JPH0617419B2 - Method for producing fluorinated ammonium type polymer - Google Patents

Description

The present invention relates to a novel fluorine-containing ammonium type polymer. More particularly, it relates to an ammonium type fluorocarbon polymer which can be used as an anion exchanger having excellent durability.

Anion exchangers, especially membranous ion exchangers, are used in fields such as electrodialysis.

Conventionally, as a membrane-like anion exchanger, a copolymer or polymer mixture obtained by various combinations of hydrocarbon-based monomers and modified by a polymer reaction are generally used.

However, conventional anion exchangers such as these are
For example, it deteriorates remarkably when used in the presence of chlorine. Therefore, there is a demand for an anion exchanger that is less likely to deteriorate under such conditions.

As a membrane anion exchanger developed for the purpose of improving durability, a fluoropolymer such as poly (tetrafluoroethylene) and an inorganic anion exchanger such as zirconium oxide hydrate are mixed and compression molded. The above-mentioned products are known (Japanese Patent Laid-Open No. 50-35079). However, generally, the ion-exchange function of the inorganic anion exchanger composed of such an amphoteric metal oxide largely depends on the hydrogen ion concentration of the environment in use, and in some cases, the ion-exchange ability is reversed. For example, zirconium oxide hydrate acts as an anion exchanger at pH 6 or lower, but conversely acts as a cation exchanger at pH 6 or higher. Further, near neutrality, the ion exchange capacity is hardly expressed. Therefore, the use conditions of the membrane-like anion exchanger including such an ion exchanger must be significantly limited.

There is also known a method of surface-fluorinating a hydrocarbon-based anion exchange membrane to give a durable membrane (JP-A-52-4489), but this method usually achieves a sufficient degree of fluorination. Since it is difficult to do so, it is difficult to industrially obtain an anion exchange membrane having desired performance.

The present inventors have focused their attention on the excellent durability of fluoropolymers, and as a result of earnest research on the development of anion exchangers based on fluoropolymers, as a result, anion exchange having excellent durability. Invented the body and its manufacturing method.

That is, the present invention comprises a main chain composed of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and at the end of the pendant chain, all the nitrogen atoms in which all the bonds are hydrogen atoms or carbon atoms are included. A molecular weight of about 50,000 to about 3 having an atomic group in which at least one of the nitrogen atoms forms a quaternary ammonium salt.
It provides, 000,000, preferably about 900,000 to about 2,500,000 fluorine-containing ammonium type polymers.

In the present specification, the pendant chain means a substituted or unsubstituted alkyl group, a perfluoroalkyl group or an aromatic group bonded to the main chain composed of a perfluorocarbon polymer chain, and the carbon-carbon bond has a hetero atom or an aromatic group. A ring may intervene.

Specific embodiments of the atomic group forming the end of the pendant chain of the polymer of the present invention include (In the formula, a is an integer of 2 to 5, R ¹ and R ² are lower alkyl groups or alkyl groups having an amino group or a quaternary ammonium group, R ³ and R ⁴ are lower alkyl groups, and Z is
Represents a counter ion of a quaternary ammonium ion. However,
At least one of R ¹ and R ² is an alkyl group having an amino group or a quaternary ammonium group. Further, R ² and R ³ may be combined to form a polymethylene chain having an amino group or a quaternary ammonium group. ) (In the formula, R ¹ ′ is a hydrogen atom, a lower alkyl group or an alkyl group having an amino group or a quaternary ammonium group, and a, R ² , R ³ , R ⁴ and Z have the same meanings as described above.

However, at least ^one of R ¹ ′ and R ² is an alkyl group having an amino group or a quaternary ammonium group.

(Wherein R ² ′ is a hydrogen atom, a lower alkyl group or an alkyl group having an amino group or a quaternary ammonium group, R 2
³ 'is a hydrogen atom or a lower alkyl group, a and R ^1'
Represents the same meaning as described above. R ² ′ and R ³ ′ may together form a polymethylene chain having an amino group or a quaternary ammonium group. However, at least ^one of R ¹ ′ and R ² ′ is an alkyl group having an amino group or a quaternary ammonium group. ) Can be given.

In the present specification, an alkyl group having an amino group or a quaternary ammonium group means one or more nitrogen atoms (amine nitrogen atoms) in which all bonds are hydrogen atoms or carbon atoms in the alkyl chain. It is preferably an alkyl group having 1 to 5 nitrogen atoms and one or all of the nitrogen atoms thereof being optionally quaternary ammonium, and specific examples thereof include the following structures.

As a specific embodiment of the polymer of the present invention, a pendant chain is represented by the general formula (In the formula, X is a fluorine atom, a chlorine atom or a —CF ₃ group, and
Represents an integer of 0 to 5, m represents 0 or 1, and n represents an integer of 1 to 5, but these numbers may be different for each pendant. Y represents an atomic group in which all the bonds include three or more nitrogen atoms formed by hydrogen atoms or carbon atoms, and at least one or more of the nitrogen atoms form a quaternary ammonium salt. And a fluorine-containing ammonium type polymer having a structure represented by the formula (1). The case where each pendant in the definition of l, m, and n differs from each other is specifically the case of a ternary or more copolymer synthesized from two or more fluoroolefin monomers having different l, m, and n. means. This copolymer is exemplified below.

(Where x represents p or p '. When x is p, y and z are positive integers, x / y + z is 2 to 16 and y + z = q. When x is p' , Y and x
Represents a number as an average value, and x / y + z is an average value of 2
To 16 and y + z = q '. l'and l "
Is an integer of 0 to 5, m'and m "are 0 or 1, and n'and n" are integers of 1 to 5, respectively. X and Y have the same meanings as described above. ) Further, as a specific embodiment of the main chain of the polymer of the present invention,
The main chain is a general formula An ammonium type polymer which is a linear perfluorocarbon random polymer chain consisting of repeating units represented by the formula (wherein p and q are integers and the ratio p / q is within the range of 2 to 16). You can

Furthermore, as a specific embodiment of the main chain of the polymer of the present invention,
The main chain is a general formula (In the formula, p'and q'represent numbers as an average value, and the ratio p '/ q' is within the range of 2 to 16.)
An example is an ammonium type polymer which is a linear perfluorocarbon random polymer chain consisting of repeating units represented by

The fluoropolymer of the present invention is composed of a main chain composed of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and at the end of the pendant, a nitrogen atom in which all bonds are made of hydrogen atoms or carbon atoms. It can be produced by reacting an aminofluorocarbon polymer having an atomic group containing 3 or more with an alkylating agent.

As an example of the pendant chain of the aminofluorocarbon polymer used as the starting material, the general formula (In the formula, R ¹ ″ and R ² ″ are a hydrogen atom, a lower alkyl group or an alkyl group having an amino group, provided that at least ^{one of} R ¹ ″ and R ² ″ is an alkyl group having an amino group. R ² ″ and R ³ ′ may together form a polymethylene chain having an amino group. X, R ³ ′, a, l, m
And n have the same meanings as described above. ) Can be mentioned.

As an example of the main chain of the aminofluorocarbon polymer used as a starting material, a general formula A linear perfluorocarbon random polymer chain composed of repeating units represented by the formula (p and q are integers and the ratio p / q is 2 to 16) can be mentioned.

Further, as an example of the aminofluorocarbon polymer used as a starting material, a general formula (In the formula, X, R ¹ ″, R ² ″, R ³ ′, a, l, m and n represent the same meaning as described above, p ′ and q ′ represent a number as an average value, and the ratio p ′ thereof. / Q 'is an average value of 2 to 1
A fluorocarbon polymer composed of a repeating unit represented by the formula (6).

Examples of the lower alkyl group as the substituent in the above general formula include methyl group, ethyl group, n- and i-propyl group, n-,
Examples thereof include i-, s-, and t-butyl groups.

In the present specification, the alkyl group having an amino group means
An alkyl group having one or more amine nitrogen atoms in the alkyl chain, preferably one to five amine nitrogen atoms. Specific examples thereof include the following structures.

Examples of the aminofluorocarbon polymer used as a starting material include polymers having the following repeating units.

As the alkylating agent, a super strong acid salt of lower alkyl iodide or bromide or tri-lower alkyloxonium and the like, for example, methyl iodide, ethyl bromide, n-propyl bromide, n-butyl iodide, trimethyloxonium fluoro. borate _{((CH 3) 3 OBF 4} ), triethyloxonium fluoroborate _{((C 2 H 5) 3} OBF 4), trimethyloxonium tetrafluoroborate hexachloroantimonate _{((CH 3) 3 OS b} Cl 6), dimethyl sulfate,
Examples thereof include methyl trifluoroacetate, methyl trifluoromethanesulfonate, methyl p-toluenesulfonate, ethyl p-nitrobenzenesulfonate and the like.
When alkylating, methanol, ethanol, methylene chloride, chloroform, carbon tetrachloride, sulfolane, N,
N-dimethylformamide, nitromethane, N-methyl-2-pyrrolidone and the like can be used as a solvent.

Alkylation can be carried out under conventional conditions. For example, it can be easily carried out by contacting the starting aminofluorocarbon polymer 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 at least an equivalent amount, preferably a double amount or more with respect to the amino group to be converted. Usually, a large excess is used with respect to the latter in order to allow the reaction to proceed rapidly and completely.

When a solvent is used, it is preferable to use an amount such that the starting aminofluorocarbon polymer can be sufficiently immersed.

Although the alkylation reaction varies depending on the type of alkylating agent, solvent temperature, etc., it can be carried out under the above-mentioned reaction conditions for about 10 hours to 5 days.

The hydrogen atom on the nitrogen atom of the pendant chain terminal atomic group of the fluorine-containing ammonium type polymer obtained by the method of the present invention may be substituted with a lower alkyl group in the present alkylation reaction, and in this case as well, It is a range. This substitution reaction is particularly remarkable when the nitrogen atoms are bonded via three or more carbon atoms.

Further, Z is a counter ion of a quaternary ammonium ion and is initially derived from an alkylating agent, and when the ionic species is a monovalent anion, one of the ions is used, and when the ionic species is divalent, Z is used. It means 1/2 of that ion. Examples thereof include halogen anions such as bromine and iodine, tetrafluoroborate ions, hexachloroantimonate ions, super strong acid ions such as trifluoromethanesulfonic acid, sulfonic acid ions such as benzenesulfonic acid and toluenesulfonic acid, and acetic acid ions. And a monoalkylsulfate ion.

These counterions may be exchanged for other ions if desired. This exchange of ions is carried out by conventional methods, such as KF, NaCl,
It can be easily achieved by treating the ammonium-type polymer obtained in the present invention with a salt of an alkali metal such as LiCl, LiBr, LiI, NaOH, KOH, NaNO ₃ or K ₂ SO ₄ . As an example of Z after the counterion exchange, one fluorine, chlorine,
Examples thereof include anions of halogen such as bromine, hydroxide ions, acetate ions, sulfate ions, and 1/2 sulfate ions.

The aminofluorocarbon polymer used as a starting material is composed of a main chain composed of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain. (Wherein W represents a lower alkoxyl group, a hydroxyl group, a group in which a hydrogen atom of the hydroxyl group is replaced with a tri (lower alkyl) silyl group or an ammonium group, or a halogen atom) is a fluorocarbon polymer having a substituted carbonyl group, formula (Wherein R ¹ ″, R ² ″, R ³ ′ and a have the same meanings as described above), and the pendant chain is terminated with a general formula. (In the formula, R ¹ ″, R ² ″, R ³ ′ and a have the same meanings as described above), and the resulting structure is reacted with a reducing agent.

At this time, the pendants of the fluorocarbon polymer having a substituted carbonyl group used as a starting material are represented by the general formula The groups represented by (wherein X, W, l, m, and n have the same meanings as described above) can be exemplified. In addition, the main chain has the general formula A linear perfluorocarbon random polymer chain composed of repeating units represented by the formula (p is an integer of 3 to 15 and q is an integer of 1 to 10) can be exemplified.

Also the general formula A fluorocarbon polymer comprising a repeating unit represented by the formula (X, W, l, m, n, p ′ and q ′ have the same meanings as described above) can be exemplified.

Examples of the halogen of W in the above formula include fluorine, chlorine, bromine and the like. Examples of the lower alkoxyl group include methoxyl group, ethoxyl group, n-propoxyl group, n-butoxyl group, s-butoxyl group and n-pentoxyl group.

The group in which the hydrogen atom of the hydroxyl group is replaced with a tri (lower alkyl) silyl group specifically means a trimethylsilyloxy group, a triethylsilyloxy group, a t-butyldimethylsilyloxy group or the like. Further, the group in which the hydrogen atom of the hydroxyl group is replaced with an ammonium group, Or, it means -OH (CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ etc., and a carbonyl group It forms a carboxylic acid ammonium salt by combining with.

These fluorocarbon polymers are well known as a cation-exchangeable carboxylic acid type perfluorocarbon polymer (particularly as a cation exchange membrane for electrolysis of a saline solution in the form of a membrane) or a precursor thereof.

Among these fluorocarbon polymers, those having an acid halide type at the pendant chain end include, for example, perfluorocarbon polymers having the same skeleton and having a carboxyl group at the pendant chain end (where W is a hydroxyl group in the above formula, Can be easily prepared by reacting a halogenating agent such as a chlorinating agent. In this case, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like can be used as the chlorinating agent, but thionyl chloride or phosphorus pentachloride in phosphorus oxychloride is preferably used from the viewpoint of reaction efficiency. .

The reaction temperature depends on the state of the raw materials and the chlorinating agent, but is generally in the range of 50 ° to 150 ° C.

Further, the silyl ester type is obtained by adding tri (lower alkyl) silyl chloride, N, O-
It can be obtained by acting a silylating agent such as bistri (lower alkyl) silylacetamide.

As the polyamine represented by the above general formula, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N-dimethyldiethylenetriamine,
Di (trimethylene) triamine, N, N-dimethyl-di (trimethylene) triamine, N, N, N ', N'-tetramethyldi (trimethylene) triamine, N-ethyl-N-
Methyl-di (trimethylene) triamine, N, N-dimethyl-tri (trimethylene) tetramine, N- (N ',
N'-dimethylaminopropyl) ethylenediamine, N
-(Aminoethyl) piperazine, N- (aminopropyl) piperazine, N-pyrrolidinoethyltriethylenetetramine, N- [3,3-bis (N ', N'-dimethylaminomethyl) propyl] propanediamine, etc. It can be illustrated. At this time, a corresponding silylamine in which the hydrogen atom on the nitrogen atom in the above general formula is replaced by a trimethylsilyl group or the like can be used instead of the above polyamine.

The reaction with these polyamines can be carried out in a liquid amine or using a solvent. In this case, when a substance other than an acid halide type polymer or an ester type polymer is used as a starting material, a silylating agent such as trimethylchlorosilane, bistrimethylsilylacetamide, and hexamethyldisilazane is added to the above general formula in order to improve the conversion rate of the reaction. It is particularly preferable to use it together with the diamine represented by the formula (3) above. Especially, when the first silylating agent is used, it is preferable to carry out the reaction in the presence of a tertiary amine such as triethylamine or N-methylpyrrolidine. The amount of polyamine with respect to the starting material is at least equivalent, preferably 3 equivalents or more, and most preferably a large excess amount. The reaction may be carried out in the presence of a tertiary amine.

Diethyl ether, tetrahydrofuran,
Ethers such as dioxane, hydrocarbons such as benzene, toluene and hexane, acetonitrile and the like can be used. When W in the above formula is a lower alkoxyl group among the starting materials, that is, when the pendant chain end is a carboxylic acid ester type, alcohols such as methanol and ethanol can be used as a solvent in addition to these solvents.

The amount of the solvent used may be such that the fluorocarbon polymer having a substituted carbonyl group used is sufficiently immersed. Of course, a larger amount may be used. The reaction temperature is not particularly limited, but is usually about -30 ° C to about 150 ° C, preferably about 0 ° C to 80 ° C.

Then, a reducing agent is allowed to act on the obtained fluorocarbon polymer having a carboxylic acid amide group to produce an aminofluorocarbon polymer.

As the reducing agent, aluminum hydride, alkylaluminum hydride such as diisobutylaluminum hydride, lithium aluminum hydride, diborane and the like can be used, but diborane is excellent in terms of reaction efficiency and easy post-treatment. ing. The diborane to be used can be used, for example, by being generated by reacting sodium borohydride with a boron trifluoride ether complex, or various borane complexes (dimethyl sulfide complex and the like) can be used.

The amount of the reducing agent is equal to or more than the equivalent amount with respect to the functional group in the fluorocarbon polymer having a carboxylic acid amide group, and is generally a large excess amount. The concentration in the solvent is about 0.01 to 5 molar concentration, preferably 0.1 to 2 molar concentration.

The reaction with this reducing agent proceeds smoothly in an ether solvent such as tetrahydrofuran, dioxane, or diethylene glycol dimethyl ether. The amount of the solvent used may be such that the fluorocarbon polymer having a carboxylic acid amide group to be used is sufficiently immersed. Of course, a larger amount may be used. Further, the reaction temperature is not particularly limited, but in the initial stage of the reaction, the reaction is carried out while keeping the temperature within the ice cooling temperature to room temperature,
Thereafter, heating to a reflux temperature to 100 ° C. is preferable for completing the reaction.

Used as a starting material in the preparation of the polymers of the invention.
The fluorocarbon polymer having a substituted carbonyl group can be used in various shapes such as a flat film shape, a tube shape, a fiber shape and a powder shape. Then, at that time, the target fluorine-containing ammonium type polymer can be obtained in a corresponding shape.

The fluorine-containing ammonium type polymer obtained by both methods of the present invention contains a polymer having the following repeating units.

The fluorine-containing ammonium type polymer of the present invention has a chlorine resistance, in particular, even though it partially has a hydrocarbon group.
Extremely excellent in base resistance or solvent resistance. Further, no change is observed even after repeated shrinkage due to drying and swelling in a solvent (including water), and its handling is very easy as compared with conventional anion exchangers. Therefore, for example, in the case of a membrane-shaped ammonium type polymer, it is difficult to use with conventional anion exchange membranes, for example, as a membrane for organic electrolytic reaction, as a membrane for various dialysis under severe conditions, etc. It is possible. Further, it can be used in various shapes as a resin capable of performing anion exchange with a quaternary ammonium group in the presence of various solvents. It can also be used as various catalysts such as a cyanohydrin synthesis catalyst, a phase transfer catalyst or a halogenation reaction catalyst.

Further, the tubular fluorine-containing ammonium type polymer can be used as a multi-tubular module in a space-saving dialysis device, and can also be used in a system for removing interfering anions in ion chromatography.

Further, the anion exchange membrane generally has an increased number of exchange groups per pendant chain, as compared with the raw material membrane, and thus has a feature that it has a low membrane resistance and can be electrolyzed at a low cell voltage.

As described above, the fluorine-containing ammonium type polymer of the present invention has a great industrial value due to its excellent durability and the like.

It is already known that the heat resistance and chemical resistance of the fluorinated polymer, especially the perfluorocarbon polymer, are remarkably higher than those of the general hydrocarbon polymer. However, the ammonium-type polymer of the present invention has a durability far exceeding expectations despite having a hydrocarbon group in the pendant chain. That is, even if the main chain is stabilized because it is a perfluorocarbon polymer chain, it is expected that denaturing decomposition of the hydrocarbon group of the pendant chain and removal of the functional group due to it will be unavoidable under severe conditions. In spite of the above, the fluorine-containing ammonium type polymer of the present invention has very little such deterioration.

Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples. The term "amine type polymer" used herein means an aminofluorocarbon polymer and the term "amide type polymer" means a fluorocarbon polymer having a carboxylic acid amide group. The term end group, which is also used, is
It represents an end group of a pendant chain. The infrared absorption spectrum means the transmission spectrum unless otherwise specified, and the dyeing test was carried out 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: 0.05% methanol solution of bromothymol blue Basic cresol red: Cresol red Solution of 0.05% water-methanol solution with about 1% of 10% NaOH solution Basic thymol blue: A solution of 0.05% methanol solution of thymol blue with about 1% of 10% NaOH solution The electric resistance of the membrane is 0.5N. After fully equilibrated with a saline solution, the film was measured in a 0.5N saline solution at an alternating current cycle of 1000 cycles at a temperature of 25 ° C. The transport number of the membrane was measured between the 0.5N saline solution and the 2.0N saline solution. It is calculated from the potential using the Nernst equation.

The ion exchange capacity of the fluorinated ammonium type polymer is obtained by completely salt exchanging the ammonium chloride type polymer,
It was determined by quantifying the chlorine ion which was present as a counter ion in the polymer by the Horhard method (Vorhard method).

The conversion rate was calculated from the value of nitrogen in elemental analysis, taking the exchange capacity of the raw material copolymer as 100% and taking into consideration the increase or decrease in the equivalent weight due to the change in the terminal group.

Example 1 The membrane obtained in Reference Example 8 was immersed in a solution of 8 ml of methyl iodide in ml of N, N-dimethylformamide and heated at 60 ° C. for 96 hours to obtain an ammonium iodide type polymer membrane. Then, this membrane was immersed in 40 ml of a 10% methanol solution of lithium chloride and heated at 60 ° C. for 24 hours (the solution was exchanged in the middle).

Then, it was washed in methanol at 60 ° C. for 10 hours to obtain an ammonium chloride type polymer film.

The infrared absorption spectrum of this film is shown in FIG.

Infrared absorption spectrum (cm ⁻¹ ) 3400, 3050 to 2950, 2360, 1630,
1490 to 1450, 1350 to 960, 860 to 48
0.

The film was dyed yellow-orange with cresol red, red with basic cresol red, orange with thymol blue, dark blue with basic thymol blue, orange with bromothymol blue, and blue-green with basic bromothymol blue.

The obtained membrane had an ion exchange capacity of 1.0 meq / g dry membrane, an electric resistance of 6.0 Ωcm ² , and a transport number of 0.87. This film exhibited excellent durability especially under strongly basic conditions, and the above values were not changed even when heated at 50 ° C. for 100 hours in ethylenediamine in the presence of ethylenediamine / hydrochloride. On the other hand, the commercially available hydrocarbon anion exchange membrane was immediately blackened under the above conditions and the membrane was destroyed.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

Example 2 The membrane obtained in Reference Example 9 was immersed in 27 ml of anhydrous tetrahydrofuran under an argon atmosphere, and 0.5 g of sodium borohydride was added. Then, a solution of 1 ml of boron trifluoride ethyl ether complex in 3 ml of tetrahydrofuran was cooled with ice water for 30 minutes.
The mixture was added dropwise over 1 minute and stirred for 1.5 hours. Then, the mixture was heated under reflux at room temperature for 30 minutes and further 20 hours. The film was taken out, washed in methanol under heating under reflux for 15 hours, and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a light brown transparent amine-type polymer film. In the infrared absorption spectrum of this film, the absorption at 1720 cm ⁻¹ derived from amide carbonyl disappeared, indicating that the reduction to the amine type film was completely progressed. The conversion rate calculated from the elemental analysis values was about 81%. This film was not stained with crystal violet or basic thymol blue, but was stained red with cresol red and red with thymol blue. The infrared spectrum of the obtained film is shown in FIG.

Infrared absorption spectrum (cm ^-1 ) 3300, 300-2750, 2375, 1480-1
450, 1340-960, 840, 780-490 This film consisted of a copolymer consisting essentially of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6) The obtained membrane is immersed in a solution of 8 ml of methyl iodide in 32 ml of N, N-dimethylformamide and heated at 60 ° C. for 78 hours to form an ammonium iodide type polymer membrane. Got Then, the membrane is immersed in 40 ml of 10% lithium chloride in methanol,
The mixture was heated at 60 ° C. for 24 hours (the solution was changed during the heating).

Then, it was washed in methanol at 60 ° C. for 8 hours to obtain an ammonium chloride type polymer film.

The infrared absorption spectrum of this film is shown in FIG.

Infrared absorption spectrum (cm ⁻¹ ) 3600 to 3200, 3020, 2970, 2820,
2350, 1630, 1490 ~ 1420, 1330 ~
1040,990-960,840,740-490.

This film was dyed yellow orange with cresol red, dark red with basic cresol red, orange with thymol blue, black with basic thymol blue, orange with bromothymol blue, and light green with basic bromothymol blue. The exchange capacity of the obtained membrane was 1.4 meq / g dry membrane, the electric resistance was 1.0 Ωcm ² , and the transport number was 0.85. Even after the membrane was immersed in a chlorine-saturated aqueous solution at 60 ° C. for 1000 hours, almost no change was observed in these values. Further, no change was observed even after the operation of treating the solvent in methanol at 65 ° C. for 48 hours and then vacuum-removing the solvent at 40 ° C. was repeated 5 times.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6.) Example 3 Carboxyl type polymer film obtained by the method of Reference Example 1 (7.
5 cm ² ) was immersed in 16 ml of anhydrous acetonitrile, 1.8 ml of N- (aminoethyl) piperazine, 1.9 ml of triethylamine and 1.8 ml of trimethylchlorosilane were added, and the mixture was heated at 80 ° C. for 96 hours under an argon atmosphere. The film was taken out, washed with ether, and then dried under reduced pressure at 60 ° C. for 15 hours to obtain an amide type polymer film.

Infrared absorption spectrum (cm ^-1 ) 3350, 3000 to 2750, 2355, 1750 ~
1680, 1560-1510, 1470-1430,
1360-960,850-480 This membrane consisted essentially of a copolymer of the following repeating units:

(P ₁ ′ / q ₁ ′ 7.6) Under an argon atmosphere, the obtained membrane is immersed in 170 ml of anhydrous tetrahydrofuran to give 3.0 g of sodium borohydride.
Was added. Next, boron trifluoride ethyl ether complex 6ml
Was added dropwise to a 10 ml solution of tetrahydrofuran under ice-water cooling for 35 minutes and stirred for 55 minutes. 55 minutes at room temperature then 2 more
The mixture was heated under reflux for 1 hour. The film was taken out, washed in methanol with heating under reflux for 10 hours, and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a light brown transparent amine-type polymer film. In the infrared absorption spectrum of this film, the absorption at 1750 to 1680 cm ⁻¹ derived from amide carbonyl has disappeared,
It was shown that the reduction to the amine type membrane was completely proceeded.
The conversion rate calculated from the elemental analysis values was about 85%. This film was not stained with crystal violet or basic thymol blue, but was stained yellow with cresol red and pale orange with thymol blue.

Infrared absorption spectrum (cm ^-1 ) 3370, 3210, 3100, 3000-2800,
2370, 1480 to 1440, 1370 to 930, 8
40-490 This film consisted of a copolymer consisting essentially of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6) The obtained membrane is immersed in a solution of 10 ml of methyl iodide in 40 ml of N, N-dimethylformamide and heated at 60 ° C. for 120 hours to obtain an ammonium iodide type polymer. A film was obtained. Then, this membrane was immersed in 50 ml of a 10% lithium chloride methanol solution and heated at 60 ° C. for 24 hours (the solution was exchanged during the process).

Then, it was washed in methanol at 60 ° C. for 8 hours to obtain an ammonium chloride type polymer film.

Infrared absorption spectrum (cm ⁻¹ ) 3600 to 3150, 3050 to 2300, 1630,
1490-950, 920, 790-480.

This film is yellow with cresol red, yellow-orange with basic cresol red, orange with thymol blue, turquoise with basic thymol blue, orange with bromothymol blue, dark blue with basic bromothymol blue, and a quaternary ammonium group Existence was confirmed. The electric resistance of the obtained film was 3.2 Ωcm ² , and the transport number was 0.86.
This film also showed excellent base resistance like the film obtained in Example 1.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₁ ′ / q ₁ ′ ≈7.6) Example 4 Carboxyl type polymer film (1 obtained by the method of Reference Example 1
2 cm ² ) is soaked in 32 ml of anhydrous acetonitrile, 4.0 ml of triethylenetetramine and 3.7 ml of trimethylamine and 3.5 ml of trimethylchlorosilane are added, and under argon atmosphere,
Heated at 80 ° C. for 96 hours. The film was taken out, washed with ether, and dried under reduced pressure at 60 ° C. for 20 hours to obtain an amide type polymer film.

Infrared absorption spectrum (cm ^-1 ) 3350, 3000-2800, 2360, 1750-
1700, 1530, 1440, 1360 to 960, 8
50-490 This membrane consisted of a copolymer consisting essentially of the following repeating units:

(P ₁ ′ / q ₁ ′ ≈7.6) (including a cross-linked product with amino groups at some ends) Under an argon atmosphere, the obtained membrane is immersed in 380 ml of anhydrous tetrahydrofuran, and 10 g of sodium borohydride
Was added. Next, boron trifluoride ethyl ether complex 20
It was added dropwise to a 20 ml solution of tetrahydrofuran in 50 ml under ice-water cooling for 50 minutes and stirred for 1.5 hours. Then, the mixture was heated under reflux for 30 minutes at room temperature for 39 hours. The membrane was taken out, washed in methanol under heating under reflux for 10 hours, then under reduced pressure at 60 ° C. for 24 hours.
After drying for an hour, a light brown transparent amine-type polymer film was obtained. In the infrared absorption spectrum of this film, the absorption at 1750 to 1700 cm ⁻¹ originating from amide carbonyl disappeared, showing that the reduction to the amine type film was completely progressed. As a result of calculating the conversion rate from the elemental analysis value, it is about 44%
(When the crosslinked structure is not taken into consideration). This film was not stained with crystal violet, basic cresol red or basic thymol blue, but was stained yellow with cresol red and orange with thymol blue.

Infrared absorption spectrum (cm ⁻¹ ) 3400, 3210, 2950, 2860, 2370,
1610, 1460, 1370 to 930, 850, 81
0-490 This film consisted of a copolymer consisting essentially of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6) (Partially containing cross-linked product) The obtained membrane is immersed in a solution of 10 ml of methyl iodide in 40 ml of N, N-dimethylformamide and heated at 60 ° C. for 96 hours. Then, an ammonium iodide type polymer film was obtained. Then, this membrane was immersed in 50 ml of a 10% lithium chloride methanol solution and heated at 60 ° C. for 24 hours (the solution was exchanged during the process).

Then, it was washed in methanol at 60 ° C. for 8 hours to obtain an ammonium chloride type polymer film.

Infrared absorption spectrum (cm ⁻¹ ) 3730 to 3100, 3050 to 2850, 2380,
1680, 1490 to 1450, 1400, 1350
950, 800-480.

This film is yellow with cresol red, brown with basic cresol red, light yellow with thymol blue, blue with basic thymol blue, yellow with bromothymol blue, light blue with basic bromothymol blue, and quaternary ammonium group Existence was confirmed. The obtained film had an electric resistance of 12 Ωcm ² and a transport number of 0.88. This film showed excellent durability against organic solvents such as methanol, acetone and dioxane.

Example 5 Carboxyl type polymer film (9
cm ² ) was immersed in 32 ml of anhydrous dimethoxyethane, 5.0 ml of triethylamine, 8.0 ml of di (dimethylaminopropyl) amine and 4.7 ml of trimethylchlorosilane were added, and the mixture was heated under argon atmosphere for 30 minutes at 90 ° C. for 72 hours. The film was taken out, washed with ether, and dried under reduced pressure at 60 ° C. for 20 hours to obtain an amide type polymer film.

Infrared absorption spectrum (cm ^-1 ) 3400-2600, 2600-2300, 1720-
1640, 1640-1510, 1500-940, 9
00-480 Except for the mesh part, this film consisted essentially of a copolymer consisting of the following repeating units.

(P ₂ ′ / q ₂ ′ ≈6.5) Under an argon atmosphere, the film obtained above was immersed in 27 ml of anhydrous tetrahydrofuran, and 0.5 g of sodium borohydride was added. Then, a solution of 1 ml of boron trifluoride ethyl ether in 3 ml of tetrahydrofuran was added dropwise over 20 minutes while cooling with ice water, and 1.
Stir for 5 hours. Then, the mixture was heated under reflux at room temperature for 30 minutes and then for 20 hours. The membrane was taken out, washed in methanol with heating under reflux for 15 hours, and dried under reduced pressure at 60 ° C. for 24 hours to obtain an amine-type polymer membrane.

Infrared absorption spectrum (cm ^-1 ) 3000, 2700, 2550-2300, 1450-
Absorption at around 1700 cm ⁻¹ derived from 930,870 to 460 amide carbonyl disappeared, indicating that the reduction to the amine type membrane was completely proceeded.

This film was stained orange with cresol red and orange with thymol blue, and was not stained under each basic condition.

This membrane consisted of a copolymer consisting essentially of the following repeating units except for the mesh part.

(P ₂ ′ / q ₂ ′ ≈6.5) The obtained membrane was immersed in a solution of 10 ml of methyl iodide in 40 ml of N, N-dimethylformamide and heated at 60 ° C. for 72 hours to obtain an ammonium iodide type polymer membrane. It was Then, this membrane was immersed in 40 ml of a 10% methanol solution of lithium chloride and heated at 60 ° C. for 25 hours (the solution was exchanged on the way).

Then, it wash | cleaned in methanol at 60 degreeC for 7 hours, and obtained the ammonium chloride type polymer film.

Infrared absorption spectrum (cm ^-1 ) 3500-3300, 3050-2750, 2370,
1620, 1510-1380, 1330, 900, 7
80-480.

The film was stained yellow with cresol red and blue with basic thymol blue. The obtained film had an electric resistance of 4.5 Ωcm ² and a transport number of 0.86. This film is also used in Example 1
Similar to the film obtained in 1., it showed excellent base resistance.

This membrane consisted of a copolymer consisting essentially of the following repeating units except for the mesh part.

(P ₂ ′ / q ₂ ′ ≈6.5) Example 6 Carboxyl type polymer film (9 obtained by the method of Reference Example 1
cm ² ) was immersed in 32 ml of anhydrous dimethoxyethane, and 8 ml of di (dimethylaminopropyl) amine triethylamine 5.
0 ml and 4.7 ml of trimethylchlorosilane were added at room temperature, and the mixture was heated at 90 ° C. for 72 hours under an argon atmosphere. The film was taken out, washed with ether, and dried under reduced pressure at 60 ° C. for 20 hours to obtain an amide type polymer film.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₁ ′ / q ₁ ′ ≈7.6) Under an argon atmosphere, the obtained membrane was immersed in 27 ml of anhydrous tetrahydrofuran and 0.5 g of sodium borohydride was added. Next, the solution was added dropwise to a solution of 1 ml of boron trifluoride ethyl ether complex in 3 ml of tetrahydrofuran under ice-water cooling for 20 minutes and stirred for 1.5 hours. Then, the mixture was heated under reflux at room temperature for 30 minutes and further 20 hours. The film was taken out, washed in methanol under heating under reflux for 15 hours, and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a light brown transparent amine-type polymer film. In the infrared absorption spectrum of this film, the absorption at around 1700 cm ^-1 derived from amide carbonyl disappeared, indicating that the reduction to the amine-type film had proceeded completely. As a result of calculating the conversion rate from the elemental analysis value, it was about 57%. This film was not stained with crystal violet, basic cresol red or basic thymol blue, but was stained yellow with cresol red and orange with thymol blue. The infrared absorption spectrum of the obtained film is shown in FIG.

Infrared absorption spectrum (cm ⁻¹ ) 2950, 2900 to 2750, 2380, 1460,
1340-950,840,780-490 This membrane consisted essentially of a copolymer of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6) The obtained membrane was immersed in a solution of 10 ml of methyl iodide in 40 ml of methanol and heated at 60 ° C. for 72 hours to obtain an ammonium iodide type polymer membrane. Then, this membrane is immersed in 40 ml of a 10% methanol solution of lithium chloride and the temperature is kept at 60 ° C.
It was heated for an hour (the solution was changed on the way).

Then, it wash | cleaned in methanol at 60 degreeC for 7 hours, and obtained the ammonium chloride type polymer film.

The infrared absorption spectrum of this film is shown in FIG.

Infrared absorption spectrum (cm ^-1 ) 3500-3200, 3030, 2950, 2380,
1630, 1480, 1330 to 930, 840, 78
0-480.

The film was stained yellow with cresol red and blue with basic thymol blue. The obtained membrane has an ion exchange capacity of 0.73 meq / g dry membrane and an electric resistance of 3.3Ω.
The cm ² and the transport rate were 0.86. This film also showed excellent base resistance like the film obtained in Example 1.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₁ ′ / q ₁ ′ ≈7.6) Example 7 Carboxyl type polymer film (9 obtained by the method of Reference Example 1
cm ² ) is soaked in 32 ml of anhydrous acetonitrile and di (aminopropyl) methylamine 4.4 ml triethylamine 3.7 ml
And trimethylchlorosilane 3.5 ml are added under ice water cooling,
It heated at 80 degreeC in argon atmosphere for 94 hours. The film was taken out, washed with ether, and dried under reduced pressure at 60 ° C. for 20 hours to obtain an amide type polymer film.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₁ ′ / q ₁ ′ ≈7.6) (Partially Containing Cross-Linked Body) Under an argon atmosphere, the obtained membrane was immersed in 27 ml of anhydrous tetrahydrofuran, and 0.5 g of sodium borohydride was added. Next, the solution was added dropwise to a solution of 1 ml of boron trifluoride ethyl ether complex in 3 ml of tetrahydrofuran under ice-water cooling for 20 minutes and stirred for 1.5 hours. Then, the mixture was heated under reflux at room temperature for 30 minutes and further 20 hours. The film was taken out, washed in methanol under heating under reflux for 15 hours, and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a light brown transparent amine-type polymer film. In the infrared absorption spectrum of this film, the absorption at around 1700 cm ^-1 derived from amide carbonyl disappeared, indicating that the reduction to the amine-type film had proceeded completely. As a result of calculating the conversion rate from the elemental analysis values, it was about 56% (value calculated for all non-crosslinked types). This film was not stained with crystal violet or basic thymol blue, but was stained red with cresol red and deep orange with thymol blue.

Infrared absorption spectrum (cm ^-1 ) 3200, 3000-2750, 2350, 1490-
1430, 1360-930, 840-480 This film consisted of a copolymer consisting essentially of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6) (Partially containing cross-linked product) The obtained membrane is immersed in a solution of methyl iodide (6 ml) in N, N-dimethylformamide (24 ml) and heated at 60 ° C. for 92 hours. Then, an ammonium iodide type polymer film was obtained. Then, this membrane was immersed in 30 ml of 10% methanol solution of lithium chloride and heated at 60 ° C. for 45 hours (the solution was exchanged on the way).

Then, it was washed in methanol at 60 ° C. for 9 hours to obtain an ammonium chloride type polymer film.

Infrared absorption spectrum (cm ⁻¹ ) 3600 to 3200, 3050, 2950, 2380,
1620, 1480, 1350-940, 790-47
0.

The film was dyed yellow with cresol red, red with basic cresol red, yellow-orange with thymol blue, dark orange with bromothymol blue, and dark blue-green with basic bromothymol blue. The electric resistance of the obtained film was 6.0 Ωcm ² , and the transport number was 0.87. This film showed excellent durability against organic solvents such as methanol, acetone and dioxane.

Example 8 The tubular amine-type polymer obtained in Reference Example 10 was placed in a solution of methyl iodide in N, N-dimethylformamide (volume ratio 1: 4) and reacted at 60 ° C. for 50 hours. After washing the obtained tube-shaped polymer with methanol, it was placed in a methanol solution of lithium chloride (1.28 molar concentration) at 60 ° C. for 24 hours.
Reacted for hours. This tubular polymer was heated to 60 ° C. in methanol to obtain the objective tubular ammonium chloride type polymer. The obtained tubular polymer was colored black with basic thymol blue in the dyeing test, yellow-orange with cresol red, orange with thymol blue and bromothymol blue, and dark red with basic cresol red to give an anion exchange group. Was confirmed.

The exchange capacity of the obtained tubular anion exchanger was 1.3.
It was a meq / g dry resin.

No change was observed even after the procedure of treating the solvent in methanol at 65 ° C. for 48 hours and then vacuum removing the solvent at 40 ° C. was repeated 5 times.

This tubular copolymer consisted essentially of the following repeating units:

(In the formula, p ₄ ′ / q ₄ ′ is about 6.4) Example 9 The powdery amine-type polymer obtained in Reference Example 11 was dissolved in methyl iodide in N, N-dimethylformamide (volume ratio 1:
It was put in 4) and reacted at 60 ° C. for 50 hours. The obtained powdery polymer was washed with methanol and then reacted in a methanol solution of lithium chloride (1.28 molar concentration) at 60 ° C. for 24 hours. This powdery polymer was heated in methanol at 60 ° C. to obtain the desired powdery ammonium chloride type polymer. The obtained powdery polymer was not dyed with crystal violet in the dyeing test, and was colored black with basic thymol blue and yellow-orange with cresol red.
The presence of anion exchange groups was confirmed.

The exchange capacity of the obtained powdery anion exchanger was 1.3 meq / g dry resin.

No change was observed after the procedure of treating the solvent in methanol at 65 ° C. for 48 hours and then vacuum-removing the solvent at 40 ° C. was repeated 5 times.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₅ ′ / q ₅ ′ is about 6.5) Example 10 The same as Example 2 except that the acid chloride polymer film (7.5 cm ² ) obtained by the method of Reference Example 7 was used as the raw material film. The above operation was performed to obtain an ammonium chloride type polymer film via the amide type polymer film and the amine type polymer film. The infrared absorption spectrum of the obtained film was almost the same as that of the film obtained in Example 2. The exchange capacity of the obtained membrane was 1.6 meq / g dry membrane, the electric resistance was 0.5 Ωcm ² , and the transport number was 0.84.
It showed the same basic resistance as the membrane of Example 2.

The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₃ ′ / q ₃ ′ is about 6.4) Reference Example 1 (raw material preparation example) Copolymer film obtained by copolymerization with [Nufion 125 (trade name) manufactured by DuPont, film thickness 125 μ, SO
_{The 3} H equivalent exchange capacity of 0.83 meq / g dry membrane was treated with 2N hydrochloric acid, then treated with sulfonyl chloride, then treated with hydrogen iodide, and washed with alkali to make the membrane a sodium carboxylate salt type. The film was treated with a 3.24N hydrochloric acid aqueous solution, washed with water, and dried under reduced pressure to obtain a carboxyl polymer film.
The structure of the pendant chain of this membrane is Is. This film has an infrared absorption spectrum of 1780.
It showed strong carbonyl absorption at cm ^-1, and was stained blue with crystal violet.

The membrane consisted of a copolymer consisting essentially of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6) Reference Example 2 (raw material preparation example) Carboxyl type polymer film obtained by the method of Reference Example 1 (3.
6 cm ² ) was immersed in 10 ml of n-butyl alcohol, 1.73 g of hydrogen chloride was absorbed at room temperature, and then heated at 65 ° C. for 65 hours. The film was taken out and dried under reduced pressure at 60 ° C. for 24 hours to obtain an n-butyl ester type polymer film. This film is 1
It showed a strong carbonyl absorption at 790 cm ^-1 . It was not stained with crystal violet.

Does this membrane consist essentially of a copolymer of the following repeating units: (P ₁ ′ / q ₁ ′ is about 7.6) Reference Example 3 (raw material preparation example) Reference is made to a film using a polytetrafluoroethylene mesh as a support in a copolymer with [a DuPont Nafion 415 (trade name) mesh part excluding SO ₃ H conversion capacity 0.91 meq / g dry film] The same treatment as in Example 1 was carried out to obtain a carboxyl type polymer film. The film was stained blue with crystal violet.

This membrane was composed of a copolymer consisting essentially of the following repeating units except for the mesh part.

(P ₂ ′ / q ₂ ′ is about 6.5) Reference Example 4 (raw material preparation example) The copolymer obtained by the copolymerization with was formed into a film [film thickness 50 μ, SO ₃ H conversion capacity 0.95 meq / g dry film] and then saponified to give a sodium salt type film. After further treating the membrane with concentrated hydrochloric acid-methanol (3: 1),
It was heated in 3.24N hydrochloric acid, washed with water, and dried under reduced pressure to obtain a carboxylic acid film. The membrane consisted essentially of a copolymer consisting of the following repeating units:

(P ₃ ′ / q ₃ ′ is about 6.4) Reference Example 5 (raw material preparation example) The copolymer obtained by copolymerization with
0.625 mm), outer diameter 0.875 mm, SO ₃ H conversion capacity 0.92 meq / g dry resin), saponified, further treated with 2N hydrochloric acid according to a known method, then converted to sulfonyl chloride, and then iodinated. The membrane was treated with hydrogen and washed with alkali to form a sodium carboxylic acid salt type. The membrane was treated with a 3.24N hydrochloric acid aqueous solution, washed with water, and dried under reduced pressure to obtain a tubular carboxyl-type copolymer. The structure of the pendant chain of this copolymer is Is. This tube has an infrared absorption spectrum of 1
It showed a strong carbonyl absorption at 780 cm ^-1, and was stained blue with crystal violet.

The tube consisted essentially of a copolymer consisting of the following repeating units:

(P ₄ ′ / q ₄ ′ is about 6.4) Reference example 6 (raw material preparation example) Copolymer powder obtained by co-polymerization and saponification with [Nufion 511 (trade name) manufactured by DuPont, SO ₃ H conversion capacity 0.91 meq / g dry resin, potassium sulfonate type] is 5N hydrochloric acid Was hydrolyzed and treated with phosphorus pentachloride to give a sulfonyl chloride. Then, in the same manner as in Reference Example 1, hydrogen iodide treatment, alkali washing and hydrochloric acid treatment were carried out to obtain a powdery carboxyl type polymer. This powdery polymer
When using a KBr disk and examining the infrared absorption spectrum, 17
It showed carbonyl absorption around 80 cm ^-1 , and was stained blue with crystal violet.

This powder consisted essentially of a copolymer consisting of the following repeating units:

(P ₅ ′ / q ₅ ′ is about 6.5) Reference Example 7 (raw material preparation example) The carboxyl-type polymer film obtained by the method of Reference Example 4 was treated with phosphorus pentachloride-phosphorus oxychloride (weight ratio 1: 1). .6) in 120 ° C. for 24 hours. Further, it was washed in carbon tetrachloride and then dried. This film showed a strong carbonyl absorption at 1800 cm ^-1 in the infrared spectrum. The membrane consisted essentially of a copolymer consisting of the following repeating units:

(In the formula, p ₃ ′ / q ₃ ′ is about 6.4.) Reference Example 8 Carboxyl type polymer film obtained by the method of Reference Example 1 (7.
5 cm ² ) was immersed in 23 ml of anhydrous acetonitrile, N- (dimethylaminopropyl) ethylenediamine 2.8 g triethylamine 2.7 ml and trimethylchlorosilane 2.5 ml were added, and the mixture was heated at 80 ° C. for 91 hours in an argon atmosphere. The membrane is taken out, washed with ether, and then under reduced pressure at 60 ° C for 20 minutes.
After drying for an hour, an amide type polymer film was obtained. The infrared absorption spectrum of the obtained film is shown in FIG.

Infrared absorption spectrum (cm ⁻¹ ) 3240, 3000 to 2750, 2360, 1720,
1620, 1550 to 1520, 1460 to 1430,
1360-960,860-480 This membrane consisted essentially of a copolymer of the following repeating units:

(P ₁ ′ / q ₁ ′ ≈7.6) Under an argon atmosphere, the obtained membrane was immersed in 27 ml of anhydrous tetrahydrofuran and 0.5 g of sodium borohydride was added. Then, a solution of 1 ml of boron trifluoride ethyl ether complex in 3 ml of tetrahydrofuran was added dropwise over 30 minutes under ice-water cooling, and the mixture was stirred for 1.5 hours. Then, the mixture was heated under reflux at room temperature for 30 minutes and further 20 hours. The film was taken out, washed in methanol under heating under reflux for 15 hours, and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a light brown transparent amine-type polymer film. In the infrared absorption spectrum of this film, the absorption at 1720 cm ⁻¹ derived from amide carbonyl disappeared, indicating that the reduction to the amine type film was completely progressed. The conversion rate calculated from the elemental analysis values was about 74%. This film was not stained with crystal violet or basic thymol blue, but was stained red with cresol red, dark blue with bromothymol blue, and red orange with thymol blue. The infrared absorption spectrum of the obtained film is shown in FIG.

Infrared absorption spectrum (cm ^-1 ) 3300, 3000-2760, 2360, 1470-
1440, 1350-950, 840-480 This membrane consisted essentially of a copolymer of the following repeating units:

(P ₁ ′ / q ₁ ′ is about 7.6) Reference Example 9 Carboxyl type polymer film obtained by the method of Reference Example 1 (7.
5 cm ² ) is immersed in 32 ml of anhydrous acetonitrile, and N, N-
Dimethyldi (trimethylene) triamine 4.3 g Triethylamine 3.7 ml and trimethylchlorosilane 3.5 ml were added, and the mixture was heated at 80 ° C. for 113 hours in an argon atmosphere.
Remove the membrane, wash with ether, and then under reduced pressure at 60 ° C for 2
After drying for 0 hour, an amide polymer film was obtained. The infrared absorption spectrum of the obtained film is shown in FIG.

Infrared absorption spectrum (cm ⁻¹ ) 3200, 3000 to 2750, 2370, 1720,
1630, 1530, 1470 to 1440, 1375,
1340-1030, 990-960, 840-490 This membrane consisted essentially of a copolymer of the following repeating units:

(P ₁ ′ / q ₁ ′ ≈7.6) Reference Example 10 The tubular carboxyl-type copolymer (50 cm) obtained by the method of Reference Example 5 was immersed in 160 ml of anhydrous acetonitrile, and the tube was filled with the same solvent. , Triethylamine 12.4 ml, N, N-dimethyldi (trimethylene)
11.3 ml of triamine and 11.4 ml of trimethylchlorosilane were added, and the mixture was heated at 90 ° C. for 72 hours under an argon atmosphere.
The tube was taken out and dried at 60 ° C. under reduced pressure to obtain a tubular amide polymer. When the obtained tube-shaped amide polymer was arranged and its infrared absorption spectrum was examined,
The spectrum of the film obtained in Example 2 almost matched. Conversion rate is 78%. When the resulting tubular polymer was sliced into slices and examined for dyeability with respect to crystal violet, it was not dyed at all.

The amide-type polymer that constitutes this tube is essentially a repeating unit. (P ₄ ′ / q ₄ ′ ≈ 6.4).

Under an argon atmosphere, the tubular amide polymer obtained by the above reaction was immersed in dry diethylene glycol dimethyl ether, and the tube was filled with diethylene glycol dimethyl ether. Then, after adding sodium borohydride (to 0.53 mol concentration) and stirring and cooling well, a dry diethylene glycol dimethyl ether solution of a boron trifluoride ether complex (0.62 mol equivalent to sodium borohydride) was added dropwise under ice cooling. did. The mixture was reacted for 2.5 hours under cooling and further for 34 hours at 100 ° C. The obtained tubular amine-type polymer was washed with methanol and dried, and its infrared absorption spectrum was examined. As a result, it was almost the same as the spectrum of the film obtained in Example 2. Conversion rate of 75%. When the obtained tubular polymer was sliced and examined for dyeability, it showed the same dyeability as in Example 2.

This amine-type polymer consisted essentially of the following repeating units:

(P ₄ ′ / q ₄ ′ ≈6.4) Reference Example 11 The powdery carboxyl-type polymer (1.0 g) obtained by the method of Reference Example 6 was immersed in 165 ml of anhydrous acetonitrile, and 9.3 ml of triethylamine and N, N-dimethyl were added. -7.5 ml of di (trimethylene) triamine and trimethylchlorosilane
8.55 ml was added and the mixture was heated at 90 ° C. for 80 hours under an argon atmosphere to obtain an amide type polymer. The powder thus obtained was used as a KBr disk, and the infrared absorption spectrum was measured to be 1700 cm
Absorption derived from amidocarbonyl was observed near ^-1 .
Conversion rate of 75%. The powdery polymer obtained was not dyed with crystal violet at all.

The amide-type polymer constituting this powder consisted essentially of the following repeating units.

(P ₅ ′ / q ₅ ′ ≈6.5) The obtained powdery amide-type polymer was reduced with diborane by the same procedure as in Reference Example 8 and excessively collected to obtain a powdery amine-type polymer. It was The conversion rate was 72%. When the obtained powder was used as a KBr disk and the infrared absorption spectrum was examined, the absorption of amidocarbonyl existing near 1700 cm ^-1 was completely disappeared.

This powder was not stained with crystal violet or basic thymol blue, but was stained red with cresol red and red with thymol blue.

This amine-type polymer consisted essentially of the following repeating units:

(P ₅ ′ / q ₅ ′ ≈6.5) Reference Example 12 (Example of Use) Using the membranes obtained in Examples 2 and 5, hydrochloric acid was electrolyzed. A commercially available hydrocarbon-based anion exchange membrane was also used for comparison. The electrolysis conditions are as follows.

Membrane area: 9.6 cm ² , Electrode: Platinum electrolyte solution: Anode / cathode = 6N hydrochloric acid / 6N hydrochloric acid Current density: 5 A / dm ^{2 The} results are shown in Table 1.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1, FIG. 3 and FIG. 5 are diagrams showing infrared absorption spectra of typical examples of the fluorine-containing ammonium type polymer of the present invention, and FIG. 4 and 7 are infrared absorption spectra of a typical example of an aminofluorocarbon polymer used as a starting material, and FIGS. 6 and 8 are fluorocarbon polymers having a carboxylic acid amide group as the starting material. It is a figure which shows the infrared absorption spectrum of a representative example of a combination.

Front page continuation (72) Inventor Toru Kiyota 591, Tomita, New Nanyo City, Yamaguchi Prefecture (72) Hiroyuki Watanabe 972, Oita, Shinnanyo City, Yamaguchi Prefecture Judgment Panel Judge Kunio Tsuji Judge Kento Kondo Seiichiro Numabe

Claims (5)

[Claims] 1. A main chain composed of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and at the end of the pendant, three or more nitrogen atoms in which all bonds are hydrogen atoms or carbon atoms are formed. A method for producing a fluorine-containing ammonium type polymer, which comprises reacting an aminofluorocarbon polymer having an atomic group containing it with an alkylating agent. 2. As a starting material, the pendant chain is represented by the general formula: (In the formula, a is an integer of 2 to 5, R ³ ′ is a hydrogen atom or a lower alkyl group, and R ¹ ″ and R ² ″ are a hydrogen atom, a lower alkyl group or an alkyl group having an amino group.
At least one of R ¹ ″ and R ² ″ is an alkyl group having an amino group. R ² ″ and R ³ ′ may together form a polymethylene chain having an amino group. X is a fluorine atom, a chlorine atom or a —CF ₃ group, l is an integer of 0 to 5, and m is 0 or 1, and n represents an integer of 1 to 5, but these numbers may be different for each pendant.)
The method for producing a fluorine-containing ammonium type polymer according to claim 1, wherein the aminofluorocarbon polymer represented by 3. A starting material, the main chain of which is of the general formula (In the formula, p and q are integers, and the ratio p / q is 2 to 16.) An aminofluorocarbon polymer which is a linear perfluorocarbon random polymer chain consisting of repeating units represented by The method for producing a fluorine-containing ammonium type polymer according to claim 1 or 2, which is characterized. 4. A starting material of the general formula (In the formula, a is an integer of 2 to 5, R ³ ′ is a hydrogen atom or a lower alkyl group, and R ¹ ″ and R ² ″ are a hydrogen atom, a lower alkyl group or an alkyl group having an amino group.
At least one of R ¹ ″ and R ² ″ is an alkyl group having an amino group. R ² ″ and R ³ ′ may together form a polymethylene chain having an amino group. X is a fluorine atom, a chlorine atom or a —CF ₃ group, l is an integer of 0 to 5, and m is 0 or 1, and n represents an integer of 1 to 5, but these numbers may be different for each pendant.
p ′ and q ′ represent numbers as an average value, and their ratio p ′
/ Q 'is an average value of 2 to 16. The method for producing a fluorine-containing ammonium type polymer according to claim 1, wherein an aminofluorocarbon polymer having a repeating unit represented by the formula (1) is used. 5. An aminofluorocarbon polymer used as a starting material comprises a main chain composed of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and a general formula is provided at the end of the pendant chain. (Wherein W represents a lower alkoxyl group, a hydroxyl group, a group in which a hydrogen atom of the hydroxyl group is replaced with a tri (lower alkyl) silyl group or an ammonium group, or a halogen atom). , General formula (In the formula, a is an integer of 2 to 5, R ³ ′ is a hydrogen atom or a lower alkyl group, and R ¹ ″ and R ² ″ are a hydrogen atom, a lower alkyl group or an alkyl group having an amino group.
At least one of R ¹ ″ and R ² ″ is an alkyl group having an amino group. R ² ″ and R ³ ′ may together form a polymethylene chain having an amino group.) To react the end of the pendant chain with a general formula (In the formula, a is an integer of 2 to 5, R ³ ′ is a hydrogen atom or a lower alkyl group, and R ¹ ″ and R ² ″ are a hydrogen atom, a lower alkyl group or an alkyl group having an amino group.
At least one of R ¹ ″ and R ² ″ is an alkyl group having an amino group. In addition, R ² ″ and R ³ ′ may be united to form a polymethylene chain having an amino group, and the resulting structure may be converted into a structure represented by the formula (2) and reacted with a reducing agent. The method for producing a fluorine-containing ammonium type polymer according to any one of claims 1 to 4.