JPS6357443B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing polymer electrolytes. Polymer electrolytes are polymeric compounds with groups that can be dissociated in aqueous solutions or polar organic solvents, and there are various types such as water-soluble, water-insoluble, organic solvent-soluble, insoluble, and infusible. There are various shapes such as granular, fibrous, tubular, and membrane, and they are used industrially in various fields. For example, water-soluble ones are used as flocculants and catalysts, while insoluble ones are widely used in ion exchange and catalysts, and especially membrane-like ones are widely used in electrodialysis, diffusion dialysis, diaphragms for electrode reactions, etc. . On the other hand, fluorine-bonded organic compounds exhibit unique properties in various aspects. For example, in the case of dyes, it is said that the color tone becomes hypochromic, the clarity increases, and the fastness to sunlight increases. In addition, surfactants have a remarkable ability to lower surface tension, and those with a small amount of carbon have a large surfactant effect. Furthermore, fluorine-containing polymers exhibit excellent chemical resistance and heat resistance. For example, a copolymer of perfluoro (3,6-dioxa-4-methyl-7-octensulfonyl fluoride) and tetrafluoroethylene is hydrolyzed as a polymer electrolyte that exhibits little performance deterioration even in high temperature and oxidizing atmospheres. The obtained cation exchange resin and cation exchange membrane are known. It is known that when a fluorine atom is introduced into an organic compound in this way, it is imparted with unique physical properties different from those of a simple hydrocarbon-based organic compound. Based on the above-mentioned background, the present inventors have
In particular, as a result of repeated research on the synthesis of cationic polymer electrolytes that combine cationic charges and fluorine atoms, we found that 1,8-diaza-dibicyclo(5,4,0)undecene-7

[Formula] has surprisingly good reactivity with fluorine-containing polymer compounds,
The inventors discovered that a cationic polymer electrolyte can be easily obtained and completed the present invention. That is,
The present invention relates to a fluorine-containing polymer compound having a molecular weight of 500 or more, having a fluorine atom bonded within the molecule, and having a halogen atom other than a fluorine atom in the main chain (having a fluorine atom bonded within the molecule). , which has a cation exchange group bonded thereto or has a functional group into which a cation exchange group can be introduced by post-treatment, and at least one structural unit selected from the group consisting of vinylidene fluoride and vinyl fluoride. 1,8-diaza-bicyclo(5,4,0)undecene-7 is reacted with 1,8-diaza-bicyclo(5,4,0)undecene-7. The fluorine-containing polymer compound used for producing the polymer electrolyte of the present invention includes halogen atoms other than fluorine atoms, which have fluorine atoms bonded to the main chain,
For example, it is a fluorine-containing polymer compound having a molecular weight of 500 or more and having chlorine, bromine, and iodine combined. however,
Among the above-mentioned fluorine-containing polymer compounds, those having a fluorine atom bonded within the 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 having fluorinated Fluorine-containing polymer compounds having at least one constituent unit selected from the group consisting of vinylidene and vinylidene fluoride are excluded. The fluorine-containing polymer compound used in the present invention has a halogen atom other than fluorine in the main chain, and the halogen, especially chlorine, is bonded to the structural unit of 1,8-diaza-bibicyclo(5,4,0 ) Undecene-7 (hereinafter abbreviated as DBC) binds selectively. For example, it binds to an ethylene trifluoride-chloride unit to replace chlorine, or it forms a double bond in the main chain at the same time as it binds. Of course,
DBC also bonds to -CHCl-CH ₂ - units, etc., but in the case of polymer compounds with such structural units, either they do not have fluorine atoms or the fluorine atoms are separated and removed by the reaction. Therefore, fluorine atoms remain in the polymer electrolyte obtained by using a fluorine-containing polymer compound that combines other fluorine atoms and has a constituent unit that does not react with DBC, or by controlling the reaction conditions. It is desirable to implement it as follows. That is, the fluorine-containing polymer compound used in the present invention may be a so-called homopolymer composed of repeating a single constituent unit having the above properties, or it may be a so-called homopolymer composed of repeating a single constituent unit having the above properties, or it may be a so-called homopolymer composed of repeating a single constituent unit having the above properties. It may also be a copolymer composed of. 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 non-polymers has a unit reactive with DBC. In such cases
The proportion of structural units that react with DBC in the copolymer varies depending on the intended use of the obtained polymer electrolyte, but on average 10% or more reacts in terms of molar ratio among all the structural units of the copolymer. It is desirable that active building blocks are included. On the other hand, other structural units in the copolymer that are difficult to react with DBC include -CF ₂ -CFH-, -CF ₂ -CF ₂ -,

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(n is 0 or a positive integer; R ₁ is H or a saturated/unsaturated linear/cyclic hydrocarbon group with 1 to 16 C; fluorine-containing group; X is OH, halogen, OR ₁ )
and other fluorine-containing polyvinyl, polyallyl compounds, etc., particularly those having fluorine atoms bonded are preferred without limitation. Also included in the above copolymers
Structural units that are difficult to react with DBC include hydrocarbon-based units if fluorine atoms still remain in the resulting polymer electrolyte after reacting the DBC with a fluorine-containing polymer compound. good. 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. 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 a liquid state, 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, if the molecular weight is extremely low, such as trifluoromonochlorinated ethylene oligomers, an alcohol such as methanol may be used; When the molecular weight becomes large, aromatic compounds such as benzene are used, and when the molecular weight becomes even larger, fluorine-based solvents, dimelformamide, 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 DBC reaction may proceed as it is or by swelling the polymer compound with an appropriate solvent at room temperature or under heating. The solvent used in this case is appropriately selected from dimethyl sulfoxide, dioxane, dimethyl formamide, etc., or a fluorine-containing solvent depending on the type of polymer compound. In addition, when heating and reacting under normal pressure, it is necessary to conduct 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. The polymer electrolyte obtained in the present invention can be used in all systems using conventional polymer electrolytes. For example, if it is water-soluble, it can be used as a flocculant, or if it is granular, it can be used as an ion exchanger, and if it is membrane-like, it can be used as an ion exchange membrane. In this case, when DBC is combined with a fluorine-containing polymer compound, it becomes a cationic polymer electrolyte, but the present invention is not necessarily intended to produce only a cationic polymer electrolyte. If an anionic functional group is bonded to the fluorine-containing polymer compound in advance, or if a functional group that can be easily converted to an anionic functional group is bonded to the fluorine-containing polymer compound, it may be used as is or An anionic functional group can be easily introduced by a conversion reaction into an anionic functional group, and an amphoteric polymer electrolyte can also 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, a carboxylic acid group, a phosphoric acid group, a phosphorous acid group, a phenolic hydroxyl group, or a thiol group. , a sulfate ester group, a phosphate ester group, a phosphite ester group, an acid amide group having a dissociable hydrogen atom, a metal chelate compound having a negative charge, etc. In addition, fluorine-containing polymer compounds
After binding DBC, an anionic functional group may be introduced. 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, if there is an anionic functional group inside and a layer with DBC bonded on the surface, conversely,
For example, there is a layer that combines DBC, and the surface layer has a layer of anionic functional groups. Further, in the case of a membrane-like material, there may be a layer reacted with DBC on only one side, and a layer bonded with an unreacted or anionic functional group on the back side. Alternatively, there may be a DBC-reacted layer on both sides and a layer containing an unreacted or anionic functional group inside, or vice versa. Of course, when DBC is uniformly bound to the uniform presence of anionic functional groups,
A so-called amphoteric layer, an amphoteric resin, an amphoteric membrane, etc. may be produced. Some specific examples will be explained below. A copolymer of vinyl chloride and ethylene trifluoride monochloride was dissolved in toluene to form a homogeneous polymer solution. After pouring this onto a horizontal glass plate, the toluene was evaporated and the remaining film was placed in DBC. By immersion, the DBC can be bonded to a film to obtain an anion exchange membrane. In addition, an oligomer of ethylene trifluoride monochloride with a molecular weight of 500 to 2000 is mixed with DBC in an amount smaller than one equivalent of chlorine in the oligomer,
When left for one week at room temperature, the mixture becomes a black oil, which dissolves very well in water and has a cationic charge, as confirmed by the fact that it selectively adsorbs to the cation exchange resin. Furthermore, a finely powdered polymeric compound of ethylene trifluoride monochloride is uniformly mixed with an oily oligomer of ethylene trifluoride monochloride, and then this is formed into granules,
When heated and immersed in DBC, the granules turn black and exhibit anion exchange properties. Further, by treating this with methyl iodide, a strongly basic anion exchange resin can be obtained. Alternatively, a copolymer of ethylene trifluoride and ethylene tetrafluoride in fine powder form is uniformly mixed with an oligomer of ethylene trifluoride monochloride, and this is heated and pressurized to form a film-like polymer compound. . Then convert this to DBC
Warm it inside and soak it for a long time. This results in a weakly basic anion exchange membrane, which can also be further treated with an alkylating agent such as methyl iodide or dimethyl sulfate to form a strongly basic anion exchange membrane. The content of the present invention will be explained in more detail in the following Examples, but the content of the present invention is not restricted by these Examples. Example 1 1,8-diaza-bicyclo(5,4,
0) Add 720 parts of undecene and mix evenly.
Stirring was continued at 30° C. for 24 hours. It became a dark brown oily liquid, and when this was poured into 100 parts of pure water, it became a uniform brown aqueous solution. Next, this was dried on a water bath to remove moisture, and then heated to 100°C and reduced pressure to 4 mmHg to remove unreacted substances. The resulting oily brown liquid was water-soluble, and when the cation exchange resin and anion exchange resin were immersed in 1 g of aqueous solution, it selectively adhered to the cation exchange resin. Elemental analysis of the oily brown liquid obtained revealed that the N content was 4.2%. Example 2 8 parts of a fine powder polymer of ethylene trifluoride monochloride (trade name Daiflon, manufactured by Daikin Industries KK) and an oligomer of monochloroethylene trifluoride (Daifloil #10, molecular weight 800, manufactured by Daikin Industries KK) were mixed as much as possible. Spread the mixture uniformly on an aluminum foil, cover with another aluminum foil from above, sandwich it between hot plates, and heat it to 240℃ to give a temperature of 0.10
A sheet with a thickness of mm was obtained. Add this to 1,8-diaza-bicyclo(5,4,0) undecene-7.
After soaking at 45℃ for one week, washing with water and then
After being alternately equilibrated with 1N-HCl and 1N-NaOH, the electrical resistance was measured by alternating current for 1000 cycles at 25°C in 1N-HCl and found to be 28Ω-cm ² . Also, for membranes immersed in hydrochloric acid, 0.5N−
The membrane potential was measured using NaCl/2.5N-NaCl, and the ring ratio was calculated to be 0.77. Moreover, the exchange capacity as a weakly basic ion exchanger was 0.62 meq/dry membrane. Example 3 A copolymer consisting of 75 parts of trifluoromonochloride ethylene and 25 parts of tetrafluoroethylene was prepared by the following method.
That is, 400 parts of water to 100 parts of the mixture of both monomers,
Emulsion polymerization was carried out using 2 parts of sodium perfluorooctanoate, 0.13 parts of hydrogen peroxide, and sodium formaldehyde sulfoxy. To 75 parts of the above copolymer in fine powder form, 25 parts of the trifluoromonochloride ethylene oligomer used in Example 2 was added, mixed uniformly, and heated to 0.100 mm on a hot plate heated to 240°C. It was molded into a sheet with a thickness of . Next, this sheet was immersed in dimethyl sulfoxide in advance to swell it, and then immersed in a mixture of 65 parts of 1,8-diaza-bicyclo(5,4,0)undecene-7 and 35 parts of dimethyl sulfoxide, and heated at 70°C. and heated for 2 weeks. After washing the obtained black sheet with water and equilibrating it alternately in 1N-HCl and 1N-NaOH, the electrical resistance was measured in the same manner as in Example 2 in 1N-HCl and found to be 53Ω-cm ² . The ring ratio was determined from the membrane potential according to Example 2 and was found to be 0.75. Also, the exchange capacity is 0.68 milliequivalent/
It was a gram dry film. Next, this membrane was immersed in methyl iodide to alkylate the weakly basic anion exchange groups to make them strongly basic. When the electrical resistance of this membrane was measured in 0.5N-NaCl, it was 33Ω-cm ² and the ring ratio similarly determined from the membrane potential was 0.82. Example 4 A polymer compound was obtained by copolymerizing tetrafluoroethylene and propylene by a conventional method. Then, this powder was fluorinated with fluorine gas while still in fine powder form. The propylene portion was fluorinated, and elemental analysis showed a fluorine content of 57%. The copolymer used had a ratio of propylene to tetrafluoroethylene of about 3:1. Furthermore, infrared (IR) analysis revealed that -CH ₃ in the propylene units and -H in the main chain of the copolymer were partially fluorinated. Next, the fine powder of this polymer was dispersed in ethylene dichloride, and bromine gas was fed to further bromine the remaining hydrogen. When this was subjected to elemental analysis to determine the Br content, it was found to be 10.3%. Next, the resulting fluorinated and brominated copolymer was heated and pressurized to form a lump, which was then ground to form a granular copolymer. This was kept in 1,8-diazabicyclo(5,4,0)undecene-7 at 80℃ for one week, and then 1N-
Conditioned with HCl and 1N-NaOH,
The exchange capacity was determined to be 0.35 milliequivalents/gram dry resin.

Claims (1)

[Scope of Claims] 1. A fluorine-containing polymer compound having a molecular weight of 500 or more, having a fluorine atom bonded within the molecule, and having a halogen atom other than a fluorine atom in the main chain (a fluorine-containing polymer compound having a fluorine atom bonded within the molecule). at least one member selected from the group consisting of vinylidene fluoride and vinyl fluoride, which has a cation exchange group bound to it or has a functional group into which a cation exchange group can be introduced by post-treatment. 1. A method for producing a polymer electrolyte, which comprises reacting a fluorine-containing polymer compound having a structural unit (excluding a fluorine-containing polymer compound) with 1,8-diazabicyclo-5,4,0-undecene-7. 2. The production method according to claim 1, wherein the fluorine-containing polymer compound is a polymer or copolymer having a trifluoride-ethylene chloride structural unit. 3 The fluorine-containing polymer compound is present in at least one direction 1
The manufacturing method according to claim 1, which is a film-like material having a size of cm or more. 4. The manufacturing method according to claim 1, wherein the polymer electrolyte is a soluble liquid substance. 5. The manufacturing method according to claim 1, wherein the polymer electrolyte is a granular material.