JPS608309A - Nitrogen-containing fluorocarbon polymer and its production - Google Patents

Abstract

PURPOSE:To produce the titled polymer having tertiary amino group, and suitable as a synthetic intermediate of an anion exchange material having excellent durability, by reacting a specific perfluorocarbon polymer having a carboxamide group in the pendant chain with a reducing agent. CONSTITUTION:A fluorocarbon polymer consisting of a main chain composed of a perfluorocarbon polymer chain and pendant chains bonded to the main chain, and having tertiary amino group of formula II at the terminal of said pendant group, is obtained by reacting (A) a fluorocarbon polymer consisting of a main chain composed of a perfluorocarbon polymer chain and pendant chains bonded to the main chain and having carboxamide group of formula I (R<1> and R<2> are lower alkyl or together form tetramethylene or pentamethylene) at the terminal of said pendant chain with (B) a reducing agent such as sodium borohydride, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel nitrogen-containing fluorocarbon polymer. More specifically, the present invention relates to a nitrogen-containing fluorocarbon polymer useful as an intermediate for the synthesis of an anion exchanger with excellent durability.

Anion exchangers, particularly membrane ion exchangers, are used in fields such as electrodialysis.

Conventionally, membrane-like anionic exchangers (1) and copolymers or polymer mixtures obtained by various combinations of hydrocarbon monomers modified by polymer reaction have been used.

However, such conventional anion exchangers tend to deteriorate under severe conditions, such as when used in the presence of chlorine. Therefore, there is a demand for an anion exchanger that is less susceptible to 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 inorganic anion exchangers made of amphoteric metal oxides greatly depends on the hydrogen ion moisture content of the environment during use, and in some cases, the ion exchange ability may be reversed. happen. For example, hydrated zirconium oxide acts as an anion exchanger at pH 6 or lower, but conversely acts as a cation exchanger at pH 6 or higher. Furthermore, in the vicinity of neutrality, its ion exchange ability is hardly expressed. Therefore, the usage conditions of membrane anion exchangers containing such ion exchangers are extremely limited.

In addition, a method of making a durable membrane by fluorinating the surface of an ion-preventing membrane f made of a hydrocarbon system is also known (Japanese Patent Laid-Open No. 52-4489), but this method usually requires a sufficient degree of fluorination. Therefore, it is difficult to obtain a saturated ion exchanger having the desired performance.

The present inventors 1. took advantage of the excellent durability of fluoropolymers, and as a result of repeated research on the development of ion exchangers using fluoropolymers as substrates, the superior fc
We have invented an anion exchanger with long lifespan.

The present invention provides a nitrogen-containing fluorocarbon polymer useful as an intermediate for producing an anion exchanger with excellent durability.

That is, a main can consisting of the H Verfluoro tetracarbon polymer chain of the present invention, and a pendant bonded to the main can. 11 and its pendant) 171 has the general formula % (in the formula, R' and Hp are lower alkyl groups or R' and R1
This invention provides a nitrogen-containing fluorocarbon T1 aggregate f that cures a tertiary amine group represented by a tetramethylene group or a pentamethylene group formed by the following.

The nitrogen-containing fluorocarbon polymer of the present invention is:

The pendant chain has the general formula (wherein, or represents a pentamethylene group, m is an integer from 0 to 5, m is 0 or #''J1, n is an integer from 1 to 5, but these numbers may differ for each pendant). Preferably, it is made of

The nitrogen-containing fluorocarbon polymer of the present invention has a general formula (in which p and qFi numbers are expressed, and the ratio i is 2 to 1).
A powdery perfluorocarbon random polymer chain consisting of a repulsive unit represented by 6) is preferable.

Furthermore, the di-base-containing fluorocarbon polymer of the present invention has the general formula (wherein X, R' and R''t1 represent the same meanings as above,
m', m', and n' each have an average value of 0 to 5,
represents the number of mouth to l and l to 5, p' and q'
is a nitrogen-containing fluorocarbon polymer having a tertiary amino group, and is preferably a nitrogen-containing fluorocarbon polymer having a tertiary amino group, represented by PL, where the ratio p/q' is 2 to 16 on average.

The lower alkyl group of lζ1 and R' is methyl2! I
! l.

Examples include ethyl group, propyl group, and butyl group.

The nitrogen-containing fluorocarbon polymer of the present invention includes, for example, a polymer consisting of the following middle* repeating units.

vagina gift ・ l to C-CF ― h CF, CI to CF, C 几N (C hole inserted C)INN(CHI)1 ci to C bird C1(,N(C几Cl).

$ C1 finger/CI'% CF'5-CF 0 CF-C1%N (CI mountain p1 The nitrogen-containing fluorocarbon polymer of the present invention is a heat-resistant, acid-resistant, and alkali-resistant solid, and has a flat film shape and a naive shape. ,
It can be in the form of stones such as powder.

The nitrogen-containing fluorocarbon polymer of the present invention is treated with an alkylating agent to quaternize its t153 Aa amino groups. type polymer). For example, in the nitrogen-containing fluorocarbon polymer of the present invention, R'A (I represents a lower alkyl group, A is a halogen atom, -〇(1).

By acting with an alkylating agent represented by J3F4, -0 (R, 5bcls, representing a sulfonic acid residue, a carboxyl ridge residue, etc.), the pendant chain terminal structure is shown in the following formula (4) J! It can be converted into a long term.

In the formula, Z i, the counter ion of i ammonium ion, halogen anion, °old', 5bc4, sulfone ri °C in 1 °on, sonorubone tube: ゛2 ion tube is depleted.

As alkylating agent R'A, Si1, for example methyl iodide,
Ethyl bromide, n-propyl bromide, trimethyloxonium fluoroborate ((C1l,)A 0ISF4),
Triethyloginium fluorobole) (tct l
l5) aOBI+4-containing trimethycytrimethyloxozachloroantimonate ((CIIJsO8l)Cee),
Trifluoromethane sulfone "戊METHYL?", "i." can be used. At that time, methanol, ethanol,
Methylene chloride, chloroformo-tetrafluoride, and lambda charcoal can be used as solvents.

Here, if it is necessary to change the counterion of the ammonium type polymer according to qrh et al. .

Although the ammonium type polymer prepared in this way has some hydrocarbon groups, it has extremely excellent properties such as chlorine resistance and 1liI solvent properties. In addition, no change is observed even when wet and dry gas is turned over, and its handling is much easier compared to conventional anion exchangers.Therefore, for example, ammonium type 1n Regarding combination, in conventional 1-sen ion exchange BQpl, V: usage 1゛÷''g1t, for example, 4n iff, i'' for reaction reaction, 1 membrane,
It can be used as a crotch for various types of dialysis under severe 6L conditions. It can also be used in various forms as a handle fat that can perform anion exchange using quaternary heptadium groups in the coexistence of a moderate amount of solvent.

Also, tube-shaped ammonium π231 (combined fl t 1 r
, space-saving dialysis device 1' as a J-multiple Tr-shaped module
1", and can also be used in a system for removing interfering anions in ion chromatography. Unlike conventional cross-linked anion exchangers,
Since the anion exchange membrane 1 derived from the nitrogen-containing fluorocarbon polymer of the present invention is of a non-crosslinked type, it can sufficiently cope with changes in conditions during use.

The ammonium-type polymer produced by the nitrogen-containing fluorocarbon polymer of the present invention has excellent durability and therefore has a very high industrial value.

It is well known that fluorocarbon AS polymers, especially perfluorocarbon polymers, have significantly higher heat resistance and chemical resistance than general L-hydrogen polymers. However, the nitrogen-containing fluorocarbon polymer of the present invention and the ammonium type 1 polymer produced therefrom have durability that far exceeds expectations despite having hydrocarbon groups in the pendant chains. That is, since the main chain is a perfluorocarbon polymer 6'Af, the main chain kl
: Even if it is stabilized, it cannot be stabilized under a harsh oxidizing atmosphere.
Although it was predicted that the degeneration and decomposition of the hydrocarbon group in the pendant chain and the resulting detachment of the functional group would be inevitable,
In the case of the ammonium type polymer derived from 5 to 1,000 # of the fluorine-containing perfluorocarbon polymer of the present invention, the deterioration of the grains is as low as 2:2.

The nitrogen-containing fluorocarbon polymer of the present invention can be produced from a fluorocarbon offshore polymer having an acid amide group.

That is, the perfluorocarbon ■1 is composed of a main ffi consisting of a combined ftjl >, and a pentane dob bonded to this, and the pendant i''J''1 has a terminal Q::A with 1 -C-NR'R' (in the formula R1 and R2 has the same meaning as above) Calhoun expressed by Moriwasu)! A fluorocarbon offshore coalescence having f>4 amide groups is reacted with a reducing agent to form a perfluorocarbon ■i coalescence N? (consisting of a main body 61 consisting of It can be produced by preparing a fluorocarbon polymer having a tertiary amino group represented by the following formula.

In this method (hereinafter referred to as the method of the present invention), the starting material
(Pentane dob: 1 of (・71, general formula % formula % (in the formula
+ can be -, which exemplifies the group represented by ; (j, representing taste) in the above-mentioned cycle. Is it the main chain of the mackerel? , general formula %
The force is expressed by the formula % (1) and q &:l: rMI notation, same closure 1; fFIJ can be shown.

Dimensions are all 1, IZ is cut 3-, and the unit is a general formula (in the formula, X, IN', R2, p', 111', n', p' and C
It is possible to show the anti-19 unit expressed by the self-shozen enclosure (representing the A-yomi of Buku) by 1 ni.

The fluorocarbon polymer having carbonyl amide groups used as the starting material in the process of the present invention contains 314H%
The reaction can be carried out in various shapes such as shape, tube shape, ;). can be done.

As a reducing agent, suine, aluminum oxide, alkyl aluminum hydride such as diisobutyl aluminum hydride,
Water: ≦Thium aluminum chloride, diborane, etc. can be used, but in terms of reaction efficiency, the use of diborane (
5. The diborane to be used can be generated by, for example, reacting boron trifluoride ether complex with thorium borohydride, or borane's σitr□l; (such as dimethyl sulfide complex) can be used. can.

The amount of the reducing agent is generally 1.1° or more per 1 unit of the starting material Takenaka Kanzu. The degree of error in the solvent described later is about 0.05 to 5 molar concentration, preferably 0.2 to 2 molar concentration.

In the process of the present invention, the reaction t: proceeds in a nityl-based solution such as 1:1 tetrahydrofuran, 18-phosphorus, di:C ethylene glycol dimethyl ether, etc. 41,1:. (
'friff, ';', E;・JT]-r; is a fluorocarbon having one polybamide group!1[It is sufficient that the union is sufficiently immersed. Of course, even if there is more IJ than fj5i+ It's good. As for the reaction temperature, the phase difference l!1.: Although there is no fixed if, in the early stage of the reaction, the reaction is carried out by keeping it around p'111j1 of the ice-cooled pansocarbon i'1~chamber 'i1.?' , its τ!, Nico'l:; I) i(, IM
The reaction mixture can be heated to 100°C to 100°C.
1 and then fqtl.

Thu) 1', The fluorocarbon offshore body having an acid amide group used as the starting l proboscis in the method of Ming consists of a main f11 consisting of a perfluorocarbon offshore body and a pendant f:'l bonded to this, and the pendant end of the chain gj
1. Calhon j to 1, 2: r-Sternor j to FT'
″) 18 combination, for example Ij + ξ formula or CF.

-CF ■ () (wherein,
11 combinations of halocarbonyl type or ester ilJ represented by ±=mi or lower alkoxyl di, 1mi), for example, 1i2 (R' and d (2 represents extinguishing like fj 12 times) with the general formula INI) 1iIli can be obtained by amidation with .

Below, the pilot IJI will be explained in more detail with examples. I! I am able to explain. In the Examples and Reference Examples, the infrared 1-scale spectrum corresponds to the Group 311A spectrum. Cheerful Satoshi! The color, color, etc. are the results of tests carried out in methanol unless otherwise noted. 'I mij'?
x water n'' (AC 1000 N/L in liquid, temperature R (25
Measured at °C,) 1 ring ratio, 0,5 N
)suX71Water i7; ? 1! ξ and 2. Occurs between ON food and warm water solution = Ii: 'Nl the Nernst equation from the Miden can! lf1'3-2: I got J with what I did.

Length'Mlj ('r・111 Under the concave air of Alcon Valley, dissolve sodium boronitride in dry diethylene glycol dinotyl ether with water (0,
53 monozu:'>Urf) t,,substantially opposite to this (I414th CI?2 mock l i', C-CF (p'+/q+ 4□ 0-5) carvone [12 amide The type polymer 11q (the 1j side that was treated in Example 5, Example 1) was immersed. A dry diethylene glycol dimethyl ether solution of boron trifluoride trifluoride salt complex (water) (0.62 mol equivalent to sodium boronate: 1+i) was added dropwise under ice. By reacting for 5 hours under cooling and further at 100'C for 184 days, the 1 absorption at 1700cvr in the infrared Ql'r, 11''! spectrum disappeared, and the amine type polymer (terminal group -C112NMe, ) Once the reduction to the membrane has completely progressed, wash the membrane with methanol, dry thoroughly, and then determine its infrared absorption spectrum.

The obtained infrared absorption spectrum is shown in FIG. Conversion rate 8
8%.

Infrared absorption spectrum (Cm) 2970.2850, 2800.2360.147F)
~145"139 ri, 1350~1040,98
0,930,860°835.730,640~610
, 560-490° It was also found that the obtained amine-type 111 combined membrane was not stained by crystal violet ore 1 cresol, and it was found that ion 41 groups were not present at all in the membrane. Amine-type square combination r (
=dewo)ppC0 () CI et al. 1, C-CF (r':/'1: ・'=・6.5) Actually; 1 example 2 Repeat j14. An amide type polymer consisting of position C10 [F%C-Chi' (IIS/(2.9 in 1'2)]4'j (film obtained in Reference Example 2 described later) was used as an example. 1 and 4:J This method was used to reduce the amine type polymer film (S).The conversion rate was 95%.

The infrared absorption spectrum of the obtained film was obtained in Example 1.
t, almost coincided with that of the membrane, and the absorption based on amide carbonyl near 1700c+n completely disappeared by 7rj. The resulting membrane was not stained at all by crystal violet or cresol red.

This membrane actually consisted of a polymer consisting of the following repeating units.

C.F.

F', C-C11"(P'v/'q; middle 2.9) real nog B+ (9'I koi real 5°・'i, unit Ctan■ ii', c-er ' (ps/bow + 6.5) ry of a carbonaceous amide type polymer having a mesh support made of polybut-2-fluoroethylene, 1.
<By carrying out the amide type 71, which was prepared in Reference Example 3 described later, in the coalescence 11 series and the oxidation treatment of times 4 and p, the amine type 1 [1 coalesced film was transformed into the amine type 1 [1]. . Its infrared absorption spectrum is shown in Figure 2152, but at 1700 cm
The absorption around −' completely disappears.

Infrared 11゛) collection spectrum (ca-''): U200
+29 ri 0~27',)0.2400~2300
゜1440.1390.1300~920,720~4
The membrane obtained at 80° was not stained at all by crystal violet or cresol red.

The membrane consisted essentially of a polymer consisting of the repeating units described below.

C.F.

sCCF (6.5 in p', /q's) Example 4 For a carbon ridge amide type copolymer membrane similar to the membrane used in Example 3 (the membrane obtained in Reference Example 4), An amine type polymer film was obtained by carrying out the same operation as in Example 1 except that dry tetrahydrofuran was used as the solvent and the reaction temperature was set to its reflux temperature. The obtained membrane matched well with the membrane obtained in Example 3 in both its spectrum and dyeability, and was a polymer membrane consisting of substantially the same repeating units.

Example 5 The tubular amide type obtained in Reference Example 5 was prepared in dry diethylene glycol dimethyl ether under an argon atmosphere.
(Immerse the mixture and add diethylene glycol dimethyl ether into the tube. Then add sodium borohydride (at 0.53 mol Cal).
After stirring and cooling, a dry diethylene glycol dimethyl ether solution of boron trifluoride ether S (0.62 molar equivalent to sodium hydride) was added dropwise under ice cooling. .5 hours, then 100
The reaction was heated at ℃ for 21 hours. The obtained tubular amine type polymer (CHINMet) was washed with methanol and then dried, and the infrared absorption spectrum (f) was examined and found to be almost identical to the spectrum of the membrane obtained in Example 1.

Conversion rate 85ch. The resulting tubular polymer was cut into rings and tested for leprosy against crystal violet and cresol red, but no dyeing was found.

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

(-+C rebuttal is 7F size C.F.

- 1", C-CF (6.4 in P4/94) Example 6 The powdered amide type polymer obtained in Reference Example 6 was reduced with diborane in the same manner as in Example 1. , a powdery amine-type polymer (terminal group -Cklz
NMet) was obtained. This material was not stained with crystal violet or cresol red at all, and the conversion rate was 79%. When the infrared absorption spectrum of the obtained powder IKBr disk was examined, it was found that 1700 cm
The absorption of amide carbonyl that existed nearby had completely disappeared.

Infrared absorption spectrum (cm-') 3020~2780.1500~1460.1260~
1'200°1170~1120.1070.980.
930.865.

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

-E(-CF, C support layer 01 buttocks C.F.

F, C-CF (pS/q; Medium 6.5 N Reference Example 1 (yA material preparation example) Copolymer film obtained by polymerization [Nafion 114 (trade name) manufactured by DuPont, film thickness 100μ, sulfonic acid Converted exchange capacity 0.91mm! J equivalent % - 7g dry membrane] 2
After treatment with normal hydrochloric acid, it was converted into sulfonyl chloride, then treated with hydrogen iodide, and washed with alkali to obtain a carboxylic acid sodium salt form. The structure of the pendant chains of this film-like copolymer is 10 CF, CFOCF, CO, and Na. This membrane was mixed with 8N hydrochloric acid/methanol (-volume ratio 1=l
), hydrolyzed and esterified, and then treated at 120°C in phosphorus pentachloride/phosphorus oxychloride (weight ratio 1:1.6).
Heated for 24 hours. Thereafter, it was washed in carbon tetracarbon and dried. The obtained film exhibits strong carbonyl absorption at 180'Qcm in the infrared absorption spectrum. Also 2
Since there are absorptions considered to be derived from C-H absorption near 980.2880 and 1440 cm, most of the terminal groups of the pendant chains are -CO! A mixed-type g-coalescence film was obtained in which the film was M-containing and some ω0 groups were mixed therein.

This mixed polymer film was mostly composed of repeating units of b 1;', C-0F CFt Cue C1(s). The value of p:/QS was about 6.5.
Met.

In this way, the mixed polymer membrane prepared in step 1 was prepared by R in dry ether.
D't, and dimethylamine gas (1,3
Molar concentration) The reaction was carried out under cooling for 6 hours and at room temperature for 18 hours. 3-Heavy U water-methanol mixed solution (volume ratio 1:1)
After washing at 80°C for 5 hours and drying under reduced pressure overnight, a colorless and transparent amide type polymer 1 (terminal group -CNM(t)) was removed. Its infrared absorption spectrum f is shown in Figure 3. .

Infrared absorption spectrum (c+a) 3300.2950.2825-. 2360,1705
゜1500.1470.1410.1300-1100
．． 980°920.730.650~610.560~
600゜2950.1500~1410cx KC-H
Absorption due to amide carbonyl is observed at 1705c1n. In addition, the conversion rate calculated from the nitrogen value in elemental analysis was 92% with respect to So,i (exchange volume). It was found that no ionic group was present in tl:, :.

This membrane is mostly F2 1i', C-CF (p;/q; medium 6.5) It consisted of antisa units.

Reference example 2 (raw material preparation example) CF2=CI"2 and CF2-CF"0CF2 CF'0
CFt CF"2 C07CISs is a well-known CF.

The copolymerized cog polymer obtained by the method was made into a film (film thickness 110μ, C02H exchange γ1 exchange ratio 1.4
Milliequivalents/g dry film).

This polymer consisted essentially of the following antiwar units:

(EfCI et CI", size CF, 〒F size stomach F, C-CF 〇 F2 ch: -Co 2 CJ-I.

(pS/q'z'=□-2,9) Using this methyl ester type polymer membrane and dimethylamine, an amide type polymer (terminal Group-〇NMe, )
A membrane was obtained (conversion rate 95%). The infrared absorption spectrum of the obtained film almost matched the spectrum of the film obtained in Reference Example 1, indicating that the desired end group exchange was progressing efficiently. Note that the obtained amide type iH4 combined moon 4 was not stained with crystal violet or cresol red at all.

This amide'AM combination consisted essentially of the following repeating units:

Cao Xi F, C-CF' (2.9 in p;/q'2) Reference Example 3 (Raw materials: ar, l Example) C-Xun-CF, and CF, = CFOCF2CF'OC1 et al.
Copolymerized CF with F2SO2F.

Polydetrafluoroethylene made of polyethylene film used as a special holiday / ζ film [DuPont Nafion 41]
5 (trade name)] was subjected to the same treatment as in Reference Example 1 to obtain an amide type polymer film.

The infrared absorption spectrum is shown in FIG.

Infrared absorption spectrum (cm,) 3300.2950, 2750, 2380, 1690° 1500-1400.1320-950, 760-48
The membrane obtained at 0° was not stained at all by crystal violet or cresol red.

This membrane consisted essentially of a polymer consisting of the following antinuclear units.

(ps/q's 6.5) Reference Example 4 (FFA material preparation example) The same film used as the raw material in Reference Example 3 was treated with 2N hydrochloric acid, and then treated with sulfonyl chloride. and further treatment with hydrogen iodide. This was immersed in total methanol to form a methyl Nisder type 1p1 combined membrane, and further treated with methyl orthoformate for FIT to obtain a complete methyl ester type polymer membrane (a). This film was treated with dimethylamine in the same manner as in Reference Example 1 except that dry tetrahydrofuran was used instead of ether as a solvent, washed and dried to form an amide 1 type polymer (terminal group -CNM). , e2) Obtained clothes.Obtained/
This crotch is the crotch that was marked in reference Relly 3 and its spectrum,
Both the dyeability and dyeability matched well, and the polymers were practically composed of the same repeating units.

Reference Example 5 (Raw material preparation example) CF,=CF2 and CF2=CF-0-Cllia-CF-0-CF, □-CF'2-So□F0F.

The copolymer obtained by copolymerization with +1 is made into a tube (
Inner diameter 0.62521111, outer diameter 0.875 m*, 5
After the OsH equivalent exchange volume was 0.92 (IJ Naokage/zo dry resin), it was hydrolyzed. Next, after treatment with 2N hydrochloric acid, the polymer was converted to sulfonyl chloride, then treated with hydrogen iodide, and R'It was added to methanol to form the tubular polymer into a carbibone-coated methyl ester type. The pendant chains of the tubular ester type (1) obtained by this series of operations were converted into 10CF, CF-OCF, Co, and Me. This tubular ester type polymer of Fs was heated at 120°C for 23 hours in phosphorus pentachloride/phosphorus oxychloride (1:1.6), washed in carbon tetrachloride, and then Dry,
A tubular mixed polymer consisting mostly of ester groups and a portion of 1-tachloride groups was obtained. This polymer consisted of the following anti-iri units in terms of 7f.

F2 1i", C-CF ■ 0 II CF2-C-W'(p:/q'4: 6.4, W' represents a methoxyl group or a chlorine atom). The inside of the tube was replaced with dry diethyl ether. Dimethylamine gas was passed through this while cooling with water (1.3
up to molarity). After that, I decided to leave the room at home temperature for 6 hours at 19 ℃.
After reacting for an hour, aqueous sodium bicarbonate-methanol (volume 11
It was washed at 60° C. for 6 hours at a ratio of 1:1) and dried overnight under reduced pressure. When the obtained tube-shaped amide type polymer (terminated group -CNMeI) was arranged and its infrared absorption spectrum was examined, it almost coincided with the spectrum of the film obtained in Reference Example 1. Conversion rate is 90%.

The obtained tubular polymer was cut into rings and the dyeability to crystal violet and cresol red was tested.
There was no staining at all.

The amide parif 1<coalescence of this membrane is substantially reversed ∆! Unit CF.

3C-CF (P'4/qS: 6-4) It consisted of

Reference Example 6 (Raw material preparation example Coj1)2 combined powder obtained by saponification [manufactured by Devon Co., Ltd. Nafion 511 (trade name), SO, H equivalent exchange volume 0.91 mm Naochi/y dry resin, sulfone fermentation 3. Potassium salt type] was hydrolyzed with 5N hydrochloric acid and treated with phosphorus pentachloride. ! 1 to form a sulfonyl chloride. It was then converted into a carboxylic acid form by treatment with hydrogen iodide, and then absorbed in methanol to convert most of the carboxyl groups into methyl esters. A powdery methyl ester type polymer was obtained by further treatment with methyl orthoformate.

Infrared absorption spectrum (3) 2970-2860, 1800.1480-1415° 1280-1200, 11.75-1110.980,
840°780.740,635,555,510°-
This membrane consists essentially of repeating units CF.

■ F, C-CF 〇F, -cot　el(3 (ps/qchikiro, 5) It was a polymer crotch made of.

This powdered methyl ester type polymer was subjected to the same operation as in Example 1 in dry tetrahydrofuran.This product was not dyed with crystal violet or cresol red.
The conversion rate based on elemental analysis was 85. When the infrared absorption spectrum of the obtained powder was examined using a KBr disk, absorption derived from amide carbonyl was observed near 1700 m2.

Infrared absorption spectrum (cm) 2960.1710, 1410.1280~1200° 1170~1130, 1070,980,920,80
0°780.740,640,550,510° This polymer consists essentially of repeating units, CF.

h', c-CF book (ps/q'+ -F=6.5) It consisted of

Reference Example 7 (Usage Example) The amine type polymer obtained in Example 1 was placed in a methanol solution of methyl iodide (volume ratio 1:4), and the solution was heated to 48 °C at 60 °C.
Allowed time to react. After washing the resulting membrane with methanol, it was washed with lithium chloride in methanol solution (1.28 molar concentration).
The reaction was carried out at 60°C for 24 hours. This film was heated to 60°C in methanol, and a quaternary ammonium chloride copolymer film f! :Obtained.

The resulting membrane was not stained with crystal violet and red with bromocresol purple (
It was colored blue-purple in basic water) and yellow-orange with cresol red (red-purple in basic water), confirming the presence of ion exchange groups. The obtained infrared absorption spectrum of the crotch is shown in FIG.

Infrared absorption spectrum (cm) 3300, 3030, 2950, 2810, 2
350.

1640.1485.1415.1300~1060°980.925,840,740,650~600°5
However, the absorption of 3300.1640 cm is considered to be due to water in the membrane.The exchange volume of this anion exchange membrane is 0.82 mg equivalent/g dry membrane, electricity The resistance was 3.3Ωd% @ the rate was 0.87.This film was heated at 60℃
No change was observed in these values even after 1000 hours of immersion in a chlorine-saturated aqueous solution. 6 in methanol
After treatment at 5° C. for 48 hours, no change was observed even after the operation of removing the solvent under vacuum at 40° C. was repeated 5 times and once.

Reference Example 8 (Usage Example) The amine type t:I combined membrane obtained in Example 3 was subjected to the same treatment as in Reference Example 7 to obtain an ammonium chloride type polymer membrane. The infrared absorption spectrum is shown in FIG.

Infrared absorption spectrum (cln) 3250.2900, 2800.2400~2300° 1620.1470, 1400, 1300~900°7
50-500° However, the absorption of 3250.1620cIL is considered to be due to water in the membrane. By staining with cresol red in methanol, the entire layer except for the reinforcing material was uniformly dyed yellow-orange. The electrical resistance of the obtained film was 7.2Ω
d, the transport number was 0.90.

Reference Example 9 (Usage Example) The current-voltage curve in hydrochloric acid electrolysis using the pA obtained in Reference Example 8 is shown in (a) in FIG. The results obtained using a commercially available hydrocarbon thread anion exchange membrane are also shown as a comparative example (Figure (b)). The electrolysis conditions are as follows.

Membrane area: 9.6 d, electrode: platinum electrolyte; anode/cathode - 6N tower acid/'6N hydrochloric acid temperature; room temperature. Exchange membrane (father exchange capacity 9-1.3 milliequivalents/V
・Although its exchange capacity is smaller than that of dry membranes, its electrical resistance is comparable. In addition, despite the conditions in which chlorine was generated on the anode side and hydrogen was generated on the cathode side, an increase in membrane resistance and damage to the crotch were observed even in long-term IL tests, indicating that the product had a long life.Reference Example 10 (Usage Example) Implementation The tubular amine type polymer obtained in Example 5 was dissolved in a methanol solution of methyl iodide (volume 14 Jfs 1:4).
and reacted at 60°C for 500 hours. After washing the obtained tubular polymer with methanol, it was reacted in a methanol solution of lithium chloride (1.28 molar concentration) at 60° C. for 24 hours. This tubular polymer was dissolved in methanol for 6 hours.
The mixture was heated to 0°C to obtain the desired tubular ammonium chloride type polymer.

The resulting tubular polymer was dyed with bromocresol purple and cresol red in a dyeing test.
(in methanol), the presence of anion exchange groups was confirmed.

The exchange capacity of the obtained tubular anion exchanger is o,
so milliequivalents/V dry resin. 60 of this stuff
Even after being immersed in a chlorine-saturated 11 aqueous solution at ℃ for 100 hours,
No change was observed in this value.

Further, no change was observed even after treatment in methanol at 65° C. for 48 hours, and then repeating the operation of removing this solvent at 40° C. five times.

Reference Example 11 Usage Example The powdered amine type polymer obtained in Example 6 was placed in a methanol solution of methyl iodide (volume ratio 1:4) and reacted at 60°C for 500 hours. The obtained tubular 7J'7 aggregate was washed with methanol and reacted in a methanol solution of lithium chloride (1.28 mol'&'2 U) at 60°C for 24 hours. This tubular polymer was dissolved in methanol for 60 min.
C. to obtain the desired powdered ammonium chloride type polymer. The obtained powdered polymer was colored reddish-purple with bromocresol purple and yellow with cresol red (each in methanol) in a dyeing test, confirming the presence of anion exchange groups.

Infrared absorption spectrum (ffi-1) 3040~2820.1530~1460.1280~
1200°1170~1100,980,930,84
0,740°635.550,510°The exchange capacity of the obtained powdered anion exchanger is o, so
It was milliequivalent/g of dried yuzu butter. Even after this product was immersed in a 60° C. chlorine saturated aqueous solution for 100 hours, no change was observed in this value.

Also, after 65' in methanol and treated for 48 hours,
Even after repeating the operation of removing the solvent at 40"C five times, the change in FiF did not occur.

[Brief explanation of drawings]

FIGS. 1 and 2 are diagrams showing infrared absorption spectra of an example of the monotin-based fluorocarbon 7Tζ itself of the present invention, and FIGS. the law of nature! ↓This is a diagram showing the infrared absorption spectrum of a fully processed fluorocarbon polymer having a carboxylic acid amide group used as a binder. FIG. 7 is a diagram showing the infrared green absorption spectrum of the transmutant
The figure is from JO) Chin-containing fluthrocarbon produced by Ij9! FIG. 4 is a diagram illustrating the relationship between current and voltage when power is applied using f. ! 1 Permit Applicant: Representative of Sagami Chuoka Yosenkyu Nor Foundation q! J Applicant Toyo'v! Continued from page 1 of JDA Kogyo Co., Ltd. 0 Inventor: Yamato-type Chuorinkan 5, 16-4, late sowing 0 Inventor: Akira Akimoto, 1107-25 Edomari, Hofu City, 0 Inventor: Toru Kiyota, Shinnanyo City 591-0 Tomita, Oaza Inventor Hiroyuki Watanabe 972 Oaza Tomita, Shinnanyo City @ Applicant Sagami Central Chemical Research Institute No. 5, 1-4 Marunouchi, Chiyoda-ku, Tokyo Procedural amendment: 11 October 29, 1982 'l''j4'l Agency J, i1゛ Kazuo Wakasugi Tono1 !J+
Fl, Nokushi Showa 58 'tar ri'1r, +i No. 11606
2-jj2 Name of the invention a-Chip-terminated fluorocarbon polymer and its Hayabusa! ! 11
Bui '1J211, story Wjshi; (585) 5! +11
4 Amendment instruction 1'a; [ Spontaneous hli correct ■ 5 No increase in the number of inventions due to amendment ゛ , 13. Jl
, -6, Detailed explanation of the invention in the specification subject to amendment, Part 7, Contents of amendment (1) Re1, page 12, two lines from the bottom, ``...retired unit...'' was replaced with ``... ...Repeat unit..." is corrected. (2) In the fourth line from the bottom of page 18 of the specification, "...F-containing, tethered perfluorocarbon polymer" is corrected to "...F-containing, elemental perfluorocarbon bond." (3) On page e and izo of the specification, line 1, ``...the campon amide group...J'' is corrected to ``...the carbonaceous amide group...''. (4) On page 622 of the specification, in the second line from the bottom, change "...carboxylic ester group..." to "--placed carbonyl group..."
"..." I corrected myself. (5) Correct r (p'@/2.9 in Q'l)J in the last line of page 626 of the specification to r (p't/3.1 in Yumaka)J. (6) Specification F, page 329, line 3: “This crotch is essentially...
" is corrected to "This membrane is substantially... except for the mesh and shell parts." (7) Page 837 of details, 3 lines from the bottom r (p';/q'
Yo middle school 2.9) J to r (p'Q/ q'p, middle school 3.1)
J and δ stop. (8) Clarification 1γ) On page 3B, line 10, ``This membrane is ``substantially...'' is corrected to ``This membrane is substantially other than the mesh portion...''. Procedures Amendment Written by Kazuo Wakasugi, Commissioner of the Japan Patent Office, dated October 29, 19801, Indication of the case, Patent Application No. 116062, filed in 1982, 2, Name of the invention included, Elementary fluorocarbon polymer and process for producing the same, 3, Amendment Relationship with cases involving patent applicants (representative applicant) Address: 74 (
+4560-4 Tomita, Shinnanyo City, Yamaro Prefecture Date of amendment order Voluntary amendment 5 Number of inventions increased by amendment None 6 Subject of amendment (I) Detailed explanation of the invention in the specification (1) Description Column for a brief explanation of the drawings (!IF) Drawing 7, Contents of amendment (1) Column for detailed explanation of the invention in the specification (1) Specification 5
Add the following statement after line 4 on page o (after the end of Reference Example 11 and before the brief explanation of the drawings): Reference Example 12 (Raw Material Preparation Example) CP, : CP, and CF2 == Cli'OC'F,
eFOcF,OF,O Co-cp with O,F. Copolymer film obtained by polymerization [Nafion L25 (trade name) manufactured by DuPont, film thickness 125μ, exchange capacity in terms of sulfonic acid 0.834! J equivalent. The structure of the pendant chains of this film-like copolymer is 10 CF, CFOCFCO, Na and CF
. be. This membrane was washed with 8N hydrochloric acid/methanol (volume ratio 1:1).
) for hydrolysis and esterification, then phosphorus pentachloride phosphorus oxychloride (weight ratio 1:1.6)
℃ for 24 hours. Thereafter, it was washed in tetracyclized carbon and then dried. The obtained film exhibits strong carboxylic absorption at 1800c+q'''' in the infrared absorption spectrum. Also, 2 (1B0.2800 and Ul
4 4 There is an absorption near 0an-' that is considered to be derived from C-IL@ yield, so most of the terminal groups of the pendant chains are 1CO2Me groups, and some are 10oct groups. A type polymer film was obtained. This mixed polymer membrane consisted essentially mostly of the following repeating units: 7jゝ2 F, C-CF CF -CO Cll 1l3 (p's/q',, medium 7.6) Implementation f17 Mixed polymer membrane obtained in Reference Example 12 (9ctI) tt
The mixture was immersed in 30 ml of dry tetrahydrone, added with pyrrolidine 4-, and heated under an argon atmosphere for 44 hours. The membrane was taken out and dried under reduced pressure at 60 U for 20 hours to obtain an amide type polymer membrane. The infrared high yield spectrum is shown in FIG. Infrared absorption spectrum (crn-') 3400, 29
70.2890.27B0,2600.2360171
0~1680.1440.1340~1030,'9
80. 930,915,800~480°This film is substantially -(,cp・0"゛・)-total-(-〇F・CF);7.
-■ F2 (p/, /q/, medium 7.6) The membrane obtained above, consisting of a copolymer consisting of repeating units of 112, was treated with dry tetrahydrone run 2 under an argon atmosphere.
Sodium borohydride 10
Added 2. Next, boron trifluoride ethyl ether complex 2
Add 0ml of tetrahydrofuran 5d solution to 20ml under ice water.
The mixture was added dropwise over a period of minutes and stirred for 1.5 hours. Thereafter, the hind abdomen was heated under reflux for 65 hours and then taken out and washed with methanol under heating under reflux for 8 hours. The membrane was taken out and dried under reduced pressure at 60° C. for 20 hours to obtain an amine type polymer. In the infrared absorption spectrum of this film, absorption around 1700 F derived from amide carbonyl disappeared, indicating that reduction to an amine type film had completely progressed. The conversion rate determined from the nitrogen value in elemental analysis was 90%. Furthermore, the obtained amine type polymer film was not stained with crystal violet, cresol red, thymol blue, or bromothymol blue. FIG. 9 shows the infrared absorption spectrum of the obtained film. Infrared absorption spectrum (on"") 3230.2980-27 (io, 2370, 1465
, 1430.14.10,135 (1-1020,98
0,920.770~480° This film is substantially -(-CF'2CF',9w(CF'piece Fpsa-(p≦
/q'6, F7.6). Reference Example 13 (Usage Example) The amine type polymer membrane obtained in Example 7 was placed in a dimethylformamide solution of methyl iodide (volume ratio 1:4), and 6
The reaction was carried out at 0°C for 72 hours. After washing the obtained membrane with methanol, it was reacted in a methanol solution of lithium chloride (1,zs molar concentration) at 60C for 24 hours. A polymer membrane was obtained. In the staining test, the obtained membrane was not stained with crystal violet, but was colored yellow with cresol red (dark red in basic water), promothymol blue-orange, and thymol blue on the wound, confirming the presence of anion exchange groups. The infrared absorption spectrum of the obtained film is shown in Figure 10.
s 1300~950°930.840,780~4
80 (However, 3400.1630 is water absorption) Also, the exchange capacity of this anion exchange membrane is 0.72 ml J Toho/ri・
Dry membrane, electrical resistance is 5.4Ω0) 1.1m rate HO, aa
And ivy. Example 8 A mixed polymer membrane (16cm) obtained in Reference Example 12 was immersed in 30a1 of dry tetrahydrofuran, 4.96ml of diethylamine was added, and the mixture was heated under reflux for 120 hours under an argon atmosphere, and the P2-0 membrane was taken out. 2 at 60℃ under reduced pressure
After drying for 0 hours*h, an amide type polymer film was obtained. The infrared absorption spectrum is shown in FIG. Infrared absorption spectrum (an"') 3100~2670, 2500.1730~1610° 1480~1440.1415~1385.1350~
1'030.980,870,830,81.0~49
0° The membrane consisted of a copolymer consisting essentially of repeating units. The membrane obtained above was placed in 200 g of dry tetrahydrofuran under an argon atmosphere. Then, 10 tons of sodium borohydride was added. Next, boron trifluoride ethyl ether complex 20 II! A solution of t in tetrahydrofuran 5 ag was added dropwise in an ice water bath over 20 minutes, and the mixture was stirred for 1.5 hours. Thereafter, the membrane was heated under reflux for 65 hours and then taken out and washed in methanol under reflux for 8 hours. Take out the membrane and store it under reduced pressure.
It was dried at 0° C. for 20 hours to obtain an amine type polymer film. In the infrared absorption spectrum of this film, the absorption around 1700d-1 derived from amide carbonyl disappeared, indicating that the reduction to amine-type pus had completely progressed. Calculated from the value of nitrogen in elemental analysis: 60%
Met. Also, the obtained amine type polymer film beam. Not stained by listal violet. Obtained. Infrared absorption spectrum of the film (cm'''1) 36B0, 3400.29B0, 2950, 2900.
840. 780-490. This membrane consists essentially of c-CF. CI! +2 -1- Cp 2Cli'
-yi-1・t1 CF. It is made of a copolymer consisting of repeating units of (p';/' (1, ',, 7.6). Reference Example 14 (Usage Example) The membrane obtained in Example 8 was iodized. 'tfi & pickled in 100 4g solution of methyl 25- in dimethylformamide, 60
℃-c: 120 hours 1J heating to obtain an ammonium iodine type polymer film. This membrane was then soaked in a 10% methanol solution of lithium chloride 125*I! It was immersed in 4C and heated at 60°C for 24 hours (replacement of the melt 11 and 1). Thereafter, it was immersed in methanol and washed at 60°C for 1.5 hours to obtain an ammonium chloride type polymer film. This one was stained with Crystal Violet, yellow with Cresol Red, and orange with LeFleu 1C. The infrared absorption spectrum of this film is shown in Figure t^13. Infrared absorption spectrum <an″″) 3500-3250, 3000.2flOO, 23G0
. 1630, 1450, 13fiO=940,840,7
80-480. The ion exchange capacity of the obtained membrane is o. 4e mm weight/? Dry membrane, electrical resistance is 33.8Ω・I? J, transportation number is 0.91
Met. Like the film of Reference Example 3, this film also showed excellent chlorine resistance. This membrane is essentially (・cF', cF2 −)−(− CFQOF U−
It is composed of a copolymer consisting of anti-I units of A3-p'61 F2 (1/). (I) Column for a brief explanation of the drawings in the specification (1) On page 50, line 6 of the specification, change “Fig. 1 and 2 are of the present invention...” to “Fig. 1, Fig. 2, Fig. Figures 9 and 12 show the present invention.
"..." I corrected myself. 2) On page 50, line 8 of the specification, "...Figures 3 and 4 are of the present invention..." was replaced with "...Figures 3, 4, 8, and 11. This is corrected as "..." of the present invention. (3) On page 50, lines 11 and 12 of the specification, "...Figure 5 and the TTSA figures are of the present invention..." was replaced with "...Figure 5,
%61i, 1, Figure 10 and Figure M13ij of the present invention...
・” I corrected it. (6) Drawings (1) Add attached drawings (Figures 18, 119, 10, 11, 12, and 13). 8. List of attached documents (1) Added drawings Higashidori

Claims (9)

[Claims] (1) A main chain consisting of a perfluorocarbon polymer chain,
The end of the pendant chain bonded to this is a tetramethylene group or a benzene group formed by the general formula A nitrogen-containing fluorocarbon polymer having a tertiary amino group represented by (representing a methylene group). (2) The pendant chain has the general formula (in the formula, X is a fluorine atom, a chlorine atom, or a -CFs group, and R1 and R2 are a lower alkyl group or a tetramethylene group formed by R8 and a horse together) (1, , jii: an integer from 0 to 5, m represents an integer from 0 to 5; however, these numbers may differ from pendant to pendant) 1. The nitrogen-containing fluorocarbon polymer according to the first claim of the patent, which is a patent claim. (3) The main E'l represents the general formula (in the formula p and qiJ:!:S\number, and the ratio p/
Claim 1 or i1% 2 is a general perfluorocarbon random polymer m consisting of ashing units represented by q is 2 to 16 and R''< IUI.
'J(ffe f-nitrogen-containing fluorocarbon polymer. (4) General formula (wherein,
The tetramethylene group formed by the above also represents a 7-pentamethylene group, and l', m' and n' each represent a number from 0 to 5.0 to 1.1 to 5 as an average value. , p' and q' each represent a number, and the ratio p/q' is in the range of 2 to 16 on average).
The nitrogen fluorocarbon polymer described in any one of Items 1 to 3. (5) 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 1 -C-NR'R2 (in the formula R' and R2U lower alkyl group or UR' and R2
A fluorocarbon polymer having a carboxylic acid amide group represented by a tetramethylene group or a pentamethylene group formed together with a reducing agent is reacted with a reducing agent to form a perfluorocarbon polymer f1. Consists of a main chain and a pendant chain 1 connected to it,
A fluorocarbon polymer having a tertiary amino group represented by the general formula % (wherein R1 and Elementary fluorocarbon aqua [method of production of combination. (6) As a starting material, the pendant chain has the general formula
〇1 (In the formula, X represents a fluorine atom, a chlorine atom, or a -CFs group, and R' and R2 represent a lower alkyl group or a tetramethylene group or a pentamethylene group formed by R1 and R2 together, l is an integer from 0 to 5, m is 0
or 1, n represents an integer from 0 to 5, but these numbers may be J+ for each pendant), and using a fluorocarbon polymer having a carboxylic acid amide group as a product, the pendant tq is General formula (in the formula
, R', R2, 11, rn, and n have the same meanings as above). (7) As a starting material, the main lamp 1 has the general formula (in the formula p
is an integer from 3 to 15, and q is an integer from 1 to 10), the linear perfluorocarbon random polymer chain is a linear perfluorocarbon random polymer chain having an amide group, 7. The manufacturing method according to claim 5 or 6, which obtains a fluorocarbon polymer having the same main chain as the fluorocarbon polymer having a tertiary amino group. (8) Departure! General formula (in the formula
r゛ represents a group, 1<1 and R2 are a low-modified `λ alkyl group, or a tetramethylene group formed by n' and R2 being one star, or a phantom pentamethylene group. 4', a and n'it each represent a number from 0 to 5.0 to 1.1 to 5 with the average a11'j, and 7, 〆 and q' represent a number, and their ratio p7ct' is the average 2 in value
-9λ formula (in the formula, X, Iυ, R', J', m', n ′, p′ and q
8. The manufacturing method according to claim 5 or 7, for obtaining a fluorocarbon polymer having a tertiary amine group, which is composed of a platelet unit represented by (' represents the same meaning as above). (9) According to any one of claims 5 to 8, wherein the reaction is carried out in a solvent! , +V construction method. Claims 5 to 9 in which the αO) reaction is initially carried out at room temperature or under cooling, and further the reaction is completed under heating.
The manufacturing method described in any of the paragraphs. The nitrogen-containing fluorocarbon polymer having an acid amide group used as an αυ starting material consists of a main chain consisting of penfluorocarbon polymer #1'l and a pendant chain bonded to this, and the end of the pendant chain has a general formula (formula A perfluorocarbon polymer having a substituted carbonyl group represented by the general formula 1 formula % (wherein R' and R1 are lower thylkyl groups or R1 and R2
If the tetramethylene group formed by <
The production according to any one of claims 5 to 10, which is obtained by reacting with a secondary amine represented by "t" pencumesalene group 'f1: (represented by) and amidating it. Method.