering》Volume 64 page 203 then uses
Aminating agent of the N- butylimidazoliums as brominated polyphenylether, obtained anion-selective membrane are led suitable for all-vanadium flow battery
Domain.
To make to possess cross-linked structure from the anion-selective membrane that brominated polyphenylether is formed, except using previous molecular structure
Ethylenediamine containing 2 amidos as aminating agent outside, periodical《Journal of Membrane Science》Volume 425 page 131
Research paper uses 1,4- diazabicylos [2.2.2] octane（Abbreviation DABCO）As aminating agent, DABCO molecular structures contain 2
Cross-linked structure anion-selective membrane is obtained by the reaction in amido, 2 amidos with bromomethyl respectively.Publication No. CN103304830B's
Chinese patent then forms cross-linked structure using the method for forming half interpenetrating network structure membrane material, in brominated polyphenylene ethereal solution
It is passed through front three amine gas and carries out aminating reaction, 1-chloro-4-methyl-benzene monomer, divinylbenzene crosslink agent and freedom are added in reaction solution
Base reacts thermal initiator, and after polymerisation occurs for heating, 1-chloro-4-methyl-benzene forms cross-linked structure strand with divinylbenzene,
Film liquid obtains cross-linked structure anion-selective membrane coated on screen cloth after drying.Periodical《Journal of Membrane
Science》Brominated polyphenylether is then dissolved in and is formed by styrene and 1-chloro-4-methyl-benzene by the research paper of page 115 of volume 515
In the mixed solvent, add N- methylimidazoles and N- vinyl imidazoles, after aminating reaction, then film liquid applied, dries film forming,
Heat polymerization occurs for drying course medium vinyl, obtains cross-linked structure anion-selective membrane.Periodical《Separation and
Purification Technology》The research paper of page 226 of volume 156 is added in brominated polyphenylene ethereal solution by dimethylamine
The dimethylvinylsiloxy benzyl amine to be formed is reacted with 1-chloro-4-methyl-benzene, then film liquid is applied, dries film forming, ethylene in drying course
Heat polymerization occurs for base, obtains cross-linked structure anion-selective membrane.
The friendship based on brominated polyphenylether formed by aminating agents such as ethylenediamine of the molecular structure containing 2 amidos or DABCO
Connection type anion-selective membrane, these aminating agents also serve as crosslinking agent simultaneously, and crosslink unit is hydrophilic quaternary ammonium group, is not deposited in film
In hydrophobic molecular chain structure, the mechanical stability and thermal stability of film are affected.By being blended in brominated polyphenylene ethereal solution
Simultaneously the anion-selective membrane that polymerisation and cross-linking reaction are formed occurs in film forming procedure for 1-chloro-4-methyl-benzene monomer, prepares
Process is complicated, employs the monomers such as expensive N- vinyl imidazoles or 1-chloro-4-methyl-benzene, and heating process can not make ethylene
It is relatively low that fully polymerization, the degree of cross linking occur for base.
The content of the invention
The present invention provides a kind of anion containing covalently cross-linked structure using macromolecule engineering plastics polyphenylene oxide as base material and selects
The preparation method of selecting property film to overcome the drawbacks described above of the prior art, possesses the cross-linking type anion-selective membrane hydrophobic
Molecular chain structure, and production cost is relatively low, the degree of cross linking can be adjusted on demand.The film is suitable for diffusion dialysis and electrodialytic process.
Purpose to realize the present invention, the preparation method of cross-linking type anion-selective membrane provided by the present invention, including
Following steps：Poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation is dissolved in organic solvent, it is carbon containing then to add in molecular structure
The unsaturated tertiary amine of carbon double bond carries out the 1st step amination with the part bromomethyl in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation
Reaction then adds saturation tertiary amine and carries out the 2nd step with remaining bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation
Aminating reaction obtains reaction solution after the completion of reaction；Oil-soluble initiator is dissolved in reaction solution, film liquid is made；Film liquid is applied
On base material, basement membrane is obtained after heating, drying, basement membrane is inserted in the aqueous solution dissolved with water soluble oxidized-reduction initiator fully
It impregnates, takes out and wash with water after immersion, just obtain cross-linking type anion-selective membrane.
The organic solvent is N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or two
Methyl sulfoxide.
The unsaturated tertiary amine of the carbon-carbon double bonds be N, N- dimethylallylamine, N, N- Diethyl Allylnimes,
Methacrylic N, N-dimethylamino ethyl ester, methacrylic acid N, N- diethylamino ethyl ester, acrylic acid N, N- dimethylamino
Base ethyl ester, acrylic acid N, N- diethylamino ethyl ester or N- vinyl imidazoles；The molal quantity of unsaturated tertiary amine gathers for bromomethylation
The 10%-60% of bromomethyl molal quantity in 2,6- dimethyl -1,4- phenylates.
The saturation tertiary amine is trimethylamine, triethylamine, N, N- dimethyl amines, N, N- diethyl methyl amines or N- methyl miaows
Azoles；The molal quantity of saturation tertiary amine is at least 40% of the bromomethyl molal quantity in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation.
The oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, peroxidating ten
Two acyls, the peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate or di-cyclohexylperoxy di-carbonate；Oil-soluble triggers
The molal quantity of agent is the 0.1%-10% of unsaturated tertiary amine molal quantity.
The water soluble oxidized-reduction initiator is made of Oxidizing and Reducing Agents；The oxidant for hydrogen peroxide,
Sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate；The reducing agent be sulphite, bisulfites or thiosulfate, it is above-mentioned
The cation of salt can be sodium ion, potassium ion or ammonium ion；The molar ratio of oxidant and reducing agent is 0.5-2:1, it is water-soluble
The concentration of oxidation-reduction initiator aqueous solution is 0.5%-10%.
The heating, drying temperature is 50 DEG C -140 DEG C.
When soaking time of the basement membrane in water soluble oxidized-reduction initiator solution is 2-24 small.
The methyl bromide degree of the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation is 30%-80%.
The preparation method of the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation is：By poly- 2,6- dimethyl -1,4- phenylates
It is dissolved in chlorobenzene, adds in bromine simple substance or N- bromo-succinimides in the solution, it is small to be warming up to 100-160 DEG C of reaction at least 4
When, polymeric solid is isolated after reaction obtains poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation.
The base material is woven cloths or non-woven cloth, such as terylene mesh, polypropylene fibre screen cloth, nylon net cloth, virtue can be used
Synthetic fibre screen cloth etc..
The 1st step aminating reaction of the present invention uses the unsaturated tertiary amine of carbon-carbon double bonds, and amido is reacted with part bromomethyl
Afterwards, introduce carbon-carbon double bond on polyphenylene oxide macromolecular chain, remaining unreacted bromomethyl in the 2nd step aminating reaction with saturation
Reactive tertiary amine generates quaternary ammonium group.Heating, drying is formed during basement membrane, and oil-soluble initiator has triggered carbon-carbon double bond polymerization anti-
Should, so as to form cross-linked structure；Not fully, remainder carbon-carbon double bond is in basement membrane for carbon-carbon double bond polymerisation in the step
It polymerize when being soaked into water soluble oxidized-reduction initiator solution, so as to obtain cross-linked structure anion-selective membrane.
The two step aminating reactions of the present invention have difference in functionality, and the 1st step aminating reaction can shape in the introducing of polyphenylene oxide macromolecular chain
Into the carbon-carbon double bond of cross-linked structure, the 2nd step aminating reaction then introduces quaternary ammonium ion cation exchange groups in macromolecular chain, by adjusting this
The degree of cross linking of film is adjusted in the aminating agent ratio of two step aminating reactions.The molal quantity of the unsaturated tertiary amine of carbon-carbon double bonds far fewer than
Bromomethyl, amido are fully reacted, and correspondingly carbon-carbon double bond is introduced in each polyphenylene oxide strand, the saturation uncle then added in
Amine is reacted with remaining bromomethyl；This precedence so that each polyphenylene oxide strand is full cross-linked, ensure that ion selective membrane
Cross-linked structure controllability.The hydrophobic molecule chain formed after carbon-carbon double bond polymerization ensure that mechanical stability and the thermostabilization of film
Property；Economic tertiary amine ensure that relatively low film production cost.
The cross-linking type anion-selective membrane of the present invention has the advantages that production cost is relatively low, the degree of cross linking can be adjusted on demand,
Cross-linked structure is hydrophobic, and film machinery and thermal stability are high, suitable for electrodialysis and diffusion dialysis application process.
Specific embodiment
Technical solution is further illustrated the present invention below by embodiment, these embodiments are intended merely to show this hair in detail
Bright technical concept and its exploitativeness, is not limiting the scope of the invention, is made using the technology of the present invention design
Equivalence replacement and it is flexible still within protection scope of the present invention.
Embodiment 1
110 g chlorobenzenes are added in three-neck flask, are heated to 50 DEG C, add in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylates of 20 g, stirring；It treats
After poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate is completely dissolved, add in 26.7 g bromine simple substance, be warming up to 145 DEG C reaction 8 it is small when；Solution exists
Chlorobenzene is evaporated in vacuo out at 110 DEG C, remaining dope is dried at 80 DEG C, obtains poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation.
Poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate solid of bromomethylation is dissolved in deuterochloroform, by spectral analysis of the nuclear magnetic resonance,
The phenyl ring bromination degree of poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation is 38%, and methyl bromide degree is 56%.
Embodiment 2
110 g chlorobenzenes are added in three-neck flask, are heated to 50 DEG C, add in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylates of 20 g, stirring；It treats
After poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate is completely dissolved, 44 g N- bromo-succinimides are added in；110 DEG C are warming up to, adds in 1 g
Azodiisobutyronitrile；Then be warming up to 145 DEG C reaction 8 it is small when；Feed liquid is poured into ethanol solution, and the solid of precipitation is bromomethyl
Change poly- 2,6- dimethyl -1,4- phenylates；Solid is in 80 DEG C of drying.
Poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation is dissolved in deuterochloroform, passes through spectral analysis of the nuclear magnetic resonance, bromine first
The phenyl ring bromination degree of poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of baseization is 55%, and methyl bromide degree is 52%.
Embodiment 3
110 g chlorobenzenes are added in three-neck flask, are heated to 50 DEG C, add in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylates of 20 g, stirring；It treats
After poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate is completely dissolved, 33g N- bromo-succinimides are added in；110 DEG C are warming up to, adds in 1 g
Azodiisobutyronitrile；Then be warming up to 145 DEG C reaction 8 it is small when；Feed liquid is poured into ethanol solution, and precipitation solid is bromomethylation
Poly- 2,6- dimethyl -1,4- phenylates；Solid is in 80 DEG C of drying.
Poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate solid of bromomethylation is dissolved in deuterochloroform, by spectral analysis of the nuclear magnetic resonance,
The phenyl ring bromination degree of poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation is 35%, and methyl bromide degree is 32%.
Embodiment 4
110 g chlorobenzenes are added in three-neck flask, are heated to 50 DEG C, add in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylates of 20 g, stirring；It treats
After poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate is completely dissolved, 52g N- bromo-succinimides are added in；110 DEG C are warming up to, adds in 1 g
Azodiisobutyronitrile；Then be warming up to 145 DEG C reaction 8 it is small when；Feed liquid is poured into ethanol solution, and the solid of precipitation is bromomethyl
Change poly- 2,6- dimethyl -1,4- phenylates；Solid is in 80 DEG C of drying.
Poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate solid of bromomethylation is dissolved in deuterochloroform, by spectral analysis of the nuclear magnetic resonance,
The phenyl ring bromination degree of poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation is 73%, and methyl bromide degree is 76%.
Above-described embodiment only gives the situation that methyl bromide degree is 32%, 52%, 56% and 76%, is not to illustrate the present invention
The preparation method of the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation of offer can only prepare the bromine of above-mentioned four kinds of methyl bromide degree
Methylate poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate, those skilled in the art's introduction according to the present invention, by adjusting raw material proportioning and
Technological parameter can produce the poly- 2,6- diformazans of bromomethylation of arbitrary bromination angle value of the methyl bromide degree in the range of 30-80%
Base-Isosorbide-5-Nitrae-phenylate, in order to save length, then this no longer illustrates and repeats one by one.
Embodiment 5
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
In dimethylformamide, 0.8 g N, N- dimethylallylamine is then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, so that N, N- bis-
Methacrylic amine carries out aminating reaction, reaction knot with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation
34.2 g trimethylamine aqueous solutions are added dropwise in beam again（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine gathers with bromomethylation
Remaining bromomethyl in 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is obtained after the completion of reaction；By 1 g azos
Bis-isobutyronitrile is dissolved in reaction solution, and film liquid is made；Film liquid is coated on the terylene mesh of 0.1 mm thickness, is placed in 80oC baking ovens
In 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite
Molar ratio 1:1, aqueous solution total solid content 1%, by basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water after taking-up, just
Obtain anion-selective membrane.
Embodiment 6
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
In dimethylformamide, 1.6g N, N- dimethylallylamine is then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, so that N, N- bis-
Methacrylic amine carries out aminating reaction, reaction knot with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation
30.4 g trimethylamine aqueous solutions are added dropwise in Shu Houzai（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine and bromomethylation
Remaining bromomethyl in poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction, and 1 g is even
Nitrogen bis-isobutyronitrile is dissolved in reaction solution, and film liquid is made；Film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 80oC baking ovens
In 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite
Molar ratio 1:1, aqueous solution total solid content 1%, by basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water after taking-up, just
Obtain anion-selective membrane.
Embodiment 7
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
In dimethylformamide, 2.4 g N, N- dimethylallylamine are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, so that N, N- bis-
Methacrylic amine carries out aminating reaction, reaction knot with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation
26.6 g trimethylamine aqueous solutions are added dropwise in Shu Houzai（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine and bromomethylation
Remaining bromomethyl in poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction；1 g is even
Nitrogen bis-isobutyronitrile is dissolved in reaction solution, and film liquid is made；Film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 80oC baking ovens
In 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite
Molar ratio 1:1, aqueous solution total solid content 1%, basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water, obtain after taking-up
Anion-selective membrane.
Embodiment 8
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
In dimethylformamide, 3.2 g N, N- dimethylallylamine are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, so that N, N- bis-
Methacrylic amine carries out aminating reaction, reaction knot with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation
22.8 g trimethylamine aqueous solutions are added dropwise in Shu Houzai（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine and bromomethylation
Remaining bromomethyl in poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction；1 g is even
Nitrogen bis-isobutyronitrile is dissolved in reaction solution, and film liquid is made；Film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 80oC baking ovens
In 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite
Molar ratio 1:1, aqueous solution total solid content 1%, by basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water, obtain after taking-up
To anion-selective membrane.
Embodiment 9
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
In dimethylformamide, 3.5g n,N-dimethylaminoethyl methacrylate is then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small,
So that methacrylic N, N-dimethylamino ethyl ester and the part bromomethyl in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation
Aminating reaction is carried out, 30.4 g trimethylamine aqueous solutions are added dropwise again after reaction（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small,
So that trimethylamine carries out aminating reaction with the remaining bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation, reaction terminates
Reaction solution is made afterwards；1 g azodiisobutyronitriles are dissolved in reaction solution, film liquid is made；Film liquid is coated to 0.1 mm thickness to wash
On synthetic fibre screen cloth, be placed in 80oC baking ovens 12 it is small when, obtain basement membrane；It prepares and has dissolved the water-soluble of potassium peroxydisulfate and sodium hydrogensulfite
The molar ratio 1 of liquid, potassium peroxydisulfate and sodium hydrogensulfite:1, basement membrane is soaked into 4 in above-mentioned aqueous solution by aqueous solution total solid content 1%
Hour, it is rinsed with water after taking, obtains anion-selective membrane.
Embodiment 10
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Film liquid is formed in dimethylformamide, 2.0 g N- vinyl imidazoles are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small；So that N- second
Alkenyl imidazoles carries out aminating reaction with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation, after reaction
30.4 g trimethylamine aqueous solutions are added dropwise again（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine and bromomethylation poly- 2,
Remaining bromomethyl in 6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction；By 1 g azos two
Isobutyronitrile is dissolved in reaction solution, and film liquid is made；Film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 12 in 80oC baking ovens
Hour, obtain basement membrane；It prepares and has dissolved the aqueous solution of potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite rub
That ratio 1:1, aqueous solution total solid content 1%, by basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water after taking, obtain it is cloudy from
Sub- selective membrane.
Embodiment 11
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Film liquid is formed in dimethylformamide, 3.2 g N, N- dimethylallylamine are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, with
Make N, N- dimethylallylamine and the part bromomethyl progress amination in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation are anti-
Should, 9.6 g N- methylimidazoles are added dropwise again after reaction, when 40 DEG C of reactions 24 of constant temperature are small, so that N- methylimidazoles and bromomethyl
The remaining bromomethyl changed in poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction；By 1 g
Azodiisobutyronitrile is dissolved in reaction solution, and film liquid is made；Film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 80oC bakings
In case 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and bisulfite
The molar ratio 1 of sodium:1, aqueous solution total solid content 1%, by above-mentioned basement membrane be soaked into aqueous solution 4 it is small when, be rinsed with water, obtain after taking
To anion-selective membrane.
Embodiment 12
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Film liquid is formed in dimethylformamide, 2.4 g N, N- dimethylallylamine are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, with
Make N, N- dimethylallylamine and the part bromomethyl progress amination in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation are anti-
Should, 30.4 g trimethylamine aqueous solutions are added dropwise again after reaction（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine
Remaining bromomethyl in 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate poly- with bromomethylation carries out aminating reaction, and reaction is made after reaction
Liquid；0.5 g azodiisobutyronitriles are dissolved in reaction solution, film liquid is made；Film liquid is coated on 0.1 mm thick polyester screen cloths,
Be placed in 80oC baking ovens 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate
With the molar ratio 1 of sodium hydrogensulfite:1, aqueous solution total solid content 1%, by basement membrane be soaked into aqueous solution 4 it is small when, use water after taking-up
It rinses, obtains anion-selective membrane.
Embodiment 13
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Film liquid is formed in dimethylformamide, 2.4 g N, N- dimethylallylamine are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, with
Make N, N- dimethylallylamine and the part bromomethyl progress amination in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation are anti-
Should, 30.4 g trimethylamine aqueous solutions are added dropwise again after reaction（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine
Remaining bromomethyl in 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate poly- with bromomethylation carries out aminating reaction, and reaction is made after reaction
Liquid；1.0 g dibenzoyl peroxides are dissolved in reaction solution, film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 80o
In C baking ovens 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sulfurous
The molar ratio 1 of sour hydrogen sodium:1, aqueous solution total solid content 1%, by basement membrane be soaked into aqueous solution 4 it is small when, be rinsed with water after taking-up,
Obtain anion-selective membrane.
Embodiment 14
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N- first
Film liquid is formed in base pyrrolidones, 1.6 g N, N- dimethylallylamine are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, so that
N, N- dimethylallylamine carry out aminating reaction with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation,
30.4 g trimethylamine aqueous solutions are added dropwise again after reaction（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine and bromine
The remaining bromomethyl to methylate in poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction；It will
1 g azodiisobutyronitriles are dissolved in reaction solution, and film liquid is coated on 0.1 mm thick polyester screen cloths, and it is small to be placed in 80oC baking ovens 12
When, obtain basement membrane；Prepare mole of the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite
Than 1:1, aqueous solution total solid content 1%, by basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water after taking-up, obtain it is cloudy from
Sub- selective membrane.
Embodiment 15
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Film liquid is formed in dimethylformamide, 1.6 g N, N- dimethylallylamine drop is then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small,
So that N, N- dimethylallylamine and the part bromomethyl progress amination in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation are anti-
Should, 30.4 g trimethylamine aqueous solutions are added dropwise again after reaction（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine
Remaining bromomethyl in 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate poly- with bromomethylation carries out aminating reaction, and reaction is made after reaction
Liquid；1 g azodiisobutyronitriles are dissolved in reaction solution, film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 80oC baking ovens
In 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite
Molar ratio 1:1, aqueous solution total solid content 0.2%, by basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water after taking-up,
Obtain anion-selective membrane.
Embodiment 16
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Film liquid is formed in dimethylformamide, 1.6 g N, N- dimethylallylamine are then added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, with
Make N, N- dimethylallylamine and the part bromomethyl progress amination in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation are anti-
Should, 30.4 g trimethylamine aqueous solutions are added dropwise again after reaction（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine
Remaining bromomethyl in 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate poly- with bromomethylation carries out aminating reaction, and reaction is made after reaction
Liquid；1 g azodiisobutyronitriles are dissolved in reaction solution, obtain film liquid；Film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in
In 80oC baking ovens 12 it is small when, obtain basement membrane；Prepare the aqueous solution for having dissolved hydrogen peroxide and sodium sulfite, hydrogen peroxide and sulfurous
The molar ratio 1 of sour sodium:1, hydrogen peroxide and sodium sulfite account for the 1% of aqueous solution quality altogether, and basement membrane is soaked into above-mentioned aqueous solution
4 it is small when, be rinsed with water after taking, obtain anion-selective membrane.
Embodiment 17
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 1 the method for embodiment is dissolved into 80 g N, N-
Then 1.6 g N, N- dimethylallylamine are added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, so that N, N- diformazan in dimethylformamide
Base allyl amine carries out aminating reaction with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation, and reaction terminates
30.4 g trimethylamine aqueous solutions are added dropwise again afterwards（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine gathers with bromomethylation
Remaining bromomethyl in 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction；By 1 g azos
Bis-isobutyronitrile is dissolved in reaction solution, obtains film liquid；Film liquid is coated on 0.1 mm thick polyester screen cloths, is placed in 12 in 80oC baking ovens
Hour, obtain basement membrane；It prepares and has dissolved the aqueous solution of potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and sodium hydrogensulfite rub
That ratio 1:1, aqueous solution total solid content 1%, basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, be rinsed with water after taking-up, obtain it is cloudy from
Sub- selective membrane.
Embodiment 18
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Then 1.6 g N, N- dimethylallylamine are added dropwise, when 40 DEG C of reactions 24 of constant temperature are small, so that N, N- diformazan in dimethylformamide
Base allyl amine carries out aminating reaction with the part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation, and reaction terminates
30.4 g trimethylamine aqueous solutions are added dropwise again afterwards（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small, so that trimethylamine gathers with bromomethylation
Remaining bromomethyl in 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate carries out aminating reaction, and reaction solution is made after reaction；By 1 g azos
Bis-isobutyronitrile is dissolved in reaction solution, obtains film liquid；0.08 mm non-woven fabrics of thickness is immersed into film liquid, the nonwoven for being impregnated with film liquid is laid
It is placed among two panels polyethylene terephthalate thin film, bubble that may be present, is placed in 80oC baking ovens among extrusion film
12 it is small when, remove film, obtain basement membrane；Prepare the aqueous solution for having dissolved potassium peroxydisulfate and sodium hydrogensulfite, potassium peroxydisulfate and Asia
The molar ratio 1 of niter cake:1, aqueous solution total solid content 1%, basement membrane be soaked into above-mentioned aqueous solution 4 it is small when, rushed after taking-up with water
It washes, obtains anion-selective membrane.
Embodiment 19
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Film liquid is formed in dimethylformamide, 1.6 g N, N- dimethylallylamine are then added dropwise and are added drop-wise in film liquid, 40 DEG C of constant temperature
React 24 it is small when so that part bromomethyl in N, N- dimethylallylamine and the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation
Aminating reaction is carried out, 30.4 g trimethylamine aqueous solutions are added dropwise again after reaction（Concentration 30%）, when 40 DEG C of reactions 24 of constant temperature are small,
So that trimethylamine carries out aminating reaction with the remaining bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation, reaction terminates
Reaction solution is made afterwards；1 g azodiisobutyronitriles are dissolved in reaction solution, obtain film liquid；0.08 mm non-woven fabrics of thickness is immersed into film
Liquid, the non-woven fabrics for being impregnated with film liquid are positioned among two panels polyethylene terephthalate thin film, among extrusion film there may be
Bubble, be placed in 130oC baking ovens 12 it is small when, remove film, obtain basement membrane；Potassium peroxydisulfate and sodium hydrogensulfite have been dissolved in preparation
Aqueous solution, the molar ratio 1 of potassium peroxydisulfate and sodium hydrogensulfite:1, aqueous solution total solid content 1%, basement membrane is soaked into above-mentioned water-soluble
In liquid 4 it is small when, be then rinsed with water, obtain anion-selective membrane.
Embodiment 20
Poly- 30 g of 2,6- dimethyl -1,4- phenylates of the bromomethylation as made from 2 the method for embodiment is dissolved into 80 g N, N-
Then liquid in dimethylformamide is added dropwise to 38 g trimethylamine aqueous solutions（Concentration 30%）, when 40 DEG C of constant temperature reaction 24 is small after obtain
Film liquid；Film liquid is coated on 0.1 mm thick polyester screen cloths, be placed in 80oC baking ovens 12 it is small when, obtain anion-selective membrane.
In the above embodiments 5-20, embodiment 5-19 is the embodiment for embodying technical concept of the present invention, embodiment
20 be comparative example.Embodiment 5-19 is using the poly- 2,6- dimethyl -1,4- of bromomethylation made from embodiment 2 and embodiment 1
Phenylate come illustrate the present invention technical concept exploitativeness, be not to illustrate bromomethylation poly- 2,6- made from embodiment 3 and 4
Dimethyl-Isosorbide-5-Nitrae-phenylate can not achieve the present invention, those skilled in the art's introduction according to the present invention, according to embodiment 3 and 4
The poly- 2,6- dimethyl -1,4- phenylates of bromomethylation obtained and methyl bromide degree are in the range of 30-80% and different from embodiment
Poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation of 1-4 remains to realize the present invention, is intended merely to save length, no longer one at one stroke
Example repeats.Same reason, embodiment 5-19 are from the multi-solvents, a variety of unsaturated tertiary amines, a variety of full listed by the present invention
In tertiary amine, a variety of oil-soluble initiators and a variety of water soluble oxidizeds-reduction initiator, representational one or more are chosen
Come illustrate the present invention exploitativeness, those skilled in the art according to be not related in embodiment 5-19 above-mentioned solvent, insatiable hunger
With other materials in tertiary amine, saturation tertiary amine, oil-soluble initiator and water soluble oxidized-reduction initiator, can similarly realize
The present invention also no longer repeats one by one herein.
Technical target of the product made from above-described embodiment is tested below, it can be real with prove the method for the invention
The property applied and products obtained therefrom is best in quality.
1st, diffusion dialysis performance test
Using standard HG/T 5112-2016《Diffusion dialysis cavity block》Specified in diffusion dialysis device, diffusion dialysis device includes
Dialysing compartment and diffuser casing, two Room are separated by anion-selective membrane, and dialysate is hydrochloric acid and frerrous chloride mixed solution（Hydrochloric acid
3.0 mol/L of concentration, 0.3 mol/L of frerrous chloride concentration）, diffusion liquid is pure water, by measuring hydrogen ion and iron in diffusion liquid
The concentration of ion calculates hydrogen ion dialysis coefficent and metal ion leadage coefficient with the variation of diffusion time.Choose embodiment 5-
Product made from 17 respectively tested by two pieces of sampling, and the results are shown in table below.
Standard HG/T 5112-2016《Diffusion dialysis cavity block》It is required that hydrogen ion dialysis coefficent should be not less than 5 × 10-7M/s, acid/
Salt separation factor should be not less than 15.The hydrogen ion for the anion-selective membrane that the method for the invention makes as can be seen from the table
Dialysis coefficent and acid/salt separation factor are up to standard, and the anion-selective membrane obtained by the method for the invention is suitable for diffusion
Dialysis process.
2nd, electrochemical property test
Using similar to books written by Heiner Strathmann《Ion-exchange membrane separation
processes》（ISBN: 978-0-444-50236-0）The face electricity of film prepared by the membrane potential test device measurement of middle Fig. 3 .17
Resistance and transport number, the both ends of the test device are metal electrode, and cavity block is positioned over the centre of device, and film both sides are placed at film
Ag/AgCl reference electrodes, the effective membrane area S of ion selective membrane is 7 cm2.When measuring surface resistance, inject in a device
The NaCl solution of 0.5 mol/L applies 50 mA DC current I, two reference electrodes when film sample is not placed in measurement by metal electrode
Potential difference E1With the potential difference E of two reference electrodes when placing film sample2.When measuring transport number, the solution of film sample both sides is respectively
The NaCl solution of 0.1 mol/L and 0.5 mol/L do not apply electric current, measure the potential difference E of two reference electrodes3。
The calculation formula of surface resistance R is as follows：
The calculation formula of transport number t is as follows：
Wherein E0For standard electric potential difference, R is gas constant（8.314 J/K/mol）, T is the absolute temperature of solution, and F is faraday
Constant（96480C/mol）, a1/a2Refer to the activity ratio of film both sides solution.It chooses product made from embodiment 17-19 and respectively samples
Three pieces are tested, and as a result see the table below.
The surface resistance of existing business homogeneous-phase anion selective membrane is generally 3-8 Ohmcm2, transport number is generally 0.96-
0.99.Can be seen that the surface resistance of the anion-selective membrane of the method for the invention making is relatively low from upper table, transport number is higher, this
Cavity block obtained by invention the method is suitable for electrodialytic process.
3 organic solvent resistances are tested
As a comparison, embodiment 20 is prepared for non-crosslinked type anion-selective membrane.Choose embodiment 15 and 16 be made product and
The dry state film two panels of each 2.5 cm of clip diameter, chooses non-crosslinked type anion-selective membrane prepared by embodiment 20, and clip is straight
The dry state film of 2.5 cm of footpath four carries out contrast test；It is immersed in after above-mentioned diaphragm is weighed in n,N-Dimethylformamide, it is permanent
50 DEG C of 4 hours of placement of temperature, diaphragm is taken out, drying is weighed, and numerical value of weighing obtains impregnating front and rear coating materials matter after deducting screen cloth quality
Amount, and then the mass loss rate of diaphragm is calculated, the results are shown in table below.
As can be seen from the table the method for the invention make anion-selective membrane be soaked into organic solvent almost without
Mass loss illustrates that the anion-selective membrane obtained by the method for the invention possesses cross-linked structure, which causes
Diaphragm has good solvent resistance, and performance is stablized.
Claims (10)
1. a kind of preparation method of cross-linking type anion-selective membrane, it is characterised in that comprise the following steps：Bromomethylation is gathered
2,6- dimethyl-Isosorbide-5-Nitrae-phenylate is dissolved in organic solvent, then add in molecular structure carbon-carbon double bonds unsaturated tertiary amine with
Part bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation carries out the 1st step aminating reaction, then adds saturation uncle
Amine carries out the 2nd step aminating reaction with remaining bromomethyl in poly- 2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylate of bromomethylation, after the completion of reaction
To reaction solution；Oil-soluble initiator is dissolved in reaction solution, film liquid is made；By film liquid coated on base material, obtained after heating, drying
Basement membrane is inserted in the aqueous solution dissolved with water soluble oxidized-reduction initiator and fully impregnated by basement membrane, is taken out after immersion and is used water
Cleaning, just obtains cross-linking type anion-selective membrane.
2. the preparation method of cross-linking type anion-selective membrane according to claim 1, it is characterised in that described is organic
Solvent is N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide (DMSO).
3. cross-linking type anion-selective membrane preparation method according to claim 1, it is characterised in that the carbon containing carbon
The unsaturated tertiary amine of double bond be N, N- dimethylallylamine, N, N- Diethyl Allylnimes, methacrylic acid N, N- dimethyl
Amino ethyl ester, methacrylic acid N, N- diethylamino ethyl ester, acrylic acid N, N- dimethylamino ethyl ester, acrylic acid N, N- diethyl
Base amino ethyl ester or N- vinyl imidazoles；The molal quantity of unsaturated tertiary amine is in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation
Bromomethyl molal quantity 10%-60%.
4. cross-linking type anion-selective membrane preparation method according to claim 1, it is characterised in that the saturation uncle
Amine is trimethylamine, triethylamine, N, N- dimethyl amines, N, N- diethyl methyl amines or N- methylimidazoles；The molal quantity of saturation tertiary amine
40% of bromomethyl molal quantity at least in the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation.
5. cross-linking type anion-selective membrane preparation method according to claim 1, it is characterised in that the oil-soluble
Initiator is azodiisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dilauroyl peroxide, peroxidating trimethylacetic acid uncle
Butyl ester, di-isopropyl peroxydicarbonate or di-cyclohexylperoxy di-carbonate；The molal quantity of oil-soluble initiator is unsaturation
The 0.1%-10% of tertiary amine molal quantity.
6. cross-linking type anion-selective membrane preparation method according to claim 1, it is characterised in that the water solubility
Oxidation-reduction initiator is made of Oxidizing and Reducing Agents；The oxidant for hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate or
Ammonium persulfate；The reducing agent is sulphite, bisulfites or thiosulfate, the cation of above-mentioned salt can be sodium from
Son, potassium ion or ammonium ion；The molar ratio of oxidant and reducing agent is 0.5-2:1, water soluble oxidized-reduction initiator solution
Concentration be 0.5%-10%.
7. cross-linking type anion-selective membrane preparation method according to claim 1, it is characterised in that the heating is dried
Dry temperature is 50 DEG C -140 DEG C.
8. cross-linking type anion-selective membrane preparation method according to claim 1, it is characterised in that the basement membrane is in water
When soaking time in soluble oxygenated-reduction initiator solution is 2-24 small.
9. cross-linking type anion-selective membrane preparation method according to claim 1, it is characterised in that the bromomethylation
The methyl bromide degree of poly- 2,6- dimethyl -1,4- phenylates is 30%-80%.
10. the cross-linking type anion-selective membrane preparation method according to claim 1 or 9, it is characterised in that the bromine first
The preparation method of the poly- 2,6- dimethyl -1,4- phenylates of baseization is：Poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate is dissolved in chlorobenzene,
Bromine simple substance or N- bromo-succinimides are added in solution, be warming up to 100-160 DEG C of reaction at least 4 it is small when, divide after reaction
It separates out polymeric solid and obtains the poly- 2,6- dimethyl -1,4- phenylates of bromomethylation.
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| CN109265714A (en) * | 2018-06-30 | 2019-01-25 | 浙江工业大学 | A kind of preparation method of the cross-linking type anion-exchange membrane of low-water-content |
| CN109265714B (en) * | 2018-06-30 | 2021-06-08 | 浙江工业大学 | Preparation method of cross-linked anion exchange membrane with low water content |
| CN109758917A (en) * | 2018-09-18 | 2019-05-17 | 张伟 | A kind of preparation method of bivalent cation selective ion exchange membrane |
| CN109758917B (en) * | 2018-09-18 | 2021-07-02 | 张伟 | Preparation method of divalent cation selective ion exchange membrane |
| CN110560181A (en) * | 2019-09-04 | 2019-12-13 | 中国科学技术大学先进技术研究院 | Preparation method of anion exchange membrane |
| CN110560181B (en) * | 2019-09-04 | 2022-08-02 | 中国科学技术大学先进技术研究院 | Preparation method of anion exchange membrane |
| CN111036099A (en) * | 2019-12-25 | 2020-04-21 | 山东天维膜技术有限公司 | Preparation method of crosslinked polysulfone anion exchange membrane |
| CN113621158A (en) * | 2021-09-02 | 2021-11-09 | 浙江工业大学 | Preparation method of ion exchange membrane with mono/divalent anion separation cross-linking type amphoteric structure |
| CN114695933A (en) * | 2022-03-10 | 2022-07-01 | 武汉轻工大学 | Semi-interpenetrating anion exchange membrane and preparation method and application thereof |
| CN114695933B (en) * | 2022-03-10 | 2023-12-22 | 武汉轻工大学 | Semi-interpenetrating anion exchange membrane and preparation method and application thereof |
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