JPS619414A - Polyaminofluorocarbon polymer and its production - Google Patents

Abstract

PURPOSE:To produce the titled polymer useful as an intermediate for the synthesis of an anion exchanger of excellent durability, by reacting a specified fluorocarbon polymer with a reducing agent. CONSTITUTION:A fluorocarbon polymer which has a carbonamide group of formula I (wherein R<1> and R<2> are each H, a lower alkyl, or an amino group-containing alkyl and R<3> is H, or a lower alkyl, or R<1> and R<2> may be combined together to form an ethylene, provided that at least one of these groups is an amino group-containing alkyl and a is 2-5) at the terminal of a pendant chain bonded to the main chain comprising a perfluorocarbon polymer is reacted with a reducing agent (e.g., diborane) in an amount at least equivalent to that of the functional groups in the polymer to obtain a polyaminofluorocarbon polymer having an amino group of formula II at the terminal of a pendant chain bonded to the main chain comprising a perfluorocarbon polymer chain.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel nitrogen-containing fluorocarbon polymerization method. More specifically, the present invention relates to polyaminofluorocarbon polymers useful as synthetic intermediates for anion exchangers with excellent durability.

Anion exchangers, especially membrane ion exchangers, are used in fields such as electrodialysis, diffusion dialysis, and various batteries.
6. Conventional membranous anion exchangers are generally produced by introducing anion exchange groups into copolymers or polymer mixtures obtained by various combinations of hydrocarbon monomers through a polymer reaction.
A large fly is used.

However, conventional anion exchangers cannot be used under harsh conditions.
For example, use or swelling in the presence of chlorine, strong bases, etc.
Significant deterioration occurs due to repeated shrinkage. 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 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.

Ihi.

It is also known to make a durable membrane by surface fluorinating anion exchange membranes made of hydrocarbons (Japanese Unexamined Patent Publication No. 52-4489), but this method usually requires a sufficient degree of fluorination. Since this is difficult to achieve, 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 based on fluoropolymers, we found that anion exchangers with excellent durability Invented the body.

The present invention provides a polyaminofluorocarbon polymer that is useful as an intermediate for producing anion exchangers with excellent durability.

That is, the present invention consists of a main chain consisting of a fully fluorocarbon polymer chain and a pendant chain bonded to the main chain, and the end of the pendant chain has the general formula % (wherein a is an integer of 2 to 5, R' represents a hydrogen atom, a lower alkyl group, or an alkyl group having an amino group, W represents a hydrogen atom, a lower alkyl group, or an alkyl group having an amino group, and R3 represents a hydrogen atom or a lower alkyl group.

Further, W and W may be combined to form an ethylene group.

However, at least one of R' and R2 is an alkyl group having an amino group. ) A polyaminofluorocarbon polymer having an amino group represented by the following is provided.

In addition, in this specification, the pendant chain means a substituted or unsubstituted alkyl group, 4-fluoroalkyl group, or aromatic group, and even if a hetero atom or an aromatic ring is present in the carbon-carbon bond, good. In addition, an alkyl group having an amino group refers to one or more amine nitrogen atoms in the alkyl chain,
It preferably refers to an alkyl group having 1 to 5 alkyl groups, and specific examples thereof include the following structures.

CHt CHtN CHtCHtNMet , -C) (
tCI(tN”'a ”s NM”z.

H Takashi - CH, CH, N CH, CH, N CH, CH, NM
e, -CH,CH,CH,NPAe,.

HH Furthermore, this alkyl group having an amino group represents an integer of R4, and represents a hydrogen atom, a lower alkyl group, or an alkyl group having an amino group. 9. The polyaminofluorocarbon polymer of the present invention has a pendant chain having the general formula (wherein It represents an integer from 1 to 5, but these numbers may be different for each pendant chain. A, R', R' and W have the same meanings as above.) It is preferable to have a structure represented by the following.

The polyaminofluorocarbon polymer of the present invention is a linear perfluorocarbon random polymer chain whose main chain is represented by the general formula (where p and q represent numbers, and the ratio p/q is 2 to 16). It is preferable that

Further, the nitrogen-containing fluorocarbon polymer of the present invention has a general formula (where p' and q' each represent a number as an average value, and the ratio p'/q'#i is in the range of 2 to 16). (a, X, J, m, n, R', l? and R3 have the same meanings as above) is preferably a polyaminofluorocarbon polymer.

Examples of the lower alkyl group in the above general formula include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, S-butyl group, i-butyl group, t-butyl group, etc. can do. Examples of the polyaminofluorocarbon polymer of the present invention include polymers comprising the following repeating units.

Juboshi + + + + tenao
ΦThe nitrogen-containing fluorocarbon polymer of the present invention is a heat-resistant, acid-resistant, and alkali-resistant solid, and can be in the form of a flat film, a tube, a powder, or the like.

The nitrogen-containing fluorocarbon polymer of the present invention is not only useful as a durable weakly basic anion exchange membrane, but also has excellent durability by quaternizing its amino groups through the action of an alkylating agent. It can be converted into a strongly basic anion exchanger (hereinafter referred to as ammonium type polymerized polymer).

Examples of alkylating agents include methyl iodide, methyl bromide, bromide, n-propyl chloride, isobutyl bromide, n-butyl iodide, dimethyl sulfate, trimetheroxonium fluorogole). [(CHI).

0BF4],) ') Ethyloxonium flumeroborate [(C*H,), OBF, 3, trimethyloxonium hexachloroantimone) r-(CH
s)sO8bclt), methyl trifluoromethanesulfonate, methyl heptafluoropropionate, etc. can be used. In this case, methanol, ethanol, methylene chloride, chloroform, tetrachloride, etc. can be used as a solvent.

Here, if it is necessary to exchange the counter ion of the obtained ammonium type polymer, use Na(J) instead of the usual method.

This can be carried out by treatment with an alkali metal salt such as LiCA', LiBr+LiI+NaOH, KOH or Ni-8On.

Although the ammonium type polymer obtained by K process has some hydrocarbon groups, it has good chlorine resistance and
Excellent chemical resistance such as ethylenediamine resistance and solvent resistance. In addition, it is stable even after repeated shrinkage due to drying and swelling in a solvent, and is much easier to handle than conventional anion exchangers. Therefore, for example, membrane-shaped ammonium-type polymers can be used in applications that were difficult to use with conventional anion exchange membranes, such as diaphragms for organic electrolytic reactions, and membranes for various types of dialysis under harsh conditions. It is possible. It also has EfJ ability to be used in its proper form as a resin capable of anion exchange using quaternary ammonium groups in the coexistence of various solvents. It can also be used as a catalyst for cyanohydrin synthesis, a phase transfer catalyst (a), a halokenization reaction catalyst, and various other catalysts.

Furthermore, the ammonium type 1 complex in the form of a membrane can be used as a multitubular module in a space-saving dialysis device, and can also be used in a system for removing interfering anions in ion chromatography. As described above, the ammonium type polymer produced from the nitrogen-containing fluorocarbon polymer of the present invention has excellent durability, and therefore has extremely high industrial value.

It is already known that the heat resistance and chemical resistance of hepta-based polymers, particularly perfluorocarbon polymers, are significantly higher than those of general hydrocarbon-based polymers. However, the nitrogen-containing fluorocarbon polymer of the present invention and the ammonium type polymer produced therefrom have durability that far exceeds expectations, despite having hydrocarbon groups in the pendant chains. In other words, even though the main chain is stabilized because it is a perfluorocarbon polymer chain, under severe conditions it is inevitable that the hydrocarbon groups in the pendant chains will denature and decompose and the resulting detachment of functional groups will occur. Although it was expected, such deterioration is extremely rare in the ammonium type polymer derived from the fluorine-containing perfluorocarbon polymer of the present invention.

The polyaminofluorocarbon polymer of the present invention can be produced from a fluorocarbon monomer having acid amide groups.

That is, it consists 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, (in the formula, a, R', R' and R' represent the same meanings as above). A fluorocarbon polymer having a carboxylic acid amide group is reacted with a reducing agent to form a main chain consisting of a perfluorocarbon polymer chain and a pendant chain kneaded together. a, R', R' and R1 have the same meanings as above).

The beta/tant chain of the fluorocarbon complex having a carboxylic acid amide group used as a starting material in the method of the present invention has the general formula (a+X+R'+R'', R'+/, m+n+p and q have the same meanings as above). The main chain thereof can be exemplified by a linear perfluorocarbon random polymer consisting of repeating units represented by the general formula (in which p and q have the same meanings as above). An example of a combined chain is a general formula (in the formula a I X HR' r R' I R' +
1) m + n + p' and q' have the same meanings as above)) can be exemplified.

The fluorocarbon polymer having a carboxylic acid amide group used as a starting material in the method of the present invention can be subjected to the reaction in the form of a flat film, a Qi film, a fiber, a powder, etc. polyaminofluorocarbon polymers can be obtained in each corresponding form.

As the reducing agent, alkylaluminium hydride such as aluminum hydride, diisobutylaluminum hydride, lithium aluminum hydride, diborane, etc. can be used, but diborane is superior in terms of reaction efficiency. The diborane used can be generated, for example, by reacting sodium borohydride with a boron trifluoride ether complex, or various complexes of borane (such as dimethyl sulfide complexes and tetrahydrofuran complexes) can be used.

The amount of the reducing agent is generally an equivalent amount or more, generally in large excess, relative to the functional group in the starting material. The concentration in the solvent described later is about 0.001 to 5 molar, preferably 0.01 to 2 molar.

In the method of the present invention, the reaction proceeds smoothly in an ether solvent such as tetrahydrofuran, dioxane, or diethylene glycol dimethyl ether.

The amount of solvent used may be such that the fluorocarbon polymer having a carboxylic acid amide group to be used is sufficiently immersed therein. Of course, a larger amount may be used. Although there are no particular limitations on the reaction temperature, it is recommended to carry out the reaction by keeping it in the range of ice-cold temperature to room temperature in the early stage of the reaction, and then heating it to reflux temperature to 100°C to complete the reaction. preferable.

The fluorocarbon polymer having a carboxylic acid amide group used as a starting material in the method of the present invention consists of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to this main chain, and has a substituted carbonyl group at the end of the pendant chain. Polymers, for example, those with the general formula (in the formula, A carbonyl type, carboxyl type, silyl ester type, carboxylate type or lower alkyl ester type polymer represented by (. represents a group substituted with an ammonium group or a lower alkoxyl group), for example, a general It can be produced by reacting with an amine represented by the formula (in which a, R' + R" and rt" have the same meanings as above) to amidate it.

In this case, 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, a group in which the hydrogen atom of a hydroxyl group is replaced with an ammonium group is 0NI (4,
On (CHs)-.

ON (CJb C84)s, 0N(CHz C
H+)-, ON (CH+)-.

(2) (Means He, etc.) and forms a carboxylic acid ammonium salt by bonding with a carbonyl group (-C-').

As the amine represented by the general formula (1), -t□
□Intoxication diethylenetriamine/, triethylenetetramine, tetraethylenepentamine, N,N-dimethyldiethylenetriamine, di(trimethylene)triamine, N,N-dimethyldi(trimethylene)triamine, N,N,N'
, N'-tetramethyldi(trimethylene)triamine, N-ethyl-N-methyldi(trimethylene)triamine, N,N-dimethyl-tri(trimethylene)tetramine, N-(N',N'-dimethylaminopropyl)ethylenediamine, N Examples include -(N', N'-diethylaminoethyl)piperazine, N-(N', N'-dimethylaminepropyl)piperazine, and N-pyrrolidinoethyltriethelenetetramine. On this occasion,
A corresponding silylamine in which the hydrogen atom on the nitrogen atom in the above general formula O) is replaced with a trimethylsilyl group or the like can also be used in place of the above amine.

In this reaction, in order to improve the conversion rate of the reaction, it is preferable to use a silylating agent such as trimethylchlorosilane, 2-strimethylsilylacetamide, hexamethyldisilazane, etc. together with the e-amine represented by the above general formula fl+, and especially for the initial When using a silylating agent, it is preferable to carry out the reaction in the presence of a tertiary amine such as triethylamine or N-methylpyrrolidine.

Further, the reaction with these amines can be carried out in a liquid amine or using a solvent. In addition, ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, and diocane, hydrocarbons such as benzene, toluene, and hexane, and acetonitrile can be used as the solvent.

The reaction temperature varies depending on the type and shape of the raw material polymer, the amine used, etc., but is generally in the range of 0°C to 100°C.

The present invention will be described in detail below using Examples and Reference Examples.ii
,! 11. I will clarify. The term "amine type polymer" used herein means the polyaminofluorocarbon polymer of the present invention, and the term "amide type polymer" means a fluorocarbon polymer having a carboxylic acid amide group in the starting material. do. The terminal candy used in the same way is
It represents the terminal group of a pendant chain. In addition, unless otherwise specified, infrared absorption spectra mean transmission spectra, and the dyeing experiments were carried out using the following dyeing baths.

Crystal Violet: Crystal Violet 0
05% methanol solution Cresol Red: 005% methanol solution of Cresol Red Thymol Blue: Thymol Blue 00, 05% methanol solution Gromothymol Blue: 0.0 of Cromothymol Blue
5% methanol solution basic cresol red: 005% of cresol red
A solution prepared by adding approximately 1% of a 10% NaOH aqueous solution to a water-methanol solution.Basic Thymol Blue: A solution of approximately 1% of a 10% NaOH aqueous solution added to a 005% methanol solution of Thymol Blue.The electrical resistance of the membrane is 0.5N. After sufficient equilibration with a saline solution, the membrane was measured in a 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.
．． It was calculated using the Nernst equation from the membrane potential generated between the 5N saline solution and the 2.08 saline solution. Unless otherwise specified, the exchange capacity for nitrogen-containing copolymers was evaluated by drying the copolymer at 60°C for 24 hours under reduced pressure, and then measuring the chamber temperature content for elemental analysis. .

Further, the conversion rate was calculated from the nitrogen value in elemental analysis, assuming the exchange capacity of the raw material copolymer as 100%, and taking into account the change in equivalent weight due to a change in the end group.

Example 1 Under an argon atmosphere, the membrane obtained in Reference Example 8 was immersed in 27 ml of anhydrous tetrahydrofuran, and o.s.g of sodium borohydride was added thereto. Next, 1 ml of boron trifluoride ethyl ether complex was added dropwise to 5 ml of tetrahydrofuran shoulder solution over 30 minutes while cooling with ice water, and the mixture was stirred for 15 hours. Thereafter, the mixture was heated under reflux at room temperature for 30 minutes and further for 20 hours. The membrane was taken out, washed in methanol under heating under reflux for 15 hours, and then dried under reduced pressure at 60° C. for 24 hours to obtain a pale brown transparent amine type polymer membrane. In the infrared absorption spectrum of this film, the absorption at 1,720cm'' derived from amide carbonyl disappeared, indicating that reduction to an amine-type film had completely progressed.The conversion rate was calculated from elemental analysis values. I was disappointed,
It was about 74%. This membrane was not stained with crystal violet or basic thymol blue, but was stained red with cresol red, dark blue with bromothymol blue, and red-orange with thymol blue. The infrared absorption spectrum of the obtained film is shown in FIG.

Infrared absorption spectrum (cm-') 3300, 5
000~2760, 2360.1470~1440.1
350-950.840-480 This membrane consisted essentially of a copolymer consisting of the following repeating units:

Ken-CRCF, +-(-CF! CF juice-1'?
+ ・ ■ CF*CHtNH+CrutNH(C)I, squareNMet(
p', / q' is about 7.6) Example 2 Carboxyl type polymer M obtained by the method of Reference Example 1 (
7,5 cut) was crushed in 32 ml of anhydrous acetonitrile, and N,N-dimethyldi(trimethylene)triamine 4
．． 3 g of triethylamine, 3.7 ml of triethylamine, and 3.5 ml of trimethylchlorosilane were added thereto, and the mixture was heated at 80° C. for 113 hours under an argon atmosphere. The membrane was deposited, washed with ether, and then dried at 60° C. for 20 hours under reduced pressure to obtain an amide type polymer membrane. The infrared absorption spectrum of the obtained film is shown in FIG.

Infrared absorption spectrum (cm-') 3200.3000~2750,2370,1720°1630.1530.1470~1440,1375°1340~1030.990~960,840~490
This membrane consisted essentially of a copolymer consisting of the repeating units described below.

Under an argon atmosphere, the obtained membrane was immersed in anhydrous tetrahydrofuran 27d ffl, and sodium borohydride 05
g was added. Slightly boron trifufluoride ethyl ether complex 1
Add 50ml of tetrahydrofuran to 5ml of WI solution under ice water cooling.
The mixture was added dropwise over minutes and stirred for 185 hours.

Thereafter, the mixture was heated to reflux at room temperature for 30 minutes and further under VC for 20 hours.

The membrane was taken out, washed in methanol under heating under reflux for 15 hours, and then dried under reduced pressure at 60° C. for 24 hours to obtain a pale brown transparent amine type polymer membrane. This film has an infrared absorption spectrum of 1720 cm derived from amide carbonyl.
absorption disappeared, indicating that the reduction to the amine type film had completely progressed.

The conversion rate was calculated from elemental analysis and was approximately 81%. This membrane was not stained with crystal violet or basic thymol blue, but was stained red with cresol red and red with thymol blue. FIG. 6 shows the infrared absorption spectrum of the obtained film.

Infrared absorption spectrum (cm",) 3300.3000~2750,2375.1480~
1450.1340~960,840,780~490
This membrane consisted essentially of a copolymer consisting of repeating units as described below.

CF-CFy Example 3 The same operation as in Example 2 was performed except that the n-butyl ester type polymer membrane (Z5clit) obtained by the method of Reference Example 2 was used as the raw material membrane, and the amide type polymer membrane was used. An amine-type vehicle composite membrane was obtained. The infrared absorption spectrum of the obtained film matched that of the film obtained in Example 2.

This membrane consisted essentially of the same copolymer as the amine type polymer membrane obtained in Example 2.

Example 4 The same operation as in Example 2 was carried out except that the acid chloride type polymer membrane (7,5d) obtained by the method of Reference Example 7 was used as the raw material membrane, and amine was transferred through the amide type polymer membrane. A type polymer membrane was obtained. The infrared absorption spectrum of the obtained film almost matched that of the film obtained in Example 2.

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

Nozomiko Example 5 A carboxyl type polymer film obtained by the method of Tani Example 1 (7
, 5c++ is immersed in 16 ml of anhydrous acetonitrile,
N-(aminoethyl)piperazine 1.8 ml, triethylamine 1. qrni and trimethyl chloride 71
．． 8 ml was added and heated at 80'C for 96 hours under an argon atmosphere. The membrane was taken out, washed with ether, and dried under reduced pressure at 60' for 15 hours to obtain an amide type polymer membrane.

Infrared absorption spectrum (c, m-') 335 (1,3000-2750,2355.1750
~1680.1560~1510.1470~1430
゜1660～960. t150-480 This no-yield polymer was made up of a copolymer consisting of ten repeating units.

Under an argon atmosphere, the obtained membrane was immersed in 170M anhydrous tetrahydrofuran, and 3.0M sodium borohydride was added.
g was added. Next, 10 mA of tetrahydrofuran of boron trifluoride ethyl ether complex 6d! I-liquid ice water emperor 3
It was added dropwise over 5 minutes and stirred for 55 minutes. Then at room temperature 55
The mixture was heated under reflux for 21 hours. The membrane was taken out, washed in methanol under heating under reflux for 10 hours, and then heated under reduced pressure at 60°C.
The mixture was dried for 24 hours to obtain a light brown transparent amine type polymer film. In the infrared absorption spectrum of this film, the absorption at 1,750 to 1,680 cm derived from amide carbonyl disappeared, indicating that reduction to an amine-type film had completely progressed.The conversion rate was determined from elemental analysis values. As a result of calculation, approximately 8
It was 5%. This membrane was not stained with crystal violet or basic thymol blue, but was stained yellow with cresol red and pale orange with thymol blue.

Infrared absorption spectrum (cm"") 3370.3210.3j00.3000~2800°2370.1480~1440.1370~930°8
40-490 This membrane consisted essentially of a copolymer of the repeating units listed below.

Fe ■ CF3-CF CF=CHyNH-(CH-) N NH(p:/q:
is approximately 7.6) Example 6 Carboxyl type polymer membrane obtained by the method of Reference Example 1 (1
2 ffl) in 52 ml of anhydrous acetonitrile, 4.0 ml of triethylenetetramine, 3 pots of trimethylamine, and 5.5 ml of trimethylchlorosilane.

was added and heated at 80° C. for 96 hours under an argon atmosphere. The membrane was taken out, washed with ether, and dried under reduced pressure at 60°C for 20 hours to remove the amide type polymer membrane.

Infrared absorption spectrum (cm-') 350, 3000~2800, 2360.1750~
1700.1530, 1440.1360~960°8
50-490 This membrane consisted essentially of a copolymer consisting of the following repeating units:

exposure -H.

In an argon atmosphere (including a cross-linked product with some terminal amine groups), the obtained membrane was heated using 680 d of anhydrous tetrahydrofuran.
10 g of sodium borohydride was added. Next, it was added dropwise to a solution of boron trifluoride ethyl ether complex 20 in 20 ml of tetrahydrone run over 50 minutes on ice and stirred for 15 hours. Thereafter, the mixture was heated under reflux for 30 minutes at room temperature for 39 hours. The membrane was taken out, washed in methanol under heating under reflux for 10 hours, and then dried under reduced pressure at 60° C. for 24 hours to obtain a pale brown transparent amine type polymer membrane.

In the infrared absorption spectrum of this film, the absorption at 1750 to 1700 cm-' derived from amide carbonyl disappeared, indicating that reduction to an amine type film had completely progressed. As a result of calculating the conversion rate from elemental analysis values, it is approximately 44
% (taking into account the cross-linked structure).This membrane was not stained by crystalline (iolenide, basic cresol red, and basic thymol 7L), but it was yellow and thymol stained by cresol sifton. dyed orange by blue] Also.

Infrared absorption spectrum (cm-') 3400.3210, 2950.2B60, 70° 1610.1460. ．． 1370-930,850,8
10-490 This membrane consisted essentially of a copolymer consisting of the following repeating units:

C.F.

CFs CF Example 7 Carboxyl type polymer membrane (9
d) in 62-ml of anhydrous dimethoxyethane and 5.0 ml of triethylamine. 8.0 ml of di(dimethylaminepropyl)amine and trimethylchlorosilane4. y
ml and heated for 30 minutes at temperature under argon atmosphere for 90 minutes.
Heated at ℃ for 72 hours. The membrane was taken out, washed with ether, and dried under reduced pressure at 60° C. for 20 hours to obtain an amide type polymer membrane.

Infrared absorption spectrum (cm −' ) 3400~2600.2600~2500.1720~
1640, l540~1510.1500~940,9
00-480 This membrane, except for a portion of mesh, consisted essentially of a copolymer consisting of the following repeating units. “→CFt CF＊←
→CF, CF juice - f”!l Q20Ft CFs-Cp (p:/q: medium 65) Under an argon atmosphere, the membrane obtained above was immersed in anhydrous tetrahydrofuran 2yral, and sodium borohydride 05I
added. Next, a solution of 1 part of boron trifluoride ethyl ether in 3-tetrahydro7ran was added dropwise over 20 minutes on ice and stirred for 15 hours. Thereafter, the mixture was heated to reflux at room temperature for 60 minutes and then for an additional 20 hours.

The membrane was taken out, washed in methanol under heating under reflux for 15 hours, and dried under reduced pressure at 60° C. for 24 hours to obtain an amine type polymer membrane.

Extra-meth absorption spectrum (cm”) 5000.2700.2550~2300.1450~
930.870-460 Absorption around 1700 cm derived from amide carbonyl disappeared, indicating that reduction to an amine-type film had progressed completely.

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

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

0CRCH-N(CHw CHjCHxNMe鵞')x
(p:/q: !;65) Example 8 Carboxyl type polymer membrane obtained by the method of Reference Example 1 (9
d) in 52 ml of anhydrous dimethoxyethane, 7678 ml of di(dimethylamine propyl), 5.0 ml of triethylamine and 4.7 ml of trimethylchlorosilane.
was added at room temperature and heated at 90° C. for 72 hours under an argon atmosphere. The membrane was taken out, washed with ether, and then heated under reduced pressure for 6
It was dried at 0° C. for 20 hours to obtain an amide type polymer film.

Under an argon atmosphere, the obtained membrane was immersed in 27 ml of anhydrous tetrahydrofuran, and 05 g of sodium borohydride was added.
added. Next, boron trifufluoride ethyl ether complex 1
The mixture was added dropwise to 3 ml of tetrahydrofuran solution over 20 minutes on ice and stirred for 15 hours. Thereafter, the mixture was heated under reflux for 60 minutes at room temperature for 20 hours. The membrane was taken out and washed in methanol under heating under reflux for 15 hours, then heated under reduced pressure at 60°C for 24 hours.
After drying for a period of time, a transparent amine-type polymer film having a pale six-tone color was obtained.

In the infrared absorption spectrum of this film, absorption around 1700 cm-' derived from amide carbonyl disappeared, indicating that reduction to an amine type film had completely progressed. Conversion rate based on elemental analysis values)′? The result was approximately 57%. This membrane was not stained by Crystal Bioleft basic cresol red and basic thymol blue, but was stained yellow by cresol red and orange by thymol blue. FIG. 4 shows the infrared absorption spectrum of the obtained film.

Infrared absorption spectrum (cm-1) 2950, '2900 - 2750, 2380, 1460
1540-950, 840, 780-490 This membrane consisted essentially of a copolymer consisting of the following repeating units.

1←CRCFt←→CF*CF and- ・1G ■ CR CF glue-CF CRCHyN (C)h CHt9H*NMtt)!
(p:/q: is about 7.6) Example 9 Carboxyl type polymer membrane obtained by the method of Reference Example 1 (9
d) was diluted with 3 ml of anhydrous acetonitrile, and di(aminopropyl)methylamine 4. 4 ml, triethylamine 67
rnl and trimethylchlorosilane s. -s ml was added to ice water and heated at 80° C. for 94 hours under an argon atmosphere. After weaving the membrane and washing with ether, under reduced pressure,
It was dried at 60° C. for 20 hours to obtain an amide type polymer film.

The obtained membrane was immersed in 27 d of anhydrous tetrahydrofuran under an argon atmosphere, and 05 g of sodium borohydride was added. Next, add Hyousui Teio 2 to a solution of 1 ml of boron trifluoride ethyl ether 10TA in 5 ml of tetrahydrofuran.
The mixture was added dropwise over 0 minutes and stirred for 15 hours. Then at room temperature 60
The mixture was heated under reflux for 20 hours. The membrane was spun out and washed in methanol under heating under reflux for 15 hours, then heated at 60°C under reduced pressure.
The mixture was dried for 24 hours to obtain a light brown transparent amine type polymer film. As a result of this conversion, the absorption near 1700 cm-'' originating from the amide carbonyl disappeared in the infrared absorption spectrum, indicating that the reduction to the amine type film had completely progressed.The conversion rate was determined from the elemental analysis values. As a result of calculation, approximately 56%
(All values calculated as non-crosslinked type). This membrane was not stained with crystal violet or basic thymol blue, but was stained red with cresol red and deep orange with thymol blue.

Infrared absorption spectrum (cm”) 5200, 3000-2750, 2350.1490
~1430, 1360-930, 840-480 This membrane consisted essentially of a copolymer consisting of the following repeating units:

Ft CF Hatake-CF adhesion (contains some cross-linked product) Example 10 The film-like copolymer (50 cm) obtained by the method of Reference Example 5 was coated with anhydrous acetonyl l-IJ l 16
After soaking in 01111 and filling the same solvent in the tip, add 2.4 ml of triethylamine 1, N, N.
-dimethyldi(trimethylene)triamine 11.3ml
and 114 ml of trimethylchlorosilane were added thereto, and the mixture was heated at 90° C. for 72 hours under an argon atmosphere.

The Ticoob was taken out from JIy and dried at 60° C. under HHi to obtain a dupe-like amide type polymer. When the obtained chive-like amide type polymers were arranged and their infrared absorption spectra were examined, the spectrum almost matched that of the film obtained in Example 2. When the tubular polymer with a conversion rate of 78% oVtt was cut into width slices and examined for stainability with crystal violet, no staining was found.

The amide type car combination that makes up this team is essentially a CF unit.

忽FmCCF CFt CN+CH き+N+cut-)-NMetH
It consisted of sHs (p'/q':64).

The chevron-shaped amide type polymer obtained in the above reaction was immersed in dry diethylene glycol dimethyl ether under an argon atmosphere, and the chib was also filled with diethylene glycol dimethyl ether. Next, sodium borohydride was added (to a molar concentration of 0.053 molar concentration), and after stirring and cooling, a solution of boron trifluoride ether complex (dry diethylene glycol dimethyl ether solution per 0.62 mol of sodium borohydride) was added dropwise under water cooling.

The reaction was continued under cooling for 25 hours and then at 100° C. for 34 hours. When the obtained chip-like amine type polymer was washed with methanol and dried, and its infrared absorption spectrum was examined, it almost matched the spectrum of the thin film obtained in Example 2. Conversion rate 75%.

When the obtained chive-like polymer was cut into width slices to test its dyeability, it showed the same dyeability as in Example 2.

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

FsCCF CF-CJhN+CH*+ N+CI (= square NMetH
"I ("(p', / q: 64) Example 11 The powdered carboxyl type polymer (1.0 g) obtained by the method of Reference Example 6 was dissolved in anhydrous acetonate) 'BL (ff and triethylamine 9.3 m/,
N,N-dimethyldi(trimethylene)triamine 7
．． Add 5 ml and trimethylchlorosilane 855-
The mixture was heated at 90° C. for 80 hours in an argon atmosphere to obtain an amide type polymer. When the infrared absorption spectrum of the obtained powder was examined using a KBr disk, absorption derived from amide carbonyl was observed near 1700 cm''.Conversion rate 7
5%. The powdered polymer obtained was not dyed with Crimetal Violet at all.

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

RF, C-C11"sign CF, -C-N-+CrumasuN(C)hchiNM6H"H" (p:/q::65) Diborane was added to the obtained powdered amide type polymer. The reduction was carried out in the same manner as in Example 1, and a powdered amine type polymer was obtained by one-pass collection.The conversion rate was 72%.The obtained powder was used as a KBr disk and infrared absorption spectrum was obtained. When investigated, it was found that the absorption of amide carbonyl that existed near 1700 cm'' disappeared during photocombination.

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

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

Reference Example 1 (X!L material preparation example) Copolymer film obtained by polymerization [Nafion 125 (trade name) manufactured by Dupo 7, film thickness 125μ, 5O1H
The membrane was treated with 2N hydrochloric acid, converted into a sulfonyl chloride, treated with hydrogen iodide, and washed with alkali to form the membrane into a sodium carboxylate salt type. This membrane was treated with a 3.24N aqueous hydrochloric acid solution, washed with water, and dried under reduced pressure to obtain a carboxyl type polymer membrane. The structure of the pendant chains of this membrane is 0CFyCFOCFtCOy).

It showed strong carbonyl absorption at 1780 cm'' in the cuttle, and was stained blue by crystal violet.

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

Frame F-CFr) drunkenness-(CF’tCF箭 ■ C.F.

CF, -CF 70 FtCOt H (p:/q: is approximately Z6) Reference Example 2 (Raw Materials - Moon Production Example) Carboxyl type polymer membrane obtained by the method of Reference Example 1 (3
, 6i) in 10 ml of n-butyral:l:I-k, and after absorbing 176 g of chlorinated ice cream at room temperature, the mixture was heated to 65°C.
The mixture was heated for 65 hours. The membrane was taken out and dried under reduced pressure at 60°C for 24 hours to obtain an n-butyl ester type polymer membrane. This film showed strong carbonyl absorption at 1790 cm-'' and was not stained with crystal violet.

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

? F.

CFs CF CF, Co, C) I, ClCHjCHs(p:/q'
, is about Z6) & Example 3 (raw material preparation example) Ci'p ``'' CJ, 't and Cli'z = CF'0
CFtCP”0CFtCF*5Co-CFs with OyF A film using a polytetrafluoroethylene mesh as a support [Nafion 4 manufactured by DuPont]
Reference Example 1
A carboxyl type polymer film was obtained by processing in the same manner as above. This membrane was stained blue with crystal violet.

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

Thousand CF'2 CR+-I CRCF←- SQG C.F.

CFs CF CFtCO2H (p'/q' is about 65) Reference example 4 (raw material preparation example) CF92CFt and CFt ''= CFOCFt CF'
CF with OC1't CFt COtMe.

The copolymer obtained by copolymerization is made into a film [thickness: 50
μ, 5O3H exchange capacity: 095 mm/filtration: 1), heat treated in 324N hydrochloric acid, washed with water, and dried under reduced pressure to obtain a carboxylic acid film. The membrane consisted essentially of a copolymer also comprising the repeating units described below.

CFs -CF CRCRCOJI (p:/qF is about 64) Reference example 5 (raw material preparation example) CFy--CFt and CF, = CF-0-CF, -C
F-0-CFt-CFt-80, F Master CF.

The copolymer obtained by copolymerization with is made into a tube (inner diameter 0.625 myt, outer diameter 0.875 mm, SO, H equivalent exchange capacity 0.92 mm 17 mm/g dry resin), and then saponified, Furthermore, after treatment with 2N hydrochloric acid according to a known method, sulfonyl chloride treatment, then hydrogen iodide treatment,
After washing with alkali, the membrane was made 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 chive-like carboxyl type copolymer. The pendant chain structure of this copolymer was 10CR.
CF with CFOCRCOx'H.

be. This chive is 17 in the infrared absorption spectrum.
It showed strong carbonyl absorption at 80 cm'' and was stained blue by crystal violet.

Cheap consisted essentially of a copolymer consisting of the following repeating units.

C.F.

Replacement CF, -CF C1i''2CO2H (p:/Q: is about 64) Reference example 6 (raw material preparation example) (4Fy = CFt and CFs = CFOCFtCFOC
Copolymer powder obtained by co-CFs polymerization and saponification with FtCR5o-F [Nafion 511 (trade name) manufactured by Devon Co., Ltd., SO, H conversion capacity o, 91 milliequivalents/g, dry resin, potassium sulfonate salt [type] was hydrolyzed with 5N hydrochloric acid and converted to sulfonyl chloride by treatment with phosphorus pentachloride.

Then, hydrogen iodide treatment, alkali washing, and hydrochloric acid treatment were performed in the same manner as in Reference Example 1 to obtain a powdered carboxyl type polymer. This powdered polymer was used as an IG3r disk, and its infrared absorption spectrum showed carbonyl absorption near 1780 cm-', and was dyed blue by crystalline (iolet).

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

R CF, -CF CFICo-)1 (p:/q- is about 65) Reference Example 7 (Raw Material Preparation Example) The carboxyl type polymer membrane obtained by the method of Reference Example 4 was treated with phosphorus pentachloride-oxychloride. Phosphorus (weight ratio 1:1.6
) for 24 hours at 120°C. Furthermore, after washing in carbon tetrachloride, it was dried. This film showed a strong carbonyl absorption at 1800 Cm7' in the infrared spectrum. This film consisted essentially of a copolymer consisting of the following repeating units.

CFs CF' CF, CF, CC/ (In the formula, pl, /q/, are approximately 64.) Reference Example 8 Carboxyl type vehicle composite membrane obtained by the method of Reference Example 1 (7
, 5i) in anhydrous acetonitrile 231117! N-(dimethylaminoglobil)ethylenediamine 2
．． 8,9,) 2.7 ml of ethylamine and 2.5 ral of human+) methylchlorosilane were added and heated at 80° C. for 91 hours under an argon atmosphere. The membrane was taken out, washed with ether, and then dried under reduced pressure at 60° C. for 20 hours to obtain an amide type polymer membrane. FIG. 5 shows the infrared absorption spectrum of the obtained film.

Infrared absorption spectrum (cm-') 324111.5000-7750,2560,172
0°1620.1550~1520.1460~143
0°1360-960, 860-480 This membrane consisted essentially of a copolymer consisting of the following repeating units.

CF! ■ CFtCNH+C city+N+C1(*) NMe at
H3 (p'/q'= 7.6) Reference Example 9 (Usage Example) The membrane obtained in Example 1 was immersed in a 52 tnl solution of methyl iodide 8a/N,N-dimethylformamide at 60°C for 96 hours. It was heated to obtain an ammonium iodine type polymer film. Next, this membrane was immersed in a 10% lithium chloride methanol solution 4011/, and heated at 60° C. for 24 hours (the solution was replaced in the middle).

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

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

Infrared absorption spectrum (cm-') 3400.3050-2950,2560.1/+30
'.

1490~1450.1350~960,860~48
0° This membrane was stained yellow-orange with cresol red, red with basic cresol red, orange with thymol blue, dark blue with basic thymol blue, orange with bromothymol pull, and blue-green with basic bromothymol blue.

The obtained membrane had an ion exchange capacity of 1.0 meq/S dry membrane, an electrical resistance of 6.0 Ωd, and a transport number of 087. This desorption shows excellent durability especially under strongly basic conditions,
For example, no change was observed in the above values even when heated at 50° C. for 100 hours in ethylenediamine in the presence of ethylenediamine/hydrochloride.

On the other hand, a commercially available hydrocarbon-based anion exchange membrane immediately turned black and was destroyed under the above conditions.

This J daughter was fruitfully composed of a codono7 combination consisting of the following repeating units.

■ Fs Reference Example 10 (Usage Example) The membrane obtained in Example 2 was immersed in a methyl iodide 8-〇N,N-dimethylformamide 62III solution and heated at 60°C for 78 hours to form an ammonium iositotype polymer membrane. I got it. Next, this membrane was immersed in 40 d of a 10% lithium chloride methanol solution and heated at 60° C. for 24 hours (the solution was replaced in the middle).

Thereafter, it was washed in methanol at 60° C. for 8 hours to obtain an ammonium chloride type polymer film. The infrared absorption spectrum of this film is shown in FIG.

Infrared absorption spectrum (cm") 3600~3200, 3020, 2970, 2820°2350.1630.1490~1420.1330~
1040.990~960,840,740~490° This film turns yellow-orange with cresol red, dark red with basic cresol red, orange with thymol blue,
Black due to basic thymol blue, orange due to bromothymol blue, basic bromo anti is 1.0Ω d1 transport number is 0
．． It was 85. Even when this film was immersed in a chlorine-saturated aqueous solution at 60° C. for 1000 hours, there was almost no change in these values. 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.

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

→CF*CFt←BCRCF←- p4, qS Reference Example 11 (Usage example) The membrane obtained in Example 5 was immersed in a solution of 10% methyl iodide and 40% N,N-dimethylformamide, and was heated at 60°C. 120
The mixture was heated for a period of time to obtain an ammonium iodine type polymer film.

This membrane was then soaked in a 10% methanol solution of lithium chloride.
0- and heated at 60° C. for 24 hours (the solution was replaced halfway).

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

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

Infrared absorption spectrum (cm”) 36[)D~3150.3050~2300.l530
゜1490-950, 920, 790-480゜This film is yellow due to cresol red, yellow-orange due to basic cresol red, orange due to thymol blue, bluish-green due to basic thymol blue, orange due to bromothymol pull, and orange due to basic bromo. It was stained dark blue with thymol blue, and the presence of quaternary ammonium groups was confirmed. The obtained film had an electrical resistance of 32 Ωd and a transference number of 0.86. This film also showed excellent base resistance like the film obtained in Reference Example 9.

Reference Example 12 (Usage Example) The film obtained in Example 6 was treated with methiodide/L/101n1. N of
, soaked in N-dimethylformamide 4otd solution, 6
The ammonium iodine type polymer film (4) was heated at 0°C for 96 hours. Next, this membrane was immersed in 50 d of a 10% lithium chloride methanol solution and heated at 60°C for 24 hours (
(The solution was exchanged halfway through.)

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

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

Infrared 11. lλ yield spectrum (cm-″)) 730~3
100.3050~2850.2380°1680.1
．． 490-1450, 1400.1350-950.8
00-480° This film is yellow due to cresol red, brown due to basic cresol red, pale yellow due to thymol blue, blue due to basic thymol blue, and blue due to bromothymol blue.
The sample was stained yellow by the dye, and pale blue by the basic bromothymol blue, confirming the presence of quaternary ammonium groups. The electrical resistance of the obtained film was 12Ωd, and the transference number was 0.88.
Met. This film also showed excellent base resistance like the film obtained in Reference Example 9.

Reference Example 13 (Usage Example) The membrane obtained in Example 7 was immersed in 40 ml of a solution of 10-methyl iodide in N,N-dimethylformamide, and heated to 72°C at 60°C.
The mixture was heated for a period of time to obtain an ammonium iodine type polymer film.

This membrane was then soaked in a 10% lithium chloride methanol solution 4
The sample was immersed in 0° C. and heated at 60° C. for 25 hours (the solution was replaced midway through).

Thereafter, it was washed in methanol at 60° C. for 7 hours to obtain an ammonium chloride type polymer film.

Infrared absorption spectrum (cm”) 5500-3300.5050-2750.2370°1620.1510-1380.1330-900°7
80-480° This membrane was stained yellow with cresol red and blue with basic thymol blue. The obtained film had an electrical resistance of 4.5 Ωd and a transference number of 086. This film also showed excellent base resistance like the film obtained in Reference Example 9.

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

■ Reference Example 14 (Usage Example) The membrane obtained in Example 8 was immersed in a 40-solution of N,N-dimethylformamide containing 10 ml of methyl iodide, and heated at 60°C for 72 hours.
Heat for an hour and form ammonium iodine.

A combined membrane was obtained. Next, this membrane was immersed in a methanol solution of 10% lithium chloride and heated at 60°C for 25 hours (
(The solution was exchanged halfway through.)

Thereafter, it was washed in methanol at 60° C. for 7 hours to obtain an ammonium chloride type polymer film.

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

Infrared absorption spectrum (cm”) 3500-5200, 3030.2950.2580°1630.1480.1330-930,840°78
0-480° This membrane was stained yellow with cresol red and blue with basic thymol blue.

The ion exchange capacity of the 4I membrane is 0.76 meq/
The dry film had an electrical resistance of 36 Ωd and a transport number of 0.86. This film also showed excellent base resistance like the film obtained in Reference Example 9.

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

? F' Reference Example 15 (Usage Example) The membrane obtained in Example 9 was heated with 6d of methyl iodide and 24 mA of N,N-dimethylformamide! Immerse in solution and heat at 60℃ for 9
The mixture was heated for 2 hours to obtain an ammonium iodine type polymer film. Next, this membrane was immersed in a 10% methanol solution of lithium chloride, and heated at 60° C. for 45 hours (the solution was replaced in the middle).

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

Infrared absorption spectrum (cm-') 3600-3200.305'0,2950,2580
゜1620.1480,1350~940,790~4
70. .

This membrane was stained yellow with cresol red, red with basic cresol red, yellow-orange with thymol blue, dark orange with bromothymol blue, and deep blue-green with basic bromothymol blue. The electrical resistance of the obtained film is 60Ωis 'l'1iii ratio is 087.
It was. This film also exhibited excellent durability similar to the crotch obtained in Reference Example 10.

Reference Example 16 (Usage Example) The tubular amine type polymer obtained in Example 10 was placed in a solution of methyl iodide in N,N-dimethylformamide (volume ratio 1:4) and reacted at 60°C for 500 hours. . After washing the obtained tubular polymer with methanol, it was incubated at 60°C in a methanol solution of lithium chloride (128 molar concentration).
The reaction was allowed to proceed for 4 hours. This tubular polymer was heated to 60° C. in methanol to obtain the desired tubular ammonium chloride type polymer. The obtained tubular polymer is
In the staining test, basic thymol blue causes black color.
It was colored yellow-orange by cresol red, orange by thymol blue and bromothymol blue, and dark red by basic cresol red, confirming the presence of anion exchange groups.

The exchange capacity of the obtained chive-shaped anion exchanger was 13
Millimeter M/g dry resin.

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

This tubular copolymer consisted essentially of the following repeating units:

CF! F,C-CF Reference Example 17 (Usage Example) The powdered amine type polymer as expected in Example 11 was prepared by adding a solution of methyl iodide in N,N-dimethylformamide (volume tW ratio 1).
:4) and reacted at 60°C for 500 hours. After washing the powdered polymer with methanol, it was placed in a methanol solution of lithium chloride (128 molar concentration) at 60°C for 2 hours.
The reaction was allowed to proceed for 4 hours. This powdered polymer was heated to 60° C. in methanol to obtain the desired powdered ammonium chloride type polymer. The obtained powdered polymer was not stained with crystal violet in a dyeing test, but was colored black with basic thymol blue and yellow-orange with cresol red, confirming the presence of ion exchange groups.

The exchange capacity of the resulting powdered anion exchanger was 16 meq/g dry resin.

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

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

-(CF, CF specification -(CFtCF←- s + q'- CF tube CFs CF (p'/q' is about 66) Reference Example 18 Using Ja obtained in Reference Example 10 and Reference Example 13 Hydrochloric acid was electrolyzed using bamboo.For comparison, a commercially available hydrocarbon anion exchange membrane was also used.'[i-The solution conditions are as follows.

Membrane area: 96cr; Electrode: Platinum electrolyte; Anode/Cathode: 6N hydrochloric acid/6N hydrochloric acid Current density: 5A/dze The results are shown in Table 1.

Table 1 Membrane of Reference Example 10 1.0 1.40 Membrane of Reference Example 16 4.5 1.55 Commercially available membrane Approx. 2.5 14,

[Brief explanation of the drawing]

1, 3 and 4 are diagrams showing infrared absorption spectra of each example of the nitrogen-containing fluorocarbon polymer of the first invention, and FIGS. 2 and 5 are diagrams showing the infrared absorption spectra of each example of the nitrogen-containing fluorocarbon polymer of the first invention, FIG. 8 is a diagram showing infrared absorption spectra of each example of a fluorocarbon polymer having a carboxylic acid amide group used as a starting material, and FIGS. 6 to 8 show infrared absorption spectra of examples of fluorocarbon polymers having a carboxylic acid amide group, and FIGS. FIG. 3 is a diagram showing an infrared absorption spectrum of an anion exchanger. Patent applicant Sagami Central Chemical Research Institute Representative patent applicant Toyo Soda Kogyo Co., Ltd. a) 0 3600 3200
2eD02400 2000 1900 1800
1700 16■+500 1400 1300 12
00 1100 1000 900' eoo 7
00 600 500 400cm1'4000 36
00 3200 2&00 2400 2000
1900 1800 1f00 1600 15
001400 1300 1200 4100 1α
X) 900 800 700, 600
500 400 crn procedural amendment t1: November 30, 1980 Manabu Shiga, Commissioner of the Patent Office 1 Display of case 1982 Patent Application No. 130132 2 Name of invention Polyaminofluorocarbon polymer and its manufacturing process 6 Case of person making amendment Relationship Representative patent applicant address 1114560 Oaza Tomi, Shinnanyo City, Yamaguchi Prefecture 746
Address, phone number 4585) 3? , +1 6 Detailed explanation of the invention in the specification subject to the amendment 7 Contents of the amendment (1) In the 4th line from the bottom of page 41 of the specification, "(I/q't is approximately 64)" is changed to r (p' s/ (J's is approximately 6.4). (2) Correct the chemical formula on page 69, line 1 of the specification to M. (3) Correct the chemical formula on page 69, line 2 of the specification [(I/ Correct '16) in qr to [(go/7.6 in qr) J. (4) Correct the chemical formula in the bottom two lines of page 70 of the specification as follows. (5) Correct the last line of page 70 of Mei RI. Correct "R/I is approximately &5.)" to "[R/I is approximately 7.6)". (6) Specification, page 71, line 1o and page 72, line 12 [The infrared absorption spectrum of this film is shown in Figure. ” to be deleted. (7) The chemical formula on the last line of page 75 of the specification and the opening on the left side of the chemical formula [(脣/qf+7.6)” are corrected to “(go/yi+7.6)”.

Claims (11)

[Claims] (1) A main chain consisting of a perfluorocarbon polymer chain,
It consists of a pendant chain bonded to this, and at the end of the pendant chain there is a general formula ▲ a mathematical formula, a chemical formula, a table, etc. Alkyl group having an amino group, R^2
represents a hydrogen atom, a lower alkyl group, or an alkyl group having an amino group, and R^3 represents a hydrogen atom or a lower alkyl group. Further, R^1 and R^3 may be combined to form an ethylene group. However, at least one of R^1 and R^2 is an alkyl group having an amino group. ) A polyaminofluorocarbon polymer having an amino group represented by (2) The pendant chain has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, represents an integer from 1 to 5, but these numbers may differ from pendant to pendant. a, R^1, R^2 and R^3 represent the same meanings as above. The polyaminofluorocarbon polymer according to claim 1. (3) Linear pel whose main chain is represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. The polyaminofluorocarbon polymer according to claim 1 or 2, which is a fluorocarbon random polymer chain. (4) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, p' and q' each represent a number as an average value, and the ratio p'/q' is in the range of 2 to 16,
a, x, l, m, and n represent the same meanings as above. ) The polyaminofluorocarbon polymer according to any one of claims 1 to 3, comprising a repeating unit represented by: (5) a main chain consisting of a perfluorocarbon polymer chain;
It consists of a pendant chain connected to this, and at the end of the pendant chain there is a ▲mathematical formula, chemical formula, table, etc.▼ (In the formula, a, R^1, R^2, and R^3 represent the same meanings as above.) A fluorocarbon polymer having a carboxylic acid amide group represented by the above is reacted with a reducing agent, and this is made up of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to the main chain, and the end of the pendant chain has a general formula ▲. There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, a, R^1, R^2 and R^3 represent the same meanings as above.) It is characterized by being a fluorocarbon polymer having an amino group represented by A method for producing a polyaminofluorocarbon polymer. (6) As a starting material, the pendant chain has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (where x, l, m, n, a, R^1, R^2 and R^3
represents the same meaning as above. ) is used, and the pendant chain as a product has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula a, X, R^1, R^2, R^3, l, m and n
It means the same as above. ) A manufacturing method according to claim 5 for obtaining a polyaminofluorocarbon polymer represented by: (7) As a starting material, a linear perfluorocarbon random polymer chain whose main chain is represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, p and q represent the same meanings as above) The method according to claim 5 or 6, wherein a fluorocarbon polymer having an amide group is used to obtain a polyaminofluorocarbon polymer having the same main chain as the fluorocarbon polymer. (8) As starting materials, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, a, x, R^1, R^2, R^3, l, m, n
, p' and q' have the same meanings as above. ) using a fluorocarbon polymer having a carboxylic acid amide group consisting of repeating units represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, a, x, R^1, R^2, R^ 3, l, m, n
, p' and q' have the same meanings as above. ) The manufacturing method according to claim 5 or 7, for obtaining a polyaminofluorocarbon polymer consisting of repeating units represented by: (9) The method according to any one of claims 5 to 8, wherein the reaction is carried out in a solvent. (10) Claims 5 to 9 in which the reaction is initially carried out at room temperature or under cooling, and is further completed under heating.
The manufacturing method described in any of the paragraphs. (11) The nitrogen-containing fluorocarbon polymer having an acid amide group used as a starting material consists of a main chain consisting of a perfluorocarbon polymer chain and a pendant chain bonded to this, and the end of the pendant chain has the general formula ▲ mathematical formula, Chemical formulas, tables, etc. are available ▼ (In the formula, W represents a halogen atom, a hydroxyl group, a group in which the hydrogen atom of a hydroxyl group is substituted with a tri(lower alkyl)silyl group or an ammonium group, or a lower alkoxyl group.) A perfluorocarbon polymer having a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, a, R^1, R^2 and R^3 represent the same meanings as above.) The manufacturing method according to any one of claims 5 to 10, which is obtained by reacting and amidating the same.