JPS6055524B2 - Method for producing amphoteric ion exchange resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing amphoteric ion exchange resins.

Amphoteric ion exchange resins exist in various shapes such as granules, fibers, tubes, and membranes, and are used industrially in various fields.

The present inventors have been engaged in research on the production of amphoteric ion exchange resins, and have found that 1,8-diazadibicyclo(5,4,0)
Undecene-7QN◆ has surprisingly good reactivity with certain synthetic polymer compounds,
The inventors discovered that amphoteric ion exchange resins can be easily obtained and completed the present invention.

That is, the present invention has a fluorine atom bonded in the molecule, has a cation exchange group bonded, or has a functional group into which a cation exchange group can be introduced by post-treatment, and has vinylidene fluoride and fluoride. If necessary, a synthetic polymer compound having at least one constituent unit selected from the group consisting of vinyl is reacted with 1,8-diazabicyclo(5,.4,0)undecene-7. This is a method for producing an amphoteric ion exchange resin characterized by introducing a cation exchange group. The composite polymeric compound used to produce the amphoteric ion exchange resin of the present invention has a fluorine atom bonded within the molecule, a cation exchange group bonded, and a fluorine-containing compound. Vinylidene (-CF, -CH, -) and vinyl fluoride (-CH
It is a composite polymeric compound having a structural unit of F-CH2-).

That is, as the composite polymer compound used in the present invention, 5 may be a so-called homopolymer composed of repeating the above-mentioned single constituent unit, or it may be composed of two or more different constituent units. Even if it is a copolymer that is
(2) The copolymer may be any of random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization.
Therefore, it is necessary that at least one of the structural units in these copolymers has a unit reactive with ■°C, ie, a vinylidene fluoride or vinyl fluoride structural unit. In such a case, the proportion of structural units that react with T℃ in the copolymer varies depending on the purpose of use of the obtained polymer electrolyte, but the average molar ratio among all the structural units of the copolymer is It is desirable that 10% or more of reactively active structural units be contained. On the other hand, other copolymerized structural units constituting the copolymer with the above structural units include, for example, (n is 0 or a positive integer; R1 is H or a saturated/unsaturated linear chain with 1 to 16 C; Cyclic hydrocarbon type, fluorine-containing group; X is 0H1
Among polyvinyl and polyallyl compounds containing halogen, 0R1) and other fluorine, those having fluorine atoms bonded are particularly preferred without limitation.

The copolymerization unit contained in the above copolymer may be carbonized if fluorine atoms still remain in the resulting amphoteric ion exchange resin after reacting the DBC with a fluorine-containing polymer compound. It may be hydrogen-based. For example, it may correspond to one monomer unit of a polymer compound obtained by polymerizing a conventionally known hydrocarbon vinyl or allyl compound such as.

The fluorine-containing polymer compound used in the present invention may be one having the above-mentioned properties, but in general, one having a molecular weight of 500 or more and a solid powder or granule is most preferably used. If an anionic functional group, that is, a cation exchange group, is bonded to the fluorine-containing polymer compound used in the present invention, it may be used as is, or it may be bonded with a functional group that can be easily converted into an anionic functional group. When such a functional group is present, an anionic functional group can be easily introduced by a reaction of converting the functional group into a cation exchange group, and an amphoteric ion exchange resin can be obtained.

In this case, the anionic functional group is a conventionally known functional group that becomes negatively charged in an aqueous solution, such as a sulfonic acid group,
Carboxylic acid group, phosphoric acid group, phosphorous acid group, phenolic hydroxyl group, thiol group, sulfuric acid ester group, phosphoric acid ester group, phosphorous acid ester group, acid amide group having a dissociable hydrogen atom, metal chelate compound. These include things that have a negative charge. Further, after bonding DBC to the fluorine-containing polymer compound, these anionic functional groups may be introduced by post-treatment. In particular, in the case of granular or film-like materials, different ion-exchangeable groups may be present in the surface layer and the interior.

In other words, there is an anionic functional group inside, and the surface layer has a
In some cases, there is a layer in which . Further, in the case of a film-like material, there may be a layer reacted with...C on only one side, and a layer bonded with an unreacted or anionic functional group on the back side. Alternatively, there may be a layer having a temperature of 1.degree. C. on both sides, and a layer having an unreacted or anionic functional group inside, or vice versa. Of course, DBC is uniformly bonded to the uniform presence of anionic functional groups, resulting in the so-called amphoteric layer, amphoteric resin,
A case where an amphoteric membrane or the like is manufactured may also be used. There are no particular limitations on the means for bonding DBC to the above-mentioned fluorine-containing polymer compound.

When the fluorine-containing polymer compound is in liquid form, it may be mixed and reacted with DBC as it is or in the presence of a suitable solvent at room temperature or under heating. In this case, the solvent will vary depending on the type and degree of polymerization of the fluorine-containing polymer compound used.
For example, aromatic compounds such as alcohol benzene, fluorine-based solvents, dimethylformamide, dimethyl sulfoxide, etc. are used. Of course, the oligomer of the fluorine-containing polymer compound may be dispersed in a solvent such as water, and the DBC may be dissolved in the water and reacted. Further, when the fluorine-containing polymer compound is a solid, the polymer compound may be swollen with an appropriate solvent and the reaction may be allowed to proceed at room temperature or with heating.

The solvent used in this case is dimethyl sulfoxide,
Dioxane, dimethylformamide, etc., or a fluorine-containing solvent is appropriately selected depending on the type of polymer compound. In addition, when the reaction is carried out under normal pressure, it is necessary to carry out the reaction at a temperature below the temperature at which the fluorine-containing polymer compound does not decompose, below the temperature at which DBC does not decompose, and below the boiling point of the solvent used. It is. Further, the reaction time, reaction method, and reaction apparatus may be appropriately selected depending on the type of polymer electrolyte to be produced. EXAMPLES In order to explain the present invention more specifically, examples will be described below, but the content of the present invention is not restricted by these examples. Example 1 Ethylene tetrafluoride 2 to 5 ethylene trifluoride monochloride
A copolymer containing 30 m of vinylidene fluoride and vinylidene fluoride was prepared in the following manner.

That is, 400 W of water per 10 C of the total monomer mixture)
, 2 parts of sodium perfluorooctanoate, 0. Emulsification was carried out using hydrogen peroxide and sodium formaldehyde sulfoxy in Part B. Next, this was formed into granules of about 60 mesh, and then immersed in a bath containing 1,2-dichloroethane and chlorosulfonic acid at a weight ratio of 1:1 for 6 to 10 V. After washing with sulfuric acid and successively washing with dilute sulfuric acid, soaked in 3.0N NaOH at 60°C.
It was immersed for 1 m. After drying the granules under reduced pressure, they were again immersed in 1,8 diazabicyclo(5,4,0) undecene-7 with 6C)C for one week. The obtained black granular resin was air-dried and then immersed in methyl iodide for alkylation treatment. In this way, an amphoteric ion exchange resin having both a sulfonic acid type cation exchange group and a strongly basic anion exchange group was obtained. When the exchange capacity was measured, the cation exchange capacity was 0.58 meq/g dry resin, and the anion exchange capacity was 0.45 meq/g dry resin.

Example 2 3 parts of ethylene trifluoride monochloride, 10 parts of ethylene tetrafluoride, and 60 m of vinylidene fluoride were placed in 40 parts of water, and 2 parts of sodium perfluorooctanoate and 0.15 parts of hydrogen peroxide were added as dispersants. Polymerization was carried out at 25° C. for 1 m using sodium formaldehyde sulfoxy as a polymerization aid, and after salting out with calcium chloride, a finely powdered polymer was obtained.

After drying this, it was heated to 0.15m using a heat breather.
This is then immersed in dimethylformamide to swell it, and then immersed in a bath consisting of 1 part of carbon tetrachloride and 2 parts of chlorosulfonic acid with a purity of 90% or higher to undergo chlorsulfonation treatment. Did. Take out the membrane 1, 2
After thorough washing with -dichloroethane and air drying, 1,8-diazabicyclo(5,4,0) was applied to only one side of the membrane.
It was brought into contact with Undecene-7 at 80°C for 3 hours. Then,
After washing this membrane with water, it was immersed in NaOH at room temperature for a period of time to be hydrolyzed. This is due to the presence of sulfonic acid groups on one side of the membrane, and the amphoteric layer on the other side in which the 1,8-diazabicyclo(5,4,0)undecene-7 and sulfonic acid groups are bonded. An ion exchange membrane having the following properties was obtained. Using this membrane, a 0.5N-NaCl solution was placed in both chambers, and the electrical resistance of the DC current was measured with the membrane surface containing the amphoteric layer facing the anode at 1 JAI dr1t without stirring the liquid.11
It was 5Ω-d. On the other hand, when the direct current electrical resistance of the same film was similarly measured with the side on which the J amphoteric layer was present facing the cathode, it was found to be 23 Ω-d.

That is, the above-mentioned ion exchange membrane was a cation exchange membrane having a layer bonding weakly basic anion exchange groups on one side of the membrane surface. In addition, the electrical resistance of a membrane subjected to only the sulfonation monohydrolysis without treating one side of the membrane with the above base was 23 Ω-d when measured under the same conditions. Next, using the above cation exchange membrane, the layer containing weakly basic anion exchange groups was directed toward the cathode, and the anode was coated with ruthenium oxide and titanium oxide on a titanium lath material. Using a nickel-plated soft iron wire mesh, a saturated saline solution was poured into the anolyte and electrolyzed at a current density of 30 AId, and 5.0N-NaOH was constantly obtained from the cathode chamber by supplying pure water.

What is the current efficiency for NaOH acquisition? It was %. The amount of NaCl in NaOH was 120 ppm calculated as 48% NaOH. Example 3 Vinyl fluoride was emulsion polymerized in 7C) using α,α-azobisisobutyronitrile as a polymerization initiator at a pressure of 7 for 2 hours.

Claims (1)

[Scope of Claims] 1 A compound having a fluorine atom bonded within its molecule, having a cation exchange group bonded thereto, or having a functional group into which a cation exchange group can be introduced by post-treatment, and vinylidene fluoride and A fluorine-containing polymer compound having at least one constituent unit selected from the group consisting of vinyl fluoride and 1,8-diaza-bicyclo(
5,4,0) A method for producing an amphoteric ion exchange resin, which comprises reacting with undecene-7 and introducing a cation exchange group as necessary. 2. The manufacturing method according to claim 1, wherein the fluorine-containing polymer compound is a film-like material having a size of 1 cm or more in at least one direction. 3. The manufacturing method according to claim 1, wherein the amphoteric ion exchange resin is in the form of powder or granules.