JPS6084313A - Ammonium-form polymer and its production - Google Patents

Abstract

PURPOSE:The titled polymer usable as an anion exchanger of excellent durability, prepared by bonding a pendant chain terminated with a specified ammonium group to a perfluorocarbon polymer main chain. CONSTITUTION:The titled polymer is prepared by bonding a pendant chain terminated with an ammonium group of formula I (wherein R<1>, R<2>, R<3>, and R<4> are each a lower alkyl, and R<2> and R<3> may be combined together to form tetramethylene or pentamethylene, and Z is a counter ion to the quaternary ammonium ion) to a main chain comprising a perfluorocarbon polymer, e.g., a polymer comprising recurring units of formulas II and III (wherein p' and q' represent each an average value, and p'/q' is 2-16). This polymer is useful as an anion exchanger of excellent durability, especially, membraneous anion exchangers used in the field of electrodialysis.

Description

[Detailed description of the invention] The present invention relates to a novel ammonium-type compound.

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 dialysis.

Conventional membranous anion exchangers have generally been made by modifying copolymers or polymer mixtures obtained by combining various hydrocarbon monomers through polymer 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 anion exchanger that exhibits less deterioration under such conditions.

A membrane anion exchanger developed for the purpose of improving durability is a mixture of a fluoropolymer, such as poly(tetrafluoroethylene), and an inorganic anion exchanger, such as a hydrated zirconium oxide. Compression molded products are known (
#! f Kaisho 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.

In some cases, a reversal of ion exchange capacity occurs. 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.

Furthermore, a method is known in which a hydrocarbon-based anion exchange membrane is surface-fluorinated to make it durable (Japanese Patent Application Laid-Open No. 52-4489), but this method does not work.

Since it is usually difficult to achieve a sufficient degree of fluorination, it is difficult to obtain an anion exchange membrane having the desired performance industrially.

The present inventors focused on the excellent durability of fluoropolymers17. As a result of intensive research into the development of anion exchangers based on fluoropolymer, we have invented an anion exchanger with excellent durability and a method for producing the same.

That is, the present invention consists of a main chain consisting of a fluorocarbon polymer chain and a pendant chain bonded to the main chain, and the end of the pendant chain has the general formula (wherein R1, R2, R3 and R4 are lower alkyl groups) However, R2 and R3
Provides an ammonium type polymer in which u can also be combined with a tetramethylene group (7 can form a tamethylene group; Z represents a counter ion of a quaternary ammonium ion), and a method for producing the same. It is.

In this specification, the term "dundant chain" refers to an unsubstituted alkyl group, a difluoroalkyl group, or an aromatic group bonded to the main chain consisting of a fluoromerocarbon polymer chain. However, a hetero atom or an aromatic ring may be present in the carbon-carbon bond.

More specifically, the present invention first provides a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and the end of the pendant chain has a general formula R1R2 (wherein R1, R2, R3, R4 and Z have the same meanings as above).

A specific embodiment of the polymer of the present invention is [7] in which the pendant chain is a fluorine atom, a chlorine atom, or a -CF3 group, l is an integer of 0 to 5, m is 0 or 1, n represents an integer from 1 to 5, but these θ may be different for each pendant. Ammonium having a structure represented by Z, R', 1 (2, R3 and R4 have the same meanings as above) Type polymers can be mentioned.The above 4, m,
Specifically, j! is different from the case where it is different for each pendant in the definition of n! This refers to the case of a ternary or more copolymer synthesized from two or more types of fluoroolefin monomers having 1m and n. Examples of this copolymer are shown below.

(In the formula, X represents p or p'; 6x is p;

y and 2 represent positive integers -X/7"Z is 21 (16) and y+z==q. If Representation 7, z/y
+ z is 2 to 16 in 1,000 ゛ average value, y + z =
q / is. m′ and! " is an integer from O to 5, m
' and m'' represent 0 or 1, and n' and n'' represent integers from 1 to 5, respectively. ) Furthermore, as a specific embodiment of the main chain of the polymer of the present invention,
A linear perfluorocarbon random polymer whose main chain consists of repeating units represented by the general formula %) (where p and q represent integers and the ratio p/q is within the range of 716) Examples include ammonium-type polymers that are chains.

Furthermore, as a specific embodiment of the main chain of the complex of the present invention,
The main knowledge is expressed by the general formula % formula % (in the formula, p' and q' represent the average value and the number of 1, respectively, and the ratio p'/q' is not 2 [it is within the gππ circle of 716). Ammonium-type polymers, which are linear perfluorocarbon random polymer chains consisting of repeating units, can be created.

Second, the present invention is based on the first method [7] The main chain is composed of a fluorocarbon polymer chain, and a pendant chain is bonded to the main chain, and the end of the pendant chain has a general formula (in the formula R2 and R3 has the same meaning as above].

R1' must be a hydrogen atom or a lower alkyl group. ) A fluorocarbon polymer having a diamino group represented by (In the formula, R1, R2, R3, R' and Z ij Oi
l Oe+! : Represents the meaning of the same Gi. However, R
4 is a group derived from an alkylating agent, R is the same as R4 when R is a hydrogen atom, and is the same as 1/ when H1/ is a lower alkyl group. ) The present invention provides a method for producing an ammonium type polymer, which is characterized in that it is an ammonium type polymer represented by:

Examples of pendant chains of fluorocarbon polymers having diamino groups used as starting materials in the first method of the present invention and F7 have the general formula (wherein X, R1', R2,1 (3-z, m and n are ) can be used to express the same meaning.

As an example of the main chain of a fluorocarbon polymer having diamino groups used as a starting material in the first method of the present invention,
A linear fluorocarbon random monomer chain consisting of repeating units of the general formula % (where p and q represent numbers and the ratio p/q is from 2 to 16) can be mentioned.

Further, as an example of the fluorocarbon polymer having a diamino group used in the first method of the present invention with the starting material (7), the general formula (wherein X, R1', R2, R3, !, m and n are the same as above) A fluorocarbon having a diamino group, consisting of a repeating unit represented by p/ and q'V (representing a number of 2 and the ratio p/A/ being an average value of 2 to 16) Polymers can be mentioned.

In the above general formula, Hl represents a hydrogen atom or a lower alkyl group [7, R2 and R3 represent a lower alkyl group,
These lower alkyl groups include methyl group, ethyl group,
Examples include n- and i-propyl groups, n-1i-, s- and t-methyl groups. Furthermore, R2 and R3 may be combined to form a tetramethylene group or Fi, -<ntamethylene group, and these polymethylene chains may have a lower alkyl group. These R1'
, R2 and R3 Examples of the fluorocarbon polymer having a diamino group used as a starting material in the first method of the present invention and 12 include polymers consisting of the following repeating units.

(1) Shocking・0F・寥0F・? F deaf ■ (21 (OF20F VC, F20F early F2 F2 1 F2
represents a lower alkyl group, and A represents a portion of the alkylating agent other than the lower alkyl group. R4 is a methyl group, an ethyl group, n- and 1-
Examples include propyl group, n-11- and S-methyl group.

A is an iodine atom, a bromine atom, a dimethyloxonium fluoroborate group, a diethyloxonium fluoroborate group, a dimethylogisonium hexafluoroantimonate group, a trifluoroacetic acid group, a trifluoromethanesulfonic acid group, a monoalkyl sulfate group, p- ) A luenesulfonic acid group, p-nitrobenzenesulfonic acid group, etc. can be exemplified.

Therefore, an alkylating agent [7] such as a superacid salt of lower alkyl iodide or bromide or tri-lower alkyl oxonium, such as methyl iodide, ethyl bromide, n-propyl bromide, n-methyl iodide, etc. .

Trimethyloxonium fluoroborate ((C143
)308F4),)ethyloxonium fluoropole) ((C2H5)308F4), trimethyloxonium hexachloroantimone) ((CH3)30
Examples include SbC/6), dimethyl sulfate, methyl trifluoroacetate, methyl trifluoromethanesulfonate, methyl p-)luenesulfonate, and ethyl p-nitrobenzenesulfonate. Methanol, ethanol, methylene chloride for alkylation.

Chloroform, carbon tetrachloride, sulfolane, N, N-
Dimethylformamide 1. Nitromethane, N-methyl-2
- Using pyrrolidone etc. as a solvent [7].

Alkylation can be carried out under conventional conditions. For example, this can be easily carried out by bringing the starting material, a fluorocarbon 1f polymer having a tertiary amino group, into contact with an alkylating agent or a solution thereof at a temperature of about θ°C to about 100°C.

The alkylating agent is used in at least an equivalent amount, preferably about double the amount, relative to the tertiary amine group to be converted. Usually, a large excess amount is used relative to the latter in order to allow the reaction to proceed quickly and completely.

When using a solvent, it is preferable to use one that can sufficiently soak the fluorocarbon polymer having diamino groups, which is the starting material.

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

The lower alkyl groups of H2 and R3 in the general formula at the pendant chain terminals of the ammonium type polymer obtained by the method of the present invention are no-2 derived from the starting material, a fluorocarbon polymer having a diamino group, and R1 is R1/ When is a hydrogen atom, it is the same as the group derived from the alkylating agent, ie, R4, and when Rt/ is a lower alkyl group, it is the same as the group derived from the starting material, ie, R1'.

H4 is a group derived from the alkylating agent.

In addition, 2 is a counter ion to the quaternary ammonium ion, which originally originates from the alkylating agent.If the ion 1tN is a monovalent anion, it will contain two of the ions, and if the ion species is divalent, it will contain two of the ions. One ion tastes 6 times. Examples include bromine and iodine anions, tetrafluoro F1 cerate ions, hexachloroantimonate ions, super strong acid ions such as trifluoromethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, etc. Carboxylic acid ions such as sulfonic acid ions and acetate ions,
Monoalkyl sulfate ions, etc.

These counterions may be exchanged with other ions if necessary. This ion exchange can be carried out using conventional methods such as KF',
Nacx, LtCCLiBr, LiI, NaO
H.

This can be easily achieved by treating the ammonium type polymer obtained in the present invention with an alkali metal salt such as KOH, Nal'lO3 or 2S04. Examples of Z after this counterion exchange include two halogen anions such as fluorine and chlorine bromine, a hydroxide ion, an acetate ion, a nitrate ion, or one sulfate ion.

Thirdly, the present invention provides a second method consisting of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and at the end of the pendant chain 1C-W (wherein W is lower alkoxyl). A fluorocarbon polymer having a substituted carbonyl group represented by a hydroxyl group, a hydroxyl group, a group in which the hydrogen atom of the hydroxyl group is substituted with a tri(lower alkyl)silyl group or an ammonium group, or a halogen atom) is prepared by the general formula (in the formula R1', R2 and R3 have the same meanings as above) to convert the terminal end of the dandant chain into a structure represented by the general formula (wherein R1/, R2 and R3 have the same meanings as above). The main chain consisting of a perfluorocarbon polymer chain and the pendant chains bonded thereto are converted into monomers by reacting with a reducing agent, and the terminals of the pendant chains have a general formula (RI/, R2, and R3). is a fluorocarbon polymer having a diamino group represented by (represents the same meaning as above), and further reacts this with an alkylating agent to form a main chain consisting of an R-fluorocarbon polymer chain and a pendant chain bonded thereto. At the end of the dandant chain, there is a general formula (where R1, R2, R3, R4 and Z have the same meanings as above. However, (7R4 is a group derived from an alkylating agent, and R1 is a group where R1/ is When R1' is a hydrogen atom, it is the same as R4, and when R1' is a lower alkyl group, it is the same as R1/. This is what we provide.

The second method of the present invention is explained using the reaction formula for converting the terminal group as follows.

The dandant chain of the fluorocarbon 11 complex having a substituted carbonyl group used as a starting material in the second method of the present invention has the general formula % (wherein X, W, !, m, and n are as specified elsewhere). An example is a group represented by the following. In addition, its main chain is expressed by the general formula -(ch'2-aF2earlyCF''2-(CF2) (in the formula, p is an integer of -15, not 3, and q is an integer of 710, not 1). A linear halufluorocarbon random polymer chain consisting of repeating units can be exemplified.

Further, 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) can also be referred to as a fluorocarbon polymer.

In the above formula, W is a halogen and [7 is fluoride, salt.

Examples include bromine and the like. The lower alkoxyl groups include methoxyl group, ethoxyl group, n-propoxyl group, n-cytoxyl group, S-zotoxyl group, n-
-Bentoxyl group etc. can be mentioned.

Further, 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 -butyldimethylsilyloxy group, and the like.

In addition, a group in which the hydrogen atom of a hydroxyl group is substituted with an ammonium group is -0NH4, -0N(OH3) 3, -0N (0 day 2 CH3) 3-HH 1 A bond with a carbonyl group (-C-) [7 and a carboxylic acid It forms ammonium salts.

As the fluorocarbon polymer having a substituted carbonyl group that can be used in the second method of the present invention, the following fluorocarbon polymers having repeating units can be exemplified.

(1)+CF2CF2Naf 1000F20F)-.

p I q ■ ? F2 (2)+CF20F2-)-7-(CF2CF→-7p
I q IF2 CF20F20F2COCH2CH2CH30=C,0
GH2GH,,CH2CH2(51+GF2CFz←C
F20F-)-.

p′ cloudy ell“2C]lI゛2COH (6)+CF20F2ψOF? F etc. ? F2 0F3-CF, 0 11 0-OF20F' (7) QF20F2-7 (to OF20F').

? F2? F2 (9 RiverF20F2+-,-(OF20F) These fluorocarbon polymers are cation-exchange carboxylic acid type perfluorocarbon polymers (particularly as cation-exchange membranes for saline electrolysis) or their precursors. It is well known as.

Among these fluorocarbon polymers, bendane) <
61 The acid halide terminal is, for example, a perfluorocarbon polymer having the same skeleton and a carboxyl group at the pendant chain end (this corresponds to one in the above formula where W is a hydroxyl group), and a chlorinating agent, etc. It can be easily reduced to 1% by using a halogenating agent. In this case, chlorinating agents such as thio, chloride, phosphorus pentachloride, phosphorus pentachloride, phosphorus oxychloride, etc. can be used, but in terms of reaction efficiency, thionyl chloride or pentachloride in sulfur oxychloride can be used. Preferably, phosphorus is used.

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

In addition, silyl ester type polymers contain tri(lower alkyl)silyl chloride in addition to the above carboxyl type polymer.
It can be obtained by the action of a silylating agent such as bistri(lower alkyl)silylacetamide.

The diamines represented by the above general formula used in the first stage reaction of the second method of the present invention include id, N, N-dimethyl-1,3-i lopanediamine, N, N-diethyl-1
, 3--7'lopanediamine, N-ethyl-N-mef-1,3-propanethiaban, tJ-isomethyl-N-
Methyl-1,3-propanediamine.

N,N,N/-) dimethyl-1,3-propanediamine, N,N-dimethyl-N'-propyl-1,3-propanediamine, N-(3-aminopropyl)-2-pi, becolin, Examples include 3-pyrrolidinoprobylamine, 3-piperidinoprobylamine, N,N-dimethyl-1.4-methanediamine, and N,N-dimethyl-1,5-methanediamine. . In this case, a corresponding silylamine in which 19 hydrogen atoms on the nitrogen atom in the above general formula are replaced with a trimethylsilyl group or the like may be used in place of the above diamine.

The reaction with these amines can be carried out by contacting the gaseous amine with the membrane, in a liquid amine, or using a solvent. In this case, when using a starting material other than an acid halide type polymer or an ester type polymer, a silylating agent such as trimethylchlor 7ran, bistrimethylsilylacetamide 1, hexamethyldisilazane, etc. is used to improve the conversion rate of the reaction. It is particularly preferable to use diamines represented by the above general formula, and in particular, when using the first silylating agent, it is preferable to carry out the reaction in the presence of a tertiary amine such as triethylamine or N-methylpyrrolidine. preferable.

The amount of diamine relative to the starting material is small (equivalent).

Preferably the amount is 3 equivalents or more, most preferably a large excess. The reaction may also be carried out in the presence of a tertiary amine.

As a solvent, diethyl ether, tetrahydrofuran,
Ethers such as dioxane, benzene.

Hydrocarbons such as toluene and hexane, acetonitrile, etc. can be used. Among the starting materials used in method 20 of the present invention, when W in the above formula is a lower alkoxyl group, that is, when the pendant chain terminal is a carboxylic acid ester type, these solvents, alcohols such as methanol, ethanol, etc. Similar things (r-su.

It can be used as

The amount of solvent to be used may be such that the fluorocarbon polymer having substituted carbonyl groups to be used is sufficiently immersed therein. Of course, you may also use more. There are no particular limitations on the reaction temperature of the animals, but the reaction is usually carried out at a temperature of about -30'C to about 150°C, preferably about 0°C to 80°C.

The thus obtained fluorocarbon polymer having carbon r9 amide groups is reacted with a 1μ'1 base agent in the second stage reaction.

As the reducing agent, aluminum hydride, algyl aluminum hydride such as diisobutyl aluminum hydride, lithium aluminum hydride, diborane, etc. can be used, but diborane is preferred in terms of reaction efficiency and ease of post-treatment. covered.

The diborane used can be generated, for example, by reacting a boron trifluoride ether complex with sodium borohydride, or various complexes of poran (such as dimethyl sulfide complexes) can be used.

The amount of the reducing agent is generally a large excess of at least an equivalent amount to the functional group in the 1-fluorocarbon polymer having a carboxylic acid amide group. 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 proceeds smoothly in an ether solvent such as tetrahydrofuran, dioxane or diethylene glycol dimethyl ether.

The amount of kI medium to be used may be such that the fluorocarbon polymer having a carboxylic acid amide group to be used is sufficiently immersed therein. It may be used in a larger amount than the amount required. In addition, there are no particular limitations on the reaction temperature, but in the first stage of the reaction, it is recommended to carry out the reaction by keeping it in the range of ice-cold temperature to room temperature, and then heating it to the reflux temperature to 100°C to complete the reaction. preferable.

The thus obtained b) amine group-containing fluorocarbon polymer is reacted with an alkylating agent in the third step to form the target ammonium type fluorocarbon polymer. This third stage reaction is exactly the same as the reaction in the first method of the invention.

The fluorocarbon polymer having diamino groups or substituted carbonyl groups used as a starting material in both methods of the present invention can be used in various forms such as a flat film, a tube, a fiber spear, and a powder. [7] In this case, the target ammonium type fluorocarbon polymer can be obtained in a corresponding shape.

The ammonium-type fluorocarbon polymers obtained by both methods of the present invention include the following reciprocal polymers.

(+)(OF2CF220F2(EF)7?P゛2 2C! 0 (2+-CGF20F2￥CF2C, F year old F2 sO2θ Br0 C[(3 2NOθ 23 F 2 2Y3t“0 (Force (CF2CF,)-BaCF2CF juice.

p Iq ? F2 (8) -CC:F20F2)-BaGF2CF)-.

p 1 q? F2 Although the ammonium type polymer of the present invention has a hydrocarbon group in part, it is extremely excellent in oxidation resistance such as chlorine resistance and solvent resistance. In addition, no change is observed even after repeated shrinkage due to drying and swelling in a solvent (water), and handling is much easier than with conventional anion exchangers. Therefore, for example, membrane-shaped ammonium-type polymers can be used in applications that are difficult to use with conventional anion exchange membranes, such as diaphragms for organic electrolytic reactions, membranes for various dialysis under harsh conditions, etc. is possible. It is also a resin that can perform anion exchange with quaternary ammonium groups in the coexistence of a suitable amount of solvent. It can also be used as a catalyst for cyanohydrin synthesis, a phase transfer catalyst, or a halogenation reaction catalyst.

In addition, the tubular ammonium type Aj combination can be used as a multi-If type module in a space-saving dialysis device, and can also be used in a system for removing interfering anions in an ion chromatograph. Since the conventional crosslinked type [(t ion candidate body and p, and the ammonium type lj combination of the present invention) 14.j ion exchange membrane is a non-crosslinked type, it can sufficiently respond to changes in conditions during use. can.

Furthermore, compared to the raw material 11@, the anion exchange membrane has
Because the number of exchange groups per pendant chain is increased, membrane resistance is generally low (it also has the characteristic that electrolysis can be performed with a low sliding voltage).

As described above, the ammonium type polymer of the present invention has great industrial value due to its excellent durability.

It is already known that the heat resistance and chemical resistance of fluorine-based polymers, particularly perfluorocarbon polymers, are significantly higher than those of general hydrocarbon-based polymers. However, the ammonium type 44 complex of the present invention has a durability of t7 that far exceeds expectations, despite having a hydrocarbon group in the pendant chain. In other words, even if the main chain is stabilized because it is a perfluorocarbon polymer chain, under excessively harsh conditions the hydrocarbon groups in the pendant chains are undeniably decomposed and the resulting detachment of the functional groups is unavoidable. Although this was expected to be a problem, the ammonium type composite of the present invention exhibits very little such deterioration.

The present invention will be explained in more detail below with reference to Examples and Reference Examples. As used herein, the term amine-type association refers to a nitrogen-containing fluorocarbon polymer having a diamino group, and the term amide-type polymer refers to a fluorocarbon group having a carboxylic acid amide group. Also used [7
The term terminal group referred to herein refers to the terminal group of a pendant chain. Further, unless otherwise specified, infrared absorption spectrum means transmission spectrum, and the dyeing test was conducted using the dyeing bath shown in G11 below.

Crystal Violet: Crystal Violet 0
．． 05% methanol solution Cresol Red: 0.05% methanol solution of Cresol Red Thymol Blue: 0 ()5% methanol solution of Thymol Blue Bromothymol Blue: 0.0 of Furomthymol Blue
5% methanol solution Basic cresol red: 0.05 of cresol red
% water-methanol bath solution to which about 1% of 10% NaOH aqueous solution was added Basic thymol blue: A solution of about 1% of 10% NaOH aqueous solution to 0.05% methanol solution of thymol blue. Electrical resistance of membrane. After sufficiently equilibrating with 0.5N saline solution, 1000 AC cycles in 0.5N saline solution,
It was measured at a temperature of 25°C, and the transfer number of the membrane was 0.5.
N saline solution and 2. It was calculated using the Nernst equation from the membrane potential generated between the ON saline solution.

The ion exchange capacity of the ammonium type polymer is determined by the Holhardt method, after completely exchanging the ammonium chloride type polymer.
This was determined by quantitative determination using the Vorhard method.

Further, the conversion rate was calculated based on the nitrogen value in elemental analysis, assuming that the raw material copolymer was replaced at 100%, and taking into account the change in equivalent weight due to the change in the end group.

Example 1 The membrane obtained in Reference Example 10 was subjected to FitfPJ in a solution of 50 d of methyl iodide in 200 ml of dimethylformamide, and heated at 60°C.
A polymer film of [7, ammonium iodine].
(The bath liquid was replaced midway) and heated to 7. After that, it was immersed in methanol and washed at 60°C for 19 hours to form an ammonium chloride type vehicle composite membrane.

The membrane was stained blue with basic thymol blue, yellow with cresol red, orange with thymol blue and bromothymol blue, and dark red with basic cresol red.

The infrared absorption spectrum of this film is not shown in Section 1.1.

Infrared absorption spectrum (cm-') 3400.3020, 2950, 2820, 2400° 1630.1470, 1380 ~ 1020,970° 8
95,840.820-470゜This film consists essentially of lower g20 units.2〕,11
It consisted of one combination.

? F2 0F -C:F 1 (in the formula, p //q/ is approximately 7.6) 1 Ion exchange companies of the obtained membrane have a 1.15 milliJ equivalent/
The I dry film has an electrical resistance of 1.7 Ωcm 2 and a transport number of 0.
It was 85.

Example 2 The membrane obtained in Tanigi Example 10 was immersed in a bath solution containing 2 ml of ethyl iodide and 8 Inl of methanol, and heated at 60° C. for 72 hours.
An ammonium iodine type polymer film was obtained.

This membrane was then soaked in a 10% methanol solution of lithium chloride.
It was immersed in 0ml of water and heated at 60°C for 25 hours (the solution was replaced halfway). After that, it was immersed in methanol and heated to 60℃ for 18 hours.
ammonium chloride type 11 coalesce 1ii'
I got g. This membrane was stained deep red with a basic cresol red aqueous solution and dark blue with resistant bromothymol blue. B4 The ion exchange capacity of the membrane is 0.
．． 90 mlJ per N'c/g - dry membrane, electrical resistance is 4
．． At 0Ω, the transfer number was 1.86. The infrared absorption spectrum of this film is shown in Figure 2.

Infrared absorption spectrum (cIrL~1) 3400.3000~2900.2700~2.50 (
1゜2370.1630.1490~1420,135
fl~950, 780~480 (3400.1630 water absorption) This membrane consisted essentially of a copolymer consisting of anti-fertility units of manure.

F2 CLi' -CF 1 Example 3 The membrane obtained in Reference Example 10 was immersed in an 8ml solution of butyl iodide in methanol and heated at 60°C for 72 hours to obtain an ammonium iodine)'' type polymer membrane. .

This membrane was then soaked in a 10% methanol bath solution of lithium chloride.
(It was immersed in HJ and heated at 60°C for 25 hours (replaced melting in the middle). Then, it was immersed in methanol and heated at 60°C for 1 hour.
After washing for 8 hours, an ammonium chloride fi polymer film was obtained. This membrane was stained red with a basic cresol red aqueous solution and dark blue with basic bromothymol blue. The electrical resistance of the obtained film was 5.5Ω, and the transference number was 0.
．． It was 87. The infrared absorption spectrum of this film is M3
O shown in lyI Infrared absorption spectrum (cr/1) 3400.3030~2870.2700~2550°2370.1630,1490~1450.1350~
950.920. '840,760~480. (however,
3400.1630 (Water Absorption) This membrane consisted essentially of a copolymer consisting of the following repeating units:

F2 ■ 0F 3-OF 2Gll"" (in the formula, pl'A' is about 7.6) Example 4 The membrane obtained in Reference Example 11 was treated with methyl iodide 501+I/! Immerse in dimethylformamide 200mJ bath at 60°C.
Heated for 72 hours to produce ammonium iodine ``A!!]+
A combined membrane was obtained. Next, this membrane was immersed in 250 d of a 10% methanol solution of lithium chloride at 60°C for 28 hours (
Replace the solution midway) Heat [7. After that, the nails were soaked in methanol and washed at 7.60°C for 19 hours to obtain an ammonium chloride nail clipping experience.

This membrane was not stained with basic thymol blue, but was stained yellow with cresol red, orange with thymol blue and hypromothymol blue, and dark red with basic cresol red.

The infrared absorption spectrum of this film matched the spectrum of the film of Example 1.

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

F2 CF3-CF (in the formula, p1'/q' is about 7.6) The ion exchange rate of the obtained membrane was 1.10 mEhJ.

7g dry film, electrical resistance 2.0Ω, tax rate 085
Met.

Example 5 A carboxyl type vehicle composite membrane obtained by the method of Reference Example 4 (
42cIrL2) in 160 ml of anhydrous dimethoxyethane, and 712.4 ml of triethylamine-N, N#
May-y-ru 1.3-'ronoxiamine 11.3rn
f and trimethylchlorosilane ll, 4+uJ,
Heated for 72 Wf at 90° C. in an argon atmosphere [7 hours]. The membrane was taken out and dried under reduced pressure at 60°C for 24 hours. The infrared absorption spectrum of this film matched that of the amide film of Reference Example 10.

This membrane consisted essentially of a copolymer consisting of anti(y units) as described below.

CF 2 CF' -GF 1 Under an argon atmosphere, the amide type "1" composite membrane obtained above was added to 300 mt' of anhydrous tetrahydrofuran with rQ ol.
Then 4.5 I of sodium borohydride was added. Next, boron trifluoride ethyl ether complex 9d was added to Hyosui Teio, 35
The mixture was added dropwise over a period of minutes and stirred for 1.5 hours. Then at room temperature 30
The mixture was further heated under reflux for 17 hours. After cooling, take out the membrane and
The mixture was washed with methanol for 22 hours under heating under reflux (7) to obtain an amine type polymer film. The infrared absorption spectrum of this film was consistent with that of the amine film of Reference Example 10.

The -1 absorption of 1720 disappeared, indicating that the reduction had completely progressed. The conversion rate was about 77%. This membrane was not stained with basic thymol blue or basic bromothymol sol, but was stained yellow with Cresollet 9, yellow-orange with thymol blue, and silky with bromothymol blue.

This membrane consisted essentially of a copolymer consisting of repeating units as described below.

→CF2CF2 Left is CF2 (3I Sairan CF20H2NGH2(](20H2NMe 2(pl
'A□' is approximately 7.6.

The membrane obtained above was immersed in a solution of 5Qmg of methyl iodide in 200d of dimethylformamide and heated at 60°C for 72 hours.
．． An ammonium iodine type polymer fir,'I was obtained.

This membrane was then soaked in a 10% methanol solution of lithium chloride.
The trap was immersed in a 50-liter medium and heated at 60'C for 281 hours (the solution was replaced halfway). σ) The bales were immersed in methanol and washed at 60°C for 19 hours to obtain an ammonium chloride type polymer film. These 11 leaves were stained yellow by cresol red, orange by thymol blue and bromothymol blue, and dark red by cresol red.

C2) The infrared absorption spectrum matched the spectrum of the film of Example 1.

Infrared absorption spectrum (-1) 3400.3020, 2950, 2820, 2400° 1630.1470.1380 ~ 1020.970° 8
95.840, 820-470° This membrane consisted essentially of a copolymer consisting of the following repeating units:

F2 CF3-CF The electrical resistance of the obtained film is 2.2ΩcrrL2, and the transference number is 0.
．． It was 85.

Carboxyl type polymer membrane obtained by the method of Reference Example 1 (
42cm2) was immersed in 170ml of anhydrous dimethoxyethane, 12.4me of triethylamine, 11ml of N,N-trimethyl-1,3-propanediamine and 11.4ml of trimethylchlorosilane were added, and the mixture was heated at 90°C under an argon atmosphere. Heat for 52 hours at ■7.

The membrane was taken out and dried at 60°C for 24 hours under reduced pressure 9::L
L.

An amide type polymer film was obtained. The infrared absorption spectrum of this film is shown in FIG.

Infrared absorption (cm) 33B0,3200,2950.2880.2B40°2780.2400,1700,1655,1530°1460.1420.1360~1020,980°8
45.800-460° This membrane consists of substantially the following repeating units: 1.800-460°. [Ro41:
.

It was made of polymer.

→CF2CF25Me0F20F亙70F2CF3-CF (pl'/ql is approximately 7.6) The amide type polymer membrane obtained above was reduced in the same manner as in Example 5 to form an amine type polymer membrane. I got it. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (cI
n, -'') 2960.2880,2830,2780,2400°1470.1360~1000,980,840°81
The absorption near 0 to 460° 1700 cIrL-1 disappeared, indicating that the reduction had completely progressed (conversion rate of about 79%). This ++<:
g uIt is not stained by basic cresol red and basic thymol blue, but yellow by cresol red,
Stained orange with thymol blue.

This membrane consisted essentially of the following anti(2) copolymer consisting of U units.

-7(OF20F2-)-7(CF20F-TpI
1 ql ■ CF 2 CF -OF' 1 CF2Cl12NCI-I2C112CI] 214Mo
2e (p1'/qt is about 7.6) The obtained amine type polymer film was treated in the same manner as in Example 1 to obtain 11 ammonium chloride type aggregates. The infrared absorption spectrum of this film is shown in FIG. The stainability was the same as in Example 1.

Infrared absorption rigidity (1) 3350.3010, 2950, 2810, 2370° 2120.1630, 1470, 13 (io~1020
The membranes at ゜970.890, 840, 810-460 are
It consisted essentially of a copolymer consisting of the following repeating units.

F2 OF -CF 1 4θ (in the formula, '/q is about 7.6) The ion exchange capacity of the obtained membrane is 084 mm/I dry membrane, the electrical resistance is 5.1 Ω CIIL2, and the transport number is is 0.87
Met.

Example 7 #Nipal side The n-butyl ester type polymer film (1.7 cm) obtained by the method of 3 was added to 15 ru of anhydrous tetrahydrofuran.
0.5 ml of N,N,N'-)dimethyl-1,3-propanediamine was added, and the mixture was heated under reflux for 74 hours under an argon atmosphere. Remove the membrane and place under reduced pressure.

Drying at 60° C. for 20 hours [7. A light brown opaque amide subtype coalescence (Result 11) film was obtained. The infrared absorption spectrum of this film is derived from esters, same as the wavelength of the film shown in Example 6.
The absorption at 90 cm disappears, and the absorption at 3000-2800 and 1
460rx-1 showed c-n absorption, and 1700, L-1 showed value (・absorption) derived from amide carbonyl.The obtained amide film was then reduced by the same method as in Example 6 to give a colorless and transparent An amine-type polymer film was obtained.The infrared absorption spectrum of this film is actually 1700 cm-, which is the same as that of the amine film in Example 6, and is derived from ami-1 carbonyl.
The absorption of ' has disappeared and the reduction to the amine type film has completely progressed. The conversion rate from ester was calculated from the original non-analytical values and was 70%. This 11φ is not stained with crystal violet or basic thymol blue, but is dyed with cresol let.
(Color: stained orange with thymol blue.

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

- 0 CF2CH2F)120H20H2NMe2 (p1'〆h' is about 7.6) The obtained amine type polymer film was treated in the same manner as in Example 1 and 45 to obtain an ammonium chloride type 1 composite film. Ta.

The infrared absorption spectrum and dyeability of this film were consistent with those of Example 1.

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

-(CF20FqCF2(3F”h (in the formula, p//q/ is approximately 7.6)1 The electrical resistance of the obtained film is 7.2ΩcIrL29 ring ratio is 0
．． It was 87.

Example 8 The membrane obtained in Reference Example 12 was immersed in a solution of 20 ml of methyl iodide in methanol B□ml and heated at 60° C. for 72 hours to obtain an ammonium iodine type combination ij+;j+.

This salt was then dissolved in a 1O% methanol solution of lithium chloride.
00ml immersed in 1K and heated at 60°C for 20 hours. (Immersed in methanol) 6
After washing at 0° C. for 8 hours, an ammonium chloride type 1 compound was obtained. This membrane was not stained with crystal violet, but was yellow with cresol red, yellow with thiol blue, yellow-orange with promothiol blue, dark red with basic cresol red, and dark red with basic bromothymol blue. It was stained blue and pale green with basic thymol blue. Figure 7 shows the infrared absorption vector of this membrane.

Infrared absorption spectrum (cm) 3600-3200, 2975, 2400, 1640 (
H2O), 1490-950, 820-480, the electrical resistance obtained was 4.3Ω, and the transference number was 0.86. This film also showed excellent chlorine resistance.

This membrane consisted essentially of a copolymer consisting of the repeating units described below.

F2 (J'3-CF - (in the formula, pl''q' is about 7.6) 2 (J'') Example 9 N, which is the substrate amine in the method of Reference Example 12.

N-diethyl-1,3-diaminopropane N-(3-
An amide type tetramer membrane was obtained in the same manner except that aminopropyl was replaced with 2.9 ml of -2-pipecoline.

Infrared absorption torque (cm-”) 3280.2900, 2350, 1720, 1530° 1450.1380~960,930,840~495
This membrane consisted essentially of a copolymer consisting of the repeating units described below.

F2 (pt'/q·+7.6) The obtained film was subjected to the same method as in Reference Example 12 to obtain an amine type polymer film. The conversion rate was calculated from elemental analysis and was approximately 84%. The stainability was similar to that of the membrane obtained in Reference Example 12.

The infrared absorption spectrum of the obtained film is shown in Figures 1 and 9.
, infrared absorption spectrum (crIL-') 3300.2
880,2350,1440.1370~950,77
0-480 This membrane consisted essentially of a copolymer consisting of the following repeating units:

Warm F2 CF3-CII゛- CF3 (p1/q1+7.6) The obtained film was then quaternized in the same manner as in Example 8 [7
, 1% ammonium chloride s-type binding compound 11j4.

This membrane was not stained with crystal violet, but was stained yellow-orange with cresol red, orange with thymol blue, bright yellow with base 4d, cresol red, blue with basic bromothymol blue, and yellow-green with basic thymol blue. It was done.

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

Infrared absorption spectrum (CIIL-1) 3600~3150.3020~2850.2750~
2350.1620 (H2O) 1480-930,78
0 to 90 The electrical resistance of the obtained film is 7.2Ωσ, and the transference number is 0.87
Met. This film also showed excellent durability.

This membrane consisted essentially of a copolymer consisting of the repeating units described below.

Example 10 A carboxyl-type IL (combined membrane (42 cm2)) obtained by the method of Reference Example 5 was immersed in 160 g of anhydrous acetonitrile, and 15.8 g of triethylamine was added to 14.8 g of N,N-dimethyl-1,3-propanediamine. Add 4#+7! and trimethylchlorosilane 14.7+l17!,
The mixture was heated at 80° C. for 72 hours under an argon atmosphere. The membrane was taken out and dried under reduced pressure at 60° C. for 24 hours to obtain an amide type polymer membrane. The infrared absorption spectrum of this film is shown in FIG.

Infrared absorption is crrL 3600-3000.3000-2850.2370°1700.1580-1400.1380-880°8
60-400° This membrane, excluding the mesh portion, was essentially composed of a monomer consisting of the following repeating units.

cF 2 cF-cF I (p2'/q2' is about 6,5) Under an argon atmosphere, the amide-type composite membrane obtained above was immersed in 300 ie of anhydrous tetrahydrofuran [7, boron hydride] IJ Mu 4.59 was added. Next, 9 ml of boron trifluoride ethyl ether complex was added dropwise over 35 minutes using ice water, stirred for 1.5 hours, heated at room temperature for 30 minutes, and further heated for 17 hours. It flowed. After cooling, take out the membrane and
The amine type polymer film was removed by washing with methanol for 22 hours under heating under reflux. The infrared absorption spectrum of this film is shown in FIG. Infrared absorption spectrum (crrt) 3300.2940, 2870, 2840, 2780° 2380.1440.1360~900.8GO~40
0゜1660CTL-' Absorption near the area disappeared (7, indicating that the reduction had completely progressed. This membrane was dyed with basic temo, -lube #-4 and tA-based bromothymol blue dye rJ!
, S. linica was stained yellow with cresol red, yellow-orange with thymol blue, and dark blue with bromothymol blue.

This membrane, excluding the mesh portion, essentially consisted of a copolymer consisting of the following repeating units in El' di.

0 ■ OF' 2 ■ OF -CF' 1 Next, the prepared membrane was heated for 72 hours in 50 ml of methyl iodide in dimethylformamide at °C to obtain an ammonium iodine type 11 combined film. Next, this lj (J is 10% of the increased lithium
Soak in 250 ml of methanol solution,
, 60''G for 28 hours (the bath liquid was replaced halfway). The sample was immersed in methanol and then subjected to anti-cleaning at 60°C for 19 hours to obtain an ammonium chloride type blood coalescence membrane.

This membrane was not stained with basic thymol blue, but was stained yellow with cresollet 9, dark red with thymol blue and bromothymol blue, and dark red with basic cresol red.

The infrared absorption characteristics of this film are shown in FIG.

Infrared absorption spectrum (cm) 3600-3100, 3050-2050, 1620.

1520-400.

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

F2CF3-CF The obtained film had an electrical resistance of 2.7Ω and a ++'fln ratio of 0.85.

Example 11 The carboxyl type polymer film (42cIrL2) obtained by the method of Reference Example 6 was treated with anhydrous acetonate (IJ Le 160)
d, triethylamine 12.4 m$, N,
N-dimethyl-1,3-propanediamine 11.3ml
11.4 m of trimethylchlorosilane were added, and the mixture was heated at 90° C. for 72 hours under an argon ash atmosphere. ; Take out the solution and dry it under reduced pressure at 60°C for 24 hours to obtain amide type IJi.
I got a combined membrane. The infrared absorption of this film is shown in FIG.

Infrared absorbing susktor (pot-1) 3 3 5 0, 2 9 5 0, 2 8 6 0
, 2 8 3 0, 2 7 8 0.

2380, 1710, 1530, 1465, 1380~
1080, 1060, 1035, 1020, 980.

910, 860, 790, 760, 730, 630.

This membrane consists essentially of descending self-traversing units]
, I+- was higher than the combined one.

F2CF-CF1 The obtained amide type polymer membrane was reduced in the same manner as in Reference Example 10 to obtain an amine type 1 combined pancreas.

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

Infrared absorption capacity (cm-”) 3310, 2960.2B70, 2830, 2780.

2400, 1725, 1465, 1400-108 (+
.

1040, 975, 630, 550, 5101 7 1
The absorption near 0CrfL-' disappeared, indicating that the reduction had completely progressed. The dyeability was similar to that of the amine film obtained in Reference Example 10.

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

→CF2CF2 story CF2CF Zeshita 313 - F2 GF 3-OF CF20F2CH2NCH2CH2CH2N (CH3)
2 (p 3'4' is approximately 6,4) then lU
The treated amine type polymer film was treated in the same manner as in Example 1 to obtain an ammonium chloride type polymer film. The infrared absorption of this membrane is shown in FIG. 16, and the 1-0 staining property was the same as in Example 1. Infrared absorption spectrum (c
m-1) 3400.3030, 2970, 2380, 1
640°1490.1380~1,080,980,8
90° 820 ~ 460° + + h = 1 energy resistance is 1.2 Ωcm",
The 4'+'+N ratio was 0.85.

This );ri consisted essentially of a synopsis consisting of the following repeating units:

■ F2 CF'-OF' 1 '/.

(In the formula, p3 q l! is about 6.4) Example 12 Acid chloride IJ obtained by the method of Reference Example 9) Pressing, 1.
Jk synthetic membrane 1.7 crrL2) was immersed in 1.5 nt of anhydrous tetrahydrochloride, 5 ml of N,N-dimethyl-j,3-zolonogundiamine Q was added, and the mixture was heated under an argon atmosphere at 74 ml. u! Heat to reflux for 4 hours. The film was taken out and dried at 60°C for 20 hours under reduced pressure, and a light brown opaque spectrum of 1790 derived from ester was found, matching the spectrum of the amide compound 1.
cm-'' absorption had disappeared.Then, the amide film thus obtained was ordered in the same manner as in Reference Example 10 to obtain a colorless and transparent amine-type ffi compound 111.Infrared radiation of this gland Absorption Suhari) / Shiha Real M1 1j11 Amine ti)
, the absorption of 1700α-1 derived from amide carbonyl disappears, and the spectrum of amine-type film I coincides with that of I.
7 shows slope 1 where the reduction of ＼ has completely progressed to 0. The conversion rate from ester was determined from the elemental analysis value of JL 141 L.
#-#, 'i pot was about 78%. This membrane contains crystal violet and J'r8-based thymol blue K +4.
It was not stained, but was stained with cresol red and yellow thymol blue in AX'1 color.

This film actually consisted of Ibara coalescence consisting of the following reaction units.

F2 CF"3-OF'(p3'/q3' is approximately 6.4) Then, the amine type 1 body 11.
lg (Similar to 9ti 1 θ: where J', 11 shi,
Also has an ammonium chloride type skewer combination membrane. This jj!
,'H's infrared: loss spectrum is shown in Example 11.
The spectra of Ill:,i and −,υ,2 were calculated.

The stainability was the same as that of Example 7/l'J] and I'J.

Infrared absorption spectrum (cm-”) 3400.3030, 2970, 2380, 1640° 1490.1380 - 1080.980, 890° 82
The electrical resistance of the obtained film from 0 to 460° is 1.3Ωcrrt2, and the transference number is 0.
．． It was 85.

This membrane consisted essentially of a comonomer consisting of the following repeating units:

Cfl"2 CF -CF 1 Example 13 A 141V tube-shaped carboxyl-type co-car assembly (50 ml) was immersed in 60 m/l' of butetonitrile by the method of Reference Example 7, and the same kj was added into the tube. medium ii
i, then triethylamine 12.4 mA, N,
N-dimethyl-1,3-propanediamine 11.3 mJ
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 type polymer (terminal group -CNHCH2CH2CH2N(CH3)2).
I got it. When the obtained tubular amide type subaggregates were lined up and their infrared absorption spectra were examined, the spectrum almost coincided with that of the film obtained in Reference Example 10. Conversion rate is 80%. When the cut tube-shaped 11 aggregate was cut into rings and examined for Ms chromaticity against crystal violet, it was not stained at all.

The amide-type imaginary combination forming this tube essentially consisted of warp units F2 3G-OF (p4'/q4' S6.6).

The tubular amide type polymer obtained by the above reaction was immersed in dry diethylene glycol dimethyl ether under an argon atmosphere, and diethylene glycol dimethyl ether was also poured into the tube. Next, sodium borohydride was added (to a concentration of 0.53 molar), stirred well, and cooled, followed by a solution of a dry diethylene glycol dimethyl ether complex of boron trifluoride ether complex (0.62 mol/kl relative to sodium borohydride). It was added dropwise while cooling with water. 2.5 hours under cooling, then 2 hours at 100"C.
The reaction was allowed to proceed for 1 hour. The obtained tubular amine type polymer was washed with methanol and dried, and its infrared absorption spectrum was examined. Conversion rate: 78%. The resulting tubular intermediate was $:n (41J LL.

When I checked the dyeability, it was found that Q of Reference Example IO and 4-1.
It showed greyish color.

This amine-type moon (combination is essentially the following anti-1d unit)'
It consisted of L.

■ F2F2O-OF'(p4'/q' +6.6) Next, the obtained tubular amide type polymer was placed in a methanol bath solution of methyl iodide (volume ratio 1:4) and reacted at 60°C for 500 hours. I set it. After washing the obtained tuno-like subcoalescence with methanol, dilithium jJ dilithium methanol solution (1
, '28 molar degree) at 60'C for 24 hours. This tubular sword 1 combination was heated to 60°C in methanol, and the tube-shaped ammonium chloride type J1 with an open mouth was heated to 60°C.
Let's combine! ]Ta.

The resulting tubular nail aggregates were either not stained with basic thymol blue in the dyeing test, yellow with cresol lebbi, orange with thymolsol and bromothymol blue, or dark red with base (i1 ucresol red). However, the presence of anion exchange groups was confirmed.

The exchange volume ti of the obtained tubular anion paternate is 1
．． The dry resin was 0.09 milJ equivalent/g.

After treatment in methanol at 65°C for 48 hours, no change was observed even after the solvent was removed under vacuum at 40°C five times.

This tubular combination consisted of a force unit of lower jtL in real)i7i terms.

■ F2 CF -CF 1 (in the formula p4'/q /+6.6) Example 14 According to the method of Reference Example 8, powdered carboxyl type symbiotic coalescence (1, Og) was mixed with 160 m/g of anhydrous dimethoxyethane.
! 12.4 ml of triethylamine, N, N
-dimethyl-1,3-propanediamine 11.31 nl
and trimethylchlorosilane 11.4. m and heated at 90° C. for 72 hours under an argon atmosphere.

ζ'-I was removed from the powder and dried at 60°C under reduced pressure to obtain powdered amide type polymer 1 (terminal group -CNHCH2CH2CH2N(CH3)2)
I got it. When the infrared absorption spectrum of the obtained powdery amide type vehicle combination was examined, the absorption position almost coincided with that of the film obtained in Reference Example 10. Conversion rate 75%. (4) When the resulting powdered polymer was examined for dyeability with crystal violet, it was not dyed at all.

The amide-type polymer that makes up this powder is essentially a repeating unit. F2 3C-CF (p5χ5'+6.5) It consisted of

The resulting powdery amide type 11 aggregate was reduced with diporane in the same manner as in Reference Example 10, and collected once to obtain a powdery amine type polymer. The conversion rate was 72%. When the obtained powdered KBr disk was subjected to infrared absorption, the absorption of amibical 71nyl present around 1700cIrL-' had completely disappeared.

The powders were either not dyed with basic thymol true and 15-promothymol clear, or dyed yellow with cresol red, yellow-orange with thymol blue, and dark blue with bromothymol pull.

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

F2 3C-OF 1 /H (p5'/q5'S6.5) Then, the obtained powdered amine-type hybrid product was placed in a methyl iodide methano-A/bath solution (volume ratio 1:4) and heated at 60°C. So 5
The reaction was carried out for 00 hours. A: Wash the removed tubular offshore body with methanol, and then wash the lithium chloride methanol bath solution (
The reaction was carried out for 24 hours at 60'C in 1.28 molar concentrated Ha[). This powdered polymer was heated to 60°C in methanol to obtain the desired powdered ammonium chloride IJ l-″′ type:
The obtained powdered polymer was colored orange with cresol red in a dyeing test, and the presence of anion exchange groups was confirmed.

I (slender powdered anion exchanger sentence translation answer: keha, 0
．． It was 96 milliequivalents/g of dry resin.

Treated in methanol at 65°C for 48 hours r1! No change was observed even after repeating the operation of removing the solvent under vacuum at 40° C. five times. The membrane consisted of a co-IJ polymer consisting essentially of the following repeating units:

(In the formula, p5A5' is about 66) Reference Example 1 (Raw material preparation example) Copolymer film obtained by polymerization [Nafion 125 (trade name) manufactured by DuPont, film thickness 125μ, 5O3H
A dried membrane with a converted exchange capacity of 0.83 milliequivalents/I was treated with 2N hydrochloric acid, converted to sulfonyl chloride, then treated with hydrogen iodide, and washed with alkali to form the membrane into a sodium carboxylate salt type. After treating this membrane with a 3.24N chloride aqueous solution,
It was washed with water and dried under reduced pressure to obtain a carboxyl type polymer membrane. The structure of the pendant chains of this membrane is 10CF20FOCF2CO2H. This film showed strong carbonyl absorption at 1780 cnt in the infrared absorption spectrum CF3 vector and was stained blue by crystal violet.

This membrane consisted essentially of a comonomer consisting of the following repeating units:

F2 0F 3-CF ■ CF2C02H (p1'/q' is approximately 7.6) Reference example 2 (raw material preparation example) Carboxyl 7%'1711 obtained by the method of reference example 1
Combine fJ (12cn2) with orthoformate f)V 4
0 ml and heated at 70°C for 2.5 hours. The membrane was taken out and dried under reduced pressure at 60° C. for 19 hours to obtain a methyl ester type vehicle composite membrane. This 119 showed a strong carbonyl absorption at 1780 cm''1 in the infrared absorption spectrum. In addition, stainability was examined using crystal violet, but no staining was found.

This skin consisted essentially of a C2+ copolymer from the following warp units.

○ ■ CF 2 CF -CF 1 ■ CF2C02CI (3 (p1'/q/ is about 7.6) Reference example 3 (raw material preparation example) Carboxyl-type sealant film obtained by the method of Reference example 1 (3
, 6σ2) in n-methyl alcohol II) ml and absorbed 73 g of hydrogen chloride at room temperature.
heated for an hour. The membrane was taken out and dried under reduced pressure at 60 DEG C. for 24 hours to obtain a -zotyl ester type composite membrane. This film showed strong carbonyl absorption at -1 of 1790. Also, it was not stained with crystal violet.

The polymer was composed essentially of a repeating unit or a copolymer.

-(OF20F2 masu-baOF 20F juice bottom p11 qt ?F2 0F 3-OF ZhanCF2C02CH2CH2CH2CH3(ps'/q
' is approximately 7.6.

Reference example 4 (raw material preparation example) Carboxyl type polymer membrane obtained by the method of reference example 1 (1
, 5cn") was immersed in anhydrous triethylamine'1rnl and heated at 60°C for 3 hours. The membrane was taken out and dried at 60°C for 24 hours under reduced pressure. A carboxylic acid triethylamine salt type 11 compound 11 showing absorption was obtained.

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

Published CF20F2 Taber 0F20F (Endp□ l qt [ ?F2 CF3-OF (pl/q' is about 7.6) Reference example 5 (raw material preparation example) CF = CF -CFOGF GFOGF'2
0F2So2F Tono2 2 2 2 CF3 A film using a polytetrafluoroethylene mesh as a support for a copolymer [DuPont 3J14j.

Nafion 415 (parts name) 5O excluding mesh part
The dried membrane was treated in the same manner as in Reference Example 1 to obtain a carboxyl type polymer membrane. This membrane was stained blue with crystal violet.

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

The copolymer obtained by the copolymerization of Reference Example 6 (raw material preparation example) was converted into Filno [film thickness 50μ, 5O3H conversion exchange +'-IN,' 0.9
5 milli equivalent m/11 dry membrane] and then saponified to obtain a sodium salt type membrane. This film is further coated with YN'4 r3L
After treatment with f'1-methanol (3:1), 3.
The mixture was heat-treated in 24 liters of Aj acid, washed with water, and dried under reduced pressure to obtain a carboxylic acid film. This membrane consisted essentially of a copolymer consisting of the following units.

The copolymer obtained by copolymerization with F2 0F 3-C; Diameter: 0.875 inches, 5O3H Sakaki trowel - Exchange capacity: 0.92 milliequivalents/g dry) After saponification, and further treatment with 2N hydrochloric acid according to a known method, sulfonyl chloride IJ The membrane was converted into a carboxylic acid I-lium salt type by treatment with hydrogen iodide and washing with an alkali. This membrane was treated with a 3.24N hydrochloric acid aqueous solution, washed with water, and dried under reduced pressure to obtain a tunic carboxyl type copolymer. This copolymerization. This tube exhibits strong carbonyl absorption at 1780 cm at 1,780 cm in infrared absorption, and also has the highest crystalline
Stained blue by knots.

This tube consisted essentially of a copolymer consisting of the lower 6 curvature units.

F2 CF -CF 1 CF2C02F ((p4'/q' is about 6.4) Copolymer powder obtained by saponification of Reference Example 8 (N material preparation example) [Nafion manufactured by DuPont] 511 (product name), 5O3H equivalent exchange capacity 0.91: equivalent weight/g, dry resin, sulfonic acid potassium salt type] was hydrolyzed with 5N hydrochloric acid and converted to sulfonyl chloride by treatment with phosphorus pentachloride.Reference Example Hydrogen iodide treatment, alkali washing, and hydrochloric acid treatment were carried out in the same manner as in 1 to obtain a powdered carboxyl-type aggregate.This powdered polymer was used as a KBr disk, and the infrared 1 absorption was found to be approximately 1780 cm + J shows carbonyl absorption,
The powder was also dyed blue with crystal violet and consisted essentially of the following repeating units:

? F2 GF -OF 1 CII゛2CO2H Reference Example 9 (Raw material toning example) Carboxyl dispersion type coalescence 1 obtained by the method of Reference Example 6
Based on phosphorus pentachloride - phosphorus oxychloride (military ratio 1:1.6)
The mixture was heated at 120° C. for 24 hours. Furthermore, after washing in carbon tetrachloride, it was dried. This film showed strong carbonyl absorption to 1809CIn-' in the infrared strontal. This membrane consisted essentially of a copolymer consisting of the repeating units described below.

F2! GF -OF 1 (in the formula, p3'/ql is about 6.4) Reference Example 10 (
Raw material preparation example) I4 star carboxyl by the method of Reference Example 1! J14
Polymer membrane (42cTL2) was coated with anhydrous dimethoxyethane J
Soaked in 00rul, triethylamine y 12.4
Ill/! , N,t-1-dimethyl-1,3-propanediamine 11.3 m (i) and trimethylchlorosilane 11.4 m were added, and the mixture was heated at 90 °C under an argon atmosphere for 7 min.
Heated for 2 hours. 11ψ was taken out and dried at 60° C. for 24 hours under reduced pressure to obtain an amide type polymer film. The infrared absorption spectrum of this film is shown in FIG.

Infrared absorption spectrum (CrrL-”) 3350.29
60,2900,2860,2810°1730.15
40,1470.1380~l O40°980.93
0,800-500 DEG This membrane consisted essentially of a copolymer consisting of the following repeating units.

-(CF2CF2 TaberGF2CF'j-7p11 q
.

OF' 2 GF -GF 1 0 11 GF 2 C'NGH2CH2C1'H2N (01(
3) 21 ((pl/q1' is about 7.6) Under an argon atmosphere, 1 piece of the amide" type locking body heated above by +4f was immersed in 300 m6 of anhydrous tetrahydrofuran, and 4.5 m of sodium borohydride was added. Next, 9 m+1! of boron trifluoride ethyl ether was added dropwise over 35 minutes in a ice bath and stirred for 1.5 hours.Then, heated at mold temperature for 30 minutes and further heated for 17 hours. After cooling BY
was taken out and washed with methanol for 22 hours under heating under reflux to obtain an amine type polymer film. This l! The infrared absorption spectrum of ψ is shown in the K<18 diagram. red evening) absorption spectrum (c
rn) 3320.2950, 2870, 2840, 2790°2400.1470.1330~1020,980°8
30.820~480°1720tx-” absorption disappears, and the edge element completely becomes j1
Indicates that 8 lines have been completed. The conversion rate was about 80%. This stripe was not stained with basic thymol blue or basic bromothymol true, but was stained yellow with cresol ret, θf orange with thymol sol, and silky with bromothymol blue.

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

HCF2CF2 Soup CF20F Masu-7p11q1? F2 0F 3-CF ■ CF2CH2NCH2CH2CH2NMe2(p1/q
/ is approximately 7.6) Reference Example 11 (Raw Material Preparation Example) 141 methyl ester type interlocking body 11+ (42 cm2) was converted to anhydrous dimethoxyethane 16 by the method of Reference Example 2.
0 rnl and 12.4 ml of triethylamine.
.

N,N-dimethyl-1,3-propanediamine 11.3
rnl and trimethylchlorosilane ii (4 ml) were added, and the mixture was heated at 90° C. for 72 hours under an argon atmosphere.

The membrane was taken out and dried under reduced pressure at 60°C for 24 hours to obtain an amide type polymer membrane. The spectrum of this 11-minute infrared absorption spectrum matched that of the amide film of Reference Example 10.

This membrane consists essentially of the following reaction units. Soak in 300ml of tetrahydrofuran (1゛↑,
Sodium borohydride 4.5! Added l. Add 9 ml of boron trifluoride ethyl ether complex under ice water/jr.
It was added dropwise over 35 minutes and stirred for 1.5 hours. Thereafter, the mixture was heated to reflux at room temperature for 30 minutes and then for an additional 17 hours. After cooling, the membrane was taken out and washed with methanol for 22 hours under heating under reflux to obtain an amine type Togai membrane. The external absorption spectrum of this 1-layer sample corresponded to that of the amine film of Reference Example 10, and that of the amine film of Reference Example 10.

The absorption at 1720 cm-'' disappeared, indicating that reduction or progress to the original metal occurred.The conversion rate was about 78%.

This membrane was not stained with basic thymol sol and basic bromothymol blue, yellow with cresol let, yellow-orange with thymol blue, and bromothymol sol.
It was stained brightly by

This membrane consisted essentially of a copolymer consisting of the repeating units described below.

F2 CF -OF 1 CF2CH2NCH2CH2CH2NMe2I ((p1'/q/ is about 7.6) Reference Example 12 Carboxylic offshore membrane obtained by the method of Reference Example 1 (1
4.3 ml of N,N-diethyl-1,3-diaminopropane in Step 2)! , anhydrous acetonitrile 32''s trimethylamine 3.7d and trimethylchlorosilane 3.
5IRl was added and heated at 80° C. for 96 hours under an argon atmosphere. The membrane was taken out, washed with ether, and then dried under reduced pressure at 60° C. for 22 hours to obtain an amide 8 type polymer (terminal group-GNHw N(Et,) 2) membrane.

The infrared absorption spectrum of the obtained film is shown in Figure 19.
0.780-480° This film was essentially composed of a co-731 combination consisting of the following recoil units.

F2 Under an argon atmosphere, the membrane obtained above was dissolved in anhydrous tetrahydrofuran 1701d and sodium borohydride 3, OI was added.

Next, the boron trifluoride ethyl ether complex 6m#) 7-trahydrofuran loml solution was heated under ice water for 30 minutes.
The mixture was heated under reflux for 30 minutes at room temperature and for 20 hours. The membrane was taken out and washed in methanol under heating under reflux for 20 hours. The membrane was taken out and heated under reduced pressure at 60°C for 24 hours. After drying for several hours, an amine polymer film was obtained. In this film, the absorption of 1720 crn-" derived from amide 9 carbonyl disappeared in the infrared absorption spectrum.
No. 1 is shown in which reduction to an amine type film has completely progressed. The conversion rate was calculated from elemental analysis and was approximately 93%. This membrane is not stained with crystal violet, basic thymol blue, or basic zolomothymol blue, but is stained yellow with cresol red, light yellow with basic cresol red, yellow-orange with thymol blue, and dark blue with promthiol blue. It was done.

FIG. 20 shows the infrared absorption spectrum of the obtained film.

Infrared absorption spectrum (cm-”) 3300.2900, 2350, 1460.1380~
940.790-490° This film consisted essentially of a co-metallic body consisting of the following diagonal units.

-(CF20F2+-ACF2CF Masushita p, 1 1 F2 CF' 3-OF (EF2C; H2N1lCH2CH20H2N(OH2
0H3) 2(pl"q' +7.6) Reference Example 13 Electrolysis of hydrochloric acid was carried out using the samples obtained in Example 1 and Example 10. Also, for the specific axis, commercially available hydrocarbon-based An anion exchange membrane was also used.The electrolytic conditions were as follows.

Membrane area: 9.6ci2, electrode: platinum Electrolyte; anode/cathode = 6N hydrochloric acid/6N hydrochloric acid Current density; 5 A/dm2 The results are shown in Table 1.

Table 1 Membrane of Example 1 1.7 1.44 Membrane of Example 10 2.7 1.48 Commercially available membrane approximately 2.5 1.49

[Brief explanation of drawings]

Figures 4, 8, 11, 14, 17, and 19 show fluorocarbon polymers having carboxylic acid amide groups that were used as intermediates in an embodiment of the second method of the present invention. It is a diagram showing the infrared absorption spectrum of the fifth
Figures 9, 12, 15, 18 and 20
The figure shows the infrared pure absorption spectrum of a fluorocarbon polymer having a diamino group used as a starting material in an embodiment of the first method of the present invention and passed as an intermediate in an embodiment of the second method. FIG.
Figures 3, 6, 7, 10, 13, and 1.6 are diagrams showing infrared absorption spectra of the ammonium type polymer of the present invention. Patent Applicant Sagami Chuo Chemical Research Institute Representative Patent Applicant Toyo Soda Kogyo Co., Ltd. Procedural Amendment Uni 1982 μm January 301'' Commissioner of the Patent Office Manabu Shiga 1 Indication of Case 1988 Patent Application No. 192473 2 Invention Name of ammonium type polymer and its manufacturing method 6 Relationship with the amended case Representative patent applicant address 4560 Tomi IJJ, Shinnanyo City, Yamaguchi Prefecture, 746
Address name (330) Toyo Sohan, Gyo Co., Ltd. Representative Toshiaki Yamaguchi Telephone number (585) 3!11 + Number of inventions increased by daily voluntary amendment 5th amendment of 4th amendment order None Target of 6th amendment ■ Details ■Claims column of the specification■ Detailed explanation of the invention column 7 Contents of amendment■ Amendments to the claims column of the specification are as shown in the attached sheet. ■ Amendments to the column of detailed explanation of the invention in the specification are as follows. (1) Specification page 14, lines 6 and 7, page 15, lines 3 and 4,
In lines 1 and 2 of page 19 and lines 4 and 3 from the bottom of page 29, "ammonium type polymer represented by" is corrected to "ammonium type polymer having an ammonium group represented by". (2) "Tertiary amino group" on page 25, line 11 and line 14 of the specification is corrected to "diamino group." (3) Correct the chemical formula on page 66, line 6 of the specification to +O Seio~〒-1. (4) On page 67 of the specification, line 6, “(pl/(11≠7.6) J is r(p’t/i,≠16)”. "Chlorsilane" is corrected to "trimethylchlorosilane." (6) "Example 20" on page 80 of the specification, line 15 is corrected as "Reference Example 10." (7) Lines 7 from the bottom of page 85 of the specification and In the same line 6, "obtained tubular polymer" is corrected to "obtained powdery polymer." 8. List of attached documents (1) Document stating the corrected scope of claims 1 copy 2 Claims (11 A main chain consisting of a perfluorocarbon polymer chain,
It consists of a pendant chain bonded to this, and the end of the pendant chain has a general formula (wherein R'', R2, R3 and t represent a lower alkyl group. An ammonium-type polymer having 7 > % nium groups, which can form pentamethylene groups (2 represents the counter ion of the quaternary ammonium ion). (2) The pendant chain has the general formula It is a fluorine atom, a chlorine atom or a -01F group, l is an integer from 1 to 5, m is 0 or 1, and n is an integer from 1 to 5, but these numbers may be different for each pendant.2 2. The ammonium type polymer according to claim 1, which has a structure represented by ゜B!, R', R'' and t have the same meanings as above. (3) A linear Verfluot carbon random polymer whose main chain consists of 11 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) The ammonium type polymer according to claim 1 or 2, which is a chain. (4) The main chain has a general formula (in the formula, p/ and q' each represent a number as an average value, and the ratio P'/q' is within the range of 2 to 16)
The ammonium type polymer according to any one of claims 1 to 5, which is a linear perfluorocarbon random polymer chain consisting of repeating units represented by: (5) Consisting of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to this, the end of the pendant chain has a general formula (wherein R2 and P represent the same meanings as above, and f is a hydrogen atom or A fluorocarbon polymer having a diamino group represented by (representing a lower alkyl group) is reacted with an alkylating agent, and this is made up of a main chain consisting of a perfluorocarbon polymer chain and a pendant v bonded to this, and the pendant chain At the end of the general formula (where R', R2, R'', R' and 2 have the same meanings as above, t is a group derived from the alkylating agent, and R1/ is hydrogen). If R1' is an atom, it is the same as t; if R1' is a lower alkyl group, it is the same as R'/.) An ammonium type polymer having an ammonium group represented by: (6) As a starting material, the bendane) [is the general formula (wherein represents.l
m represents an integer from 0 to 5, m represents an integer from 1 to 5, and these numbers may vary from pendant to pendant. ) using a fluorocarbon polymer having 4 diamino groups having the general formula % (where X, R", R", R", E', l!,
m, n and 2 have the same meanings as above. ) The manufacturing method according to claim 5, for obtaining an ammonium type polymer having pendant chains represented by: (7) 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. 7. The manufacturing method according to claim 5 or 6, wherein an ammonium type polymer having the same main chain is obtained by using a fluorocarbon polymer having a combined chain. (8) General formula (wherein, X, R", FF, R", l!, m
and n represent the same meaning as above, s P' and q' each represent a number as an average value, and the ratio p// q/
is in the range of 2 to 16 on average), and as an alkylating agent, a fluorocarbon polymer having a diamino group is used, and as an alkylating agent, t represents a lower alkyl group, and A represents an alkyl group. using an alkylating agent represented by the general formula (representing a moiety other than the lower alkyl group of the alkylating agent),
, m, n, and 2 have the same meanings as described above. (9) Consisting of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, the end of the pendant chain has a general formula (where W is a halogen atom, a hydroxyl group, or a hydrogen atom of a hydroxyl group, or a tri(lower alkyl ) A perfluorocarbon polymer having a substituted carbonyl group represented by a group substituted with a silyl group or an ammonium group, or a lower alkoxyl group, is a perfluorocarbon polymer having a substituted carbonyl group represented by the general formula (where R'', R'' and R3 have the same meanings as above). ), and the end of the pendant 1+ is reacted with a diamine represented by the general formula (wherein i', R'' and 2 have the same meanings as above).
This is converted into a structure represented by the formula (R'/R'/ , R1! and P represent the same meanings as above), and further reacted with an alkylating agent to form a main chain consisting of a perfluorocarbon polymer chain, which was bonded to the main chain. It consists of a pendant chain, and the end of the pendant chain has the general formula % (wherein R', R2, R', R'' and 2 have the same meanings as above. However, t is a group derived from an alkylating agent. R is the same as t when 11/ is a hydrogen atom, and R1/ is the same as R1/ when R11 is a lower alkyl group. A method for producing an ammonium-type polymer having OQ as a starting material, whose pendant chains have the general formula (wherein X, l, m, n, R', R2 and t
represents the same meaning as above. ) using a fluorocarbon polymer represented by the general formula (wherein X, R", R", R", R', l,
m, n and 2 have the same meanings as above. ) The manufacturing method according to claim 9, for obtaining an ammonium type polymer having pendant chains represented by: θ As a starting material, a linear perfluorocarbon random polymer whose main chain consists 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) Claim 9 or 10 to obtain an ammonium type polymer consisting of the same main chain by using a fluorocarbon polymer that is a chain.
Manufacturing method described in section. 0 Yagura As a starting material, the general formula (in the formula, The ratio is 97
A fluorocarbon polymer having a diamino group consisting of a repeating unit represented by No. 741 (with an average value in the range of 2 to 16) is used, and as an alkylating agent R'A (where t is a lower alkyl group, A represents a moiety other than the lower alkyl group of the alkylating agent) using a general formula (wherein X, R', R", R",
R', l, m, n and 2 have the same meanings as above. ) The method according to any one of claims 9 to 11 for obtaining an ammonium type polymer consisting of repeating units represented by:

Claims (1)

[Scope of Claims] (1) A main chain consisting of an ylfluorocarbon polymer chain;
It consists of a pendant chain bonded to this, and the terminal of the pendant chain has a general formula (wherein, R1, f(2, R3 and R4 represent a lower alkyl group. However, R2 and R3 together represent a tetramethylene group or An ammonium-type polymer represented by the formula (1-0) in which Z represents a counter ion of a quaternary ammonium ion. (2) The pendant chain has the general formula (wherein X is a fluorine atom, chlorine is an atom or -CF3 group, ! is an integer from O to 5, 1m is () or 1, and n is an integer from 1 to 5, but these numbers may be different for each dandent.Z, ■(1 , R2゜R3 and R4 have the same meanings as above.) The ammonium type polymer according to claim 941, n1-1. wherein p and q represent integers and the ratio p/q is in the range from 2 to 16. The ammonium type polymer according to item 1 or 2. (4) The main chain has the general formula % (where p' and q' each represent a number as an average value, and the ratio p / / q / is The ammonium type polymer according to any one of claims 1 to 3, which is a linear perfluorocarbon random polymer chain consisting of repeating units represented by (2 to 16 concave circles). (5) a main chain consisting of a perfluorocarbon polymer chain;
It consists of a pendant chain bonded to this, and the terminal of the pendant chain has a general formula (wherein R2 and R3 represent the same meanings as above, R1/
represents a hydrogen atom or a lower alkyl group. ) A fluorocarbon polymer having diamino groups represented by () is reacted with an alkylating agent, and this is made up of a main In consisting of a perfluorocarbon polymer chain, an R dund chain bonded to this, and a general Formula (wherein, R', R2, R3, R4 and Z have the same meanings as above. However, R4 is a group derived from an alkylating agent, and R1 is the same as R4 when R1/ is a hydrogen atom. and when R1 is a lower alkyl group, it is the same as R1/). (6) As a starting material, the dandant chain is one or more fluorine atoms, chlorine atoms, or -OF'groups;
R1', R2 and R3n have the same meanings as above. !
is an integer from 0 to 5; 1m is O or 1°n is an integer from 1 to 5; however, these numbers may differ from pendant to pendant. ) Using a fluorocarbon polymer having a diamino group having a structure represented by A manufacturing method according to claim 5 for obtaining an ammonium type polymer having pendant chains represented by (7) a main chain as a starting material having the general formula % (where p and q represent integers, and Ratio i is 2 to 1
Claim 5: Using a linear perfluorocarbon random polymer chain consisting of repeating units (within the range of 6), an ammonium type polymer consisting of the same main chain is obtained. The manufacturing method described in item 6 or item 6. (8) As a starting material, the general formula (wherein, , the ratio p'/q' is in the range of 2 to 16 on average), and as an alkylating agent, a fluorocarbon polymer having a diamino group consisting of repeating units represented by the general formula (wherein R4 is lower using an alkylating agent represented by the general formula (wherein X, R1, R2, R
3, R4, 1, m, n and Z have the same meanings as above); manufacturing method. (9) has a main chain consisting of a fluorocarbon polymer chain;
It consists of a pendant chain bonded to this, and the terminal of the pendant chain has a general formula (where W is a halogen protozoan hydroxyl group, a group in which the hydrogen atom of the hydroxyl group is replaced with a tri(lower alkyl/I/)silyl group or an ammonium group, or A perfluorocarbon polymer having a substituted carbonyl group represented by (representing a lower alkoxyl group) is reacted with a diamine represented by the general formula (in which H1', R2 and R3 have the same meanings as above). The ends of the pendant chains are converted into a structure represented by the general formula (in which R1/, R2 and R3 represent the same meanings as described above), and this is reacted with a reducing agent to form a main structure consisting of a k-fluorocarbon polymer chain. A fluorocarbon polymer consisting of a chain and a pendant chain bonded to the chain, and having a diamino group represented by the general formula (in the formula, R1/, R2 and R3 have the same meanings as above) at the end of the pendant chain, and further comprising: is reacted with an alkylating agent to form a fluorocarbon M (consisting of a main chain consisting of a combined chain and a pendant chain bonded to this, with the general formula (R1, R, R, R and 2 has the same meaning as above.However, R4 represents a group derived from an alkylating agent, and R1 represents R1 when R1/ is a hydrogen atom.
4, and when R1/ is a lower alkyl group, R1
is the same as ) A method for producing an ammonium type polymer, characterized in that it is an ammonium type polymer represented by: α [As a starting material, a fluorocarbon polymer whose dandant chains are represented by the general formula (in the formula, In the formula, X, R'', R2, R3, R4, j!, m, n
and Z represent the same meanings as above. ) The manufacturing method according to claim 9, for obtaining an ammonium type polymer having pendant chains represented by: αυ Starting material is a linear perfluorocarbon random polymer whose main chain consists of repeating units of the general formula %, where p and q represent integers and the ratio pA is in the range from 2 to 16. Claim 9 or 10 to obtain an ammonium type vehicle polymer consisting of the same main chain by using a fluorocarbon polymer which is a combined chain.
81. The manufacturing method according to 81. As a starting material, the general formula (wherein X, R1, R2, R3,1,m and J5;
'r: i:t: Represents the same meaning as above. p' and q' each represent the number as an average value, and the ratio p
A fluorocarbon polymer having a diamino group consisting of repeating units represented by //q / is in the range of 2 to 16 on average is used, and R'A (wherein R4 is a lower alkyl group) is used as an alkylating agent. (wherein X, R1, R2, R3, R4,1, m, D and Z have the same meanings as above) The manufacturing method according to any one of claims 9 to 11, for obtaining an ammonium type polymer consisting of a repeating unit represented by: