JPS6084314A - Method for producing ammonium type polymer - Google Patents

Abstract

PURPOSE:To produce the titled polymer useful as an anion exchanger of excellent durability, by reacting an amino group-terminated fluorocarbon polymer with an alkylating agent and bonding the product to a perfluorocarbon polymer chain. CONSTITUTION:A fluorocarbon polymer pendant chain terminated with an amino group of fourmula I (wherein R<1> and R<2> are each H, a lower alkyl, aromatic group, or a hydroxy-lower-alkyl or R<1> and R<2> may be combined together to form tetramethylene or pentamethylene) is reacted with an alkylating agent, and the product is bonded to a main chain comprising a perfluorocarbon polymer chain to produce an ammonium-form polymer composed of the perfluorocarbon polymer chain and the pendant chain bonded thereto and terminated with the group of formula I , wherein said ammonium-form polymer is represented by formula II (wherein R<1>' and R<2>' are the same as R<1> and R<2>, respectively, when R<1> and R<2> are each other than H, and are the same as R<3> (wherein R<3> is a lower alkyl derived from the alkylating agent) and Z is a counter ion to the quaternary ammonium ion) when R<1> and R<2> are each H.

Description

[Detailed description of the invention]

The present invention relates to a novel ammonium type polymerization method. 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 from various combinations of hydrocarbon monomers by polymeric reactions. However, conventional anion exchangers cannot be used under harsh conditions.
For example, it deteriorates significantly when used in the presence of chlorine. Therefore, there is a need for an ion exchanger that exhibits less deterioration under such conditions. A membrane anion exchanger developed for the purpose of improving durability is a mixture of a fluorine-based polymer, such as poly(tetrafluoroethylene), and an inorganic anion exchanger, such as a hydrated zirconium oxide, and then compression molded. A method is known (Japanese Unexamined Patent Publication No. 5O-35079). However, in general, the ion exchange function of such inorganic anion exchangers made of amphoteric metal oxides largely depends on the hydrogen ion concentration of the environment during use, and in some cases, the ion exchange capacity may be 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. Furthermore, near neutrality, its ion exchange ability is hardly expressed. Therefore, the conditions under which membrane anion exchangers including such ion exchangers are used are extremely limited. There is also a known method of surface-fluorinating anion exchange membranes made of hydrocarbons to make them more durable (Japanese Patent Laid-Open No. 52-4489), but this method usually achieves 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 fluoropolymers, and as a result of intensive research into the development of anion exchangers made of fluoropolymer as a base material, the inventors discovered that anion exchangers with excellent durability have been developed. Invented a method for manufacturing exchangers. That is, the first method of the present invention consists of a main chain consisting of a bell flumerocarbon polymer chain and a pendant chain bonded to the main chain, and the end of the pendant chain has the general formula % (wherein R1 and R2 are A fluorocarbon alkylating agent having an amino group represented by a hydrogen atom, a lower alkyl group, an aromatic group, a hydroxy lower alkyl group, or a tetramethylene group or bankmethylene group formed by R1 and R2 together. react to form the end of the pendant chain - (wherein 17 and R2' are R1, R
When 2 is other than a hydrogen atom, it is the same as R and R, respectively,
If R or R is a hydrogen atom, it is the same as R3. R3 represents a lower alkyl group derived from an alkylating agent, and Z represents a counter ion of a quaternary ammonium ion. It is something to do. 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. The fluorocarbon polymer used as a starting material in the first method of the present invention has the general formula (in the formula, X is a fluorine atom, a chlorine atom, or a -CF3 group, and R and R have the same meanings as above) , l is an integer from O to 5, m is O or 1, and n is an integer from 1 to 5, but these numbers may be different for each pendant. can do. As one aspect of the main chain of the fluorocarbon polymer used as a starting material in the first method of the present invention, the general formula → (OF2-OF2: Height length 0F2-CF u-p l
q (where p and q represent numbers and the ratio p/q is from 2 to 16).
! A/ A fluorocarbon random polymer chain can be exemplified. Said 1. In the definition of m and n, the case where they differ for each dandant specifically means the case of a ternary or more copolymer synthesized from two or more fluoroolefin monomers having different l, ICI, and n. . Examples of this copolymer are shown below. (In the formula, X represents p or p'. When X is p, y and 2 represent positive integers.) (/y+z is 2 to 16
and y + Z = q. When X is p', y and 2 represent numbers as average values, and x/y+
z has an average value of 2 to 216, and y+z=q'. l′ and! “ is an integer from O to 5, m/ and m
"represents 0 or 1, and n' and p' each represent an integer of 1 to 5. Furthermore, as a specific embodiment of the fluorocarbon polymer used as a starting material in the first method of the present invention, the general formula (formula In the middle, X, R, R, j, msn represent the same meanings as above, p/ and q/ represent numbers, and the ratio p'/q'
is 2 to 16 on average), and the fluorocarbon polymer has an amino group. In the above general formula, R1 and R2 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, n- and 1
Examples include -propyl group, n-11-1S- and t-butyl group. Examples of the aromatic group include phenyl group, tolyl group, p-chlorophenyl group, p-methoxyphenyl group, furyl group, and chenyl group. In addition, as the hydroxy lower alkyl group, 2-hydroxyethyl group, 2-hydroxy-n-
Examples include propyl group and 3-hydroxy-D-propyl group. Further, R1 and R2 may be combined to form a tetramethylene group (a) 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 R1 and R2, include polymers composed of the following repeating units. (1) (CF20F 2 + -7 + CF 2 CF 2 CF 2 CF PII Q F2O- (30-0-0F2CH2 -NH2 (2) + CJF20F20F20 H20 H20 H20 F 0F20H2 -OH3 (3) Every 2 -° F2 floors Seven F20F Ramie CF2CF2CF2CH2-NCH2CH2C■43(
51+CF20F2+-7fOF20F arm) 1) Iq F2 3G-OF 0-CF20F20H2N(OH3) 2(6) +C
F2CF,)7(-C5F20F wall F2 覦(7)+CF20F2te,iOF 20F juice-p, q
l 0F20F20F20H2N(OH3) 2CH2N(
CH3) 2 (9J +CF 20'2:F-7+air"2C
F masu ap I q Su■ F2 CF3-CF 0-CF2 (J2N(OH3) 2 F2 υ ・I F2 0 clause (-CF 20F 217th CF 20F 辷A 1
) Iq 8F2 (1G) -GCF20F2 Masuyun 0F20F Terrap I
q F2 CF3-C; F 0JOF20F20F20H2-N-OH2Q (2CH
20H The alkylating agent used in the present invention has the general formula (in the formula, R3 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). Using the compounds shown. R3 is a methyl group, an ethyl group, an n- and i-pro2 group,
Examples include n-1i- and S-methyl groups. A is an iodine atom, a bromine atom, a diethyloxonium fluoroborate group, a diethyloxonium fluoroborate group, a dimethyloxonium hexafluoroantimonate group, a trifluoroacetic acid group, a trifluoromethanesulfonic acid group, a 1000-methyl Hrfl group, p- ) Luenesulfone eM, p-nitrobenzene sulfonic acid group, etc. can be exemplified. Therefore, as alkylating agents, superstrong acid salts of lower alkyl to tri-lower alkyl oxonium iodides or bromides, such as methyl iodide, ethyl bromide, n-propyl bromide, n-butyl iodide, trimethyloxonium Nifluoroborate ((CH3) 3
08F4), triethyloxonium fluorobore)
((02Hs)aOBF4), )limethyloxodimuhexachloroantimone) ((GHa)aO8
bc16), dimethyl sulfate, methyl trifluoroacetate, methyl trifluoromethanesulfonate, methyl p-toluenesulfonate, ethyl p-nitrobenzenesulfonate, and the like. For alkylation, methanol, ethanol, methylene chloride, chloroform,
carbon tetrachloride, sulfolane, N,N-dimethylborumami), (DMF), nitromethane, N-methyl-2-
Pyrrolidone (NMP) or the like 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.degree. C. to about 100.degree. The alkylating agent is used in a small (or equivalent, preferably about double or more) amount relative to the theoretical amount of the amine group to be converted. Usually, it is used in a large excess amount relative to the latter in order to allow the reaction to proceed quickly and completely. When used, it is preferable to allow a sufficient period of time to soak the fluorocarbon polymer having amino groups, which is the starting material.Alkylation reaction varies depending on the type of alkylating agent, maximum temperature, etc., but under the reaction conditions described above. The lower alkyl group of R1/ and R2' in the general formula at the pendant chain end of the anthonium type polymer obtained by the method of the present invention can be carried out for about 10 hours, 1 to about 5 days. When R' and R2 in the fluorocarbon polymer having an amine group as a starting material are lower alkyl groups, they are the same as R and H, respectively, and when the above R and R are hydrogen atoms, The hydrogen atom is replaced by H by the action of the alkylating agent. R3 is a group derived from the alkylating agent. Also, 2 is a counter ion of the quaternary ammonium ion and is usually derived from the alkylating agent. Examples include bromine, iodine, etc.), rogene anions, tetrafluoroborate ions, hexachloroantimonate ions, super strong acid ions such as trifluoromethanesulfonic acid, sulfonic acid ions such as benzenesulfonic acid, toluenesulfonic acid, and acetic acid. These include carboxylic acid ions such as ions, monoalkyl sulfate ions, etc. These counterions may be exchanged with other ions if necessary. This exchange of ions can be carried out by one conventional method, e.g. Na(
34, LiCj, LtBr, LtI, NaOH, KO
(2) This can be easily achieved by treating the ammonium type polymer obtained in the present invention with an alkali metal salt such as ζNaNO3 or 2SO4. The present invention further comprises a main chain consisting of a fluorocarbon polymer chain and a pendant chain bonded to the main chain, and at the end of the pendant chain 1 C-W ↓ (where W is a lower alkoxy group, a hydroxyl group, or a hydrogen atom of a hydroxyl group). A fluorocarbon polymer having a substituted carbonyl group represented by a tri(lower alkyl)silyl group, a group substituted with an ammonium group, or a halogen atom) is prepared using the general formula % (in which R1 and R2 have the same meanings as above). ) to convert the end of the pendant chain into a structure represented by the general formula % (wherein R1 and R2 have the same meanings as above), and is reacted with a reducing agent to form a main chain consisting of a perfluorocarbon polymer chain and a dandant chain bonded thereto, and the end of the dandant chain has the general formula % (wherein R1 and R2 are the same as above). A fluorocarbon polymer having an amino group represented by
Furthermore, this is reacted with an alkylating agent to form a main chain consisting of a fluorocarbon polymer chain and a dandant chain bonded to this, and the end of the R dandant chain has a general formula (in the formula R1', R2' , R3 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. 0 111 Alkylating agent -CH2CH3"R"' R3 The fluorocarbon polymer having a substituted carbonyl group used as a starting material in the second method of the present invention is a dandant chain.
A group represented by the general formula % (in the formula, X, W, 1.m, and n represent the same meanings as above) can be exemplified. The main chain is a powdered perfluorocarbon random polymer chain consisting of repeating units represented by the general formula %) (where p is an integer of 3 to 15 and q is an integer of 1 to 10). I can give an example. It is also preferable to use a fluorocarbon polymer consisting of repeating units represented by the general formula (wherein X, W, 1.m, n, p' and q' have the same meanings as above) as the overall repeating unit. Examples of the halogen for W in the above formula include fluorine, chlorine, and bromine. Further, lower a group, n-bentoxyl group, S-bentoxyl 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. In addition, the groups in which the hydrogen atom of the water p group is substituted with an ammonium group are -0NH4, -0N(C
H3)3, -0N(CH2CH3)3, HH or -0N(OH2CH2CH2CH3)4
etc., and forms a carboxylic acid ammonium salt by bonding with a carbonyl group (-8-). 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. (1) (OF20F2 CF2CF napp I q 8 F2 ■ F2 0-(30CH2CH2C; H2CH3F2 ?F2 3) 3 These fluorocarbon polymers are ion-exchangeable carboxylic acid star R fluorocarbon polymers (especially film-like These fluorocarbon polymers are well known as cation exchange membranes for saline water electrolysis) or their precursors.Among these fluorocarbon polymers, those in which the pendant chain ends are acid halide, for example, %, fM n can be easily obtained by applying a halogenating agent such as a chlorinating agent. In this case, thionyl chloride, phosphorus trichloride, phosphorus trichloride, 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 sulfur oxychloride. preferable. 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-dipropylamine, l-propylamine, n-butylamine, 1-methylamine, dimethylamine, diethylamine, dipropylamine, Propylamine, methylethylamine, pyrrolidine, piperidine, bicolin, 3-ethylpyharidine, aniline,
N-methylaniline, p-) luidine, m-) luidine, p-chloroaniline, m-chloroaniline, p-fluoroaniline, 0-fluoroaniline, p-brop-dimethylaminoaniline, m-nitroaniline, 2 -aminofuran, 3-aminofuran, ethanolamine, jetanolamine, 3-human 90xypropylamine, 3
-Hydroxybutylamine and the like can be exemplified. In this case, 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. The reaction with these amines can be carried out by bringing the gaseous amine into contact with the membrane, in a liquid amine, or 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 preferably, 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 ammonia or amine relative to the starting material is small (equivalent, preferably 3 equivalents or more, most preferably a large excess). The reaction may also be carried out in the coexistence of a tertiary amine. Diethyl is used as a solvent. Ethers such as ether, tetrahydrofuran, dimethoxyethane, and dioxane, hydrocarbons such as Hanzene, toluene, and hexanoate, acetonitrile, dimethyl sulfoxide 9, etc. can be used. Starting material T'1 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 end "lfa" is a carboxylic acid ester type, in addition to these solvents, alcohols such as methanol and ethanol can also be used as the solvent. The amount of solvent used may be such that the fluorocarbon polymer having a substituted carbonyl group is sufficiently immersed therein.Of course, a larger amount may be used.Also, there is no particular limitation on the reaction temperature, but it is usually about -30"G to about The reaction is carried out at 150°C, preferably about 0°C to 80°C. The fluorocarbon polymer having a carboxylic acid amide group thus obtained is reacted with a reducing agent in the second step. As the reducing agent, aluminum hydride, hydrogen Alkyl aluminum hydrides such as diisobutylaluminum hydride, lithium aluminum hydride, diporan, etc. can be used, but use of diporan is superior in terms of reaction efficiency and ease of post-treatment. It can be generated by reacting boron trifluoride ether complex with sodium boron, or various complexes of borane (such as dimethyl sulfide complexes) can be used.The amount of reducing agent has a carboxylic acid amide group. It is generally used in a large excess amount, equivalent to or more than the functional group in the fluorocarbon polymer.The concentration in the solvent is about 0.01 to 5 molar, preferably 0.1 to 2 molar. In the second method of the present invention, the second stage reaction is carried out on tetra 1-9
The process proceeds smoothly in ether solvents such as 0-furan, dioxane, and 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. Further, there is no particular limitation on the reaction temperature, but in the initial stage of the reaction, it is preferable to carry out the reaction while keeping it in the range of ice-cooling temperature to room temperature, and then heating it to a temperature of reflux temperature to 100° C. in order to complete the reaction. The fluorocarbon polymer having amino groups obtained in this way is reacted with an alkylating agent in the third stage reaction to obtain the target ammonia type fluorocarbon polymer.This third stage reaction is The reaction is exactly the same as the reaction in the first method of the present invention.The fluorocarbon polymers containing amino groups or substituted carbonyl groups used as starting materials in both methods of the present invention are flat film-like, tube-like, i:i2 milk-like, It can be used in various forms such as powder.In this case, the target ammonium wrinkled fluorocarbon polymer can be obtained in the corresponding form.Ammonium type fluorocarbon obtained by both methods of the present invention Polymers include those consisting of repeating units such as: ○ Product 2 F2 ((3) -GCF20F2+?+CF2(7F7?F)
2 a (3 (Force -fOF20F27CF27F to 3F2 F2 CF'2 H2CH3 (11) +CF2CFz) -+CF2? 2 ?Fya? ?F2 F7)÷CF20F2+-7-+CF2Cya1 F2 ■ The ammonium type polymer obtained by both methods of the present invention has particularly high chlorine resistance even though it has some hydrocarbon groups. It has extremely excellent oxidation resistance and solvent resistance.Also, no change is observed even after repeated drying and wetting, and it is much easier to handle than conventional anion exchangers. 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. It is also available in various forms as a resin that can perform anion exchange using quaternary ammonium groups in the coexistence of various solvents.It is also a catalyst for cyanohydrin synthesis and a phase transfer catalyst. - Can be used as various catalysts such as rogogenation reaction catalysts. In addition, tubular ammonium type polymers can be used as multi-tubular modules in cost-saving dialysis equipment, and can also be used in ion chromatography. It can also be used in a system for removing interfering anions.Unlike conventional crosslinked anion exchangers, the anion exchange membrane made of ammonium type polymer obtained by both methods of the present invention is a non-crosslinked one. Therefore, it can sufficiently respond to changes in conditions during use.As described above, the anthonium type polymer obtained by both methods of the present invention has a very large value in terms of its excellent durability. It is already known that the heat resistance and chemical resistance of 1% fluorine-based polymer and fluorocarbon polymer are significantly higher than those of general hydrocarbon-based polymers.However, both methods of the present invention The ammonium type polymer obtained by
Despite having hydrocarbon groups on the pendant chains, it has far greater durability than expected. In other words, even though the main chain is stabilized because it is a perfluorocarbon polymer chain, under a harsh oxidizing atmosphere, the hydrocarbon groups in the pendant chains undergo degeneration and decomposition, and the functional groups are removed by K. Although it was expected that such deterioration would be difficult, the ammonium type polymer obtained by both methods of the present invention shows very little such deterioration. The present invention will be explained in more detail below with reference to Examples and Reference Examples. The term amine polymer used in this case refers to a nitrogen-containing fluorocarbon polymer having an amino group.
The term polymer refers to a fluorocarbon polymer having carboxylic acid amide groups, respectively. 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: Crystal Violet 0
．． 05% methanol solution Cresol red: Cresol red 0.05% methanol solution Thymol blue: Thymol blue 0.05% methanol solution Bromothymol blue: Furothymol blue 0,0
5% methanol solution Basic Cresol Red 9: Cresol Red 0.0
Bath solution made by adding about 1% of 10% NaOH aqueous solution to 5% methanol solution.Basic thymol blue: A solution of about 1% of 10% NaOH aqueous solution to 0.05% methanol solution of thymol sol.The electrical resistance of the membrane is After sufficient equilibration with a 0.5N saline solution, the measurement was performed in the 0.5N saline solution for 1000 cycles of alternating current at a temperature of 25°C, and the transfer number of the membrane was 0.
5N saline solution and 2. p generated between ON saline solution
It is calculated using the Nernst equation from 5 potentials. 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. Further, the conversion rate was calculated from the nitrogen value in elemental analysis, taking into account the change in equivalent weight due to change in the end group, with the exchange capacity of the raw material copolymer set as 100%. Example I CF2-CF2 and 0F2 = CFOCF20FOCF20
A copolymer film obtained by CF3 copolymerization with F2So2F [DuPont Nafion 114 (trade name), film thickness 100μ, sulfonic acid equivalent exchange capacity 0.911 equivalent/g dry film] was treated with 2N hydrochloric acid. , sulfonyl chloride, treatment with hydrogen iodide, and washing with alkali to obtain the carboxylic acid sodium salt form. This membranous type. 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. after that,
After washing in carbon tetrachloride, it was dried. The obtained film shows a strong carbonyl absorption at 1800 cfn-'' in the infrared absorption spectrum.Also, there are absorptions thought to be derived from C-H absorption near 2980.2880 and 1440 cm-'', so most of the carbonyl absorption is σ, ! It was 1. This mixed polymer film was mostly composed of repeating units of F2 3C-CF CF2-co□CH3. The value of p:'/q: was approximately 6.5. The mixed polymer membrane thus obtained was immersed in dry ether, and dimethylamine gas (1.3 molar concentration) was passed therein under ice cooling for 6 hours under cooling and for 18 hours at room temperature. 3%
80℃ with sodium bicarbonate water-methanol mixed bath solution (volume ratio 1:1)
After washing for 5 hours and drying under reduced pressure overnight, a colorless and transparent amide warm polymer 1 (terminal group -CNMe 2 ) film was obtained. The infrared absorption spectrum is shown in FIG. Infrared absorption is in cm-” 3300.2950.2825, 2360.1705.
1500.1470, 1410, 1300-1100.
980.920,730.650~610,560~6
00°2950.C-H absorption is observed at 1500 to 1410 cm-'', and absorption due to amide carbonyl is observed at 1705 cm-''. Further, the conversion rate calculated from the nitrogen value in elemental analysis was 92% with respect to the exchange capacity in terms of 5O3H. Furthermore, the obtained amide type polymer membrane was not stained by crystal violet or cresol red, indicating that no ionic groups were present in the membrane. Most of this film is JF20F2←OF2CFhi. 111 Electric F2 3C-OF ■ (p', /q; call 6.5) It consisted of a repeating unit. This membrane was immersed in a bath solution (0.53 molar concentration) obtained by dissolving sodium borohydride in dry diethylene glycol dimethyl ether under an Albin atmosphere. A dry diethylene glycol dimethyl ether solution of boron trifluoride ether complex (0.62 molar equivalent to sodium borohydride) was added dropwise to the solution under water cooling. 5 under cooling
By further reacting at 100°C for 18 hours, the absorption of 1700α-1 in the infrared absorption spectrum disappeared, and the amine-type polymer (terminal group -CHzNMe 2
) Reduction of the membrane 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 shown in FIG. Conversion rate 88%. Infrared absorption spectrum (cIn-”) 2970.2850.2800.2360.1475~
1455.1395.1350-1040.980.9
30.860.835.730.640~610°56
0 to 490° The obtained amine type polymer membrane was not stained by crystal violet or cresolet 9, indicating that no ionic groups were present in the membrane. This membrane was an amine polymer consisting essentially of the following repeating units: →F2Tei at 0F20F (p;/q; +6.5) The amine type polymer membrane thus obtained was placed in a methanol solution of methyl iodide (volume ratio 1:4) and heated at 60°C. The mixture was allowed to react 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 0°C for 24 hours. This membrane was dissolved in methanol for 6 hours.
Heating to 0'''C, a typical quaternary ammonium chloride type coalescence was obtained. The obtained film was not stained with crystal violet in a staining test, but was stained red with bromocresol purple (
It was colored blue-purple in basic water) and yellow-orange with cresol red (red-purple in basic water), confirming the presence of anion exchange groups. The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption spectrum (cm-'') 3300.3030.2950.2810.2350°1640.1485.1415.1300-1060.
980.925.840.740.650-600゜5
40 to 500°. However, the absorption of 3300.1640 cm-" is considered to be due to water in the membrane. Also, the exchange capacity of this anion exchange membrane is 0.82 milJ equivalent/9 dry membrane, and the electrical resistance is 3.
．． 3ΩC: In2, transference number was 0.87. Even after this membrane was immersed in a chlorine-saturated water bath solution at 60° C. for K100 hours, no change was observed in these murmurs. After treatment in methanol at 65°C for 48 hours, the solvent was removed at 40°C.
No change was observed even after repeating the vacuum removal operation five times. Example 2 0F2. ,=OF2 and 0F2=CFOCF2CFOCF
A copolymer obtained by copolymerizing 20F2Go□ (3H38F3) by a known method was formed into a film (film thickness 110μ, CO2H equivalent exchange capacity 1.4 milliequivalents/g dry film). It essentially consisted of the following repeating units: ○ F2 ■ F2O-C:F F2 (3F2-Go20H3 (II)', /q'2+3.1) Using this methyl ester type polymer membrane and dimethylamine, An amide-type polymer corresponding to 1 (terminated group -CNMe 2
) membrane was obtained (conversion rate 95%). The infrared absorption spectrum of the obtained film was 100% the spectrum of the film obtained in Example 1.
Except for the absorption of the skeleton in the vicinity of 0 to 800 cm-'', the results were almost identical, indicating that the exchange of the desired end groups was proceeding efficiently.The obtained amide type polymer film was not stained with crystal violet or cresol red at all. This amide type polymer essentially consisted of the following repeating units: (CF2CF2)-, (CF20F)7゜8F23G-CF (p', /q辷3.1) The resulting amide type polymer membrane was reduced in the same manner as in Reference Example 1 to obtain an amide type polymer membrane. Conversion rate: 95
%. The infrared absorption spectrum of the obtained film was almost the same as that of the film obtained in Example 1 except for the absorption of the skeleton part, and 17
The absorption based on amide carbonyl near 00 cm-' 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. F2 3C-CF lice (3.1 in p'!/q'2) The obtained membrane was then 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 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 the desired ammonium chloride type membrane. In the staining test, the obtained membrane was not stained with crystal violet, but was colored red with promocresol h purple (blue-purple in basic water), yellow-orange with cresol red (red-purple in basic water), and anion exchange groups. The existence of was confirmed. The exchange capacity of the obtained membrane was 1.1 milliequivalent/g dry membrane % electrical resistance was 1.80·side2. This film was also used in Example 1.
It showed excellent durability, similar to that of other films. Example 3 An amide type polymer film was obtained by subjecting a film using U as a support (Fion 415 (trade name) manufactured by DuPont) to the same treatment as in Example 1. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (crrL-”) 3300.2950.2750.2380.1690°1500~1400.1320~950,760~48
The membrane obtained at 0° was not stained at all by crystal violet or cresol red. The membrane consisted of a polymer consisting essentially of the following repeating units: F2 3C-OF The thus obtained carboxylic acid amide type polymer membrane having a polytetrafluoroethylene mesh support was subjected to the same reduction treatment as in Example 1 to obtain an amine type polymer membrane. . The infrared absorption spectrum is shown in FIG. 5, and the absorption near 1700 cm 2 completely disappears. Infrared absorption is Ccm"") 3200.2950~2790.2400~2300,
■440.1390,1300~920,720~48
0° 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. F2 an-CF ■ (p'3/q'1÷6.5) The amine cross-polymer film thus obtained was treated in the same manner as in Example 1 to obtain an an7nium chloride W polymer film. Ta. The infrared absorption spectrum is shown in FIG. Infrared absorption quictor (cm-') 3250.2900.2800.2400-2300.
1620.1470~1400.1300~900゜7
50-500° However, the absorption of 3250.1620CrrL 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 electrical resistance of the obtained film was 7.2
Ωcrn2, and the transference number was 0.90. Further, the current-voltage curve in hydrochloric acid electrolysis using this membrane is shown in FIG. 7(a). Also shown are the results using a commercially available hydrocarbon anion exchange membrane as a comparative example (
The electrolytic conditions are as follows. Membrane area: 9.6 mm Electrode: Platinum electrolyte; Anode/Cathode = 6N hydrochloric acid/6N hydrochloric acid Temperature: Room temperature As is clear from the diagram, the obtained membrane was a commercially available hydrocarbon anion exchange membrane. Although K has a smaller exchange capacity than (exchange capacity 1.3 milliequivalents/I/dry membrane), its electrical resistance has an excellent % characteristic of about the same level. 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 CF2=CF2 and CF2=CF-0-CF2-CF-0
-CF2-CF2-CF3 Tuned copolymer obtained by copolymerization with S02F (inner diameter 0.625 mm, outer diameter 0.875 mm b
5O3H equivalent exchange capacity: 0.92 milliequivalents/g of dry resin), and then hydrolyzed. Next, the tubular polymer was treated with 2N hydrochloric acid, converted to sulfonyl chloride, treated with hydrogen iodide, and immersed in methanol to obtain a carboxylic acid methyl ester. The pendant chain of the tubular ester type polymer obtained by this series of operations is 10C.
FCF20FOCF2CO2K converter was used. This tubular ester type polymer was heated at 120°C in phosphorus pentachloride/phosphorus oxychloride (weight ratio 1:1.6).
The mixture was heated for 23 hours, washed in carbon tetrachloride, and then dried to obtain a tubular mixed polymer consisting mostly of ester groups and a portion of acid chloride and do groups. It consisted essentially of the following repeating units: F2 F 30- OF (p'4/q'4-6.4. W" is a methoxyl group or

[
It shows a chlorine atom. ) This tube-shaped mixed polymer was immersed in diethyl ether, and the inside of the tube was dried and replaced with diethyl ether. Dimethylamine gas was passed through this under water cooling (1.3
up to molarity). Then under cooling, for 6 hours at room temperature
After reacting for an hour, the mixture was washed with 3% aqueous sodium bicarbonate and methanol (volume ratio 1:1) at 60°C for 6 hours, and dried under reduced pressure overnight. When the obtained tubular amide type polymer (terminal group 1 -CNλ4o2) was lined up and its infrared absorption spectrum was examined, it almost coincided with the spectrum of the amide film obtained in Example 1. Conversion rate is 90%. The obtained tubular polymer was cut into rings and tested for stainability with crystal violet and cresol red (W), and no staining was observed at all. The amide-type polymer of this membrane consisted essentially of repeating units F2 3C-CF (p'4/q'4÷6,4). The tubular amine type polymer thus obtained was placed in a methanol solution of methyl iodide (volume ratio 1:4) and heated to 60°C.
The reaction was carried out for 500 hours. After washing the obtained tubular polymer with methanol, a methanol solution of lithium chloride (1
, 28-IB', 3L concentration) at 60°C for 24 hours. This tubular polymer was prepared in methanol at 60°C.
The desired tubular ammonium chloride type polymer was obtained. The resulting tubular polymer was dyed red with bromocresol purple and yellow-orange (with cresol red) in the dyeing test.
(in methanol), the presence of toion exchange groups was confirmed. The exchange volume (it) of the obtained tubular anion exchanger is
It was 0.80 milliequivalent/g dry resin. Even after immersing this product in a 60°C fluorine-saturated water bath 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, followed by vacuum removal of the solvent at 40° C. five times. Example 5 Copolymer powder obtained by polymerization and saponification [Nafion 511 (trade name) manufactured by DuPont, 5o3H equivalent exchange capacity 0
．． 911 equivalents/g dry resin, sulfonic acid potassium salt type] was hydrolyzed with 5N hydrochloric acid and converted to sulfonyl chloride by treatment with phosphorus pentachloride. Next, it is converted to the carboxylic acid form by hydrogen iodide treatment, and then immersed in methanol to convert the carboxyl group. Most of it was converted into methyl ester. A powdery methyl ester type polymer was obtained by further treatment with methyl orthoformate. Infrared absorption spectrum (cm) 2970-2860.1800.1480-1415.
1280-1200, 1175-1110.980.8
40.780.740.635.555.510゜This membrane is essentially a repeating unit → 0F20F2+, -fcF20F'ze5 1 5 F2 3C-CF CF2-Go2CH3 (p'5/q'5÷6.5) It was a polymer powder consisting of. Dry tetrahydrol,
The same operation as in Example 1 was carried out in 40 francs. This material was not stained with crystal violet or cresol red, and the conversion rate based on elemental analysis was 85%. The obtained powder was examined for infrared absorption spectrum using a KBr disk, and an absorption derived from amide carbonyl was observed near 700 cIn''1. Infrared absorption spectrum (cm-”) 2960.1710.1410.1280-1200.
1170-1130.1070.980% 920, 8
00.780.740.640,550,510° This polymer consisted essentially of repeating units, F2 3C-OF (p'/q,'÷6.5)5. The powdered amide type polymer thus obtained was reduced with diborane in the same manner as in Example 1, and collected by filtration to form a powdered amine type polymer (terminal group -CH2NMe
z) was obtained. This material was not stained with crystal violet and cresol red at all, and the conversion rate was 79.
%Met. When the infrared absorption spectrum of the obtained powder was examined using a KBr disk, it was found that the absorption of amide carbonyl that existed near 1700 cm-'' had completely disappeared. Infrared absorption spectrum (cm-'') 3020-2780.1500 ~1460.1260~
1200.1170-1120.1070.980.9
30.865.835.735.635.555.51
0° This amine type polymer consisted essentially of the following antinomic units. 3C-OF ■ (p'5/q', ÷6.5) The powdered amine type polymer thus obtained was placed in a methanol static solution of methyl iodide (amount ratio of 1:4), and 60 The reaction was carried out at ℃ for 500 hours. After washing the obtained powdered polymer with methanol, a methanol solution of lithium chloride (1,2
8 molar concentration) for 24 hours at 60°C. This powdered polymer was heated to 60° C. in methanol to obtain the desired powdered ammonium chrome IJ v-type polymer. The obtained powdered polymer was colored reddish-purple with bromocresol purple and yellow with cresol red (each in methanol) in a dyeing test, confirming the presence of anion exchange groups. Infrared absorption spectrum (cIn) 3040~2820.1530~1460.1280~
1200.1170-1100.980.930.84
(1,74Q, 635.550.510° The exchange capacity of the obtained powdered anion exchanger is O,SO milliequivalent/g
・It was a dry resin. Even after this product was immersed in a 60° C. chlorine-saturated water bath 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, followed by vacuum removal of the solvent at 40° C. five times. Example 6 The hot cloth type polymer membrane (9 layers 2) obtained in Reference Example 1 was immersed in 30 m# of dry tetrahydrofurine, and -loridine 4Tl
1 was added thereto, and the mixture was heated under reflux for 144 hours in 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 tin cuttle (Cm) 3400.2970, 2890.2780.2600.
2360.1710~1680.1440.1340~
1030.980.930,915,800-480° This film was mostly composed of repeating units of F2 (F3C, -OF2 (p'6/q'6-7.6). The obtained membrane was immersed in 200 g of dry tetrahydrofuran under an argon atmosphere, and 10 g of sodium borohydride was added thereto.Next, 51 ml of tetrahydrofuran bath solution containing 20 mi of boron trifluoride ethyl ether complex #20 was immersed for 20 minutes under ice-water cooling. The membrane was added dropwise and stirred for 1.5 hours, then heated under reflux for 65 hours, and then the membrane was taken out and washed in methanol under heating under reflux for 8 hours.The membrane was taken out and stirred under reduced pressure for 60 hours.
An amine-type polymer film was obtained by drying at ℃ for 20 hours. In this film, the absorption around 1700 cm-" derived from amide 9 carbonyl disappeared in the infrared absorption spectrum, indicating that the reduction to an amine-type film was complete. The conversion rate calculated from the nitrogen value in elemental analysis was 90%.The obtained amine-type polymer film also contained crystal violet, cresolet, thymol slut, and hypromthymol. It was not stained blue. The infrared absorption spectrum of the obtained film is shown in Figure 9. Infrared absorption spectrum (crn-'') 3230.2980-2760, 2370.1465%
1430.1410.1350~1020.980゜9
20.770-480° This membrane consisted essentially of a copolymer consisting of repeating units of (3F22 (p'6/q'6 + 7.6). The amine-type polymer obtained above The membrane was placed in a dimethylformamide solution of methyl iodide (volume ratio 1:4) and reacted for 72 hours at 60°C.After washing the obtained membrane with methanol, it was added to a methanol solution of lithium chloride (1.28 molar concentration). ) for 24,114 hours at 60°C.The membrane was heated in methanol at 60°C for 7JIJ to obtain a quaternary ammonium chloride type polymer III.The obtained membrane was not stained with crystal violet in the staining test. The presence of anion exchange groups was confirmed by coloring yellow (dark red in basic water) with zcresol 1', orange with bromothymol blue, and yellow-orange with thymol blue.Infrared absorption of the obtained membrane The vector is shown in Figure @10. Infrared absorption spectrum (c+n-1) 3400.3000-2930.2830.2360.
2120.1630.1480.1460.1360~
950,930.840%780~480 (However, 3400.1630 is water absorption) Also, the exchange capacity of this anion/ion exchange membrane is 0.72 mi! j
The dry film had an electrical resistance of 5.4Ωcrn2 and a transport number of 0.88. This film also showed excellent chlorine resistance similar to the film obtained in Example 1. Example 7 The mixed polymer film (16cIn2) obtained in Reference Example 1 was immersed in 30 g of dry tetrahydrofuran, and aniline 5:
4 mb was added, and the mixture was heated under reflux for 120 hours under an argon atmosphere. The membranes were taken out and heated at 60°C under reduced pressure to obtain 20 membranes. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (CM''''1) 3300.3100-2B30,262Q, 2360.
1950.1750-1490.1440.135 (
+~1020,980,910.885,830,80
0-480° This film was mostly composed of repeating units of ○ F2 3C-CF (pQ/q'6÷7.6). The resulting membrane was then immersed in 200 mg of dry tetrahydrofuran under an argon atmosphere, and 10 g of sodium borohydride was added. Next, a solution of 35-7-boron ethyl ether complex 201 in tetrahydrofuran 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. Take out the membrane and 60℃ under reduced pressure.
to form an amine type polymer (terminal group -0H2N) for 20 hours.
H@) membrane was obtained. In this film, the infrared absorption near 1,700 cm-'' originating from amide carbonyl disappeared in the cuttle, indicating that reduction to an amine type film had progressed completely.Nitrogen in elemental analysis The conversion rate calculated from the value was 71%.The obtained amine type polymer film was not stained with thymol blue or bromthymol blue.The infrared absorption spectrum of the obtained film is shown in Figure 12. The infrared absorption is kutor (cm-1) 3450.3120.3080.3050.2960.
2360.1930.1790.1610.15101
1440.1350-1060.980.950.83
0.780-490° This membrane consisted of a copolymer consisting of repeating units of substantially K (CF2aF2, (OF20Ftea6168F2taku(pt/q'6÷7.6). The obtained film was immersed in a 100N solution of methyl iodide 251 in dimethylformamide and heated at 60°C for 150 hours to obtain an ammonium ioside polymer film.Then, this film was soaked in a 10% methanol bath solution of lithium chloride 1251. It was immersed in water and heated at 60°C for 24 hours (exchanging the solution halfway through).Then, it was immersed in methanol and washed at 60°C for 7.5 hours to obtain an ammonium chloride type polymer film.This film was made of crystal. Although it was not stained violet,
It was stained yellow with cresol red and orange with thymol blue. The infrared absorption spectrum of this film is the 13th
As shown in the figure. Infrared absorption spectrum (clIrs 3500-3300.3090.3060.2380.
1640.1610, 1510.1450.1350~
950% 840,800-500° The obtained membrane had an ion exchange capacity of 0.50 meq/g dry membrane, an electrical resistance of 26.2 Ωcm 2 , and a transference number of 0.91. This film also showed excellent chlorine resistance like the film of Example 1. Example 8 The mixed polymer membrane (9 m2) obtained in Reference Example 1 was immersed in 30 rnl of dry tetrahydrone run, propylamine 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 (terminal group 1 -C; NH/zo) membrane. Its infrared absorption spectrum is shown in Figure 14. Infrared absorption is kutor (cm-1) 3480.3400~3280.3100.3000~
2940.2890.2560.2360.1740~
1670.1570~1530,1460.1350~
1050.980,920.790~490° This film was mostly composed of repeating units of F2 (pS/q'6÷7·6). The resulting membrane was then immersed in 170M dry tetrahydrofuran under an Aldan atmosphere, and 3 g of sodium borohydride was added. Next, a solution of boron trifluoride ethyl ether complex 6- in tetrahydrofuran 101116 was added dropwise over 30 minutes under ice-water cooling, and the mixture was stirred for 1.5 hours. 30 at room temperature
After continuing the reaction for a minute, 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 2411 yen to form an amine type polymer (terminal group -0H2NHCH20H2G).
) i3) IP was removed. This film shows 1700517+ derived from amide carbonyl in the infrared absorption spectrum.
The absorption around 1-" disappeared, indicating that the reduction to the amine-type film had completely progressed. The conversion rate calculated from the f direct of nitrogen in elemental analysis was based on the 5O3H exchange capacity. 77%.The obtained amine type polymer film was not stained by crystal violet but was stained yellow by prothothymol blue.The infrared absorption spectrum of the obtained film is shown in Figure 15. Infrared absorption spectrum (cm-”) 3680.3250, 2980, 2890.2360°1480-1460.1350-1030.980°7
80-490° This film is substantially F2 3C-CF 0-CF2CH2NHCH2CH2C;H3(p'6/
It consisted of a copolymer consisting of repeating units of 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 ioside type polymer membrane. This membrane was then soaked in a 10% methanol solution of lithium chloride.
24 hours at 60°C (replace the solution halfway through)
Heated. After that, it was immersed in methanol and heated to 60℃ for 7 days.
After washing for 5 hours, an anthonium chloride type polymer film was obtained. This membrane was not stained with crystal violet, but was stained yellow with cresollet 9, yellow-orange with thymol blue, maroon with bromothymol blue, and dark blue with basic bromothymol blue. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (Kushi-1) 3400.3230.3020-292012820%
2360.1630.1490~1450,1420°1360~1030.1010~940.88o. 835.780-480° The ion exchange capacity of the obtained membrane is 0.61 my17 equivalents/g
The dry film has an electrical resistance of 12.5ΩcIn2. The transport index is 0.9
It was 0. This film also showed excellent chlorine resistance like the film of Example 1. Example 9 The mixed polymer membrane (16 cm") obtained in Reference Example 1 was immersed in dry tetrahydrofuran 3ON, 4.96 mlj of diethylamine was added, and the mixture was heated under reflux for 120 hours under an argon atmosphere. The membrane was taken out and refluxed for 120 hours under reduced pressure. After drying at C for 20 hours, an amide type polymer film was obtained. The infrared absorption spectrum is shown in FIG. Infrared absorption is crn''-1 3100~2670.2500.1730~1610°1480~1440.1415~1385.135Q~
1030.980,870,830.810-490° This membrane was mostly composed of repeating units of -(cF2cF'2KeyakiCF2(EFga(87F2 (pQ/qQ÷7.6)). The obtained membrane was immersed in VC under an argon atmosphere in 200 ml of dry Tetrahydrofuran 907 run, and 10 g of sodium borohydride was added.Next, a solution of 5 mg of tetrahydrofuran containing 20 ml of boron trifluoride in ethyl ether was immersed in ice water for 20 minutes. The membrane was added dropwise and 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 stirred under reduced pressure for 60 hours.
An amine type polymer film was obtained by drying at ℃ for 20 hours. This film is derived from amide carbonyl in the infrared absorbing spectrum. Absorption near 1700 cm −1 disappeared, indicating that reduction to an amine-type film had completely progressed. Based on the nitrogen value in elemental analysis, the conversion rate was 1tiL and was 60%. In addition, the obtained amine type polymer film is
Not stained by crystal violet. The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption spectrum (cIn-”) 3680.3400.2980, 2950.2900°23 0.1460.1350 to 1030.980.8
40.780~490° This film is substantially
It was composed of a copolymer consisting of repeating units of '6÷7.6). The film obtained above was immersed in a solution of 25 parts methyl iodide in 100 m# of dimethylformamide and heated at 60°C for 120 hours to obtain an ammonium ioside type polymer film. This membrane was then soaked in a 1% 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 of this film is the first
As shown in Figure 9, the infrared absorption spectrum is 3500 to 3250.3000.2900.2360.
1630.1450.1350~940,840°78
The obtained membrane has an ion exchange capacity of 0.46 milliequivalents/g dry membrane and an electrical resistance of 33.8 Ωcm2. The transport number was 0.91. This film also showed excellent chlorine resistance like the film of Example 1. Is this film actually η? It consisted of a copolymer consisting of repeating units of F2 CH3 (p'6/q'6÷7.6). The mixed polymer film (18 cm2) obtained in reference transfer 1 was immersed in 100 ml of dry ether, and 17.4 µm of ammonia gas was passed through it while cooling with ice water and reacted for 25 hours at room temperature. The flowers were taken out and dried under reduced pressure at room temperature for 20 hours. Its infrared absorption spectrum is shown in Figure S'4'+20. Infrared absorption is from Kutle (Hen-1) 3520.3400 to 3100.2980.2880.
2350.1770-1670.1610. ．． 3550
゜1410.1340～1050.980.9J5゜8
20~480° This film is mostly (OF20F-1 CF20F-)-7-p61 (1
It consisted of 6 eight F2 repeating units. 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, sodium boron trifluoride ethyl ether complex 20 TruV tetrahydrofuran 5
1 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.
The mixture was washed in methanol under heating under reflux for 8 hours. Remove the membrane and IF
5, and dried at 60°C under reduced pressure for 20 hours to obtain an amine type polymer (terminal group -CH2NH2) film. The conversion rate calculated from the value of Yamoto 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 is shown in FIG. Infrared absorption spectrum (cIn-1) 3660.3430, 2960, 2360.1605.
1360-930, 800-49o. This membrane consisted essentially of a copolymer consisting of repeating units of υ F2 3C-CF 0-CF2CH2NH2 (p'6/q'6÷7.6). The membrane obtained above was immersed in a 100 mJ solution of 25% methyl iodide in dimethylformamide and heated at 60° C. for 200 hours to obtain an ammonium iodine polymer membrane. This membrane was then soaked in a 125M 10% methanol solution of lithium chloride.
It was immersed in BVC and heated at 60'C for 24 hours (the solution was replaced halfway). After that, it was immersed in methanol and heated to 60℃ for 7 days.
．． After washing for 5 hours, an ammonium chloride type 9 polymer film was obtained. Although this film was not stained with crystal violet, it was yellower than cresolet treasure, orange with thymol blue, yellow-orange with bromthymol sol, and basic. It was stained red with Cresolette 8. The infrared absorption spectrum of this film matched well with the spectral spectrum of the film obtained in Example 1. The ion exchange capacity of the obtained membrane was 0.48 meq/g dry membrane, and the electrical resistance was 28.1Ωcrn2. The transport index is 0.91
Met. This film also showed excellent chlorine resistance like the film of Example 1. Example 11 The carboxyl type polymer film obtained by the method of Reference Example 2 (9
cm2) in 32 mt of anhydrous acetonitrile, 3.72 m1 of triethylamine, and 1.6 mt of ethanolamine.
2 mA and 7.3 ml of trimethylchlorosilane were added, and the mixture was heated at 80° C. for 76 hours under an argon atmosphere. The membrane was taken out, washed with methanol, and dried under reduced pressure at 60° C. for 24 hours to obtain an amide type polymer. The infrared absorption spectrum of the membrane is shown in FIG. Infrared absorption spectrum (crn-1) 3340.3100, 2950, 2350.1720° 1535.1430.1350~930,880~48
0° This membrane consisted essentially of a copolymer consisting of the following repeating units: ■ F2 0F 3- OF (p'/q'=7.6) 6 61 Under an argon atmosphere, the membrane obtained above was immersed in anhydrous tetrahydrofuran 1701, and sodium borohydride 3
Added y. Next is boron trinitride. Tetrahydrofuran lQml of ethyl ether complex 61
The mixture was added dropwise to the solution over 30 minutes on ice 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 to obtain an amine type polymer membrane. In this film, the absorption of 1720c+n'+'l derived from amide carbonyl disappeared in the infrared absorption spectrum, indicating that the reduction to an amine type film had completely progressed. The conversion rate was calculated from elemental analysis and was approximately 82%. This membrane does not stain with Gutstal violet, basic cresol red, basic meromthymol sol-1 basic thymol blue K, but
It was stained yellow with cresol red, orange with thymol blue, and yellow with bromothymol blue. FIG. 23 shows the infrared absorption spectrum of the obtained film. Infrared absorption spectrum (cm-') 3550-3175.3000-2820.2350.
1440.1360-950.860-500° This membrane consisted essentially of a copolymer consisting of the following repeating units: -6CF20F2), (CF20F+-7-p61(1
゜? F2 CF3-CF 0-0F2CH2NHCH20H20H (p'6/qQ
÷7.6) The membrane obtained above was immersed in a dimethylformamide 100 solution containing 25 ml of methyl iodide and heated at 60° C. for 120 hours to obtain an ammonium iodine type polymer membrane. This membrane was then immersed in 125 10% methanol solutions 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 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. - Figure 24 shows the infrared absorption spectrum of this film. Infrared absorption spectrum (ctl) 3600~3125.3000.2350.1630° 1480.1350~940,850~500°Ion exchange capacity of the obtained membrane is 0.70 meq/9 dry membrane;
The electrical resistance was 11.9Ωcrn2, and the transference number was 0.90. The membrane consisted essentially of a copolymer consisting of the following repeating units: ■ F2 CF3-CF Cage CH3 1e CF2GH2NGH2GH20HCxe occupied H3 (p'6/q'6÷7.6) This film also showed excellent chemical and solvent resistance.Example 1
2 CF2-CF2 and CF2=CFOCF20FOCF20
A film made of a copolymer with F2SO2F and a polytetrafluoroethylene mesh as a support [Nafion 4 manufactured by DuPont]
A carboxyl type polymer film (8cIn2) obtained by subjecting No. 15 (trade name) to the same treatment as in Reference Example 2 was immersed in acetonitrile 3211u, and triethylamine 3
．． 72++1! , 2.22 volumes of n-propylamine and 3.54 ml of trimethylchlorosilane were added, and the mixture was heated at room temperature for 30 minutes and then at 80° C. for 73 hours under an argon atmosphere. The membrane was taken out, washed with ether, and incubated at 60°C under reduced pressure for 20 minutes.
After drying for a while, an amide type polymer (terminal group -CNH/V)
I got it. Obtained 1 The infrared absorption spectrum of the obtained film is shown in FIG. Infrared absorption is 3330.3100.2970.2900.2350° 1720.1530.1440, 1390-1010° 980.900-440° This membrane is essentially a repeat of the following except for the mesh part. It consisted of a copolymer consisting of units. Dimension F2 CF3-OF 00F2ONHCH20H20H3 1 (p', /q', '= 6.5) The membrane obtained above was immersed in 550 nl of anhydrous tetrahydrofuran under an argon atmosphere, and 9 g of sodium borohydride was added.
added. Next, boron trifluoride ethyl ether 18 butts 1
15 of tetrahydrofuran was added dropwise to the mixture over 40 minutes using ice water, and the mixture was stirred for 1.5 hours. Then at room temperature for 30 minutes,
The mixture was further heated under reflux for 21 hours. The membrane was taken out and washed in methanol under heating under reflux for 21 hours. The thigh was taken out and dried under reduced pressure at 60° C. for 2 hours to obtain an 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 reduction to amine-type voids 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-'') 3600-3100.2950.2900.2370° 1460.1420-900, 900-440° This film is a copolymer consisting essentially of the following repeating units except for the mesh part. It consisted of:
l÷6,5) The membrane obtained above was immersed in a dimethyl formamide 240 mb bath solution containing 60 rne of methyl iodide and heated at 60°C for 72 hours to obtain an ammonium iodine)4 submerged polymer membrane. This membrane was then soaked in a 10% methanol solution of lithium chloride.
00m# and heated at 60° C. for 25 hours (the solution was replaced halfway). Thereafter, it was washed in methanol at 60° C. for 30 hours to obtain an ammonium chloride type polymer film. This membrane is not stained with crystal violet, but is stained yellow with cresol red (dark red in cyclic basic water) and orange with bromothymol blue (dark blue in basic water), indicating that it has an ion exchange group. Ta. 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, was substantially composed of a copolymer consisting of the following monomer units. F2 crystal 1■ e (p'/q' product 6.5) 3 31 The electrical resistance of the obtained film is 10.0 Qpf, and the transference number is 0.
It was 90. 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 treated with ethyl iodide '1. A methanol solution of 81 t was obtained. The pancreas was then mashed in 10% methanol solution of lithium chloride (7) for 50 minutes and heated at 60° C. for 25 hours (the solution was replaced halfway). Then crush in methanol, 6
It was washed for 18 hours at 0°C and was not ammonium stained but stained yellow with cresol red and blue with basic bromothymol blue. The ion exchange capacity of the obtained membrane was 0.82 mlJ equivalent/g
The dry film has an electrical resistance of 5.6Ωcrn2. The transport index is 0.88
Met. This film also showed excellent chlorine resistance like the film obtained in Example 1. The infrared absorption spectrum of this film is shown in Figure 28. Infrared absorption spectrum (cm-1) 3400.3040, 2970.2850.2830.
2800.2360, 1630.1480.1420.
1340-1060.980, 930.840.740
~500 (3400.1630 is water absorption) This membrane was substantially composed of a copolymer consisting of the following anti-zelkova units. F2 CF3-OF t (p', /q', ÷6.5) Reference example 1 (raw material preparation example) CF2=CF2 and CF2=GFOCF20FCFzOF
A copolymer film obtained by 8F3 copolymerization with 2SO2F' [Fion 125 (trade name) manufactured by DuPont, film thickness 125μ, exchange capacity in terms of sulfonic acid 0.831 equivalent/g dry film] was added to 2N mounds. After treatment with acid, it was converted to sulfonyl chloride, then treated with hydrogen iodide, and washed with alkali to obtain a sodium carboxylic acid salt. Chain structure bar 0 of this membranous copolymer
CF3 is 0720FOcFOO2Na. This membrane was mixed with 8 normal methanol/methanol (volume comparison 1:1).
After treatment with hydrolysis and esterification, phosphorus pentate/
120°C in phosphorus oxychloride (weight ratio 1:1.6), 2
Heated for 4 hours. Thereafter, it was washed in carbon tetrachloride and then dried. The obtained film has an infrared absorption spectrum of 1
It shows strong carbonyl absorption at 800 cm-1. Also 29
Since there are absorptions considered to be derived from O-H absorption near 80.288° and 1440cm-1, the terminal groups of most of the pendant chains are 002Me groups, and some -cocz groups are mixed. A polymer film was obtained. This mixed polymer film consisted essentially of the following repeating units: F2 F30-(3F ■ CF2-Co2CH5 (p'6/q needle 1.6) Reference example 2 (raw material preparation example) CF2-CF2 and CF2 = CFOCF20FOCF20
Copolymer film obtained by copolymerization of F2S02F and CF3 [Nafion 125 (trade name) manufactured by DuPont, film thickness 125μ, 50
3H equivalent exchange capacity 0.83 milliequivalent/I dry membrane] to 2
After treatment with normal hydrochloric acid, the membrane was converted to sulfonyl chloride, then treated with hydrogen iodide, and washed with alkali to form the membrane into a carboxylic acid sodium 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 chain of this membrane is 10CF20FOCF2
It is CO2H occupancy F3. This film has an infrared absorption spectrum of 178
It showed strong carbonyl absorption at 0 cm-1 and was stained blue with crystal violet. This membrane consisted essentially of a copolymer consisting of the repeating units described below. -C-(3F 20F 2+-T+CF 2 (EF)
76Iq6 ■ F2 CF3-CF CF2C02H (p'/q'÷7,6) 6

[Brief explanation of the drawing]

Figure 1, Figure 4, Figure 8, Figure 11, Figure 14, Figure 17
20, 22 and 25 are diagrams showing infrared grade yield spectra of a fluorocarbon polymer having a carboxylic acid amide group, which is used as an intermediate in an embodiment of the second method of the present invention. and Fig. 2, Fig. 5, Fig. 9,
12, 15, 18, 21, 23 and 26 are used as starting materials in an embodiment of the first method of the present invention, and in an embodiment of the second method FIG. 2 is a diagram showing the infrared absorption spectrum of a fluorocarbon polymer having an amine group passed through as an intermediate in
Figure 3, Figure 6, Figure 10, Figure 13, Figure 16, Figure 1
9, 24, 27, and 28 are diagrams showing the infrared absorption spectrum of the ammonium type polymer produced by one embodiment of the method of the present invention, and FIG. It is a diagram showing the relationship between current and voltage when electrolysis is performed using a membrane of the ammonium type polymer obtained in the i embodiment. It Kyusho representative patent consultant Toyo Soda Kogyo Co., Ltd. Iku (Cm-'
), Reaction (Cm-Li-21) Ko5ff (TM-Ryan, 22 Illustrated Book 2A (2); 艮11col (CM-') #26 Illustrated Procedure Correction Layer November 1980 301" Patent Agency Commissioner Manabu Shiga 1 Display of the case 1982 Patent Application No. 192474 2 Name of the invention Name of the method for producing ammonium type polymer (330) Toyo Soda Kogyo Co., Ltd. Representative Yama
Toshiaki Kuchi Telephone number (58513311) 4. Daily voluntary amendment of amendment order 5. Number of inventions increased by amendment 6. Detailed description of the invention in the specification subject to arrest 7. Contents of amendment (1) Specification page 51, 9 The line "Amine is a membrane" is corrected to "Amine is a copolymer". (2) On page 39 of the specification, line 3, the chemical formula for 0 force is corrected to "low". (3) Specification 51 Sada, 2nd page From the second line, "Reference Example 1" is corrected to "Working Example 1." (4) On page 59 of the specification, the following statement is added between the bottom two lines and the last line. [Under argon atmosphere, The tubular amide type polymer obtained above was immersed in dry diethylene glycol dimethyl ether, and the tube was also filled with diethylene glycol dimethyl ether. Then, sodium borohydride was added (up to a 0.55 molar concentration) and the tube was thoroughly diluted. After stirring and cooling, a dry diethylene glycol dimethyl ether solution of boron trifluoride ether complex (0.62 molar equivalent to sodium borohydride) was added dropwise under water cooling. For 2.5 hours under cooling, the mixture was further heated to 100'C. The reaction was carried out for 21 hours.The obtained tubular amine type polymer (terminal group -
OH, NMe, ) was washed with methanol and then dried, and the infrared absorption spectrum was examined, and the spectrum almost matched that of the film obtained in Reference Example 3. Conversion rate 85f). The resulting tubular polymer was cut into rings and examined for stainability with crystal violet and cresol red, and no staining was found. This amine-type polymer consisted essentially of the following repeating units: ÷CF, CF, Te0Ft (1!F gradient Ft F, 0-OF (dZqA middle &4)”

Claims (8)

[Claims] (1) A main chain consisting of a perfluorocarbon polymer chain,
It consists of a pendant chain bonded to this, and the end of the deep pendant chain has the general formula % (where R1 and R2 are a hydrogen atom, a lower alkyl group, an aromatic group, a hydroxy lower alkyl group, or A fluorocarbon polymer having an amine group (representing a tetramethylene group or a pentamethylene group) is reacted with an alkylating agent, and this is bonded to a main chain consisting of a perfluorocarbon polymer chain. The youngest HM of the pendant chain has a general formula (where R1/ and R2/ are the same as R1 and R2, respectively, when R1 and R2 are other than hydrogen atoms, and R1 and R2 are hydrogen atoms. is the same as R3, where R3 represents a lower alkyl group derived from the alkylating agent, and Z represents a counter ion of a quaternary ammonium ion). A method for producing an ammonium type polymer. (2) As a starting material, the pendants have the general formula %% (wherein, (wherein R", 2/, R
3, l, m, n, and Z have the same meanings as in the previous ge. ) The manufacturing method according to claim 1, for obtaining an ammonium type polymer having pendants represented by: (3) As a starting material, a linear perfluorocarbon random polymer whose main chain is composed of repeating units represented by the general formula (where p and q represent integers and the ratio p/q is within the range of 2 to 16) is used as a starting material. 3. The manufacturing method according to claim 1 or 2, wherein an ammonium type polymer having the same main chain is obtained using a fluorocarbon polymer having a combined chain. (4) As a starting material, the general formula (X-', "s n, R1, and R2 represent the same meanings as above, p' and q/ each represent a number as an average value, and the ratio p'/ q' is an average value of 2 to 16
A fluorocarbon polymer consisting of repeating units represented by the formula (in the formula, R'' represents a lower alkyl group and one represents a moiety other than the alkyl group of the alkylating agent) is used as an alkylating agent. ) using an alkylating agent represented by the general formula (where X, R1', Rz /, R3,!, ., n, Z
, p' and q' have 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) has a main chain consisting of a fluorocarbon polymer chain;
It consists of a pendant chain bonded to this, and the end of the pendant chain has a general formula (where W is a halogen atom, a hydroxyl group, a group in which the hydrogen atom of a hydroxyl group is replaced with a tri(lower alkyl)silyl group or an ammonium group, or a lower alkoxyl group). A perfluorocarbon polymer having a substituted carbonyl group represented by ) The terminal end of M is converted into a structure represented by the general formula % (in which R and R have the same meanings as above), and this is reacted with a reducing agent to form a main structure consisting of a fluorocarbon polymer chain. A fluorocarbon polymer consisting of a chain and a pendant chain bonded to the chain, and having an amine group represented by the general formula % (wherein R and R have the same meanings as above) at the end of the bend (Q), and further By reacting this with an alkylating agent, a main chain consisting of a fluorocarbon polymer chain and a pendant chain bonded to the main chain are formed, and the end of the pendant chain has a general formula (in the formula R1/, R/2, R3,2 represent the same meanings as above. (6) As a starting material, a fluorocarbon polymer whose pendant chain has an amine group represented by the general 2 (in the formula, X, J-m-ns R'', R2 represents the same meaning as above), Claim 5 provides an ammonium type polymer having a dundant chain represented by the formula (wherein X1R1', 2/, R3, l, m, n, and 2 have the same meanings as above) manufacturing method. (7) As a starting material, the main chain has the general formula +OF2-OF2-)+CF2-OF)-
'9 1 (1 (in the formula, p and q represent the same meanings as above)) The linear unit consisting of repeating units is a fluorocarbon polymer that is a fluorocarbon random polymer chain, and is composed of the same main chain. A manufacturing method according to claim 5 or 6 for producing an ammonium type polymer. (8) As a starting material, the general formula (in the formula A fluorocarbon polymer having an amine group consisting of repeating units having a value ranging from 2 to 16) is used, and as an alkylating agent 3A (wherein R is a lower alkyl group and A is an alkylating agent) is used. (representing a moiety other than the lower alkyl group to be released during alkylation)
, p' s q ' represent the same meanings 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: