JPS6358161B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a treatment method in which a fluorine-containing compound having a -SO ₂ X group (X is a halogen, hydrogen, metal ion, or organic cation) is brought into contact with a metal carbonyl compound. It provides a simple and easy way to obtain the desired results. Conventionally, fluorine-containing compounds have been widely used as solvents, surfactants, etc. for low-molecular compounds, and as engineering plastics and functional polymers for high-molecular compounds due to their unique heat resistance. It is used to take advantage of its properties such as , chemical resistance, and low surface energy. Particularly in recent years, fluorine-containing compounds having ionic charges have been extremely actively researched in the fields of surfactants, porous diaphragms, ion exchange resins, ion exchange membranes, etc., in conjunction with their unique functions. In such charged fluorine-containing compounds, widely used functional groups include sulfonic acid groups, phosphoric acid groups, carboxylic acid groups, phenolic hydroxyl groups, acid amide bonds with dissociable hydrogen atoms, and perfluorinated fluorine-containing compounds. OH bonded to the tertiary carbon is used. In particular, the most common and stable group among these is the sulfonic acid group. As such low molecular fluorine-containing compounds having a sulfonic acid group, perfluorocarbon surfactants, fluorovinyl compounds having a sulfonic acid group, particularly perfluorovinyl ether compounds, and the like are widely known. In addition, as polymeric fluorine-containing compounds, polymeric compounds in which a sulfonic acid group and a fluorine atom are bonded are known, especially perfluorocarbon-based compounds. Fluoro(3,6-dioxer-4
-Methyl-7-octensulfonyl fluoride) and tetrafluoroethylene are hydrolyzed to form polymer membranes, granules, and liquids. Therefore, in the above-mentioned fluorine-containing compounds having a sulfonic acid group, the sulfonic acid group bonded to the carbon atom to which the fluorine atom is bonded has the property of being an extremely strong acid, and does not belong to the so-called super strong acids. be. While such properties may be highly desirable in some cases, they may also be undesirable in other cases. To this end, various attempts have been made to convert such sulfonic acid groups into carboxylic acid groups with lower acid strength, and some of these have been commercialized. For example, in the case of a polymer membrane, a method is used in which a sulfonyl halide group, which is a precursor of a sulfonic acid group, is reacted with a reducing agent to form sulfinic acid, which is then further reduced to form a carboxylic acid (JP-A-52 -24176, JP-A-52-24177, etc.), a method of reacting a perfluoro compound having a functional group such as sulfonyl chloride with an iodine compound to form a carboxylic acid as -CF ₂ I (JP-A-53-125974), A method in which a compound having a sulfonyl halide group is reacted with hydrazine to convert it into sulfinic acid and then into a carboxylic acid (JP-A-53-132094), a method in which a perfluoro compound having a sulfonyl halide group is oxidized in the presence of an organic compound. and those with carboxylic acid groups (JP-A-Sho)
53-132069, 54-83982), or a method of reacting a compound having a sulfonyl chloride group with amines to form a carboxylic acid group (JP-A-54-21478, 54
-41287, 54-43191, 54-64090), etc. are widely known. All of these methods are excellent methods for converting sulfonic acid groups to carboxylic acid groups, but many of the reactions generally proceed under heating, and in particular heat treatment is required to increase the conversion rate. In many cases, additional reactions may be required. Therefore, in today's era of soaring energy values,
It is necessary to allow chemical reactions to proceed efficiently with less energy, and a simpler and more efficient method is desired. As a result of extensive research into the conversion of sulfonic acid groups into carboxylic acids, the present inventors have discovered a new method that allows the reaction to proceed under extremely mild conditions by using a metal carbonyl compound. The heading completes the invention. Furthermore, the present invention is not limited to simply converting a sulfonic acid group to a carboxylic acid group, but also utilizes a fluorine-containing compound containing a metal carbonyl compound or a modified compound thereof as a new functional substance, which is extremely useful. It's a method. Therefore, according to the present invention, -SO ₂ X group (X is halogen, hydrogen,
Provided is a method for treating a fluorine-containing compound, which comprises contacting a fluorine-containing compound having a metal ion or an organic cation) with a metal carbonyl compound. The fluorine-containing compound having an _-SO2X group in the present invention can be used regardless of whether it is a high molecular compound or a low molecular compound. In particular, the method of the invention
Such as the sulfonic acid group bonded to the carbon atom to which the above-mentioned fluorine atom is bonded, (-CFY)- _o SO ₂ X or -O(-CFY) - _o SO ₂ X (Y is halogen, hydrogen; , hydrogen, metal ions or organic ions;
It is particularly effective for high-molecular compounds and low-molecular compounds of fluorine-containing compounds, in which n is a positive integer of 1 to 20). Further, the method of the present invention is extremely effective when applying a metal carbonyl compound to a fluorine-containing compound, particularly in a polymer compound. In other words, although the reason is unknown, this metal carbonyl compound has a very strong affinity for fluorine-containing compounds, and has a particularly strong affinity for fluorine-containing polymer compounds with low surface energy. , it penetrates into the compound extremely quickly, and the bonded functional group −SO ₂
The polymer compound is modified by reacting with the polymer. Bonded to the fluorine-containing compound of the present invention -
The SO ₂
F: Metal ions such as Na ⁺ and K ⁺ , and organic cations generally

[Formula] (R is H, an alkyl group or an aryl group) etc. are generally preferred. Specifically (-CFY)- _o -SO ₂ X or -O(-
CFY) - _o SO ₂ X (Y is halogen or hydrogen; n is 1
-O(-CF ₂ )- _o SO ₂ Cl, -O(-CF ₂ )- _o SO ₂ F, -O
(-
CF ₂ )― _o SO ₂ Br, -O (―CF ₂ )― _o SO ₂ I, -O (―CF ₂ )
― _o
SO ₂ H, −O(—CF ₂ )— _o SO ₂ Na, −O(—CFCl−CF ₂
)― _o SO ₂ Cl,

【formula】

[Formula] (-CF ₂ )- _o One having a structure such as SO ₂ Cl is preferable. Further, the fluorine-containing compound of the present invention may be a low molecular compound, a high molecular compound, or an oligomer, as long as the above-mentioned functional group is bonded. For example, as a low molecular weight
There is CH ₃ OCF ₂ SO ₂ X. Note that the fluorine-containing compound is not limited to perfluoro compounds, and of course, compounds to which fluorine atoms are partially bonded are also effective. However, as mentioned above, the effectiveness of the present invention is particularly exhibited in the case of perfluorinated compounds or compounds close to it having low surface energy, and in the case of high molecular compounds. Specifically, tetrafluoroethylene, perfluoroalkyl vinyl ether, trifluoroethylene chloride, trifluoroethylene, perfluoroethylene oxide, perfluoropropylene oxide, perfluorobutadiene, vinyl fluoride, vinylidene fluoride, and hexafluoride. Propylene chloride, CF ₂ = CFO (-CF ₂ )- _o OCF = CF ₂ ,
CF ₂ = CF (-CF ₂ ) - _o CF = CF ₂ (n is a positive integer from 2 to 24),

[Formula] Copolymers of (R _f : perfluoroalkyl group), perfluoroalkyl vinyl ether sulfonyl halide, perfluoroalkylene sulfonyl halide, etc., or homopolymers of perfluoroalkyl vinyl ether sulfonyl halides, polymers thereof, Partial hydrolysates of copolymers are useful. More specifically, it is a copolymer of tetrafluoroethylene and perfluoro(3,6-dioxa-4-methyl-7-octensulfonyl halide) or a partial hydrolyzate, but is not limited thereto. do not have. Next, as the metal carbonyl compound used in the present invention, conventionally known metal carbonyl compounds can be used without any restriction. In other words, there are no restrictions on the compounds of CO and metals, and specific examples include:
Cr(CO) ₃ ; Cr(CO) ₆ ; (ArH)Cr(CO) ₃ (arene tricarbonyl chromium complexes); Mo(CO) ₆ ; [Mo
(CO) ₃ (C ₅ H ₅ )〕 ₂ ;HMO(CO) ₃ (C ₅ H ₅ );W
(CO) ₆ ;

[Formula] (Zihueruka Rubene complex);

[Formula] (Hue nylcarbene complex);

[Formula] Fe(CO) ₅ ; NaHFe(CO) ₄ ; [(CH ₃ ) ₄ N] [HFe
(CO) ₄ 〕; KHFe(CO) ₄ ;K ₂ Fe(CO) ₄ ;Na ₂ Fe(CO) ₄・1/2 Dioxane;Na ₂ Fe(CO) ₅ ;Fe ₂ (CO) ₉ ;Fe ₃
(CO) ₁₂ ; H ₂ Fe (CO) ₄ ; H ₂ Fe ₃ (CO) ₁₁ ; NaHFe
(CO) ₄ ; KHFe(CO) ₄ ; Na ₂ Fe(CO) ₄ ;

[Formula] R(CO) ₅ ; CO ₂ (CO) ₈ ; CoH (CO) ₄ ; NaCo (CO) ₄ ; Co ₂
(CO) ₆ (RC≡CR′) R and R′ are alkyl, allyl,
Indicates hydrogen. ; [hexacarbonyl-μ-(acetylene) 2 cobalt]; RCCo ₃ (CO) ₉ [nonacarbonyl (alkylidine) 3 cobalt]; Co(CO) ₂ (η
-C ₅ H ₅ ) [dicarbonyl (η-cyclopentadienyl) cobalt]; Rh ₆ (CO) ₁₆ (hexadecacarbonyl 6-rhodium); Rh ₄ (CO) ₁₂ (dodecacarbonyl 4-rhodium) [Rh (CO) ) ₂ Cl] ₂ (di-μ-chlorotetracarbonyl dirhodium); (CH ₃ ) ₄ N [Rh
(CO) ₄ 〕;

[Formula] Ir ₄ (CO) ₁₂ ;

[Formula] Ni(CO) ₄ ; Fe(CO) ₄ I ₂ ; (NH ₄ ) ₂ [Fe(CO) ₄ ]; Mg[Fe
(CO) ₄ ]; Ca [Fe (CO ₄ )]; [Co (NH ₃ ) ₆ ] H ₂ [Fe
(CO) ₄ 〕 ₂ ; (HgX) ₂ 〔Fe(CO) ₄ 〕; Fe(CO) ₄ X ₂ ; Fe
(CO) _2X2 ;Fe(CO) _5X2 ; _Fe3 (CO) _9X6 (X is _{halogen )} or _alkali metal amalgam, e.g.
Fe(CO) ₄ Na ₂ ; Iron amminecarboxylic compounds, such as Fe(CO) ₃ (NH ₃ ) ₂ , Fe(CO) ₈ (C ₅ H ₅ N) ₂ , Fe ₂
(CO) ₄ (NH ₂ CH ₂ CH ₂ NH ₂ ) ₃ ;O- of iron carvone
Phenanthroline compounds, etc.; iron mercaptotricarbonyl, for example [Fe(CO) ₃ SR] (R is an alkyl group or an aryl group); biscyclopentadienyltetracarbonyl diiron; (C ₆ H ₅ )Fe(CO) _4Fe
(C ₆ H ₅ ); pentacyanocarbonyl iron; M ₃ ′ [Fe
(CN) ₅ CO]; Fe ₂ (CO) ₈ S ₂ ; (CO) ₃ FeSFe(CO);
Iron carbonyls such as (CO) ₃ FeSFe(CO) ₂ SFe(CO) ₃ ;Fe ₂ (CO) ₈ Se ₂ are used. Furthermore, H[Co
(CO) ₄ ];M ⁿ [Co(CO) ₄ ) _o (M is n-valent metal); Co
(CO) ₅ CH ₃ OH; [Co ₂ (CO) I ₂ ]; K ₃ [Co (CO)
(CN) ₅ ] and the like are preferably used, but the compound is not limited thereto, and any metal carbonyl compound can be used without any restriction. When these metal carbonyl compounds are used in the present invention, the mode of reaction differs depending on whether the carbonyl compound is liquid, solid, or gas, and the fluorine-containing compound to be reacted is different. differs depending on the low-molecular compound, high-molecular compound, etc. Furthermore, the manner in which the reaction is carried out differs depending on whether the fluorine-containing compound to be reacted is liquid, gas, solid, or the like. Therefore, the best one may be selected as appropriate for each case. Furthermore, the carbonyl compound may be used as is,
The reaction may be carried out in a state where it is dissolved or dispersed in a solvent. The reaction can be carried out under pressures ranging from below normal pressure to above 200 kg/cm ² . When reacting in a solution state, the reaction temperature is
When a metal carbonyl compound or an appropriate solvent is used, the reaction is carried out at a temperature at which either one of the solvents remains in a solution state, and at a temperature below which the metal carbonyl or fluorine-containing compound does not decompose. When the reaction is carried out in a gaseous state, in order to increase the vapor pressure of the metal carbonyl compound, the reaction may be carried out at a high temperature to the extent that the fluorine-containing compound does not decompose. In general, taking into account the unique catalytic action of metal carbonyl compounds,
It is preferable to carry out the reaction between -50 and 250°C, particularly under warm conditions in the range of 10 to 150°C. Among the metal carbonyl compounds mentioned above, iron carbonyl compounds are particularly desirable. A solvent may or may not be used. The solvent used is preferably an organic or inorganic solvent that generally does not react with the metal carbonyl compound. More preferably, the solvent is a halogen-containing solvent that dissolves the metal carbonyl compound well, but the reaction may be carried out in a dispersed state. The solvent may be a mixture of two or more kinds of solvents, or an organic or inorganic acid or base may be added as appropriate, but an acid-added system is preferable because the reaction rate is fast. In particular, the method of the present invention is useful when the fluorine-containing compound is a high molecular compound, especially a perfluoro compound. That is, the high affinity and permeability of the metal carbonyl compound to the fluorine-containing polymer compound allows the reaction to proceed extremely quickly and smoothly. Furthermore, by coexisting an organic solvent that has a strong affinity for the fluorine-containing compound, the reaction proceeds even more smoothly. In the present invention, it is not clear what kind of reaction occurs in the fluorine-containing compound by bringing the metal carbonyl compound into contact with the fluorine-containing compound having a -SO ₂ X group bonded, but various reactions occur. As a result of the analysis, the sulfonyl halide group disappeared and a new carboxylic acid group was generated. Furthermore, when the reaction of the present invention is carried out particularly on a fluorine-containing polymer compound,
Although it depends on the type of polymer compound, other reactions that cannot be fully analyzed at present are also likely occurring. Although it is unclear what kind of reaction mechanism causes the disappearance of the sulfonyl halide and the production of carboxylic acid groups, it is thought that the reaction occurs due to the strong catalytic action peculiar to metal carbonyl groups. In the present invention, after the fluorine-containing compound and the metal carbonyl compound are brought into contact, the treated fluorine-containing compound is purified as necessary to remove the metal carbonyl compound, the used solvent, and the like. In the case of a fluorine-containing polymer compound, the metal carbonyl compound significantly penetrates into the polymer compound, and since the metal carbonyl compound is unstable, it is converted into a metal or metal oxide in the polymer. There are cases. In such a case, it may be removed by washing and extraction with an acid or a mixture of an acid and an organic solvent. Alternatively, even if the metal carbonyl compound permeates into the fluorine-containing polymer compound or remains present on the surface layer of the polymer compound, it is not necessary to extract and remove it as long as it does not interfere with the intended use. In addition, when actively utilizing the unique catalytic action of metal carbonyl compounds or their decomposition products, it is preferable to actively make them exist within, in the surface layer, or on the surface of the fluorine-containing polymer. Just use it. Specifically, when using a fluorine-containing polymer compound treated with such a metal carbonyl compound as a catalyst, for example, when using it as a catalyst in organic synthesis, it is used as an organic fluorine-containing solid acid or as a salt thereof. For example, there is a unique catalytic effect due to the synergistic effect of ion-exchanged noble metals and metal carbonyls or metal oxides. Alternatively, when a treated fluorine-containing polymer compound is used in the form of a membrane as a diaphragm for electrode reactions, the unique electrochemical catalytic action of the noble metal or metal oxide present on the membrane surface is exerted. . That is, in the fluorine-containing compound obtained by the treatment method of the present invention, new functional groups are introduced by the unique chemical reaction in the fluorine-containing compound, and at the same time, especially in the case of high molecular compounds, It is possible to utilize the inherent properties of a modified polymer compound by removing the metal carbonyl compound, and it is also possible to exhibit a unique function in the coexistence of a metal carbonyl compound and its modified compound. The content of the present invention will be specifically explained with reference to the following examples, but the present invention is not limited to the following examples. Example 1 Tetrafluoroethylene and perfluoro(3,
A copolymer of 6-dioxa-4-methyl-7-octensulfonyl fluoride), which has an exchange capacity of 0.91 meq/g dry film (H type) when hydrolyzed to form a sulfonic acid group. A polytetrafluoroethylene plain-woven fabric (400 denier threads woven at a rate of 50 threads/inch both vertically and horizontally) was sandwiched between two membrane-like materials with a thickness of 2 mils and fused together. This was made into a single film-like material, and a 2 mil of the same film was further fused thereon to form a polymeric film-like material with a resin portion of 6 mil. This was then hydrolyzed in a bath consisting of a ternary system of caustic potassium, dimethyl sulfoxide, and water to convert the sulfonyl fluoride groups to potassium sulfonate groups. This membrane was immersed in 1N hydrochloric acid to convert the potassium sulfonate groups into sulfonic acid groups, heated to 120℃ and dried under reduced pressure, and then incorporated into a reaction device capable of reacting only one side of the stainless steel membrane at 140℃. After heating to 140℃ and further reducing the pressure.
The vapor of phosphorus pentachloride heated to
A quantity of 50 cmHg was introduced, and the mixture was left to react at 140°C for 60 minutes. Next, after replacing the phosphorus pentachloride vapor with nitrogen gas, the membrane was taken out, washed with water, a portion was cut, and after drying, the membrane surface was observed using a reflection infrared absorption spectrum, and it was found that it was a sulfonic acid type membrane. 1060
The absorption at cm ^-1 disappeared, and an absorption characteristic of sulfonyl chloride groups was observed at 1420 cm ^-1 . This membrane was boiled in pure water and its electrical resistance was measured in 0.5N-KCl and found to be 350Ω-cm ² (at 25° C. and 1000 cycles of alternating current). On the other hand, the electrical resistance of the sulfonic acid type membrane before reacting with phosphorus pentachloride was 4.9 Ω-cm ² when measured under the same conditions (measured by 1000 cycles of alternating current at 25° C.). Furthermore, when these membranes were immersed in a solution of crystal violet dissolved in a mixed solution of water and isopropyl alcohol, the sulfonic acid type membranes were dyed completely uniformly, but the membranes reacted with phosphorus pentachloride were stained completely. Only one side of the sample was unstained over 25 microns. The above membrane treated with phosphorus pentachloride was immersed in a reaction vessel filled with iron pentacarbonyl Fe(CO) ₅ and sealed with nitrogen, left at room temperature for 2 days, thoroughly washed with methanol, and then depressurized. After drying, 10% in a 1:1 mixed solution of methanol and water.
The sample was immersed for 8 hours in a hydrolysis bath in which caustic soda was dissolved to convert unreacted sulfonyl chloride groups into sulfonic acid. Further, this membrane was washed with a 1:1 mixed solution of 4.0N hydrochloric acid and methanol, and then immersed again in a methanol-water-caustic soda hydrolysis bath to obtain an ion exchange membrane. By the way, this
After the reaction, the membrane treated with Fe(CO) ₅ was washed with methanol, immediately dried under reduced pressure, and then its infrared reflection spectrum was measured. As a result, absorption was observed at approximately 3400 cm ^-1 and sulfonyl at 1420 cm ^-1 . The chloride absorption disappeared and new strong absorptions attributed to carboxylic acid groups were observed at 1630 cm ^-1 and 1780 cm ^-1 corresponding to the sodium salt of sulfonic acid. Furthermore, when this membrane was washed with a hydrochloric acid-methanol solution, the absorption at 2000 cm ^-1 disappeared and the absorption at 1630 cm ^-1 became weaker. The membrane-like material obtained here was subjected to salt electrolysis. That is, it is installed in a two-chamber salt electrolysis cell made of chlorinated vinyl chloride, and the anolyte is 4.5N salt water, with hardness components removed to 0.1 ppm or less using a chelating ion exchange resin. was used. From the cathode chamber, 7.5N-NaOH was constantly added while adding pure water. The current density was 30 A/dm ² , the electrolysis temperature was 85° C., and the effective current-carrying area during electrolysis was 0.5 dm ² . When analyzed after reaching a steady state,
Obtained 7.5N−NaOH with a current efficiency of 96%, and the amount of NaCl in caustic soda was 46ppm in terms of 50% NaOH.
The electrolytic voltage was 3.68V. No change in performance was observed even after one month. On the other hand, the membrane with sulfonic acid groups was directly coated with Fe.
(CO) ₅ , washing with methanol, immersion in a caustic soda solution dissolved in a 1:1 solution of methanol and water, further washing with a mixed solution of methanol and 4.0N hydrochloric acid, and further hydrolysis. The membrane was immersed in a bath and subjected to exactly the same treatment as the membrane having sulfonyl chloride groups, and salt electrolysis was similarly carried out under the same conditions. 7.5N−NaOH was obtained, the current efficiency was 52%, the amount of NaCl in the caustic soda was 320ppm (50% NaOH conversion), and the electrolysis voltage was
It was 3.5V. Example 2 The polymer film having a sulfonyl chloride group used in Example 1 was immersed in a solution of an iron carbonyl compound dissolved in the various solvents shown in Table 1 for contact and reaction, and then in Example 1 After carrying out methanol washing, dry deaeration, washing with a hydrochloric acid-methanol mixed solution, and immersion in a hydrolysis bath in the same manner as in Example 1, infrared absorption spectra were measured, and sodium chloride was washed in the same cell as in Example 1 under the same conditions. Electrolysis was performed. Incidentally, the infrared absorption spectrum was measured after the hydrolysis treatment and further immersion in a mixed solution of hydrochloric acid and methanol.

【table】

【table】 Example 3 Perfluorocarbon compounds

[Formula] was dispersed in a solution of 10 parts of phosphorus pentachloride dissolved in 100 parts of phosphorus oxychloride, and heated under reflux at 110°C for 8 hours. Next, the precipitated perfluorocarbon compound was separated, degassed under reduced pressure, and washed with water to obtain a compound containing sulfonyl chloride. When this was analyzed by infrared absorption spectrum, an absorption clearly corresponding to the sulfonyl chloride group -SO ₂ XCl was observed at 1420 cm ^-1 . Next, this was placed in carbon tetrachloride, 1 part of iron pentacarbonyl was added to 10 parts of carbon tetrachloride, refluxed for 8 hours, the compound was separated and purified, and the infrared absorption spectrum was measured. As a result, the absorption of 1420cm ^-1 completely disappeared,
A new absorption corresponding to carboxylic acid group -COOH was observed at 1790 cm ^-1 . Example 4 Tetrafluoroethylene and perfluoro(3,
When hydrolyzed with a copolymer of 6-dioxa-4-methyl-7-octensulfonyl fluoride, the exchange capacity is 0.83 milliequivalents/gram dry resin (H type) granules with 100 to 300 meshes. Using. That is, this sulfonyl fluoride type particulate material was dispersed in a mixed solution of water-dimethylsulfoxide-KOH, and the sulfonyl fluoride group was hydrolyzed to convert it into potassium sulfonate. Next, this granular material was immersed in 1N HCl to convert it into an acid form, and then placed in a dispersion of 2 parts of phosphorus pentachloride in 10 parts of phosphorus oxychloride, and heated under reflux at 110°C to remove the sulfonic acid group. was converted into a sulfonyl chloride group. The reacted resin was press-molded at 130° C. and a pressure of 80 kg/cm ² to form a film, and its infrared absorption spectrum was measured. The same film forming and infrared absorption spectrum measurement operations were also carried out for the above copolymer and hydrolyzate. As a result, the copolymer itself was 1470 cm
After hydrolysis, a new absorption was observed ^{at 1060 cm -1 and} at the same time the absorption at 1470 cm ^-1 disappeared. Furthermore, in the reaction between phosphorus pentachloride and phosphorus oxychloride, a new absorption at 1420 cm ^-1 was observed, and the absorption at 1060 cm ^-1 disappeared. This sulfonyl chloride type resin is 1,
The mixture was dispersed in 1 part of iron pentacarbonyl dissolved in 10 parts of 1,2-trichlorotrifluoroethane, left overnight in an argon atmosphere, and then refluxed for 8 hours. After cooling, it was filtered in an argon atmosphere, degassed under reduced pressure, thoroughly washed with a 1:1 solution of 1N-HCl and methanol, and then immersed in a methanol solution of 8% caustic soda for 16 hours to undergo the treatment of the present invention. A fluorine-containing compound was obtained. When this resin was again equilibrated in a 1:1 solution of 1N-HCl and methanol to the acid form and the infrared absorption spectrum was measured as a film, the absorption at 1420 cm ^-1 observed before treatment disappeared. , a new absorption was observed at 1790 cm ^-1 . Next, when the exchange capacity of this resin was measured, almost no amount of strongly acidic ion exchange groups was detected, and the weakly acidic cation exchange capacity was determined to be 0.83 meq/g dry resin (H type). . The exchange capacity was measured according to a conventional method, but a 1:1 mixed solution of methanol and water was used as the solvent to increase the ion exchange rate. Example 5 Tetrafluoroethylene and perfluoro(3,6-dioxa-4-methyl-7) used in Example 4
-Octenesulfonyl fluoride) was converted into a sulfonyl chloride type. This was immersed in various metal carbonyl compounds shown in Table 2 and washed with methanol and 1N hydrochloric acid to form an acid form, and then the infrared absorption spectrum and weakly acidic and strongly acidic ion exchange capacities were measured. The reaction up to the measurement and the post-reaction depressurization, degassing, water washing, hydrolysis treatment, etc. were carried out under the same conditions as in Example 4.

[Table] Example 6 The fluorine-containing compounds shown in Table 3 were dispersed or dissolved in iron pentacarbonyl, and reacted with stirring at 40°C for 48 hours in an argon atmosphere. Next, iron pentacarbonyl was removed under reduced pressure, and the residue was thoroughly washed repeatedly with 1N HCl and then with water, and an infrared absorption spectrum was measured by the KBr tablet method.

【table】

[Table] Example 7 A 0.15 mm thick polymer membrane having the structure of the following formula was heated with a polytetrafluoroethylene plain woven fabric. The following reaction was carried out using the fused and press-fitted material. Rh ₂ (OOCCH ₃ ) ₄ 1 part, 1-propanol 60
1 part, 2 parts of 40% tetrafluoroboric acid were added and mixed, and carbon monoxide gas was slowly blown into this.
Orange-yellow crystals were obtained by keeping at 75-80° C. under stirring for 24 hours and then cooling. This was determined to be Rh ₆ (CO) ₁₆ based on infrared absorption spectra and other findings. This was filtered, dried, and then dissolved again in chloroform until saturated. Next, 55% of the above polymer film-like material was added to this solution.
After soaking at 25°C for an hour, it was taken out and air-dried. This was immersed in a 1:1 mixed solution of 10% NaOH in water and methanol for 16 hours at room temperature. As a result, unreacted -SO ₂ Cl and -COCl in the membrane were converted into sodium sulfonate and sodium carboxylate. After washing this membrane again with water and air drying, it was heated to 150°C in an oxygen atmosphere for 8 hours.
heated for an hour. When this film was examined for the distribution of ruthenium in the cross section of the film using an X-ray microanalyzer, it was found that ruthenium was distributed only in the surface layer (both sides) at a distance of about 10 microns. It was present in large quantities, especially on the surface. Table 4 shows the results of electrolysis of saturated saline using this membrane using the same equipment and conditions as in Example 1. Table 4 also shows that ion exchange membranes not treated according to the present invention were subjected to electrolysis of saturated saline under the same conditions. That is, the above-mentioned 0.15 mm-thick polymer membrane containing -SO ₂ Cl and -COCl functional groups was immersed in a 1:1 mixed solution of water and methanol containing 10% NaOH for 16 hours at room temperature. hand,
An ion exchange membrane having sodium carboxylate and sodium sulfonate as ion exchange groups was manufactured and compared with the membrane of the present invention.

【table】

【table】

【table】

Claims (1)

[Claims] A fluorine-containing compound characterized in that a fluorine-containing compound having a 1 -SO ₂ X group (X is a halogen, hydrogen, a metal ion, or an organic cation) is brought into contact with a metal carbonyl compound. How to process compounds. 2 - Using a fluorine-containing compound in which the -SO ₂ X group is bonded as a (-CFY) - _o SO ₂ A treatment method according to claim 1. 3 -SO ₂ X group is -O(-CFY)- _o SO ₂
and n are the same as above). 4. The treatment method according to claim 1, wherein the fluorine _- containing compound having a X group is a polymer compound. 5. The treatment method according to claim 1 or 2, wherein the fluorine-containing compound is a perfluorocarbon polymer. 6. The treatment method according to claim 5, wherein the fluorine-containing compound is a perfluorocarbon polymer film. 7. The treatment method according to claim 1, wherein the _-SO2X group is a sulfonyl chloride group. 8. The treatment method according to claim 1, wherein the metal carbonyl compound is an iron carbonyl compound.