CN104941468B - A kind of semi-interpenetrating network type anion exchange membrane and preparation method thereof - Google Patents
A kind of semi-interpenetrating network type anion exchange membrane and preparation method thereof Download PDFInfo
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- CN104941468B CN104941468B CN201510288010.4A CN201510288010A CN104941468B CN 104941468 B CN104941468 B CN 104941468B CN 201510288010 A CN201510288010 A CN 201510288010A CN 104941468 B CN104941468 B CN 104941468B
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Abstract
The invention discloses a kind of semi-interpenetrating network type anion exchange membrane and preparation method thereof, its raw material components includes polymer, polyvinyl alcohol and the cross-linking agent that the monomer of pyrrolidone containing salt is formed through homopolymerization, and with above-mentioned raw materials are blended successively, crosslinked, film forming, heat treatment and chemical treatment and be obtained, above-mentioned polymer is 1 with the mass ratio of polyvinyl alcohol:1～8, above-mentioned cross-linking agent quality used in cross-linking process is the 1～5% of above-mentioned polymer and polyvinyl alcohol gross mass, two kinds of primary raw materials of the present invention are all environmentally friendly materials, cost is relatively low, and the polymer that the monomer of pyrrolidone containing salt is formed simultaneously and PVA are respectively provided with good filming performance and thermal stability.
Description
Technical field
The invention belongs to ion exchange membrane technology field and in particular to a kind of semi-interpenetrating network type anion exchange membrane and its
Preparation method.
Background technology
Ion exchange membrane is a kind of polymeric membrane with ion-selective permeability energy, has been widely used in sea water light
The fields such as change, saline solution concentration, the purification of organic or inorganic compound, fuel cell barrier film and ion-selective electrode.Root
According to the difference selecting the ion passing through, ion exchange membrane can be divided into cation exchange membrane, anion exchange membrane and two sexual intercourses
Change the types such as film.Wherein, cation exchange membrane refers to contain acid active group in film body, and its energy selectivity is through cation
Do not allow anion-permeable.These active groups mainly have：Sulfonic group, phosphate, phosphorous acidic group, carboxylic acid group, phenolic group etc..Anion
Exchange membrane refers to contain basic activated group in film body, and it can not allow cation permeable by selectivity through anion.These are lived
Property group mainly has：Quaternary ammonium group, primary amine groups, secondary amine, tertiary amine groups etc..
Ion exchange membrane presses structure and the manufacturing process of its own, is segmented into homogeneous ion-exchange membrane, heterogeneous ion
Exchange membrane and intercrossed network type ion exchange membrane etc..The preparation method of wherein homogeneous-phase anion exchange film mainly has (1) radiation to connect
Branch method；(2) macromolecule modified；(3) homopolymerization or copolyreaction are carried out for raw material with the monomer containing active group.
CN101735471A discloses using high density polyethylene (HDPE) as basement membrane, and radiation grafting prepares the side of homogeneous alkaline anion-exchange membrane
Method, the anion exchange membrane ion selectivity of the method preparation is high, membrane resistance is low, and the method using and material non-toxic, no
Environmental pollution, but the anion exchange membrane heat stability obtaining and chemical stability are poor.Junjun Wang et al.
(Journal of Membrane Science,2014,459:86-95) with polyether-ether-ketone as matrix, chloromethyl Octyl Ether conduct
Chloromethylation reagents carry out chloromethylation, then with Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane, it are carried out quaternized again
Reaction, is finally soaked with alkali again and obtains anion exchange membrane.Macromolecule modified prepare anion exchange membrane during, chloromethane
Generally require in glycosylation reaction using the reagent with severe toxicity and carcinogenecity, and it is poor to obtain the performance uniformity of film.Traditional
Heterogeneous anion exchange membrane is predominantly organic/inorganic hybrid membrane, electric conductivity and chemical stability all poor.
Interpenetrating polymer networks (IPN) are mutually penetrated or are tangled by two or more polymer network and constituted
Chemical blend network alloy system, it can have the excellent properties of general physical blending, grafting, block polymer simultaneously, when
Only a kind of crosslinked polymer when, its product be referred to as semi-interpenetrating polymer network (SIPN).Hand over regard to intercrossed network type anion
Change the preparation of film, CN103223303A discloses a kind of preparation side of Kynoar/polyalkenes quaternary ammonium salt anion exchange membrane
Method, the matrix material with Kynoar as anion exchange membrane for the method, in olefines quaternary ammonium salt and cross-linking agent, initiator
Under effect, finally prepare polyvinylidene fluoride/polyalkenesquaternary quaternary ammonium salt cation exchange alloy membrane, this film has macromolecule IPN
Network structure, membrane surface resistance is low, and the violent chloromethylation of the condition that avoids and aminating reaction step, easily realizes extensive work
Industry metaplasia is produced.But the chemical stability of quaternary ammonium salt anion exchange membrane is poor, easily degrade under highly basic and hot environment.
CN102206386A discloses a kind of polymer anion-exchange membrane based on glyoxaline cation and preparation method thereof,
The anion exchange membrane of the method preparation has higher electrical conductivity, has good heat stability and chemical stability, can be
Use at 200 DEG C, and keep stable in strong acid, highly basic and strong oxidizer.But alkyl imidazolium cation monomer abnormal smells from the patient weight, toxicity is relatively
Greatly, relatively costly.
Content of the invention
It is an object of the invention to overcoming prior art defect, provide a kind of semi-interpenetrating network type anion exchange membrane.
Another object of the present invention is to providing the preparation method of above-mentioned semi-interpenetrating network type anion exchange membrane.
The concrete technical scheme of the present invention is as follows：
A kind of semi-interpenetrating network type anion exchange membrane, its raw material components includes the monomer of pyrrolidone containing salt through homopolymerization
Polymer that reaction is formed, polyvinyl alcohol and cross-linking agent, and with above-mentioned raw materials are blended successively, crosslinked, film forming, heat treatment and change
Learn process and be obtained, above-mentioned polymer is 1 with the mass ratio of polyvinyl alcohol:1～8, above-mentioned cross-linking agent is used in cross-linking process
Quality be the 1～5% of above-mentioned polymer and polyvinyl alcohol gross mass, the structural formula of monomer of above-mentioned pyrrolidone containing salt and
The structural formula of polymer is respectively：
Wherein R1、R2For the hydrogen atom or carbon number alkyl less than 4, R3For the hydrogen atom or carbon number alkane less than 5
Base；X-For Cl-, Br-, I-、OH-Or BF- 4；
The structural formula of above-mentioned cross-linking agent is：
Wherein, R is the straight chained alkyl of 0～4 carbon atom, and 0 carbon atom represents without alkyl.
A kind of preparation method of above-mentioned semi-interpenetrating network type anion exchange membrane, comprises the steps：
(1) homopolymerization prepares polymer：The monomer of pyrrolidone containing salt is dissolved in a solvent, adds initiator,
The quality of initiator is the 0.1～0.8% of the monomer mass of pyrrolidone containing salt, under the protection of noble gases, seals, adds
Hot reflux carries out polyreaction, and the temperature of polyreaction is 50～90 DEG C, takes out product after the completion of reaction, through cyclic washing, does
The polymer of pyrrolidone containing salt is obtained, the consumption of described initiator is the monomer mass of described pyrrolidone containing salt after dry
0.1%～0.8%；
(2) blending, crosslinked and film forming：The polymer that step (1) is obtained is dissolved in the aqueous solution of polyvinyl alcohol and must mix
Close liquid, in the aqueous solution of this polyvinyl alcohol, the mass percent of polyvinyl alcohol is 5%～20%, Deca is crosslinked in mixed liquor
Agent, obtains casting solution, uses phase inversion casting film, and described polymer is 1 with the mass ratio of polyvinyl alcohol:1～8, described friendship
The amount of connection agent is 1～5% of polymer and polyvinyl alcohol gross mass in above-mentioned mixed liquor；
(3) heat treatment of film and chemical treatment：The film obtaining in step (2) is carried out heat treatment further, then will process
Film afterwards is immersed in the acetone soln containing cross-linking agent, and the mass fraction that this contains cross-linking agent in the acetone soln of cross-linking agent is 5～
20%, take out after the completion of reaction, more scrubbed and dry after obtain described semi-interpenetrating network type anion exchange membrane, above-mentioned hot at
The temperature of reason is 110～150 DEG C, and heat treatment time is 0.5～3 hour.
In a preferred embodiment of the invention, described initiator is Ammonium persulfate. and the oxygen of sodium sulfite composition
Change reduction initiator or azodiisobutyronitrile (AIBN), or benzoyl peroxide (BPO).
In a preferred embodiment of the invention, in described step (1) solvent be can make pyrrolidone containing
The solvent that the monomer of salt and initiator are completely dissolved.
It is further preferred that the solvent in described step (1) is water, methanol, ethanol, DMF or N, N-
Dimethyl acetylamide.
In a preferred embodiment of the invention, described step (3) is：Will be further for the film obtaining in step (2)
Carry out heat treatment, then the film after processing is immersed in the acetone soln containing cross-linking agent is reacted, this contains the acetone of cross-linking agent
In solution the mass fraction of cross-linking agent be 5～20%, after the completion of reaction take out film carry out transition process, more scrubbed and dry after
Obtain described semi-interpenetrating network type anion exchange membrane, the temperature of above-mentioned heat treatment is 110～150 DEG C, and heat treatment time is 0.5
～3 hours.
It is further preferred that described transition is processed as：Described film is immersed in sodium hydroxide or potassium hydroxide aqueous solution
It is converted into hydrogen-oxygen type.
The invention has the beneficial effects as follows：
1st, the main raw material(s) of the Semi-IPN type anion exchange membrane of the present invention is the monomer of pyrrolidone containing salt and gathers
Vinyl alcohol (PVA), both environmentally friendly materials, cost is relatively low, and the monomer of pyrrolidone containing salt is formed simultaneously
Polymer and PVA are respectively provided with good filming performance and thermal stability；
2nd, the matrix material with PVA as half interpenetrating network structure for the preparation method of the Semi-IPN type anion exchange membrane of the present invention
Material, the polymer that the monomer of the pyrrolidone containing salt containing ion exchanging function group is formed is blended with PVA, and in crosslinking
Carry out crosslinking in the presence of agent, form the anion exchange membrane of half interpenetrating network structure.PVA and above-mentioned polymer all contain parent by force
Aqueouss group, is water-soluble polymer.Film after crosslinking is not only insoluble in water, and can also keep good after moisture absorption
Dimensional stability, will not be excessively swelling in water.After cross-linking reaction, chemical stability is improved blend film.
3rd, the preparation method of the present invention does not need chloromethylation in conventional anion exchange membrane preparation process and quaternized
Process, it is to avoid carcinogenecity reagent using it is therefore prevented that the membrane structure causing in quaternization process is damaged during chloromethylation
The phenomenon uneven with ammoniumization.
4th, the electrical conductivity of Semi-IPN type anion exchange membrane of the present invention, moisture content and ion exchange capacity can be by changing
In casting solution polypyrrole alkanone salt and PVA proportioning to adjust, at 25 DEG C, the electrical conductivity of this film is more than 0.02S cm-2, and
There is excellent mechanical performance.
Brief description
Fig. 1 is the infrared spectrogram of the ketopyrrolidine salt polymer prepared by the embodiment of the present invention 1, and abscissa is wave number
Wavenumber(cm-1), vertical coordinate is absorbance Transmittance (%).
Fig. 2 is the infrared spectrogram of the semi-interpenetrating network type anion exchange membrane prepared by the embodiment of the present invention 1, abscissa
For wave number Wavenumber (cm-1), vertical coordinate is absorbance Transmittance (%).
Fig. 3 is the thermogravimetric analysis figure of the semi-interpenetrating network type anion exchange membrane prepared by the embodiment of the present invention 1, abscissa
For temperature Temperature (DEG C), vertical coordinate is mass percent Weight (%).
Fig. 4 is the Chemical stability graph of the semi-interpenetrating network type anion exchange membrane prepared by the embodiment of the present invention 1, horizontal seat
It is designated as time Time (h) that film is immersed in NaOH solution, vertical coordinate is electrical conductivity Conductivity (10-2S cm-1).
Specific embodiment
Combine accompanying drawing below by way of specific embodiment technical scheme is further detailed and to describe.
Embodiment 1
Take a certain amount of N- methyl-N-vinyl ketopyrrolidine salt monomer to be added in three-neck flask, add appropriate
Deionized water, under the protection of nitrogen, adds Ammonium persulfate. and sodium sulfite (total amount is the 0.2% of monomer mass), mixing
After uniformly, stir 24 hours at 50 DEG C.Reaction after terminating is transferred to the brown color obtaining viscous body in beaker, and uses hexamethylene
Alkane is carried out, and finally product is placed in vacuum drying oven and is dried, obtains poly- (N- methyl-N-vinyl ketopyrrolidine salt)
(PNVMP).
Take a certain amount of polyvinyl alcohol (PVA) to be dissolved in 80 DEG C of deionization, be configured to mass fraction be 5% molten
Liquid, adds appropriate PNVMP, and the mass ratio making PVA and PNVMP in solution is 3:1.After dissolving completely, the hexandial of Deca
(amount of hexandial is 2% of Solute mass in above-mentioned solution), continues to stir, casting film, and film is warm at 150 DEG C
Process 1 hour, then film is placed in immersion 1 hour in the acetone soln of 10wt% hexandial, finally film is placed in 1mol L-1's
After soaking 24 hours in NaOH, it is washed till neutrality with a large amount of deionized waters, obtain hydrogen-oxygen type based on ketopyrrolidine salt half is mutual
Wear network-type anion exchange membrane.
After measured, this film is water insoluble, and the moisture content of 25 DEG C of lower films is 56.6%, and ion exchange capacity is 1.63mmol
g-1, film electrical conductivity in deionized water is 0.036S cm-1, and electrical conductivity raises with the rising of temperature, at 90 DEG C
Still there is higher electrical conductivity.
Structure determination is carried out to poly- (N- methyl-N-vinyl ketopyrrolidine salt) using infrared spectrometer, its result is such as
Shown in Fig. 1.1288cm-1The peak at place corresponds to the stretching vibration peak of C-N, 1658cm-1The peak at place is the absorption vibration peak of C=O,
At above two, peak illustrates the presence of pyrrolidone ring；3425cm-1Locate the absworption peak for-OH, 2800～3000cm-1Locate as alkane
Base is symmetrical and asymmetric stretching vibration peak.Described above it is successfully prepared PNVMP.
Using infrared spectrometer, the semi-interpenetrating network type anion exchange membrane based on ketopyrrolidine salt is measured, its
Result is as shown in Figure 2.1130cm-1Locate the characteristic peak for C-O-C, illustrate that film there occurs chemical crosslinking, meanwhile, pyrrolidone ring
Characteristic peak yet suffers from, illustrate film after crosslinking Treatment pyrrolidone ring not by broken ring.
Steady to the heat of the semi-interpenetrating network type anion exchange membrane based on ketopyrrolidine salt using thermogravimetric analyzer test
Qualitative.Sample is put in silica crucible and is tested, measurement atmosphere is nitrogen, Range of measuring temp is 30～600 DEG C,
Heating rate is 10 DEG C per minute.Its thermal gravimetric analysis results is as shown in Figure 3.It can be seen that prepared anion exchange membrane exists
There is within 280 DEG C good heat stability.
By measuring the 6mmol L that film is through 60 DEG C-1Base extraction after electrical conductivity change come characterization of membrane chemistry steady
Qualitative.6mmol L at 60 DEG C will be immersed in based on the semi-interpenetrating network type anion exchange membrane of ketopyrrolidine salt-1NaOH molten
In liquid, certain interval of time takes the film out and measures electrical conductivity at 25 DEG C for the film, and with soaking 1mmol at 25 DEG C
L-1NaOH solution in the electrical conductivity of film be compared.Under different soak times, the electrical conductivity of corresponding film is as shown in figure 4, result
Show film in 6mmol L-1NaOH solution in soak time be up to 7 days after, still there is higher stable electrical conductivity, explanation
Film has preferable chemical stability.
Embodiment 2
Take a certain amount of N- ethyl-N-vinyl ketopyrrolidine salt monomer (NVEP) to be added in three-neck flask, add
Appropriate N,N-dimethylacetamide, under the protection of nitrogen, the benzoyl peroxide adding the 0.8% of Solute mass is to cause
Agent.After mix homogeneously, it is placed in magnetic agitation 24 hours in 85 DEG C of oil baths, the brown color obtaining viscous body is shifted after terminating by reaction
To in beaker, and it is carried out with hexamethylene, be dried, obtain poly- (N- ethyl-N-vinyl ketopyrrolidine salt) (PNVEP).
Take in the deionization that a certain amount of PVA is dissolved in 80 DEG C, be configured to the solution of 10wt%, add appropriate
PNVEP, the mass ratio making PVA and PNVEP in solution is 1:1.After dissolving completely, the 1% of Solute mass in the above-mentioned solution of Deca
Glutaraldehyde, casting film, and by film at 130 DEG C heat treatment 1 hour, then acetone soln film being placed in 20wt% glutaraldehyde
Film is finally placed in 1mol L by middle immersion 1 hour-1NaOH in soak 24 hours after, with a large amount of deionized water purification membrane surfaces.
Obtain the semi-interpenetrating network type anion exchange membrane based on ketopyrrolidine salt of hydrogen-oxygen type.
After measured, this film is water insoluble, and the moisture content of 25 DEG C of lower films is 58.7%, and ion exchange capacity is 1.53mmol
g-1, film electrical conductivity in deionized water is 0.032S cm-1.
Embodiment 3
Take N- butyl-NVP salt monomer (NVBP) to be added in three-neck flask, add appropriate N,
Dinethylformamide, under the protection of nitrogen, adds the 0.5% of Solute mass azodiisobutyronitrile.After mix homogeneously, put
Magnetic agitation 24 hours in 65 DEG C of oil baths.Reaction after terminating is transferred to the brown color obtaining viscous body in beaker, and uses ring
Hexane is carried out, and finally the product obtaining is placed in vacuum drying oven and is dried, obtains poly- (N- butyl-N- vinyl pyrrole
Alkanone salt) (PNVBP).
Take in the deionization that a certain amount of PVA is dissolved in 80 DEG C, be configured to the solution of 20wt%, add appropriate
PNVBP, the mass ratio making PVA and PNVEP in solution is 6:1.After dissolving completely, the 8% of Solute mass in the above-mentioned solution of Deca
Biformyl, continue to stir, casting film, and by film at 110 DEG C heat treatment 3 hours, then film is placed in 5wt% second two
Soak 1 hour in the acetone soln of aldehyde, finally film is placed in 1mol L-1NaOH in soak 24 hours after, use a large amount of deionizations
It is washed to neutrality.Obtain the semi-interpenetrating network type anion exchange membrane based on ketopyrrolidine salt of hydrogen-oxygen type.
After measured, this film is water insoluble, and the moisture content of 25 DEG C of lower films is 51.2%, and ion exchange capacity is 1.22mmol
g-1, electrical conductivity 0.023S cm in film deionized water-1.
Embodiment 4
Take a certain amount of N- methyl-N- acrylic ketopyrrolidine salt monomer to be added in three-neck flask, add appropriate
Deionized water, under the protection of nitrogen, adds Ammonium persulfate. and sodium sulfite (total amount is the 0.5% of monomer mass), mixing
After uniformly, stir 24 hours at 65 DEG C.Reaction after terminating is transferred to the brown color obtaining viscous body in beaker, and uses hexamethylene
Alkane is carried out, and finally the product obtaining is placed in vacuum drying oven and is dried, obtains poly- (N- Methyl-N-propyl ketopyrrolidine
Salt) (PNVPP).
Take a certain amount of polyvinyl alcohol (PVA) to be dissolved in 80 DEG C of deionization, be configured to mass fraction be 20% molten
Liquid, adds appropriate PNVPP, and the mass ratio making PVA and PNVPP in solution is 5:1.After dissolving completely, the butanedial of Deca
(amount of butanedial is 6% of Solute mass in above-mentioned solution), continues to stir, casting film, and film is warm at 150 DEG C
Process 2 hours, then film is placed in immersion 2 hours in the acetone soln of 15wt% butanedial, finally film is placed in 1mol L-1's
After soaking 24 hours in NaOH, with a large amount of deionized water purification membrane surfaces.Obtain based on ketopyrrolidine salt the half of hydrogen-oxygen type
Intercrossed network type anion exchange membrane.
After measured, this film is water insoluble, and the moisture content of 25 DEG C of lower films is 65.1%, and ion exchange capacity is 1.33mmol
g-1, film electrical conductivity in deionized water is 0.021S cm-1.
Embodiment 5
With method same as Example 1, except for the difference that in polymerization procedure, the amount of initiator used is monomer mass
0.1%, reaction temperature is 50 DEG C, and solvent is ethanol.The film property indices of gained are with embodiment 1.
Embodiment 6
With method same as Example 1, except for the difference that in polymerization procedure, the amount of initiator used is monomer mass
0.1%, reaction temperature is 50 DEG C, and solvent is first alcohol and water.The film property indices of gained are with embodiment 1.
Embodiment 7
With method same as Example 1, in the heat treatment step of film, the temperature of heat treatment is 120 DEG C, heat treatment
Time is 3 hours.The film property indices of gained are with embodiment 1.
Embodiment 8
With method same as Example 2, in polymerization procedure, the temperature of polyreaction is 90 DEG C, the film items of gained
Energy index is with embodiment 2.
Embodiment 9
With method same as Example 2, in the heat treatment step of film, the temperature of heat treatment is 140 DEG C, heat treatment
Time is 0.5 hour.The film property indices of gained are with embodiment 2.
Skilled person will appreciate that, when technical scheme changes in following ranges, can be with above-mentioned enforcement
Example identical technique effect：
A kind of semi-interpenetrating network type anion exchange membrane, its raw material components includes the monomer of pyrrolidone containing salt through homopolymerization
Polymer that reaction is formed, polyvinyl alcohol and cross-linking agent, and with above-mentioned raw materials are blended successively, crosslinked, film forming, heat treatment and change
Learn process and be obtained, above-mentioned polymer is 1 with the mass ratio of polyvinyl alcohol:1～8, above-mentioned cross-linking agent is used in cross-linking process
Quality be the 1～5% of above-mentioned polymer and polyvinyl alcohol gross mass, the structural formula of monomer of above-mentioned pyrrolidone containing salt and
The structural formula of polymer is respectively：
Wherein R1, R2 are the alkyl that hydrogen atom or carbon number are less than 4, and R3 is the alkane that hydrogen atom or carbon number are less than 5
Base；X-For Cl-, Br-, I-、OH-Or BF- 4；
The structural formula of above-mentioned cross-linking agent is：
Wherein, R is the straight chained alkyl of 0～4 carbon atom, and 0 carbon atom represents without alkyl.
The preparation method of above-mentioned semi-interpenetrating network type anion exchange membrane, comprises the steps：
(1) homopolymerization prepares polymer：The monomer of pyrrolidone containing salt is dissolved in a solvent, adds initiator,
The quality of initiator is the 0.1～0.8% of the monomer mass of pyrrolidone containing salt, under the protection of noble gases, seals, adds
Hot reflux carries out polyreaction, and the temperature of polyreaction is 50～90 DEG C, takes out product after the completion of reaction, through cyclic washing, does
The polymer of pyrrolidone containing salt is obtained, the consumption of described initiator is the monomer mass of described pyrrolidone containing salt after dry
0.1%～0.8%；
(2) blending, crosslinked and film forming：The polymer that step (1) is obtained is dissolved in the aqueous solution of polyvinyl alcohol and must mix
Close liquid, in the aqueous solution of this polyvinyl alcohol, the mass percent of polyvinyl alcohol is 5%～20%, Deca is crosslinked in mixed liquor
Agent, obtains casting solution, uses phase inversion casting film, and described polymer is 1 with the mass ratio of polyvinyl alcohol:1～8, described friendship
The amount of connection agent is 1～5% of polymer and polyvinyl alcohol gross mass in above-mentioned mixed liquor；
(3) heat treatment of film and chemical treatment：The film obtaining in step (2) is carried out heat treatment further, then will process
Film afterwards is immersed in the acetone soln containing cross-linking agent and is reacted, and the quality that this contains cross-linking agent in the acetone soln of cross-linking agent is divided
Number be 5～20%, after the completion of reaction take out film, more scrubbed and dry after obtain described semi-interpenetrating network type anion exchange
Film, the temperature of above-mentioned heat treatment is 110～150 DEG C, and heat treatment time is 0.5～3 hour；Or the film that will obtain in step (2)
Carry out heat treatment further, then the film after processing is immersed in the acetone soln containing cross-linking agent is reacted, this contains cross-linking agent
Acetone soln in cross-linking agent mass fraction be 5～20%, after the completion of reaction take out film carry out transition process, more scrubbed and
Described semi-interpenetrating network type anion exchange membrane is obtained, the temperature of above-mentioned heat treatment is 110～150 DEG C, during heat treatment after drying
Between be 0.5～3 hour..
Described initiator be Ammonium persulfate. and sodium sulfite composition redox initiator or azodiisobutyronitrile
, or benzoyl peroxide (BPO) (AIBN).
In described step (1) solvent be to make the monomer of pyrrolidone containing salt and that initiator is completely dissolved is molten
Agent.
Solvent in described step (1) is water, methanol, ethanol, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
The above, only presently preferred embodiments of the present invention, therefore the scope of present invention enforcement can not be limited according to this, that is,
The equivalence changes made according to the scope of the claims of the present invention and description and modification, all should still belong in the range of the present invention covers.
Claims (6)
1. a kind of semi-interpenetrating network type anion exchange membrane it is characterised in that：Its raw material components includes pyrrolidone containing salt
Polymer, polyvinyl alcohol and cross-linking agent that monomer is formed through homopolymerization, and with above-mentioned raw materials are blended successively, crosslinked, film forming,
Heat treatment and chemical treatment and be obtained, above-mentioned polymer and the mass ratio of polyvinyl alcohol are 1: 1～8, and above-mentioned cross-linking agent is in crosslinking
Used in the process of quality be the 1～5% of above-mentioned polymer and polyvinyl alcohol gross mass, the monomer of above-mentioned pyrrolidone containing salt
Structural formula and the structural formula of polymer be respectively：
Wherein R1、R2For the hydrogen atom or carbon number alkyl less than 4, R3For the hydrogen atom or carbon number alkyl less than 5；X-For
Cl-, Br-, I-、OH-Or BF- 4；
The structural formula of above-mentioned cross-linking agent is：
Wherein, R is the straight chained alkyl of 0～4 carbon atom, and 0 carbon atom represents without alkyl；
Its preparation method comprises the steps：
(1) homopolymerization prepares polymer：The monomer of pyrrolidone containing salt is dissolved in a solvent, adds initiator, lazy
Property gas protection under, seal, be heated to reflux carrying out polyreaction, the temperature of polyreaction is 50～90 DEG C, the time is 6～48
Hour, take out product after the completion of reaction, obtain the polymer of pyrrolidone containing salt, described initiation after cyclic washing, drying
The consumption of agent is the 0.1%～0.8% of the monomer mass of described pyrrolidone containing salt；
(2) blending, crosslinked and film forming：The polymer that step (1) is obtained is dissolved in the aqueous solution of polyvinyl alcohol and obtains mixed liquor,
In the aqueous solution of this polyvinyl alcohol, the mass percent of polyvinyl alcohol is 5%～20%, and Deca cross-linking agent in mixed liquor obtains
Casting solution, uses phase inversion casting film, and described polymer is 1: 1～8 with the mass ratio of polyvinyl alcohol, the amount of described cross-linking agent
For polymer in above-mentioned mixed liquor and polyvinyl alcohol gross mass 1～5%；
(3) heat treatment of film and chemical treatment：The film obtaining in step (2) is carried out heat treatment further, then will process after
Film is immersed in the acetone soln containing cross-linking agent, and the mass fraction that this contains cross-linking agent in the acetone soln of cross-linking agent is 5～20%,
After the completion of reaction take out, more scrubbed and dry after obtain described semi-interpenetrating network type anion exchange membrane, above-mentioned heat treatment
Temperature is 110～150 DEG C, and heat treatment time is 0.5～3 hour.
2. as claimed in claim 1 a kind of semi-interpenetrating network type anion exchange membrane it is characterised in that：Described initiator was
The redox initiator of ammonium sulfate and sodium sulfite composition or azodiisobutyronitrile, or benzoyl peroxide.
3. as claimed in claim 1 a kind of semi-interpenetrating network type anion exchange membrane it is characterised in that：In described step (1)
Solvent be to make the solvent that the monomer of pyrrolidone containing salt and initiator are completely dissolved.
4. as claimed in claim 3 a kind of semi-interpenetrating network type anion exchange membrane it is characterised in that：In described step (1)
Solvent be water, methanol, ethanol, DMF or N,N-dimethylacetamide.
5. a kind of semi-interpenetrating network type anion exchange membrane as described in any claim in Claims 1-4, its feature exists
In：Described step (3) is：The film obtaining in step (2) is carried out heat treatment further, then the film after processing is immersed in containing friendship
Reacted in the acetone soln of connection agent, the mass fraction that this contains cross-linking agent in the acetone soln of cross-linking agent is 5～20%, reaction
After the completion of take out film carry out transition process, more scrubbed and dry after obtain described semi-interpenetrating network type anion exchange membrane, on
The temperature stating heat treatment is 110～150 DEG C, and heat treatment time is 0.5～3 hour.
6. as claimed in claim 5 a kind of semi-interpenetrating network type anion exchange membrane it is characterised in that：Described transition is processed
For：Described film is immersed in sodium hydroxide or potassium hydroxide aqueous solution the hydrogen-oxygen type that is converted into.
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| CN110694698B (en) * | 2019-10-21 | 2021-08-10 | 华南理工大学 | Anion exchange membrane with high anion permeability and high ion selectivity as well as preparation method and application thereof |
| CN111276724B (en) * | 2020-02-15 | 2022-11-22 | 西北工业大学 | Half-interpenetrating-network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and preparation method thereof |
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