JPH0341085B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel ammonium type polymers. More specifically, the present invention relates to an ammonium-type fluorocarbon polymer that can be used as an anion exchanger with excellent durability. Anion exchangers, particularly membrane ion exchangers, are used in fields such as electrodialysis. Conventional membranous anion exchangers have generally been made by modifying copolymers or polymer mixtures obtained by combining various hydrocarbon monomers through polymer reactions. However, such conventional anion exchangers deteriorate significantly when used under harsh conditions, such as in the presence of chlorine. Therefore, there is a need for an anion exchanger that exhibits less deterioration under such conditions. As a membrane anion exchanger developed for the purpose of improving durability, a fluorine-based polymer, such as poly(tetrafluoroethylene), and an inorganic anion exchanger, such as a hydrated zirconium oxide, are mixed and compressed. A molded version is known (Japanese Unexamined Patent Publication No. 1983-35079). However, in general, the ion exchange function of such an inorganic anion exchanger made of an amphoteric metal oxide greatly depends on the hydrogen ion concentration of the environment during use, and in some cases, the ion exchange capacity may be reversed. For example, hydrated zirconium oxide acts as an anion exchanger at pH 6 or lower, but conversely acts as a cation exchanger at pH 6 or higher. Furthermore, near neutrality, its ion exchange ability is hardly expressed. Therefore, the conditions under which membrane anion exchangers including such ion exchangers are used must be severely restricted. It is also known to make a durable membrane by surface fluorinating anion exchange membranes made of hydrocarbons (Japanese Patent Application Laid-open No. 52-4489), but this method usually requires a sufficient degree of fluorination. Therefore, it is difficult to obtain an anion exchange membrane having the desired performance industrially. The present inventors focused on the excellent durability of fluorine-based polymers, and as a result of intensive research into the development of anion exchangers based on fluorine-based polymers,
A method for producing an anion exchanger with excellent durability has been invented. That is, the first method of the present invention consists of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and the end of the pendant chain has the general formula -CH ₂ -NR ¹ R ² (in the formula R ¹ and R ² is a hydrogen atom, a lower alkyl group,
A fluorocarbon alkylating agent having an aromatic group, a hydroxy lower alkyl group, or an amino group represented by a tetramethylene group or a pentamethylene group formed by R ¹ and R ² together, General formula at the end of the pendant chain (In the formula, R ¹ ' and R ² ' are the same as R ¹ and R ² , respectively, when R ¹ and R ² are other than hydrogen atoms, and when R ¹ and R ² are hydrogen atoms, they are the same as R ³ . ( ^R3 represents a lower alkyl group derived from the alkylating agent, Z represents the counter ion of the quaternary ammonium ion)
The present invention provides a method for producing an ammonium type polymer, which is characterized in that it is an ammonium type polymer represented by: In this specification, the pendant chain means a substituted or unsubstituted alkyl group, perfluoroalkyl group, or aromatic group bonded to the main chain consisting of a perfluorocarbon polymer chain, and the carbon-carbon bond contains a hetero atom, An aromatic ring may be present. As one embodiment of the pendant chain of the fluorocarbon polymer used as a starting material in the first method of the present invention, the general formula (In the formula, X is a fluorine atom, a chlorine atom, or a _-CF3 group, ^R1 and ^R2 represent the same meanings as above,
represents an integer from 0 to 5, m represents an integer from 0 or 1, and n represents an integer from 1 to 5, but these numbers may differ from pendant to pendant. ) can be exemplified. As an embodiment of the main chain of the fluorocarbon polymer used as a starting material in the first method of the present invention, the general formula A linear perfluorocarbon random polymer chain consisting of repeating units of the formula (where p and q represent numbers and the ratio p/q is from 2 to 16) can be exemplified. Specifically, l, m, n is different from the case where l, m, n are different for each pendant in the definition of l, m, n.
This refers to the case of a ternary or more copolymer synthesized from two or more types of fluoroolefin monomers having the following. Examples of this copolymer are shown below. (In the formula, x represents p or p'. If x is p,
y and z represent positive integers, and x/y+z is 2
to 16, and y+z=q. When x is p′, y and z represent numbers as average values,
x/y+z has an average value of 2 to 16, and y+z
= q′. l' and l'' represent integers from 0 to 5, m' and m'' represent 0 or 1, and n' and n'' represent integers from 1 to 5, respectively.Furthermore, in the first method of the present invention, as a starting material As a specific embodiment of the fluorocarbon polymer used, the general formula (In the formula, X, R ¹ , R ² , l, m, n represent the same meanings as above, p' and q' represent numbers, but their ratio is
A fluorocarbon polymer having an amino group represented by p'/q' (average value of 2 to 16) can be exemplified. In the above general formula, R ¹ and R ² represent a hydrogen atom, a lower alkyl group, an aromatic group, or a hydroxy lower alkyl group, and examples of the lower alkyl group include a methyl group, an ethyl group, an n- and i-propyl group, an n-, i-,
Examples include s- and t-butyl groups. Aromatic groups include phenyl group, tolyl group, p-
Examples include chlorophenyl group, p-methoxyphenyl group, furyl group, and thienyl group. Examples of the hydroxy lower alkyl group include 2-hydroxyethyl group, 2-hydroxy-n-propyl group, and 3-hydroxy-n-propyl group. Furthermore, R ¹ and R ² may be combined to form a tetramethylene group or a pentamethylene group, and these rings may be substituted with a lower alkyl group.
Examples of the fluorocarbon polymer used as a starting material in the first method of the present invention, including specific examples of R ¹ and R ² , include polymers consisting of the following repeating units. The alkylating agent used in the present invention has the general formula R ³ A (in the formula, R ³ represents a lower alkyl group, and A represents a portion of the alkylating agent other than the lower alkyl group to be released during alkylation). A compound represented by is used. R ³ is methyl group, ethyl group, n- and i-propyl group, n-, i- and s
-Butyl group, etc. can be exemplified. A is an iodine atom, a bromine atom, a dimethyloxonium fluoroborate group, a diethyloxonium fluoroborate group, a dimethyloxonium hexafluoroantimonate group, a trifluoroacetic acid group, a trifluoromethanesulfonic acid group, a monomethylsulfate group, p- Examples include toluenesulfonic acid group and p-nitrobenzenesulfonic acid group. Therefore, as alkylating agents, superacid salts of lower alkyl iodides or bromides or tri-lower alkyl oxoniums, such as methyl iodide, ethyl bromide, n-propyl bromide, n-butyl iodide,
Trimethyloxonium fluoroborate ((CH ₃ ) ₃ OBF ₄ ), triethyloxonium fluoroborate ((C ₂ H ₅ ) ₃ OBF ₄ ), trimethyloxonium hexachloroantimonate ((CH ₃ ) ₃ OSbCl ₆ ), dimethyl sulfate , methyl trifluoroacetate, methyl trifluoromethanesulfonate, methyl p-toluenesulfonate, ethyl p-nitrobenzenesulfonate, and the like. In alkylation, methanol, ethanol, methylene chloride, chloroform, carbon tetrachloride, sulfolane, N,N-dimethylformamide (DMF), nitromethane, N-methyl-2-pyrrolidone (NMP), etc. can be used as a solvent. Alkylation can be carried out under conventional conditions. For example, this can be easily carried out by bringing the starting material, a fluorocarbon polymer having amino groups, into contact with an alkylating agent or a solution thereof at a temperature of about 0°C to about 100°C. The alkylating agent is used in an amount of at least an equivalent, preferably twice or more, based on the theoretical amount of the amino group to be converted. Usually, a large excess amount is used relative to the latter in order to allow the reaction to proceed quickly and completely. When using a solvent, it is preferable to use an amount sufficient to immerse the fluorocarbon polymer having amino groups, which is the starting material. Although the alkylation reaction varies depending on the type of alkylating agent, solvent temperature, etc., it can usually be carried out under the above-mentioned reaction conditions for about 10 hours to about 5 days. The lower alkyl groups of R ¹ ′ and R ² ′ in the general formula at the pendant chain ends of the ammonium type polymer obtained by the method of the present invention are such that R ¹ and R ² in the fluorocarbon polymer having an amino group are the starting material. In the case of a lower alkyl group, R ¹ and R ² are the same, and when R ¹ and R ² are hydrogen atoms,
The hydrogen atom is replaced by R ³ by the action of the alkylating agent. R ³ is a group derived from an alkylating agent. Further, Z is a counter ion to a quaternary ammonium ion and is usually derived from an alkylating agent. Examples include halogen anions such as bromine and iodine;
These include super strong acid ions such as tetrafluoroborate ion, hexachloroantimonate ion, and trifluoromethanesulfonic acid, sulfonic acid ions such as benzenesulfonic acid and toluenesulfonic acid, carboxylic acid ions such as acetate ion, and monoalkyl sulfate ions. These counterions may be exchanged with other ions if necessary. This ion exchange is done by the conventional method,
For example, NaCl, LiCl, LiBr, LiI, NaOH,
This can be easily achieved by treating the ammonium type polymer obtained in the present invention with an alkali metal salt such as KOH, NaNO ₃ or K ₂ SO ₄ . The present invention further provides a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and at the end of the pendant chain. (In the formula, W represents a lower alkoxyl group, a hydroxyl group, a group in which the hydrogen atom of the hydroxyl group is substituted with a tri(lower alkyl)silyl group or an ammonium group, or a halogen atom). Formula HNR ¹ R ² (R ¹ and R ² in the formula have the same meanings as above)
The ends of the pendant chains are reacted with ammonium or amine of the general formula (In the formula, R ¹ and R ² have the same meanings as above)
The structure is converted into a structure represented by the formula -CH 2 -NR 1 , which is made up of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to this, and the general formula -CH ₂ -NR ¹ is attached to the end of the pendant chain. R ² (in the formula, R ¹ and R ² have the same meanings as above)
A fluorocarbon polymer having an amino group represented by formula (In the formula, R ¹ ′, R ² ′, R ³ and Z have the same meanings as above.) . The second method of the present invention is explained using the reaction formula for converting the terminal group as follows. The pendant chain of the fluorocarbon polymer having a substituted carbonyl group used as a starting material in the second method of the present invention has the general formula (In the formula, X, W, l, m, and n represent the same meanings as above) can be exemplified. In addition, its main chain is of the general formula (In the formula, p is an integer from 3 to 15, and q is an integer from 1 to 10.
An example is a linear perfluorocarbon polymer chain consisting of repeating units represented by . Also, the general formula as an overall repeating unit A fluorocarbon polymer comprising repeating units represented by the formula (wherein X, W, l, m, n, p' and q' have the same meanings as above) is preferred. Examples of the halogen for W in the above formula include fluorine, chlorine, and bromine. Examples of the lower alkoxyl group include methoxyl group, ethoxyl group, n-propoxyl group, n-butoxyl group, i-butoxyl group, n-pentoxyl group, s
-pentoxyl group, etc. can be exemplified. The group in which the hydrogen atom of a hydroxyl group is substituted with a tri(lower alkyl)silyl group specifically means a trimethylsilyloxy group, a triethylsilyloxy group, a t-butyldimethylsilyloxy group, and the like. Groups in which the hydrogen atom of a hydroxyl group is substituted with an ammonium group include -ONH ₄ , -ONH(CH ₃ ) ₃ , -ONH(CH ₂ CH ₃ ) ₃ , -ONH ₂ (CH ₂ CH ₃ ) ₂ , -ON( _CH3 ) ₄ ,

[Formula] or -ON (CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , etc., meaning a carbonyl group

It combines with [Formula] to form a carboxylic acid ammonium salt. Examples of the fluorocarbon polymer having a substituted carbonyl group that can be used as a starting material in the second method of the present invention include fluorocarbon polymers having the following repeating units. These fluorocarbon polymers are well known as cation-exchangeable carboxylic acid type perfluorocarbon polymers (particularly as cation-exchange membranes for saline electrolysis) or precursors thereof. Among these fluorocarbon polymers, those in which the pendant chain ends are acid halide types are, for example, perfluorocarbon polymers that have the same skeleton and the pendant chain ends are carboxyl groups (in the above formula, W
This is the case for those in which is a hydroxyl group. ) with a halogenating agent such as a chlorinating agent. In this case, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, etc. can be used as the chlorinating agent, but from the viewpoint of reaction efficiency, it is preferable to use thionyl chloride or phosphorus pentachloride in phosphorus oxychloride. . The reaction temperature depends on the condition of the raw materials and the chlorinating agent, but is generally 50° to 150°C.
is within the range of The amines used in the first stage reaction of the second method of the present invention include methylamine, ethylamine, n
-Propylamine, i-propylamine, n-butylamine, i-butylamine, dimethylamine, diethylamine, dipropylamine, methylethylamine, pyrrolidine, piperidine, pipecoline, 3-ethylpiperidine, aniline, N-methylaniline, p-toluidine , m-toluidine, p-chloroaniline, m-chloroaniline,
p-fluoroaniline, o-fluoroaniline,
p-bromoaniline, p-anisidine, m-anisidine, p-dimethylaminoaniline, m-nitroaniline, 2-aminofuran, 3-aminofuran, ethanolamine, diethanolamine, 3
Examples include -hydroxypropylamine and 3-hydroxybutylamine. On this occasion,
A corresponding silylamine in which the hydrogen atom on the nitrogen atom in the above general formula is replaced with a trimethylsilyl group or the like can also be used in place of the above diamine. In addition, the reaction with these amines can be carried out by contacting the gaseous amine with the copolymer or in the liquid amine.
Alternatively, it can be carried out using a solvent. When using a starting material other than an acid halide type polymer or an ester type polymer in this reaction, a silylating agent such as trimethylchlorosilane, bistrimethylsilylacetamide, or hexamethyldisilazane may be used together with a diamine represented by the above general formula. Particularly preferred, and also when using a first silylating agent, triethylamine,
It is preferable to carry out the reaction in the presence of a tertiary amine such as N-methylpyrrolidine. The amount of ammonia or amine relative to the starting material is at least equivalent, preferably 3 equivalents or more, and most preferably a large excess. The reaction may also be carried out in the presence of a tertiary amine. As the solvent, ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, and dioxane, hydrocarbons such as benzene, toluene, and hexane, acetonitrile, dimethyl sulfoxide, and the like can be used. Among the starting materials used in the second method of the present invention, when W in the above formula is a lower alkoxyl group, that is, when the pendant chain terminal is a carboxylic acid ester type, in addition to these solvents, alcohols such as methanol and ethanol can be used. can also be used as solvents. The amount of solvent to be used may be such that the fluorocarbon polymer having a substituted carbonyl group to be used is sufficiently immersed therein. Of course, a larger amount may be used. The reaction temperature is not particularly limited, but it is usually carried out at about -30°C to about 150°C, preferably about 0°C to 80°C. The thus obtained fluorocarbon polymer having carboxylic acid amide groups is treated with a reducing agent in the second stage reaction. As the reducing agent, alkylaluminium hydride such as aluminum hydride, diisobutylaluminum hydride, lithium aluminum hydride, diborane, etc. can be used, but diborane is preferable in terms of reaction efficiency and ease of post-treatment. ing.
The diborane used can be generated by, for example, reacting a boron trifluoride ether complex with sodium borohydride, or various complexes of borane (such as dimethyl sulfide complex) can be used. The amount of the reducing agent used is an equivalent amount or more, generally in large excess, relative to the functional group in the fluorocarbon polymer having a carboxylic acid amide group. The concentration in the solvent is about 0.01 to 5 molar, preferably
The concentration is between 0.1 and 2 molar. In the second method of the present invention, the second stage reaction proceeds smoothly in an ether solvent such as tetrahydrofuran, dioxane or diethylene glycol dimethyl ether. The amount of solvent used may be such that the fluorocarbon polymer having a carboxylic acid amide group to be used is sufficiently immersed therein. Of course, a larger amount may be used. Although there is no particular limitation on the reaction temperature, it is possible to carry out the reaction by keeping it in the range of ice-cooling temperature to room temperature in the initial stage of the reaction, and then heating it to the reflux temperature to 100°C.
This is preferable for completing the reaction. The thus obtained fluorocarbon polymer having amino groups is reacted with an alkylating agent in the third stage reaction to obtain the desired ammonium type fluorocarbon polymer. This third stage reaction is exactly the same as the reaction in the first method of the present invention. The fluorocarbon polymer having an amino group or a substituted carbonyl group, which is used as a starting material in both methods of the present invention, can be used in various forms such as a flat film, a tube, a fiber, and a powder. In this case, the target ammonium type fluorocarbon polymer can be obtained in a corresponding shape. The ammonium-type fluorocarbon polymers obtained by both methods of the present invention include polymers consisting of the following repeating units. Although the ammonium type polymers obtained by both methods of the present invention partially have hydrocarbon groups, they are extremely excellent in oxidation resistance, particularly chlorine resistance, and solvent resistance. Further, no change is observed even after repeated drying and wetting, and handling is much easier than conventional anion exchangers. Therefore, for example, membrane-shaped ammonium-type polymers can be used in applications that were difficult to use with conventional anion exchange membranes, such as diaphragms for organic electrolytic reactions and membranes for various types of dialysis under harsh conditions. Usable. It can also be used in various forms as a resin capable of anion exchange using quaternary ammonium groups in the coexistence of various solvents. It can also be used as various catalysts such as cyanohydrin synthesis catalysts, phase transfer catalysts, and halogenation reaction catalysts. Further, the tube-shaped ammonium type polymer can be used as a multitubular module in a space-saving dialysis device, and can also be used in a system for removing interfering anions in ion chromatography. Unlike conventional crosslinked anion exchangers, the anion exchange membranes made of ammonium type polymers obtained by both methods of the present invention are non-crosslinked, and therefore can fully respond to changes in conditions during use. As described above, the ammonium type polymer obtained by both methods of the present invention has great industrial value due to its excellent durability. It is already known that fluorine-based polymers, especially perfluorocarbon polymers, have significantly higher heat resistance and chemical resistance than general hydrocarbon-based polymers. However, the ammonium type polymers obtained by both methods of the present invention have durability far beyond expectations, despite having hydrocarbon groups in the pendant chains. In other words, even though the main chain is stabilized because it is a perfluorocarbon polymer chain, under a harsh oxidizing atmosphere, it is unavoidable that the hydrocarbon groups in the pendant chains undergo degeneration and decomposition and the resulting removal of functional groups. Despite this prediction, the ammonium type polymers obtained by both methods of the present invention exhibit very little such deterioration. The present invention will be explained in more detail below with reference to Examples and Reference Examples. The term amine type polymer used herein means a nitrogen-containing fluorocarbon polymer having an amino group, and the term amide type polymer refers to a fluorocarbon polymer having a carboxylic acid amide group. Note that the term terminal group, which is also used, represents the terminal group of the pendant chain. Further, unless otherwise specified, infrared absorption spectrum means transmission spectrum, and the dyeing test was conducted using the following dyeing bath. Crystal Violet: 0.05% methanol solution of Crystal Violet Cresol Red: 0.05% methanol solution of Cresol Red Thymol Blue: 0.05% methanol solution of Thymol Blue Bromothymol Blue: Bromothymol Blue
0.05% Methanol Solution Basic Cresol Red: Cresol Red
A solution of approximately 1% of 10% NaOH aqueous solution added to 0.05% methanol solution Basic thymol blue: 0.05% of thymol blue
A solution prepared by adding approximately 1% of a 10% NaOH aqueous solution to a methanol solution.The electrical resistance of the membrane was measured in a 0.5N saline solution for 1000 AC cycles at a temperature of 25℃ after being sufficiently equilibrated with a 0.5N saline solution. The annulus ratio of the membrane was calculated using the Nernst equation from the membrane potential generated between the 0.5N and 2.0N saline solutions. The exchange capacity of the nitrogen-containing copolymer was evaluated by drying the copolymer at 60° C. for 24 hours under reduced pressure, and then measuring the nitrogen content by elemental analysis. In addition, the conversion rate is based on the nitrogen value in elemental analysis, and the exchange capacity of the raw material copolymer is 100%.
The calculation was made taking into account the change in equivalent weight due to changes in the end groups. Example 1 CF ₂ = CF ₂ and

A copolymer film obtained by copolymerization with [Formula] [Nafion 114 (trade name) manufactured by Dupont, film thickness 100μ, sulfonic acid equivalent exchange capacity 0.91 milliequivalent/g dry film] was treated with 2N hydrochloric acid. , sulfonyl chloride treatment, hydrogen iodide treatment, and alkali washing to obtain a carboxylic acid sodium salt form. The structure of the pendant membrane of this membranous copolymer is

[Formula]. This membrane was treated with 8N hydrochloric acid/methanol (volume ratio 1:1) for hydrolysis and esterification, and then phosphorus pentachloride/phosphorus oxychloride (weight ratio 1:1).
1.6) at 120°C for 24 hours. Thereafter, it was washed in carbon tetrachloride and then dried. The obtained film shows strong carbonyl absorption at 1800 cm ^-1 in the infrared absorption spectrum. Also 2980, 2880 and 1440cm
Since there is an absorption near ^-1 that is thought to originate from C-H absorption, the terminal groups of most of the pendant chains are -CO ₂ Me groups, and some -COCl groups are mixed in the mixed polymer film. I found out something. This mixed polymer film is mostly It consisted of repeating units. The value of p′ ₁ /q′ ₁ is approximately 6.5
It was hot. The mixed polymer membrane thus obtained was immersed in dry ether, and dimethylamine gas (1.3 molar concentration) was passed therethrough while cooling with ice for 6 hours and the mixture was reacted for 18 hours at room temperature. Washed with a 3% sodium bicarbonate solution-methanol mixed solution (volume ratio 1:1) at 80°C for 5 hours, and then washed under reduced pressure.
Amide-type polymer that is colorless and transparent when dried overnight.

[Formula] A membrane was obtained. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3300, 2950, 2825, 2360, 1705, 1500, 1470,
1410, 1300-1100, 980, 920, 730, 650-610,
560-600. 2950, C-H absorption from 1500 to 1410 cm ^-1 , 1705 cm ^-1
Absorption due to amide carbonyl is observed. Furthermore, the conversion rate calculated from the nitrogen value in elemental analysis was 92% based on the SO ₃ H equivalent exchange capacity. Furthermore, the resulting amide type polymer film was not stained by crystal violet or cresol red, indicating that no ionic groups were present in the film. This membrane is mostly It consisted of repeating units (p′ ₁ /q′ ₁ ≒ 6.5). The membrane was immersed in a solution of sodium borohydride (0.53 molar concentration) in dry diethylene glycol dimethyl ether under an argon atmosphere. In this, boron trifluoride ether complex (0.62 molar equivalent to sodium borohydride)
A solution of dry diethylene glycol dimethyl ether was added dropwise under ice cooling. 5 hours under cooling, then
By reacting at 100° C. for 18 hours, the absorption at 1700 cm ⁻¹ in the infrared absorption spectrum disappeared, indicating that reduction to an amine type polymer (terminal group —CH ₂ NMe ₂ ) film had progressed completely. The obtained membrane was washed with methanol, and after drying, its infrared absorption spectrum was measured. The obtained infrared absorption spectrum is
As shown in the figure. Conversion rate 88%. Infrared absorption spectrum (cm ^-1 ) 2970, 2850, 2800, 2360, 1475-1455, 1395,
1350〜1040, 980, 930, 860, 835, 730, 640〜
610, 560-490. Furthermore, the obtained amine type polymer membrane was not stained by crystal violet or cresol red, indicating that no ionic groups were present in the membrane. This membrane was an amine-type polymer consisting essentially of the following repeating units. (p′ ₁ /q′ ₁ ≒6.5) The amine type polymer membrane thus obtained was placed in a methanol solution of methyl iodide (volume ratio 1:4),
The reaction was carried out at 60°C for 48 hours. After washing the obtained membrane with methanol, it was reacted in a methanol solution of lithium chloride (1.28 molar concentration) at 60° C. for 24 hours.
This membrane was heated to 60°C in methanol to obtain a quaternary ammonium chloride copolymer membrane. In a staining test, the obtained membrane was not stained with crystal violet, but was colored red with bromocresol purple (bluish-purple in basic water), yellow-orange with cresol red (red-purple in basic water), and was colored with anion. The existence of exchange groups was confirmed. The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3300, 3030, 2950, 2810, 2350, 1640, 1485,
1415, 1300～1060, 980, 925, 840, 740, 650
~600, 540~500. However, the absorption at 3300 and 1640 cm ^-1 is considered to be due to water in the membrane. In addition, the exchange capacity of this anion exchange membrane is 0.82 meq/g dry membrane, and the electrical resistance is
The resistance was 3.3Ωcm ² and the ring ratio was 0.87. Even after this membrane was immersed in a chlorine-saturated aqueous solution at 60°C for 1000 hours, no change was observed in these values. After treatment in methanol at 65°C for 48 hours, this solvent was removed at 40°C.
No change was observed even after repeating the vacuum removal operation five times. Example 2 CF ₂ = CF ₂ and

The copolymer obtained by copolymerizing [Formula] by a known method is made into a film (film thickness 110μ, CO ₂ H equivalent exchange capacity
1.4 meq/g dry film). This polymer consisted essentially of the following repeating units: (p' ₂ /q' ₂ ≒3.1) Using this methyl ester type polymer membrane and dimethylamine, the corresponding amide type polymer was prepared in the same manner as in Example 1.

[Formula] A membrane was obtained (conversion rate 95%). The infrared absorption spectrum of the obtained film was almost the same as the spectrum of the film obtained in Example 1, except for the absorption of the skeleton in the vicinity of 1000 to 800 cm ^-1 , indicating that the exchange of the desired end groups was proceeding efficiently. Ta. Note that the obtained amide type polymer film was not dyed at all by crystal violet or cresol red. This amide type polymer consisted essentially of the following repeating units. (p' ₂ /q' ₂ ≈3.1) The amide type polymer membrane obtained above was reduced in the same manner as in Example 1 to obtain an amine type polymer membrane. Conversion rate 95%. The infrared absorption spectrum of the obtained film almost matched that of the film obtained in Example 1 except for the absorption of the skeleton, and the absorption based on amide carbonyl around 1700 cm ^-1 completely disappeared. The resulting membrane was not stained at all by crystal violet or cresol red. This membrane consisted essentially of a polymer consisting of the following repeating units: (p' ₂ /q' ₂ ≈3.1) Next, the obtained membrane was placed in a methanol solution of methyl iodide (volume ratio 1:4) and reacted at 60°C for 48 hours. After washing the obtained membrane with methanol, it was dissolved in a methanol solution of lithium chloride (1.28 molar concentration).
The reaction was carried out at 60°C for 24 hours. This membrane was heated to 60°C in methanol to obtain the desired ammonium chloride type membrane. The obtained membrane was not stained with crystal violet in the staining test, but was colored red with bromocresol bubble (bluish-purple in basic water), yellow-orange with cresol red (red-purple in basic water), and anion exchange. The existence of the group was confirmed. The exchange capacity of the obtained membrane was 1.1 meq/g dry membrane, and the electrical resistance was 1.8 Ω·cm ² . This film also showed excellent durability like the film of Example 1. Example 3 CF ₂ = CF ₂ and

An amide-type polymer film was obtained by treating a film [Nafion 415 (trade name) manufactured by DuPont] using a polytetrafluoroethylene mesh as a support for a copolymer with [Formula] in the same manner as in Example 1. I got it. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3300, 2950, 2750, 2380, 1690, 1500-1400,
1320~950, 760~480. The resulting membrane was not stained at all by crystal violet or cresol red. The membrane consisted of a polymer consisting essentially of the following repeating units: (q′ ₂ /q′ ₂ ≈6.5) The membrane of the carboxylic acid amide type polymer having the polytetrafluoroethylene mesh support obtained in this way was subjected to the same reduction treatment as in Example 1, thereby reducing the amine type polymer. A polymer membrane was obtained. The infrared absorption spectrum is shown in Figure 5, and the absorption near 1700 cm ^-1 completely disappears. Infrared absorption spectrum (cm ^-1 ) 3200, 2950-2790, 2400-2300, 1440, 1390,
1300~920, 720~480. The resulting membrane was not stained at all by crystal violet or cresol red. The membrane consisted essentially of a polymer consisting of the following repeating units: (p′ ₃ /q′ ₃ ≒6.5) Example 1 was applied to the amine type polymer film thus obtained.
An ammonium chloride type polymer film was obtained by performing the same treatment as above. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3250, 2900, 2800, 2400~2300, 1620, 1470~
1400, 1300~900, 750~500. However, absorption at 3250 and 1620 cm ^-1 is considered to be due to water in the membrane. By staining with cresol red in methanol, the entire membrane except for the reinforcing material was uniformly dyed yellow-orange. The obtained film had an electrical resistance of 7.2 Ωcm ² and a transference number of 0.90. Further, a current-voltage curve in hydrochloric acid electrolysis using this membrane is shown in FIG. 7a. The results obtained using a commercially available hydrocarbon-based anion exchange membrane are also shown as a comparative example (Figure b). The electrolysis conditions are as follows. Membrane area: 9.6cm ² , electrode: platinum electrolyte; anode/cathode = 6N hydrochloric acid/6
Normal hydrochloric acid temperature: room temperature As is clear from the figure, the obtained membrane has a smaller exchange capacity than a commercially available hydrocarbon anion exchange membrane (exchange capacity 1.3 meq/g dry membrane). , they have the excellent feature that their electrical resistances are about the same. Furthermore, despite the conditions in which chlorine was generated on the anode side and hydrogen was generated on the cathode side, no increase in membrane resistance or damage to the membrane was observed even in long-term current tests. Example 4 CF ₂ = CF ₂ and The copolymer obtained by _{copolymerization} with
0.92 meq/g dry resin) and then hydrolyzed. Next, after treatment with 2N hydrochloric acid, the polymer was converted into sulfonyl chloride, treated with hydrogen iodide, and immersed in methanol to form the tubular polymer into a carboxylic acid methyl ester type. The pendant chains of the tubular ester type polymer obtained by this series of operations are

Converted to [formula]. This tube-like ester type polymer is made of phosphorus pentachloride/
120℃ in phosphorus oxychloride (weight ratio 1:1.6), 23
The mixture was heated for a period of time, washed in carbon tetrachloride, and then dried to obtain a tube-like mixed polymer consisting mostly of ester groups and a portion of acid chloride groups. It consisted essentially of the following repeating units: (p′ ₄ /q′ ₄ =6.4, W ¹ represents a methoxyl group or a chlorine atom.) This tube-like mixed polymer was immersed in diethyl ether, and the inside of the tube was replaced with dry diethyl ether. Dimethylamine gas was passed through this under ice cooling (up to 1.3 molar concentration). Thereafter, after reacting for 6 hours under cooling and 19 hours at room temperature, 3%
Baking carbonate solution - methanol (volume ratio 1:1) at 60℃, 6
Washed for hours and dried under reduced pressure overnight. Obtained tubular amide type polymer

When [Formula] was arranged and its infrared absorption spectrum was examined, it almost coincided with the spectrum of the amide type film obtained in Example 1. Conversion rate 90%. The resulting tubular polymer was cut into rings and examined for dyeability with crystal violet and cresol red, and no dyeing was found. The amide-type polymer in this membrane is essentially a repeating unit. (p′ ₄ /q′ ₄ ≒6.4). The tube-shaped amide type polymer obtained above was immersed in dry diethylene glycol dimethyl ether under an argon atmosphere, and the tube was also filled with diethylene glycol dimethyl ether. Next, sodium borohydride was added (to a concentration of 0.53 molar), stirred well, and cooled. A dry diethylene glycol dimethyl ether solution of boron trifluoride ether complex (0.62 molar equivalent to sodium borohydride) was then added dropwise under ice cooling. did. The reaction was continued under cooling for 2.5 hours and then at 100°C for 21 hours. The obtained tubular amine type polymer (terminal group -CH ₂ NMe ₂ ) was washed with methanol and dried, and its infrared absorption spectrum was examined, and the spectrum was almost the same as that of the membrane obtained in Reference Example 3. . Conversion rate 85%. The resulting tubular polymer was cut into rings and examined for dyeability with crystal violet and cresol red, and no dyeing was found. This amine-type polymer consisted essentially of the following repeating units: (p′ ₄ /q′ ₄ ≒6.4) The thus obtained tubular amine type polymer was dissolved in a methanol solution of methyl iodide (volume ratio 1:4).
and reacted at 60°C for 50 hours. After washing the obtained tubular polymer with methanol, it was incubated at 60°C in a methanol solution of lithium chloride (1.28 molar concentration).
The reaction was allowed to proceed for 24 hours. This tubular polymer was heated to 60°C in methanol to obtain the desired tubular ammonium chloride type polymer. The resulting tubular polymer was colored red with bromocresol purple and yellow-orange with cresol red (each in methanol) in a dyeing test, confirming the presence of anion exchange groups. The exchange capacity of the tubular anion exchanger obtained was 0.80 meq/g dry resin. Even after this product was immersed in a chlorine-saturated aqueous solution at 60°C for 100 hours, no change was observed in this value. Further, no change was observed even after treatment in methanol at 65°C for 48 hours and subsequent removal of the solvent under vacuum at 40°C five times. Example 5 CF ₂ = CF ₂ and

Copolymer powder obtained by copolymerization with [formula] and saponification [Nafion 511 (trade name) manufactured by DuPont, SO ₃ H equivalent exchange capacity 0.91 milliequivalent/g, dry resin, potassium sulfonate salt type] It was hydrolyzed with 5N hydrochloric acid and converted into sulfonyl chloride by treatment with phosphorus pentachloride. Then, it is converted to carboxylic acid form by hydrogen iodide treatment,
Thereafter, most of the carboxyl groups were methyl esterified by immersion in methanol. A powdery methyl ester type polymer was obtained by further treatment with methyl orthoformate. Infrared absorption spectrum (cm ^-1 ) 2970-2860, 1800, 1480-1415, 1280-1200,
1175〜1110, 980, 840, 780, 740, 635, 555,
510. This membrane is essentially a repeating unit It was a polymer powder consisting of (p′ ₅ /q′ ₅ ≒ 6.5). This powdered methyl ester type polymer was subjected to the same operation as in Example 1 in dry tetrahydrofuran to obtain a powdered amide type polymer.

[Formula] was obtained. This material was not stained with crystal violet or cresol red, and the conversion rate based on elemental analysis was 85%. The obtained powder is KBr
When examining the infrared absorption spectrum using a disk
Absorption derived from amide carbonyl was observed around 1700 cm ^-1 . Infrared absorption spectrum (cm ^-1 ) 2960, 1710, 1410, 1280-1200, 1170-1130,
1070, 980, 920, 800, 780, 740, 640, 550,
510. The polymer consists essentially of repeating units, (p′ ₅ /q′ ₅ ≒ 6.5). The powdered amide type polymer thus obtained was reduced with diborane in the same manner as in Example 1, and the powdered amine type polymer (terminal group -CH ₂ NMe ₂ ) was obtained by over-collection. . This product was not stained by crystal violet or cresol red at all, and the conversion rate was 79%. When the infrared absorption spectrum of the obtained powder was examined using a KBr disc, it was found that the absorption of amide carbonyl that existed near 1700 cm ^-1 had completely disappeared. Infrared absorption spectrum (cm ^-1 ) 3020~2780, 1500~1460, 1260~1200, 1170~
1120, 1070, 980, 930, 865, 835, 735, 635,
555, 510. This amine-type polymer consisted essentially of the following repeating units: (p′ ₅ /q′ ₅ ≈6.5) The powdered amine type polymer thus obtained was placed in a methanol solution of methyl iodide (volume ratio 1:4) and reacted at 60° C. for 50 hours. After washing the obtained powdered polymer with methanol, it was reacted in a methanol solution of lithium chloride (1.28 molar concentration) at 60°C for 24 hours. This powdered polymer was dissolved in methanol for 60 min.
C. to obtain the desired powdered ammonium chloride type polymer. The obtained powdered polymer was dyed in a dye test as bromocresol purple, reddish-purple, and cresol red, yellow (each in methanol).
The presence of anion exchange groups was confirmed. Infrared absorption spectrum (cm ^-1 ) 3040~2820, 1530~1460, 1280~1200, 1170~
1100, 980, 930, 840, 740, 635, 550, 510. The exchange capacity of the obtained powdered anion exchanger is
It was 0.80 milliequivalent/g dry resin. Even after this product was immersed in a chlorine-saturated aqueous solution at 60°C for 100 hours, no change was observed in this value. Further, no change was observed even after treatment in methanol at 65°C for 48 hours and subsequent removal of the solvent under vacuum at 40°C five times. Example 6 Mixed polymer membrane obtained in Reference Example 1 (9 cm ² )
was immersed in 30 ml of dry tetrahydrofuran, 4 ml of pyrrolidine was added, and the mixture was heated under reflux for 44 hours under an argon atmosphere. The membrane was taken out and dried under reduced pressure at 60°C for 20 hours to obtain an amide type polymer membrane. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3400, 2970, 2890, 2780, 2600, 2360, 1710~
1680, 1440, 1340-1030, 980, 930, 915, 800
~480. This membrane is mostly It consisted of repeating units (p′ ₆ /q′ ₆ = 7.6). The resulting membrane was then immersed in 200 ml of dry tetrahydrofuran under an argon atmosphere, and 10 g of sodium borohydride was added. Next, 20ml of boron trifluoride ethyl ether complex and 50ml of tetrahydrofuran
ml solution was added dropwise over 20 minutes under ice-water cooling, and the mixture was stirred for 1.5 hours. After heating under reflux for 65 hours, the membrane was taken out and washed in methanol under heating under reflux for 8 hours. The membrane was taken out and dried under reduced pressure at 60°C for 20 hours to obtain an amine type polymer membrane. In the infrared absorption spectrum of this film, the absorption around 1700 cm ^-1 derived from amide carbonyl disappeared, indicating that reduction to an amine type film had completely progressed. The conversion rate calculated from the nitrogen value in elemental analysis was 90%. Furthermore, the obtained amine type polymer film was not dyed with crystal violet, cresol red, thymol blue, or bromothymol blue. FIG. 9 shows the infrared absorption spectrum of the obtained film. Infrared absorption spectrum (cm ^-1 ) 3230, 2980-2760, 2370, 1465, 1430, 1410,
1350~1020, 980, 920, 770~480. This membrane is essentially It consisted of a copolymer consisting of repeating units (p′ ₆ /q′ ₆ ≈7.6). The amine type polymer film obtained above was placed in a dimethylformamide solution of methyl iodide (volume ratio 1:4) and reacted at 60° C. for 72 hours. After washing the obtained membrane with methanol, it was reacted in a methanol solution of lithium chloride (1.28 molar concentration) at 60° C. for 24 hours. This membrane was heated to 60°C in methanol to obtain a quaternary ammonium chloride type polymer membrane. In staining tests, the resulting membrane was not stained with crystal violet, yellow with cresol red (dark red in basic water), orange with bromothymol blue, and yellow with cresol red (dark red in basic water).
It was colored yellow-orange with thymol blue, confirming the presence of anion exchange groups. The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3400, 3000 ~ 2930, 2830, 2360, 2120, 1630,
1480, 1460, 1360~950, 930, 840, 780~480
(However, 3400 and 1630 absorb water) Also, the exchange capacity of this anion exchange membrane is 0.72 milliequivalents/g, dry membrane, electrical resistance is 5.4Ωcm ² , and transference number is
It was 0.88. This film also showed excellent chlorine resistance like the film obtained in Example 1. Example 7 Mixed polymer membrane obtained in Reference Example 1 (16 cm ² )
was immersed in 30 ml of dry tetrahydrofuran, 5.4 ml of aniline was added, and the mixture was heated under reflux for 120 hours under an argon atmosphere. The membrane was removed and dried at 60°C for 20 hours under reduced pressure to form an amide type polymer.

[Formula] A membrane was obtained. The infrared absorption spectrum is the 11th
As shown in the figure. Infrared absorption spectrum (cm ^-1 ) 3300, 3100~2830, 2620, 2360, 1950, 1750~
1490, 1440, 1350-1020, 980, 910, 885,
830, 800-480. This membrane is mostly It consisted of repeating units (p′ ₆ /q′ ₆ ≒7.6). The resulting membrane was then immersed in 200 ml of dry tetrahydrofuran under an argon atmosphere, and 10 g of sodium borohydride was added. Next, 20 ml of boron trifluoride ethyl ether complex and 5 ml of tetrahydrofuran.
ml solution was added dropwise over 20 minutes under ice-water cooling, and the mixture was stirred for 1.5 hours. After heating under reflux for 65 hours, the membrane was taken out and washed in methanol under heating under reflux for 8 hours. Remove the membrane and dry it under reduced pressure at 60℃ for 20 hours to form an amine type polymer.

[Formula] A membrane was obtained. In the infrared absorption spectrum of this film, the absorption around 1700 cm ^-1 derived from amide carbonyl disappeared, indicating that reduction to an amine type film had completely progressed. The conversion rate calculated from the nitrogen value in elemental analysis was 71%. Furthermore, the obtained amine type polymer film was not stained with thymol blue or bromothymol blue. The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3450, 3120, 3080, 3050, 2960, 2360, 1930,
1790, 1610, 1510, 1440, 1350〜1060, 980,
950, 830, 780~490. This membrane is essentially It consisted of a copolymer consisting of repeating units (p′ ₆ /q′ ₆ ≈7.6). The membrane obtained above was immersed in a solution of 25 ml of methyl iodide in 100 ml of dimethylformamide and heated at 60°C for 150 hours to obtain an ammonium iodide type polymer membrane. Next, this membrane was immersed in 125 ml of a 10% methanol solution of lithium chloride and heated at 60° C. for 24 hours (the solution was replaced halfway). Thereafter, it was immersed in methanol and washed at 60°C for 7.5 hours to obtain an ammonium chloride type polymer film. This membrane was not stained with crystal violet, but was stained yellow with cresol red and orange with thymol blue. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3500-3300, 3090, 3060, 2380, 1640, 1610,
1510, 1450, 1350~950, 840, 800~500. The ion exchange capacity of the obtained membrane was 0.50 meq/
The dried film had an electrical resistance of 26.2 Ωcm ² and a transport number of 0.91. This film also showed excellent chlorine resistance like the film of Example 1. Example 8 Mixed polymer membrane obtained in Reference Example 1 (9 cm ² )
was immersed in 30 ml of dry tetrahydrofuran, propylamine was added, and the mixture was heated under reflux for 44 hours under an argon atmosphere. The membrane was removed and dried under reduced pressure at 60°C for 20 hours to form an amide type polymer.

[Formula] A membrane was obtained. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3480, 3400-3280, 3100, 3000-2940, 2890,
2560, 2360, 1740-1670, 1570-1530, 1460,
1350~1050, 980, 920, 790~490. This membrane is mostly It consisted of repeating units (p′ ₆ /q′ ₆ ≒ 7.6). The resulting membrane was then immersed in 170 ml of dry tetrahydrofuran under an argon atmosphere, and 3 g of sodium borohydride was added. Next, 6ml of boron trifluoride ethyl ether complex and 10ml of tetrahydrofuran.
ml solution was added dropwise over 30 minutes under ice-water cooling, and the mixture was stirred for 1.5 hours. After continuing the reaction at room temperature for 30 minutes, the mixture was further heated under reflux for 17 hours. Thereafter, the membrane was taken out and washed in methanol under heating under reflux for 22 hours. The membrane was taken out and dried under reduced pressure at 60°C for 24 hours to obtain an amine type polymer (terminal group -CH ₂ NHCH ₂ CH ₂ CH ₃ ) membrane. In the infrared absorption spectrum of this film, the absorption around 1700 cm ^-1 derived from amide carbonyl disappeared, indicating that reduction to an amine type film had completely progressed. The conversion rate calculated from the nitrogen value in elemental analysis was 77% based on the exchange capacity in terms of SO ₃ H.
Furthermore, the obtained amine type polymer film was not stained with crystal violet, but was stained yellow with bromothymol blue. The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3680, 3250, 2980, 2890, 2360, 1480~1460,
1350~1030, 980, 780~490. This membrane is essentially It consisted of a copolymer consisting of repeating units (p′ ₆ /q′ ₆ ≒7.6). The membrane obtained above was immersed in a solution of 25 ml of methyl iodide in 100 ml of dimethylformamide and heated at 60° C. for 120 hours to obtain an ammonium iodide type polymer membrane. Next, this membrane was immersed in 125 ml of a 10% methanol solution of lithium chloride and heated at 60° C. for 24 hours (the solution was replaced halfway). Thereafter, it was immersed in methanol and washed at 60°C for 7.5 hours to obtain an ammonium chloride type polymer film. This membrane was not stained with crystal violet, but was stained yellow with cresol red, yellow-orange with thymol blue, orange with bromothymol blue, and dark blue with basic bromothymol blue. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3400, 3230, 3020-2920, 2820, 2360, 1630,
1490~1450, 1420, 1360~1030, 1010~940,
880, 835, 780-480. The ion exchange capacity of the obtained membrane was 0.61 meq/
The dried film had an electrical resistance of 12.5 Ωcm ² and a transport number of 0.90. This film also showed excellent chlorine resistance like the film of Example 1. Example 9 The mixed polymer membrane (16 cm ² ) obtained in Reference Example 1 was immersed in 30 ml of dry tetrahydrofuran, 4.96 ml of diethylamine was added, and the mixture was heated under reflux for 120 hours under an argon atmosphere. The membrane was taken out and dried under reduced pressure at 60°C for 20 hours to obtain an amide type polymer membrane. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3100-2670, 2500, 1730-1610, 1480-1440,
1415-1385, 1350-1030, 980, 870, 830, 810
~490. This membrane is mostly It consisted of repeating units (p′ ₆ /q′ ₆ ≒7.6). The resulting membrane was then immersed in 200 ml of dry tetrahydrofuran under an argon atmosphere, and 10 g of sodium borohydride was added. Next, 20 ml of boron trifluoride ethyl ether complex and 5 ml of tetrahydrofuran.
ml solution was added dropwise over 20 minutes under ice-water cooling, and the mixture was stirred for 1.5 hours. After heating under reflux for 65 hours, the membrane was taken out and washed in methanol under heating under reflux for 8 hours. The membrane was taken out and dried under reduced pressure at 60°C for 20 hours to obtain an amine type polymer membrane. In the infrared absorption spectrum of this film, the absorption around 1700 cm ^-1 derived from amide carbonyl disappeared, indicating that reduction to an amine type film had completely progressed. The conversion rate calculated from the nitrogen value in elemental analysis was 60%. Furthermore, the obtained amine type polymer film was not stained with crystal violet. The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3680, 3400, 2980, 2950, 2900, 2360, 1460,
1350~1030, 980, 840, 780~490. This membrane is essentially It consisted of a copolymer consisting of repeating units (p′ ₆ /q′ ₆ ≒7.6). The membrane obtained above was immersed in a solution of 25 ml of methyl iodide in 100 ml of dimethylformamide and heated at 60° C. for 120 hours to obtain an ammonium iodide type polymer membrane. Next, this membrane was immersed in 125 ml of a 10% methanol solution of lithium chloride and heated at 60° C. for 24 hours (the solution was replaced halfway). Thereafter, it was immersed in methanol and washed at 60°C for 7.5 hours to obtain an ammonium chloride type polymer film. This membrane was not stained with crystal violet, but was stained yellow with cresol red and orange with thymol blue. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3500-3250, 3000, 2900, 2360, 1630, 1450,
1350~940, 840, 780~480. The ion exchange capacity of the obtained membrane was 0.46 meq/
The dried film had an electrical resistance of 33.8 Ωcm ² and a transport number of 0.91. This film also showed excellent chlorine resistance like the film of Example 1. This membrane is essentially It consisted of a copolymer consisting of repeating units (p′ ₆ /q′ ₆ ≒7.6). Example 10 The mixed polymer membrane (18 cm ² ) obtained in Reference Example 1 was immersed in 100 ml of dry ether, and 17.4 g of ammonia gas was passed through the membrane while cooling with ice water to react at room temperature for 25 hours.
The membrane was removed and dried under reduced pressure at room temperature for 20 hours to form an amide type polymer.

[Formula] A membrane was obtained. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3520, 3400~3100, 2980, 2880, 2350, 1770~
1670, 1610, 1550, 1410, 1340〜1050, 980,
915, 820-480. This membrane is mostly It consisted of repeating units (p′ ₆ /q′ ₆ ≒7.6). The resulting membrane was then immersed in 200 ml of dry tetrahydrofuran under an argon atmosphere, and 10 g of sodium borohydride was added. Next, a solution of 20 ml of boron trifluoride sodium ethyl ether complex in 5 ml of tetrahydrofuran was added dropwise over 20 minutes under ice water cooling.
Stirred for 1.5 hours. After heating under reflux for 65 hours,
The membrane was taken out and washed in methanol under heating under reflux for 8 hours. The membrane was taken out and dried at 60°C under reduced pressure for 20 hours to obtain an amine type polymer (terminal group -CH ₂ NH ₂ ) membrane. The conversion rate calculated from the nitrogen value in elemental analysis was 61%. Furthermore, the obtained amine type polymer film was not stained with crystal violet. The infrared absorption spectrum of the obtained film was
Shown in Figure 1. Infrared absorption spectrum (cm ^-1 ) 3660, 3430, 2960, 2360, 1605, 1360-930,
800-490. This membrane is essentially It consisted of a copolymer consisting of repeating units (p′ ₆ /q′ ₆ ≈7.6). The membrane obtained above was immersed in a solution of 25 ml of methyl iodide in 100 ml of dimethylformamide and heated at 60° C. for 200 hours to obtain an ammonium iodide type polymer membrane. Next, this membrane was immersed in 125 ml of a 10% methanol solution of lithium chloride and heated at 60° C. for 24 hours (the solution was replaced halfway). Thereafter, it was immersed in methanol and washed at 60°C for 7.5 hours to obtain an ammonium chloride type polymer film. This membrane was not stained with crystal violet, but was stained yellow with cresol red, orange with thymol blue, yellow-orange with bromthymol blue, and red with basic cresol red. The infrared absorption spectrum of this film matched well with the spectrum of the film obtained in Example 1. The ion exchange capacity of the obtained membrane was 0.48 meq/
g The dry film had an electrical resistance of 28.1 Ωcm ² and a transport number of 0.91. This film also showed excellent chlorine resistance like the film of Example 1. Example 11 A carboxyl type polymer membrane (9 cm ² ) obtained by the method of Reference Example 2 was immersed in 32 ml of anhydrous acetonitrile, and 3.72 ml of triethylamine and ethanolamine were added.
Add 1.62ml and 7.1ml of trimethylchlorosilane,
Heated at 80°C for 76 hours under an argon atmosphere. Remove the membrane, wash with methanol, and incubate at 60°C under reduced pressure for 24 hours.
amide type polymer after drying

[Formula] A membrane was obtained. FIG. 22 shows the infrared absorption spectrum of the obtained film. Infrared absorption spectrum (cm ^-1 ) 3340, 3100, 2950, 2350, 1720, 1535, 1430,
1350~930, 880~480. This membrane consisted essentially of a copolymer consisting of the repeating units described below. (p' ₆ /q' ₆ ≈7.6) The membrane obtained above was immersed in 170 ml of anhydrous tetrahydrofuran under an argon atmosphere, and 3 g of sodium borohydride was added. Next, boron trifluoride,
Ethyl ether complex 6ml tetrahydrofuran 10
ml solution over 30 minutes under ice water cooling, and stirred for 1.5 hours. Thereafter, the mixture was heated to reflux at room temperature for 30 minutes and then for an additional 20 hours. The membrane was taken out and dried under reduced pressure at 60°C for 24 hours.
An amine type polymer film was obtained. In the infrared absorption spectrum, this film shows 1720
The absorption at cm ^-1 disappeared, indicating that the reduction to the amine type film had completely progressed. The conversion rate was calculated from elemental analysis and was approximately 82%. This membrane was not stained by crystal violet, basic cresol red, basic bromthymol blue, or basic thymol blue, but was stained yellow by cresol red, orange by thymol blue, and yellow-orange by bromthymol blue. .
FIG. 23 shows the infrared absorption spectrum of the obtained film. Infrared absorption spectrum (cm ^-1 ) 3550~3175, 3000~2820, 2350, 1440, 1360~
950, 860~500. This membrane consisted essentially of a copolymer consisting of the repeating units described below. (p′ ₆ /q′ ₆ ≈7.6) The membrane obtained above was immersed in a solution of 25 ml of methyl iodide in 100 ml of dimethylformamide and heated at 60° C. for 120 hours to obtain an ammonium iodide type polymer membrane. Next, this membrane was immersed in 125 ml of a 10% methanol solution of lithium chloride and heated at 60° C. for 24 hours (the solution was replaced halfway). Thereafter, it was immersed in methanol and washed at 60°C for 7.5 hours to obtain an ammonium chloride type polymer film. This membrane was not stained with crystal violet, but it turned bright yellow with cresol red, orange with thymol blue, black with bromothymol blue, pale blue with basic bromothymol blue, and dark red with basic cresol red. stained. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3600~3125, 3000, 2350, 1630, 1480, 1350~
940, 850~500. The ion exchange capacity of the obtained membrane was 0.70 meq/
The dried film had an electrical resistance of 11.9 Ωcm ² and a transport number of 0.90. This membrane consisted essentially of a copolymer consisting of the following repeating units: (p′ ₆ /q′ ₆ ≈7.6) This film also showed excellent chemical and solvent resistance. Example 12 CF ₂ = CF ₂ and

A carboxyl-type polymer obtained by treating a copolymer of [formula] with polytetrafluoroethylene mesh as a support (Nafion 415 (trade name) manufactured by Dupont) in the same manner as in Reference Example 2. The combined membrane (8 cm ² ) was immersed in 32 ml of acetonitrile, 3.72 ml of triethylamine, 2.22 ml of n-propylamine, and 3.54 ml of trimethylchlorosilane were added, and the mixture was heated under an argon atmosphere at air temperature for 30 minutes and then at 80° C. for 73 hours. . The membrane was removed and washed with ether for 60 min under reduced pressure.
Dry the amide type polymer for 20 hours at °C.

I got [formula]. FIG. 25 shows the infrared absorption spectrum of the obtained film. Infrared absorption spectrum (cm ^-1 ) 3330, 3100, 2970, 2900, 2350, 1720, 1530,
1440, 1390-1010, 980, 900-440. This membrane, except for the mesh portion, consisted essentially of a copolymer consisting of the following repeating units. (p′ ₃ /q′ ₃ ≈6.5) The membrane obtained above was immersed in 550 ml of anhydrous tetrahydrofuran under an argon atmosphere, and 9 g of sodium borohydride was added. Next, a solution of 18 ml of boron trifluoride ethyl ether in 15 ml of tetrahydrofuran was added dropwise over 40 minutes under ice-water cooling, and the mixture was stirred for 1.5 hours. Thereafter, the mixture was heated to reflux at room temperature for 30 minutes and then for an additional 21 hours. The membrane was taken out and washed in methanol under heating under reflux for 21 hours. The membrane was taken out and dried under reduced pressure at 60°C for 20 hours to obtain an amine type polymer membrane. In the infrared absorption spectrum, this film shows 1720
The absorption at cm ^-1 disappeared, indicating that the reduction to the amine type film had completely progressed. This membrane was not stained with crystal violet, but was stained yellow with bromothymol blue. FIG. 26 shows the infrared absorption spectrum of the obtained film. Infrared absorption spectrum (cm ^-1 ) 3600 ~ 3100, 2950, 2900, 2370. 1460, 1420 ~
900, 900-440. This membrane, except for the mesh portion, consisted essentially of a copolymer consisting of the following repeating units. (p′ ₃ /q′ ₃ ≈6.5) The membrane obtained above was immersed in a solution of 60 ml of methyl iodide in 240 ml of dimethylformamide and heated at 60° C. for 72 hours to obtain an ammonium iodide type polymer membrane. Next, this membrane was immersed in 300 ml of a 10% methanol solution of lithium chloride and heated at 60° C. for 25 hours (the solution was replaced halfway). Then 30 at 60 °C in methanol.
After washing for several hours, an ammonium chloride type polymer film was obtained. This membrane is not stained with crystal violet but is yellow with cresol red (dark red in basic water) and orange with bromothymol blue (dark blue in basic water).
It was confirmed that it has an ion exchange group. The infrared absorption spectrum of this film is shown in FIG. 3400~2800, 2360, 1460~1410, 1350~940,
840-480. This membrane, except for the mesh portion, consisted essentially of a copolymer consisting of the following repeating units. (p′ ₃ /q′ ₃ ≒6.5) The electrical resistance of the obtained film was 10.0Ωcm ² and the transference number was 0.90.
It was hot. This film also showed excellent durability. Example 13 A part of the amine type polymer film obtained in the first step of Example 1 was immersed in a solution of 2 ml of ethyl iodide and 8 ml of methanol and heated at 60°C for 72 hours to form an ammonium iodide type polymer (terminal group -CH ₂ N EtMe ₂ .I) film was obtained. Next, this membrane was immersed in 50 ml of a 10% methanol solution of lithium chloride and heated at 60° C. for 25 hours (the solution was replaced halfway). Then immerse in methanol at 60°C.
was washed for 18 hours to obtain an ammonium chloride type polymer (terminal group -CH ₂ NMe ₂ Cl) film. This membrane was not stained with crystal violet, but was stained yellow with cresol red and blue with basic bromothymol blue. The ion exchange capacity of the obtained membrane was 0.82 meq/
The dried film had an electrical resistance of 5.6 Ωcm ² and a transport number of 0.88. This film also showed excellent chlorine resistance like the film obtained in Example 1. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (cm ^-1 ) 3400, 3040, 2970, 2850, 2830, 2800, 2360,
1630, 1480, 1420, 1340〜1060, 980, 930,
840, 740 to 500 (3400 and 1630 absorb water) This membrane consisted essentially of a copolymer consisting of the following repeating units. (p′ ₁ /q′ ₁ ≒6.5) Reference example 1 (raw material preparation example) CF ₂ = CF ₂

A copolymer film obtained by copolymerization with [Formula] [Nafion 125 (trade name) manufactured by DuPont, film thickness 125μ, sulfonic acid equivalent exchange capacity 0.83 milliequivalent/g dry film] was treated with 2N hydrochloric acid. , sulfonyl chloride treatment, hydrogen iodide treatment, and alkali washing to obtain a carboxylic acid sodium salt form. The structure of the pendant chains of this membrane copolymer is

[Formula]. This membrane was treated with 8N hydrochloric acid/methanol (volume ratio 1:1) for hydrolysis and esterification, followed by phosphorus pentachloride/phosphorus oxychloride (weight ratio 1:1).
1.6) at 120°C for 24 hours. Thereafter, it was washed in carbon tetrachloride and then dried. The obtained film shows strong carbonyl absorption at 1800 cm ^-1 in the infrared absorption spectrum. Also 2980, 2880 and 1440cm
Since there is an absorption thought to be derived from C-H absorption near ^-1 , it is clear that most of the terminal groups of the pendant chains are -CO ₂ Me groups, and a mixed polymer film with some -COCl groups is present. Obtained. This mixed polymer consisted essentially of the following repeating units: (p′ ₆ /q′ ₆ ≒7.6) Reference example 2 (raw material preparation example) CF ₂ = CF ₂

Copolymer film obtained by copolymerization with [Formula] [Nafion 125 (trade name) manufactured by DuPont, film thickness 125μ, SO ₃ H
After treatment with 2N hydrochloric acid (converted exchange capacity: 0.83 milliequivalents/g dry membrane), the membrane was converted into sulfonyl chloride, treated with hydrogen iodide, and washed with alkali to form the membrane into a sodium carboxylate salt type. This membrane was treated with a 3.24N aqueous hydrochloric acid solution, washed with water, and dried under reduced pressure to obtain a carboxyl type polymer membrane. The structure of the pendant chains of this membrane is

[Formula]. This film showed strong carbonyl absorption at 1780 cm ^-1 in the infrared absorption spectrum and was stained blue by crystal violet. This membrane consisted essentially of a copolymer consisting of the repeating units described below. (p′ ₆ /q′ ₆ ≒7.6)

[Brief explanation of drawings]

Figure 1, Figure 4, Figure 8, Figure 11, Figure 14
17, 20, 22, and 25 show the infrared absorption spectra of the fluorocarbon polymer having a carboxylic acid amide group, which was used as an intermediate in an embodiment of the second method of the present invention. FIG. 2, FIG. 5, FIG. 9, FIG. 12, FIG.
Figures 5, 18, 21, 23, and 26
The figure shows an infrared absorption spectrum of a fluorocarbon polymer having an amino group used as a starting material in an embodiment of the first method of the present invention and as an intermediate in an embodiment of the second method. Yes, Figure 3, Figure 6, Figure 10, Figure 1
3, FIG. 16, FIG. 19, FIG. 24, FIG. 27, and FIG. 28 are diagrams showing infrared absorption spectra of ammonium type polymers produced by one embodiment of the method of the present invention. FIG. 7 is a diagram showing the relationship between current and voltage when electrolysis is performed using a membrane of an ammonium type polymer obtained in one embodiment of the present invention.

[Claims]

1 In the reaction of graft polymerizing a polar group-containing vinyl compound to a diene rubber in a solution state using a radical generator, the general formula [In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each represent a C ₁ to _{C 20} alkyl group, aryl group, aralkyl group, or cycloalkyl group, and X is a halogen, HSO ₄ or
A graft characterized by the coexistence of at least one quaternary ammonium salt represented by RCOO- (where R represents a C ₁ to C ₂₀ alkyl group, aryl group, aralkyl group, or cycloalkyl group) Method for producing copolymer.

Claims (1)

(In the formula, R ¹ ' and R ² ' are the same as R ¹ and R ² , respectively, when R ¹ and R ² are other than hydrogen atoms, and when R ¹ and R ² are hydrogen atoms, they are the same as R ³ . (R ³ represents a lower alkyl group derived from the alkylating agent, Z represents the counter ion of the quaternary ammonium ion)
A method for producing an ammonium type polymer, characterized in that the ammonium type polymer is made into an ammonium type polymer represented by: 2 As a starting material, the pendant chain has the general formula (In the formula, X is a fluorine atom, a chlorine atom or a ^-CF3 group, and ^R1 and ^R2 represent the same meanings as above,
l represents an integer from 0 to 5, m represents an integer from 0 or 1, and n represents an integer from 1 to 5, but these numbers may differ from pendant to pendant. ) using a fluorocarbon polymer with a structure represented by the general formula (In the formula, X, R ¹ ′, R ² ′, R ³ , l, m, n, and Z have the same meanings as above.) The manufacturing method according to item 1. 3 As a starting material, the main chain has the general formula (In the formula, p and q represent integers, and the ratio p/q
using a fluorocarbon polymer that is a linear perfluorocarbon random polymer chain consisting of repeating units represented by (within the range of 2 to 16),
The manufacturing method according to claim 1 or 2, wherein ammonium type polymers having the same main chain are obtained. 4 General formula as starting material (In the formula, X, l, m, n, R ¹ and R ² represent the same meanings as above, p' and q' each represent a number as an average value, and the ratio p'/q' is the average value. 2 or more
A fluorocarbon polymer consisting of repeating units of the general formula R ³ A (within the formula R ³ represents a lower alkyl group, and A represents a group other than the alkyl group of the alkylating agent) is used as an alkylating agent. ) using an alkylating agent represented by the general formula (In the formula, X, R ¹ ′, R ² ′, R ³ , l, m, n, Z,
p' and q' represent the same meanings as above. ) The manufacturing method according to any one of claims 1 to 3, for obtaining an ammonium type polymer consisting of repeating units represented by: 5 Consists of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to this, with the general formula at the end of the pendant chain. (In the formula, W represents a halogen atom, a hydroxyl group, a group in which the hydrogen atom of the hydroxyl group is substituted with a tri(lower alkyl)silyl group or an ammonium group, or a lower alkoxyl group). General formula HNR ¹ R ² (In the formula, R ¹ and R ² have the same meanings as above.)
The end of the pendant chain is reacted with ammonia or amine represented by the general formula (In the formula, R ¹ and R ² have the same meanings as above)
The structure is converted into a structure represented by the formula -CH 2 -NR 1 , which is made up of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to this, and the general formula -CH ₂ -NR ¹ is attached to the end of the pendant chain. R ² (in the formula, R ¹ and R ² have the same meanings as above)
A fluorocarbon polymer having an amino group represented by (In the formula, R ¹ ′, R′ ² , R ³ , and Z have the same meanings as described above.) 6 As a starting material, the pendant chain has the general formula (In the formula, X, l, m, n, R ¹ and R ² represent the same meanings as above.) Using a fluorocarbon polymer having an amino group represented by the general formula (In the formula, X, R ¹ ′, R ² ′, R ³ , l, m, n, and Z have the same meanings as above.) The manufacturing method described in Section 5. 7 As a starting material, the main chain has the general formula (In the formula, p and q represent the same meanings as above.)
Using a fluorocarbon polymer which is a linear perfluorocarbon random polymer chain consisting of repeating units represented by, an ammonium type polymer consisting of the same main chain is obtained in claim 5 or 6.
Manufacturing method described in section. 8 General formula as starting material (In the formula, X, l, m, n, R ¹ and R ² represent the same meanings as above, p' and q' each represent a number, and the ratio p'/q' is an average value of 2 to 16 A fluorocarbon polymer having an amino group consisting of a repeating unit represented by R ³ A (in the formula, R ³ is a lower alkyl group, and A is an alkylating agent) is used as an alkylating agent. General formula using a compound represented by (representing a moiety other than the lower alkyl group to be released when (In the formula, X, R ¹ , R ² , R ³ , l, m, n, Z, p′,
q' represents the same meaning as above. ) The manufacturing method according to any one of claims 5 to 7, for obtaining an ammonium type polymer consisting of repeating units represented by: