JP3396108B2 - Method for producing ion exchange membrane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION The present invention relates to
In particular, there is little leakage of hydrogen ions and hydroxyl ions, and flexibility
Has good mechanical properties and is exposed to high temperatures,
When exposed to acids, alkalis or organic solvents
A method for producing an ion exchange membrane having good durability
You. [0002] 2. Description of the Related Art Conventionally, one method for producing an ion exchange membrane has been proposed.
GeneralIn addition, chloromethylstyrene, styrene, or 4-bi
Introduction of ion exchange group from monomer selected from nylpyridine
For functional groups suitable forCrosslinking agent and polymerization initiator
Ion-exchange groups are introduced into the mixed solution containing
Resin that functions as a matrix without
Paste resin mixture)
Things,Polyvinyl chloride or polyolefin substratePainted on
After cloth and polymerization,To the resulting filmGuide ion exchange groups
Widely used (hereinafter simply referred to as paste method)
It has been. Here, as the above matrix resin
Is, for example, ethylene-propylene copolymer, polybutylene
A polymer compound dispersible in the monomer mixture such as len,
Polystyrene, acrylonitrile-butadiene copolymer
Use soluble polymer compounds in the above monomer mixture such as
It is known. [0003] However, the above-mentioned matri
Ethylene-propylene copolymer, poly
Using saturated aliphatic hydrocarbon polymer such as butylene
In this case, the resin has a functional group suitable for introducing an ion exchange group.
Are not sufficiently compatible with the
The ion exchange resin obtained does not
It becomes unsatisfactory in durability at the time of use. one
On the other hand, when polystyrene is used, the resin becomes flexible.
Inferior, the resulting ion exchange membrane is satisfactory in flexibility and the like.
Will not be. Further, acrylonitrile-butadiene copolymer
The polymer has a functional group suitable for introducing an ion exchange group
The compatibility with the monomer and the flexibility of the resin are good.
Poor durability with use due to poor affinity with materials
Long-term use, especially in contact with acids and alkalis.
When used under severe conditions, the ion exchange resin
And the ion exchange resin part is partially peeled off from the substrate.
Problems occur. [0005] Against this background, Japanese Patent Laid-Open No. 6-322 is disclosed.
No. 156 reports that hydrogenated
Acrylonitrile-butadiene copolymer
It has been proposed. And this hydrogenated
When a copolymer is used, the resulting ion exchange membrane is good.
It has good durability, and it can be used under severe conditions as described above.
Problems such as deterioration of the exchange resin part and peeling from the substrate
Is prevented. However, on the other hand, almost
Fully hydrogenated acrylonitrile-butadiene
The use of ion-exchange copolymer makes it suitable for introducing ion-exchange groups.
The compatibility with the monomer component begins to decrease and the resulting ion exchange
The exchange membrane is composed of ions with high diffusion constants such as hydrogen ions and hydroxyl ions.
Performance is not sufficient to prevent leakage of
Was. Thus, the ion selectivity of the ion exchange membrane is
When it came, for example, the ion exchange membrane was used for electrodialysis.
At the time, the concentration of the generated acid or alkali is sufficient
Can not be increased. Accordingly, the present invention provides
It has excellent mechanical properties and durability under severe conditions
Ion selection with less leakage of hydrogen ions and hydroxyl ions
Aims to produce ion exchange membranes with excellent properties
And [0007] Means for Solving the Problems The present inventors have made the above-mentioned description.
In light of the issues, we have continued our research. as a result,
As a matrix resin, an agent with a specific iodine value
Monomeric units based on rilonitrile and aliphatic hydrocarbon-based units
The above problem can be solved by using a copolymer with
The inventors have found that the present invention can be determined and completed the present invention. That is, the present invention provides:Chloromethylstyrene,
Single unit selected from styrene or 4-vinylpyridine
body, A crosslinking agent, a polymerization initiator and an iodine value of 10 to 50
Some acrylonitrile-based monomer units and aliphatic carbonization.
A mixture consisting of a copolymer with hydrogen-based unitsPolyvinyl chloride
Or polyolefinAdhered to substrate and polymerized
rear,To the resulting filmSpecial feature is to introduce ion exchange groups.
This is a method for producing an ion exchange membrane. In the production method of the present invention, the matrix
Acrylonit having an iodine value of 10 to 50 as a resin
Of the monomer units based on ril and the aliphatic hydrocarbon units
Use a polymer. Such a copolymer has an ion exchange group.
Both monomer components suitable for introduction and compatibility with the substrate
Good, excellent in flexibility, etc., and low in the amount of unsaturated bonds
Therefore, it has good chemical stability. Therefore, the copolymerization
The ion-exchange membrane obtained by using the body as a matrix resin is flexible
Mechanical properties such as durability and durability during use.
You. Furthermore, it has excellent ion selectivity,
ON leakage can be kept extremely low.
Suitable for the concentration of acids or alkalis in electrodialysis.
I do. A monomer unit based on the above acrylonitrile
And copolymers of aliphatic hydrocarbon units
Therefore, the content of each structural unit is not particularly limited
But have a functional group suitable for introducing ion exchange groups
Consider the compatibility with the polymer and the flexibility of the resulting copolymer
If acrylonitrile is 10% based on the total weight of the copolymer,
To 60% by weight, preferably 20 to 50% by weight.
It is suitable. Further, the molecular weight of the copolymer is particularly limited.
Although not always, usually 1,000 to 1,000,000
00 preferably in the range of 50,000 to 500,000
It is preferred to do so. The form of copolymerization is
A-B type diblock type, ABA type
Any type such as reblock type or random type
It may be something. In addition, divinylbenzene,
Containing trace amounts of third monomers such as lylic acid and acrylic acid
It may be. [0011] In the present invention, this copolymer is characterized in that
Those having a constant iodine value are used. The iodine value is
It is a value representing the residual amount of unsaturated bonds in the above copolymer,
Shown in grams of iodine absorbed by 100 g of polymer
You. Therefore, in the present invention, the above copolymer is
The iodine value of the aliphatic hydrocarbon-based unit constituting
There must be an unsaturated bond corresponding to the value. here
In the case where the iodine value is less than 10, the ion-exchange group is introduced.
Compatibility with suitable monomers begins to decrease and paste-like mixing
Phase separation occurs during preparation of the product, resulting in ion exchange
The ion selectivity of the membrane decreases. On the other hand, over 50
When used for concentration of acid or alkali solution, ion exchange
It is easy to cause peeling of the exchange resin and pinholes. In the present invention, the iodine value as described above is
Units and Aliphatic Coals Based on Acrylonitrile
The copolymer with hydride-based units can be produced by any method.
May be made. Usually, acrylonitrile and conjugated diol
After copolymerization with fins, the conjugated
Unsaturated bonds present in excess in fin-based units
Further, by appropriately hydrogenating the copolymer
It is generally obtained by eliminating an appropriate amount. This
Here, the conjugated diolefin is not particularly limited.
The conjugated diolefin having 4 to 9 carbon atoms is preferably used.
Is preferred. Specifically, butadiene, isoprene, etc.
It is preferably used. Next, it is mixed with the above matrix resin.
Suitable for introducing ion exchange groupsBaseHave a single amount
The body, crosslinking agent and polymerization initiator will be described. First,
Suitable for introducing ion exchange groups used in the present invention
Functional groupMonomers having chloromethylstyrene, styrene
A monomer selected from len or 4-vinylpyridine
is there. Here, in general, styrene is an anion exchange membrane,
It can be used for the production of both cation exchange membranes. Ma
Chloromethylstyrene and 4-vinylpyridine
Can be used for the production of an anion exchange membrane. [0014] The crosslinking agent may also be a conventionally known ion exchange.
The monomers used in the production of the replacement membrane are not particularly limited.
Used for Specifically, for example, m-, p-, o-di
Vinylbenzene, divinylsulfone, butadiene, black
Loprene, isoprene, trivinylbenzenes, divinyl
Lunaphthaline, diallylamine, triallylamine, di
Divinyl compounds such as vinylpyridines;
You. [0015] Further, the polymerization initiator may also be a known polymerization initiator.
The initiator is used without particular limitation, and the ion used
It should be properly selected according to the exchange membrane substrate and molding conditions.
No. For example, if the substrate is made of polyvinyl chloride,
When using, considering the melting point of the substrate, half-life is 10 o'clock
Radical having a decomposition temperature of 110 ° C. or less to obtain a space
Using a polymerization initiator, set the polymerization temperature to 110 ° C or lower.
It is recommended that To get the above half life of 10 hours
A radical polymerization initiator whose decomposition temperature is 110 ° C or less
For example, benzoyl peroxide, methyl ethyl ketone
Ton peroxide, methyl isobutyl ketone peroxy
, Cyclohexane peroxide, methylcyclohexa
Peroxide, isobutyl peroxide, 2,4-di
Chlorobenzoyl peroxide, o-methylbenzoyl
Peroxide, bis-3,5,5-trimethylhexanoy
Luperoxide, lauroyl peroxide, p-chloro
Benzoyl peroxide, 1,1-di-tert-butyl
Luperoxy-trimethylcyclohexane, 1,1-di
-Tert-butylperoxycyclohexane, 2,2
-Di- (tert-butylperoxy) -butane, 4,
4-di-tert-butylperoxyvaleric acid-n
-Butyl ester, 2,4,4-trimethylpentylpa
-Oxy-phenoxy acetate, α-cumyl peroxy
Shineodecanoate, tert-butyl peroxyneo
Decanoate, tert-butyl peroxypyvale
G, tert-butylperoxy-2-ethylhexano
Ethate, tert-butyl peroxy-isobutyrate
G, di-tert-butylperoxy-hexahydro
Terephthalate, di-tert-butyl peroxyaze
Rate, tert-butylperoxy-3,5,5-to
Limethyl hexanoate, tert-butyl peroxy
Acetate, tert-butyl peroxybenzoate
Are used. On the other hand, when a polyolefin substrate is used,
In this case, the decomposition temperature for obtaining a half-life of 10 hours is 110.
C. to 170.degree. C. using a radical polymerization initiator.
It is recommended to set the temperature above 80 ° C. Above half
Decomposition temperature for obtaining a life of 10 hours is 110 ° C. to 170
As the radical polymerization initiator at a temperature of, for example, p-
Tanhydroperoxide, diisopropylbenzene hydride
Peroxide, α, α'-bis (tert-butyl
-Oxy-m-isopropyl) benzene, di-tert
-Butyl peroxide, tert-butyl hydroperoxide
Oxide, di-tert-amyl peroxide, tert
-Butyl cumyl peroxide, dicumyl peroxide,
2,5-dimethyl 2,5-di (tert-butylperoxide)
Xy) hexane, 2,5-dimethyl 2,5-di (ter
t-butylperoxy) hexyne-3, cumene hydropa
-Oxide, 1,1,3,3-tetramethylbutyl hydride
Loperoxide, 2,5-dimethyl 2,5-dihydropa
-Oxyhexane, 2,5-dimethyl 2,5-dihydro
Peroxyhexin-3 and the like are used. In the present invention, the ion exchange described above is used.
Functionality suitable for introducing a substituentBaseMonomer, crosslinking agent, weight
The mixture of the initiator and the matrix resin must be
A functional group suitable for introducing the ion exchange group
Examples of the monomer and the monomer copolymerizable with the crosslinking agent
For example, styrene, acrylonitrile, ethyl styrene,
Nyl chloride, acrolein, methyl vinyl ketone,
Maleic anhydride, maleic acid, its salts or esters
, Itaconic acid, its salts or esters, etc.
May be combined. Also, dioctyl phthalate, dibutyl
Phthalate, tributyl phosphate, triacetyl citrate
Butyl, styrene oxide or aliphatic acid, aromatic
Plasticizers such as alcoholic esters of acids and even monomers
A solvent or the like for dilution may be appropriately added. In the present invention, the composition ratio of each component described above
Is not particularly limited, but generally,
Functionality suitable for introducing an exchange groupBaseHaveThe specific mentioned above
5 to 150 parts by weight of the crosslinking agent based on 100 parts by weight of the monomer
Part, based on acrylonitrile having the specific iodine value
Copolymers of monomer units and aliphatic hydrocarbon units
2 to 200 parts by weight, suitable for the introduction of the ion exchange group
Monomer with functional groupBody and0 to 200 copolymerizable monomers
In the range of parts by weight, the polymerization initiator was used in an amount of 100
In the range of 0.1 to 30 parts by weight per part by weight
Is preferred. The monomer mixture obtained as described above is
Is adhered to and polymerized. Here, as the base material,
Polyvinyl chloride used as a base material for ion exchange membranes
Le, PolyolefiTheThere are no restrictions on what can be used as the material resin
Used without being used. Better as an ion exchange membrane
In order to obtain high durability, use a polyolefin substrate.
Is recommended. As a base material made of polyolefin
Are polyethylene, polypropylene, polybutene those
From copolymers or blends of these polymers
Fabrics made are preferred. In addition, non-woven fabric, net, or
Can be used without limitation. The single yarn of such a woven fabric is a monofilament
Or a multifilament. Also the warp
Ion exchange with smaller weight of weft and weft
Although the electrical resistance of the membrane can be reduced, the fabric is kept
Because of the difficulty in holding
The number is preferably in the range of 10 to 500. In addition, small number of eyes
For woven fabrics, take measures such as partial fusion of single yarn intersections.
For example, it may be less than 10 meshes.
Filament with polyethylene and sheath
Therefore, if the polyethylene portion at the intersection is fused,
Even small woven fabrics can be used. The thickness of these substrates is particularly limited.
However, a range of 10 to 500 μm is preferable. Ma
In addition, calendering is applied to these polyolefin substrates.
By compressing the intersection of warp and weft
Improve the smoothness of the substrate surface or heat-treat the substrate in advance
Dimensional change during the heat polymerization process
May be performed. In addition, corona discharge treatment
Conventionally known polyolefins such as chlorsulfonic acid treatment
The surface treatment method of the base material made of
It is recommended as a means to improve the adhesion of Attach the monomer mixture to the substrate as described above
After polymerization, the temperature is generally raised from normal temperature under pressure
However, the heating rate is not particularly limited.
It can be selected appropriately. These polymerization conditions are involved
Depending on the type of polymerization initiator, the composition of the monomer mixture, and the type of substrate
Therefore, it is important to decide
Optimal conditions, optimal electrochemical and mechanical properties
An appropriate selection may be made in consideration of the above. In addition, this paste
The method of attaching to the cloth-like substrate, for example, coating or impregnation,
A known method such as immersion may be appropriately adopted. Film-form polymer obtained by polymerization as described above
The body isHas functional groups suitable for introducing ion exchange groups used
Depending on the monomer to be used, a known ion exchange group
What is necessary is just to apply the introduction method.For example, sulfonation, chlor
Sulfonation, chloromethylation and amination, quaternary
Chlorination of ammonium, quaternary pyridinium chlorination, phospho
Nitration, sulfoniumation, hydrolysis, etc.Inside
Therefore, by selecting a method for introducing a desired ion exchange group,
RCan be a cation exchange membrane or an anion exchange membrane
it can. The amount of these ion exchange groups introduced is particularly limited.
No, but usually the ion exchange capacity is 0.1-20 meq /
g-dried film, preferably 0.5-3 meq / g-dried film
Is preferably within the range. Also, the thickness of the ion exchange membrane
The desired electrical resistance, mechanical strength, transport number, durability, etc.
However, it is generally 10 to 500 μm, preferably 40 to 500 μm.
Preferably, it is in the range of ~ 300 [mu] m. [0024] According to the present invention, the conventional paste method is used.
In the method of manufacturing an exchange membrane,
Based on acrylonitrile having an iodine value of 10 to 50
Copolymers of monomer units and aliphatic hydrocarbon units
By using, matrix resin and ion exchange resin
Or significantly improve the adhesion to the substrate, especially at high temperatures,
Excellent durability against acids, alkalis and organic solvents
Properties can be imparted. Also, this matrix
The ion-exchange membrane obtained by using resin
Excellent on selectivity, leak of hydrogen ion and hydroxyl ion
Can be obtained. Further, the ion exchange membrane obtained by the present invention comprises:
Excellent in mechanical properties such as flexibility
In addition, the electrical characteristics are good. Therefore, this ion
Exchange membranes use especially concentrated neutral salts, acid or alkaline solutions.
For electrodialysis or diffusion dialysis or for the electrode reaction diaphragm
When using as other, generally use ion exchange membrane
It shows excellent properties in the system. [0026] Hereinafter, Examples and Comparative Examples of the present invention will be described.
The present invention is not limited to these examples. In Examples and Comparative Examples, ion exchange was performed.
The numerical values used for the performance evaluation of the replacement membrane will be described below. 1) Electric resistance (unit: Ω · cm)^Two) It was measured in 0.5 N NaCl at 25 ° C. 2) Ion exchange capacity (unit: meq / g-)
Dry film) For anion exchange membranes, change from chlorine ion type to nitrate ion
Chloride ions released when substituted
And quantified. For cation exchange membranes, hydrogen ion
Released when replacing the ion form with the sodium ion form
Elementary ions were determined by acid-base titration. 3) Intra-film diffusion constant (unit: cm)^Two/ Se
c) The intra-membrane diffusion constant (D) is the ion selectivity of the ion exchange membrane.
It is a standard and determines the leakage of hydrogen ions or hydroxyl ions.
It represents. 6N-HC for anion exchange membrane
1 / pure water and 6N-NaO for cation exchange membrane
H / pure water, temperature was measured under the condition of 25 ° C.
I did. [0031] Where: m: amount of permeated HCl or NaOH (eq) S: membrane area (cm^Two) δ: film thickness (cm) ΔC: concentration difference (mol / cm^Three) t: dialysis time (sec) 4) Water permeability (unit: ml / min) Adhesion between substrate and ion exchange resin in ion exchange membrane
This is a reference, and the membrane is bent at an angle of 90 °.
About 10kg / cm^TwoUnder the pressure of 1
The amount of water per minute was measured. Embodiment 1 70 parts by weight of chloromethylstyrene, 30 parts by weight of styrene
Parts, 15 parts by weight of divinylbenzene having a purity of about 57%,
5 parts by weight of lenoxide, half as a radical polymerization initiator
A distilling temperature of 126 ° C. to obtain a life of 10 hours.
-Tert-butyl peroxide 15 parts by weight and mat
Acrylonitrile content is 44% by weight as Rix resin
% Of acrylonitrile-butadiene having an iodine value of 25
Ene copolymer (trade name: Zetpol 1020, Nippon Ze
Was added to obtain a paste-like mixture. Next, a 200-th high-density polyethylene
Net (trade name: Nip strong net, manufactured by NBC Industries, thickness 190
μm) and apply the above paste-like mixture
After coating the tellurium film as a release material, use the paste method
Was performed. The polymerization pattern is from 20 ° C. to 120
Temperature for 3 hours, hold at 120 ° C for 7 hours
Was. The thickness of the obtained film polymer was 190 μm.
Was. Next, the obtained film-like polymer was trimmed.
Luamine 10% by weight and acetone 20% by weight aqueous solution
Amination reaction was performed at 30 ° C. for 16 hours.
A 210 μm anion exchange membrane was obtained. The resulting anion
The exchange membrane has an electric resistance of 3.7 Ω · cm.^TwoAnd Ion
The exchange capacity was 1.8 meq / g-dry membrane. Also,
The diffusion constant in the film is 3.5 × 10^-7cm^Two/ Sec, water permeability
Was 0. Embodiment 2 65 parts by weight of styrene, 35 parts by weight of chloromethylstyrene
Parts, 15 parts by weight of divinylbenzene having a purity of about 57%,
25 parts by weight of butyl phthalate, triple styrene oxide
Example in the quantity part1Acrylonitrile butadier used in
10 parts by weight of a copolymer of di-tert-butyl
8 parts by weight of oxide was added to obtain a paste-like mixture. Next
In the above-mentioned polyethylene net, the above-mentioned paste
Apply mixture and use polyester film as release material
After coating, polymerization was performed by a paste method. Polymerized putter
The temperature rises from 20 ° C to 120 ° C over 3 hours,
It was kept at 120 ° C. for 7 hours. Thickness of obtained film polymer
The height was 190 μm. Next, the obtained film polymer was concentrated sulfuric acid.
(97% product), sulfonation reaction at 60 ° C for 6 hours
After that, a cation exchange membrane having a thickness of 220 μm was obtained. This
The electrical resistance of the cation exchange membrane is 3.0 Ω · cm^Two, Io
The exchange capacity was 2.0 meq / g-dry membrane. Ma
The diffusion constant in the film was 4.8 × 10^-8cm^Two/ Sec, transparent
The amount of water was 0. Application Example 1 The anion exchange membrane obtained in Example 1 and the anion exchange membrane obtained in Example 2
The cation exchange membrane into a two-chamber electrodialysis machine
Then, sodium hydroxide was concentrated. The effective area is
200cm^TwoAnd the initial concentration of sodium hydroxide solution is
The concentration was 0.1 N on both the lean side and the concentration side. Operating conditions
Is the current density of 0.05 A / cm^Two, Temperature 80 ° C, solution flow
The speed was 10 L / min. 3 hours after starting operation, concentration
The concentration of the solution reaches 6.5N, and the subsequent solution concentration is
Kept close. 12 months after the start of operation, an electrodialysis machine
Stop operation, dismantle electrodialysis machine, anion exchange
The state of the film was observed. Anion exchange membranes have
There was no change. The ion exchange capacity of the energized part was measured.
As a result, the anion exchange membrane was 1.7 meq / g-dry.
Dry membrane and cation exchange membrane are 1.9 meq / g-dry membrane.
And there is almost no change in the values before electrodialysis.
Was. When the amount of water permeation was further measured,
0.01 ml / min for the exchange membrane and 0.1 ml for the cation exchange membrane.
It was 01 ml / min. Comparative Example 1 Acrylonitrile content of 4 as matrix resin
Acrylonit having an iodine value of 258 at 1.5% by weight
Lil-butadiene copolymer (trade name: Nippol DN1)
01, manufactured by Nippon Zeon Co., Ltd.
Thus, an anion exchange membrane having a thickness of 210 μm was obtained. Profit
The resulting anion exchange membrane has an electrical resistance of 3.8 Ω · cm.^Two
With an ion exchange capacity of 1.8 meq / g-dry membrane
there were. The diffusion constant in the film is 3.5 × 10^-7cm^Two/
sec, the amount of water permeation was 1.5 ml / min. Comparative Example 2 Except that the matrix resin used in Comparative Example 1 was used
Cation exchange of 220 μm thickness in the same manner as in Example 2.
A membrane was obtained. The obtained cation exchange membrane has an electric resistance of 3.
0Ωcm^TwoAnd the ion exchange capacity is 2.0 meq /
g-dry film. The diffusion constant in the film is 4.8 × 1
0^-8cm^Two/ Sec, water permeability is 2.6 ml / min
Was. Comparative application example 1 The anion exchange membrane obtained in Comparative Example 1 and the anion exchange membrane obtained in Comparative Example 2
Exactly the same as Application Example 1 except that a cation exchange membrane was used.
Concentration of sodium hydroxide by electrodialysis under similar conditions
Was. After the start of operation, the concentration of the solution on the concentration side gradually increases
And reached 6.5N after 3 hours. After that,
The liquid concentration was kept around 6.5N. Two months after the start of operation, the solution concentration on the concentration side was
The operation of the electrodialyzer was stopped because the temperature dropped to 2.5N.
Stop, disassemble the electrodialysis machine, and observe the state of the ion exchange membrane.
I thought. Both anion exchange membrane and cation exchange membrane
The exchange resin part is missing from the base material, resulting in a pinhole
Portions were observed. The ion exchange capacity of the energized portion was measured.
As a result, the anion exchange membrane was 0.8 meq / g-dry.
Dry membrane, cation exchange membrane 0.9 meq / g-dry membrane
Had declined. Further, when the amount of water permeation was measured,
Exchange membrane is 39ml / min, cation exchange membrane is 45m
1 / min. Comparative Example 3 Acrylonitrile content of 36 as matrix resin
Acrylonitrile-pig with an iodine value of 4 by weight
Diene copolymer (trade name: Zetpol 2000, JP)
Same as Example 1 except that this Zeon) was used.
Thus, a 210 μm thick anion exchange membrane was obtained. Got
The anion exchange membrane has an electric resistance of 3.7 Ω · cm^TwoIn
And the ion exchange capacity is 1.8 meq / g-dry membrane.
Was. The diffusion constant in the film is 8.3 × 10^-7cm^Two/ Se
c, the water permeability was 0. Comparative Example 4 Except for using the matrix resin used in Comparative Example 3,
Cation exchange of 220 μm thickness in the same manner as in Example 2.
A membrane was obtained. The obtained cation exchange membrane has an electric resistance of 3.
1Ω · cm^TwoAnd the ion exchange capacity is 2.0 meq /
g-dry film. The diffusion constant in the film is 9.8 × 1
0^-8cm^Two/ Sec, and the water permeability was 0. Comparative application example 2 The anion exchange membrane obtained in Comparative Example 3 and the anion exchange membrane obtained in Comparative Example 4
Exactly the same as Application Example 1 except that a cation exchange membrane was used.
Concentration of sodium hydroxide by electrodialysis under similar conditions
Was. After the start of operation, the concentration of the solution on the concentration side gradually increases
3 hours later, it reached 4.9N, and then the concentration side solution
The liquid concentration was kept around 4.9N. Twelve months after the start of operation, an electrodialysis machine
Stop operation, dismantle the electrodialysis machine,
Was observed. The ion exchange capacity of the energized portion was measured.
As a result, the anion exchange membrane was 1.8 meq / g-dry.
Dry membrane, cation exchange membrane is 2.0meq / g-dry membrane
there were. Further, when the amount of water permeation was measured,
Exchange membrane is 0.01ml / min, cation exchange membrane is
It was 0.02 ml / min. Embodiment 3 90 parts by weight of 4-vinylpyridine, 10 parts by weight of styrene,
15% by weight of divinylbenzene with a purity of 57%, radical weight
Decomposition temperature to obtain a half-life of 10 hours as a coalescence initiator
10 parts by weight of dicumyl peroxide at 117 ° C. and
Acrylonitrile content of 3 as matrix resin
Acrylonitrile having an iodine value of 28 at 6% by weight.
Butadiene copolymer (trade name: Zetpol 2020)
L, manufactured by Zeon Corporation) and mixed in a paste form
I got something. Next, the high-density poly
150th mesh made of ethylene (trade name: Nip strong net, N
BC Industry, thickness 150μm)
And apply the polyester film as a release material.
After covering, polymerization was performed by a paste method. Heating putter
The temperature rises from 20 ° C to 120 ° C over 5 hours,
It was kept at 20 ° C. for 5 hours. Thickness of obtained film polymer
Was 150 μm. Next, the obtained film-like polymer was washed with iodide
Using a 50% by weight methyl alcohol solution,
A quaternization reaction of pyridine ring nitrogen at 16 ° C. for 16 hours,
Further, in a 1N aqueous solution of sodium chloride, at 30 ° C. for 1 hour
During the immersion, an anion exchange membrane having a thickness of 170 μm was obtained. Profit
The electrical resistance of the obtained ion exchange membrane is 6.9 Ω · cm.^Twoso
there were. When the ion exchange capacity was measured,
It was a 5meq / g-dry film. The diffusion constant in the film is
1.9 × 10^-7cm^Two/ Sec, and the water permeability was 0. Embodiment 4 90 parts by weight of styrene, 10 parts by weight of chloromethylstyrene
Parts, 10 parts by weight of divinylbenzene having a purity of about 57%,
15 parts by weight of butyl phthalate, 1 layer of styrene oxide
Acrylonitrile butadiene used in Example 3 in parts by weight
12 parts by weight of copolymer and 3 parts by weight of dicumyl peroxide
In addition, a paste-like mixture was obtained. Next, the polyethylene made in Example 3 was used.
Apply the above paste-like mixture to the mesh of
After the film is coated as a release material,
Polymerization. Heating pattern is from 20 ℃ to 120 ℃
Up to 3 hours and hold at 120 ° C for 10 hours
Was. The thickness of the obtained film polymer was 150 μm.
Was. Next, the obtained polymer film was concentrated in concentrated sulfuric acid.
(97% product), sulfonation reaction at 60 ° C for 6 hours
The reaction was performed to obtain a cation exchange membrane having a thickness of 180 μm. This
The electrical resistance of the cation exchange membrane is 4.5Ωcm^Two, Io
The exchange capacity was 1.8 meq / g-dry membrane. Ma
The diffusion constant in the film was 3.4 × 10^-8cm^Two/ Sec, transparent
The amount of water was 0. Application Example 2 The anion exchange membrane obtained in Example 3 and the anion exchange membrane obtained in Example 4
The cation exchange membrane into a two-chamber electrodialysis machine
Then, the nitric acid was concentrated. Effective membrane area is 200cm
^TwoThe initial concentration of the aqueous nitric acid solution was 0.1 at both the lean side and the concentrated side.
1N. The operating conditions were a current density of 0.05 A /
cm^TwoThe temperature was 80 ° C., and the solution flow rate was 10 L / min. luck
After the start of the inversion, the concentration of the solution on the concentration side gradually increases,
Later it reached 5.3N. After that, the concentration of the solution on the concentration side becomes
It was kept around 5.3N. Twelve months after the start of operation, an electrodialysis machine
Stop operation, dismantle electrodialysis machine, anion exchange
The state of the membrane and the cation exchange membrane was observed. Anion exchange
The appearance of the membrane and the cation exchange membrane was not particularly changed. The ion exchange capacity of the energized portion was measured.
As a result, the anion exchange membrane was 1.5 meq / g-dry.
The dry cation exchange membrane is 1.8 meq / g-dry membrane.
And the value did not change before electrodialysis. When the water permeability was further measured,
0.01 ml / min for the exchange membrane and 0.1 ml for the cation exchange membrane.
It was 01 ml / min. Embodiment 5 80 parts by weight of chloromethylstyrene, 20 parts by weight of styrene
Parts, 5 parts by weight of styrene oxide, 57% pure divinyl
15 parts by weight of benzene, halved as a radical polymerization initiator
With a decomposition temperature of 74 ° C.
5 parts by weight of ilperoxide and matrix resin
The acrylonitrile content is 36% by weight and the iodine value is
28 acrylonitrile-butadiene copolymer (product
Name: Zetpol 2020, manufactured by Zeon Corporation) 30 weight
In addition, a paste-like mixture was obtained. Then, the thickness of the polyvinyl chloride is 110 μm.
m on woven cloth (trade name: TV-7012, manufactured by Teijin)
Apply the paste mixture described above and apply polyester
After coating as a release material, polymerization by the paste method is performed.
went. Heating pattern from 20 ° C to 70 ° C for 2 hours
The temperature was raised at 70 ° C. for 5 hours. The film obtained
The thickness of the polymer was 110 μm. Next, the obtained film-like polymer was used in Example 1
Aminated in the same manner as described above.
An exchange membrane was obtained. The resulting ion exchange membrane has an electrical resistance of
2.2Ω · cm^TwoAnd the ion exchange capacity is 1.5 me
q / g-a dry film. The diffusion constant in the film is 2.7.
× 10^-7cm^Two/ Sec, and the water permeability was 0. Embodiment 6 90 parts by weight of styrene, 10 parts by weight of acrylonitrile, pure
10% by weight of divinylbenzene having a degree of
The acrylic acid used in Example 5 was added to 25 parts by weight of tributyl enoate.
10 parts by weight of lonitrile butadiene copolymer,
Add 3 parts by weight of ilperoxide and paste-like mixture
Obtained. Next, the polyvinyl chloride woven fabric used in Example 5 was used.
Apply the above paste-like mixture to a cloth and apply polyester
After coating the film as a release material, use the paste method
Polymerization was performed. The heating pattern ranges from 20 ° C to 100 ° C.
For 30 minutes and kept at 100 ° C. for 2 hours. Profit
The thickness of the obtained film polymer was 110 μm. Next, the obtained film polymer was concentrated sulfuric acid.
(97% product), sulfonation reaction at 60 ° C for 6 hours
The reaction was performed to obtain a cation exchange membrane having a thickness of 170 μm. This
The electrical resistance of the cation exchange membrane is 1.5Ωcm^Two, Io
The exchange capacity was 1.8 meq / g-dry membrane. Ma
The diffusion constant in the film was 4.1 × 10^-8cm^Two/ Sec, transparent
The amount of water was 0. Application Example 3 The anion exchange membrane obtained in Example 5 and the anion exchange membrane obtained in Example 6
Using a cation exchange membrane and sulfuric acid instead of nitric acid.
Except that the sulfuric acid was electrodialyzed under the same conditions as in Application Example 2.
Concentration was performed. 3 hours after starting operation, concentration on the concentration side
Rose to 4.7N and was kept close to this value. Start driving
12 months later, the operation of the electrodialysis machine was stopped,
The analyzer was disassembled and the state of the ion exchange membrane was observed. Shade
Both the on-exchange membrane and the cation exchange membrane have no particular change in appearance.
Did not. The ion exchange capacity of the energized portion was measured.
As a result, the anion exchange membrane was 1.5 meq / g-dry.
The dry membrane and the cation exchange membrane are 1.8 meq / g-dry membrane.
And the value did not change before electrodialysis. Further, when the amount of water permeation was measured,
Exchange membrane 0.01ml / min, cation exchange membrane
It was 0.01 ml / min. Embodiment 7 100 parts by weight of 4-vinylpyridine, 57% pure divinyl
5 parts by weight of benzene, half-life as a radical polymerization initiator
Tert with a decomposition temperature of 72 ° C. to obtain 10 hours
-Butyl peroxy-2-ethylhexanoate 6 weight
Acrylonitrile as part and matrix resin
Acrylonit having an amount of 36% by weight and an iodine value of 11
Lil-butadiene copolymer (trade name: Zetpol 20)
10, 30 parts by weight of Zeon Corporation)
Compound was obtained. Next, the thickness of polyvinyl chloride is 90 μm.
Woven cloth (trade name: TV-7275, manufactured by Teijin)
Polyester paste
And then polymerized by paste method.
Was. The heating pattern is from 20 ℃ to 50 ℃ for 1 hour.
And kept at 50 ° C. for 5 hours. Obtained film height
The thickness of the molecular body was 90 μm. Next, the obtained film-like polymer was washed with iodide
Using a 50% by weight methyl alcohol solution,
A quaternization reaction of pyridine ring nitrogen at 16 ° C. for 16 hours,
Further, in a 1N aqueous solution of sodium chloride, at 30 ° C. for 1 hour
During the immersion, an anion exchange membrane having a thickness of 170 μm was obtained. Profit
The electrical resistance of the obtained ion exchange membrane is 0.5 Ω · cm^Two,
The ion exchange capacity was 2.5 meq / g-dry membrane.
Was. Further, the water permeability was 0. Application Example 4 The anion exchange membrane obtained in Example 7 was assembled in a diffusion dialysis device.
10% by weight of dioxane and 20% by weight of iron nitrate
% Nitric acid was recovered. Effective membrane area is 200c
m^TwoThe initial nitric acid aqueous solution concentration is 5.0N on the lean side,
Pure water was flown to the concentration side. The operating conditions were 50 ° C
The solution flow rate was 20 L / min. After the start of operation,
The concentration of the solution gradually increased and reached 2.9N after 5 hours.
Was. The dioxane concentration in the recovered nitric acid is 0,
The degree was 0.5% by weight. After that, every 5 hours
Repeat the process of extracting the solution of
Was. 12 months after the start of operation, the operation of the diffusion dialysis
Stop, disassemble the device and observe the condition of the anion exchange membrane.
Was. The appearance of the anion exchange membrane was not particularly changed.
Also, the ion exchange capacity of the anion exchange membrane in the energized area
Was measured, it was 2.5 meq / g-dry film,
There was no change in the values before electrodialysis. In addition,
When the amount of water was measured, it was 0.02 ml / min.
Was. Comparative Example 7 Acrylonitrile content of 4 as matrix resin
Acrylonitrile having an iodine value of 263 at 0.5% by weight
Ru-butadiene random copolymer (trade name: Nippol)
  Example except that 1041 (manufactured by Zeon Corporation) was used.
In the same manner as in Example 7, an anion exchange membrane having a thickness of 170 μm was obtained.
Was. The obtained anion exchange membrane has an electrical resistance of 0.6Ω
cm^TwoAnd an ion exchange capacity of 2.5 meq / g-dry
It was a dry film. The water permeability is 1.1 ml / min.
Was. Comparative Application Example 3 Except for using the anion exchange membrane obtained in Comparative Example 7,
Recovery of nitric acid by diffusion dialysis under exactly the same conditions as in Application Example 4
Was done. The concentration of recovered nitric acid at the beginning of operation is 2.8N,
The concentration of xan was 0 and the concentration of iron nitrate was 0.8% by weight.
Six months after the start of operation, the concentration of the recovered nitric acid was reduced to 1.4N.
The dioxane concentration increased to 2.1% by weight,
The operation was stopped because the iron concentration increased to 1.6% by weight.
The device was disassembled and the state of the anion exchange membrane was observed. Shade
The ion-exchange resin part of the on-exchange membrane is missing from the substrate
A part of the hole was observed. Ion exchange volume
When the amount was measured, it decreased to 1.9 meq / g-dry film.
Was. When the amount of water permeation was measured, 69 ml /
min.

Claims (1)

(57) [Claims] (1) Chloromethylstyrene, styrene, or
A mixture of a monomer selected from 4-vinylpyridine , a crosslinking agent, a polymerization initiator, and a copolymer of a monomer unit based on acrylonitrile having an iodine value of 10 to 50 and an aliphatic hydrocarbon-based unit is poly PVC or Polyole
After adhering to the fin substrate and polymerizing, the resulting film
A method for producing an ion exchange membrane, comprising introducing an ion exchange group into a product.