JPS59211583A - Electrolysis and electrolytic cell - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides improvements in fluorinated ion exchange polymers, ttHff, for use in the form of films and membranes for use in chlor-alkali electrolyzers.

Fluorinated ion exchange polymers are known in the art. The fluorinated ion exchange polymer in such a membrane can be derived from a fluorinated precursor polymer that converts the dandant side 1) in the sulfonyl fluoride form. The sulfonyl fluoride functional group can be converted to the ionized form by various methods, for example, to the sulfone salt by hydrolysis with alkaline salts, to the sulfonic acid by acidification of the fluoride, and It can be converted to the sulfonamide by treatment with ammonia. Examples of such known methods are U.S. Pat. No. 3,282,875;
No. 99 and No. 3.849.243.

Such polymers and membranes exhibit many desirable properties, such as good long-term chemical stability, which make them attractive for use in the harsh chemical environments of chlor-alkali electrolyzers. Although I have
Especially when producing caustic alkali at high lI and 4 degrees,
Their current efficiency is not as high as desired. As the transport of hydroxyl ions across the membrane from the catholyte to the anolyte in a chlor-alkali electrolyzer increases, the current efficiency decreases. Thereby a relatively large amount of r in the chlorine
at: 4□:, impurities are created and relatively large amounts of chlorate and hypochlorite contaminants accumulate in the brine;
In order to maintain acceptable operation of the electrolyzer, this 1° contaminant must be removed and disposed of. A current efficiency of at least 90 C is highly desirable, L2L)8
Thus, the electric current jW 4' at high current efficiency; 1. H
1.1: ′! There is a need for polymers and membranes that enable operation at high efficiencies over long periods of time, particularly for long-term operation at high efficiency.

111. Herein, it is defined as either the ionic carboxyl form or the ionic sulfonyl and ionic carpoquinyl forms; 111.・.

Fluorinated ion exchange nail combination containing
However, it has been found that it is possible to make it using a method that has high current efficiency.

According to the invention, more particularly the repetition [2 unit [\γ(
Here, n is 1 or 2, p is 1 to 1O, q is 3 to 15, r is 0 to 10, S is 0, 1.2, or 3, and X is Collectively, it is 4 fluorine or 3 fluorine and 1 chlorine, 17 pabaF-: tyoCfi "1,)' is p's
Upper is CI・, Z is F-still is CI''', L), 1' is -COO/71-ma/ζ is -(, N,)?
1 is l! , lower alkylgo t υ-l i/ (-t)
Adashi, is R2 l? , Ct t ;/Crush 1, with OR3-C,
R3 is // straddle AI (-,) 1, M is alkali metal 3, alkali IJ 10tJ, gold 1p1 ammonium or quaternary ammonium, and t Id is the valence of "+f) A polymer having the following is provided.

Furthermore, according to the present invention, -OCL'2Cノ・'7 COO
I"No.

(Here, R1 is H, AI (1) is ρ), M is alkali metal, alkaline earth gold}11 East ammonium or quaternary ammonia l, and t is the valence of AI. ) contains a pendant side chain with <11 +it ift: +it ift
A fluorinated ion-exchanged tR composite film or material is provided.

The fluorinated ion exchange polymer in the film or membrane more particularly comprises repeating units (where n is 1 or 2, p is 1-10, q is 3-15, r is O~10, S is 0, 1, 2'!: is 3, X is 4 fluorine or 3 fluorine and 1 chlorine, //' is F or C 's'3, )' is F or CF, Z is F-selected CF, R1 is I11 lower alkyl or AI (〒), R2 is F, C1 or OR3 , (i) IA3 is H or /l/(t), M is an alkali metal, alkaline earth metal, ammonium or quaternary ammonium, and t is the valence of A4).

Ion exchange membranes composed of polymers of the present invention containing both ionizable carboxyl, flexible or ionizable carboxyl and sulfonyl groups as active ion exchange moieties are different from conventional ones due to several notable reasons. The technology of ion exchange 11 is preferable for iM+ Ii- compared to iM+ Ii-. Most importantly, the film of the present invention exhibits superior efficiency in chlor-alkali surface formation compared to similar structures containing only sulfonic acid ion exchange groups obtained by hydrolysis of pendant sulfonyl groups. , tlj4 and a laminated structure. This improvement is believed to be of great importance in industrial applicability in that it reduces the production costs of chlorine and caustic per unit.

For example, in a chlor-alkali T field producing, say, 1000 tons of chlorine per day, the direct savings in IL power due to an efficiency gain of only 1% can have extremely significant implications. .

The technologically advanced polymers of the invention are distinguished by their outstanding stability towards caustic alkalis. For example, the polymer of the present invention has a carboxyl group of 10CP'2C
OOI? It is significantly more stable to caustic than similar polymers present as pendant side chains terminated with groups.

The existing 1-tank electric fα chamber, which has been used for 10 years without any substantial improvement in design, can now be used. In order to protect against chlorine-alkali electrolyzer environments, where the need for improved ion-exchange materials has grown tremendously in the chlor-alkali industry, membranes must be What?
It must be made of materials that can withstand application and exposure to harsh environments. Hydrocarbon ion exchange membranes generally cannot withstand this environment and are therefore completely inadequate for this type of application.

For industrial use in Liaoyuan-alkali industry,
The film must have a certain strength so that it can be used for long periods of time in the production of chlorine and caustic. IIX is also an important group for the conversion of heavy water into desired products in electrolysers. +ti) efficiency. The direction of current efficiency is 1 - the raw power of salt and caustic per unit: f! 2. It can bring about a significant reduction in cost. From an industrial standpoint, the manufacturing cost of a product of unit equivalent υ is a factor that determines the industrial response of ion exchange. a carboxyl group, both a carboxyl group and a sulfonyl group, attached to a carbon atom that binds at least one fluorine atom to
1.

The ion-exchange polymer of the present invention having a pendant containing carboxyl groups, but still both carboxyl and sulfonyl groups, has a general protrusion property as 1. h-toe f'
, I', chant <": alkaline earth, W14!'+, 1-ri l! 1 multiplicity of Densaku f4, and /) It forces the molecule to jump / ζ Film 7° moss 11"
When used as a stand-alone solution, the polymer preferably has a total ion exchange capacity of 0.8 to 113 mm/i'. 7' + Q and r in the L formula for the copolymer should be used as an ion-exchange barrier in the ELECTRON 1 kitchen tank.
500.1: Exposure periods must be selected to have an equivalent weight of heavy water not too large. The resistance of the film resistance U and λ becomes too high for practical use in electrolytic cells.
p: varies somewhat depending on the thickness of the film; for most purposes, values of no greater than about 1500 are suitable for films of typical thickness.

The polymers of the invention can be made by copolymerization of a mixture of suitable monomers. The xyl-containing monomer has the formula % (VVi-COOR' is still -CiV, t?+hat
t, lower alkyl size is M(7), 4(+d is alkali metal, alkaline earth metal, ammonium or quaternary ammonium, t is the valence of AI, II'' is F' or CF3 and Y is F is CF, and n is 1 and is 2).

The most preferred monomers, which may be larger or larger compounds, are those in which j/ is -t'00 R+, where 7S' is // -Madaha (1(-)-grade alkyl, generally C'1 to Preferred because it is easier to mock.

V is -COOJ? I, where R1 is I (class alkyl monomer is /), C,! No. 789,724 by 'ngland. These compounds are C1"2=, ('FOCF2CFOCF, CF, C00
Ctm, and Hibiki CP.

H(,'F2=C' FO(CF, C' FO) 2
C'Neu゛2C''F2C00c, tl 3.

CF3 and its manufacture is described in the above-mentioned patent.

Corresponding yliν! The 1t carvone limb is a particularly useful monomer.

The production of monomers in which V is CIV is carried out by the United States!
It is written in ¥f revision 3.854326.

The first group of carboxyl-containing monomers includes, for example, vinyl fluoride, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro-(alkyl vinyl ethers).
, one or more fluorinated vinyl compounds from the second group, such as tetrafluoroethylene and mixtures thereof. In the case of a copolymer used in a salt 41-ion odour, it is desirable that the precursor vinyl monomer (r) does not contain hydrogen.

Optionally, together with the first and second group of monomers, sulfonyl shoulder-containing monomers containing the precursor group -CF2-CF, -502A (where A is 1' or C1, preferably L') I deplore the inclusion of one or more items from a third group. Other rules are the general formula CI"2=CI"-Tk
-CP'2502F', where Io is a difunctional fluorinated group consisting of 1 to 8 carbon atoms, and nρ is 0 or 1. Although the specific chemical content or i, lJ structure of the group 1 is not limiting,
However, the group T must have a fluorine atom attached to the carbon atom to which the -c p2SO,p group is attached. Other atoms attached to this carbon include fluorine, chlorine or hydrogen, and ion exchange copolymers are used in salt-o-alkali electrolysers. In the case of 173, hydrogen is generally excluded. - The 7' group in the above formula can be either branched or unbranched, i.e. directly, and can have one or more ether linkages. ~ru. The vinyl group in this group of fluorinated sulfonyl-containing comonomers is attached to the 7' group via an ether linkage, i.e. the comonomer has the formula CF?
:=C'F-(27'-CF, -502F. Examples of such sulfonyl fluoride-containing comonomers are: CF, -C
'FO(,'F, CI+', So, F.

CF −CFOCF2C′FOCF,, CF”2S
O2F”.

m- 'tcF CF,　　　(,’　F.

CII'', , -C'/l'CF, CF, 502F
, and CP'2=CFOCF2CFOCF2CF,S
o, P'■ C12 1' ゛ I C'F.

A very suitable sulfonyl fluoride-containing comonomer,
-Fluoro(3,'6-thiokizer 4-methyl-7
-octensulfonyl fluoride), C'P', =
CP'OCI? ,, CFOC'F2CF25 O,I
l', theal. S C'L''.

Sulfonyl-containing monomers can be used, for example, in U.S. Pat. ? No. 18.627 and No. 3.5611.
It is described in documents such as No. 568-.

The copolymers of the present invention can be prepared by the general commercial methods developed and used for the homopolymerization and copolymerization of fluorinated ethylene, particularly those used for tetrafluoroethylene as described in the literature. can be manufactured. A non-aqueous method for making the copolymers of the present invention is the method of U.S. Pat. No. 3,041,317, namely:
In the presence of a 4-group initiator, a 4-group initiator, a fluorocarbon + an azo compound or an azo compound, IJ at 0 to 200 °C, the draft rate of the group and 1 to 2
It includes processes by polymerization of mixtures of the desired component monomers at pressures in the range of 1,000 atm or higher.

Non-aqueous polymerizations can also be carried out in the presence of fluorinated solvents, if desired. Suitable fluorinated solvents include inert liquid fluorinated hydrocarbons such as A-fluoromethylcyclohexane, perfluorosomethylcyclohexane, fluorooctane, perfluorobenzene, etc. and, for example 1,
An inert liquid chlorofluorocarbon, such as 1,2-trichloro-1,2,2-trifluoroethane.

1. ”)・11 lfl:, 1, which can be made by using the aqueous polymerization method, 1, which can be produced by using the aqueous polymerization method, and 1 (21j method 1r of yarn)
Slurry of non-water-wet IF polymers by contact of monomers with aqueous wedges having a base initiator as described in United States Patent No. 2.393.967. 11' Acquisition of N granular military combination, trench, and no 1', United States Patent 2.559.7524 Atsushi 1ii12.59', <.

583, by contacting the monomer with an aqueous medium containing both free radical initiation and a telochemically inert dispersing agent. 1'I - Obtaining an aqueous colloidal dispersion of coalesced particles and coagulating the dispersion, all encompassing.

The polymers of the invention can be processed into films and +11q.

When using the polymer in film form <'F, j15
Usually 0.05~05 dragon (0,002~0.02 inch)
Use a desired thickness of approximately . Excessive thickness of the film helps to obtain relatively high strength, but has the disadvantage of increased electrical resistance.

The term "membrane" refers to a non-porous structure, which may have layers of different materials formed by surface modification of the film or by lamination, used to separate the chambers of an electrolytic film cell. objects, and structures having a support, such as an embedded fabric, as one layer.

According to the invention, substantially all of the pendant side chains (i.e., 90π' or more)'! , the entire length (i.e. 99-100%) is in the carboxyl form throughout the structure, and the dandant side/lJ (throughout the structure, e.g.
It is possible to produce films and membranes in the carboxyl and sulfonyl forms of 10 to 909 g each. Control in this regard is made by selecting the mixture of monomers used during the polymerization.

Similarly, it is possible to produce products in which various other functional groups are present in the pendant side chains in combination with carboxyl groups in other pendant sides 611. For example, if the precursor polymers contain sulfonyl halide groups, they can be treated with water, caustic, or other reagents such as ammonia or primary amines, thereby removing the sulfonyl groups. It can be converted into a sulfonic acid group or a salt thereof, or a sulfonamide or even an N-substituted sulfonamide group. The group in the precursor polymer is replaced by -(so2NR)mQ
(where Q is H, Ni14, an alkali metal cation and/or an alkaline earth metal cation, and m
is the valence of Q).
It is written in No. 99.

Suitable definitions for Q include NH4 and/or alkali metal cations, especially sodium or potassium. A method by which the sulfonyl groups of the precursor polymer can be converted to N-monosubstituted sulfonamide groups and salts thereof is described in US Pat.

In order for the final film or membrane to have as low an electrical resistance as possible, substantially all of the carboxyl and sulfonyl groups in the polymer must contain active cation exchange groups.
That is, it is preferably either a carboxyl or sulfonyl group that ionizes or forms a metal salt.

In this regard, it is important to note that the film or membrane to be used in the electrolyzer has a neutral layer; It is extremely light to have one.

The films and membranes of the present invention do not have a neutral or anion exchange layer.

In this regard, a fiber or textile reinforcing layer is considered a neutral layer unless the reinforcing layer has holes and the effective area of the reinforcing layer is not equal to the area of the film. do not have.

For films and membranes to be used as monosolators in chloralka 'J'CM tanks, 40 to 100
A polymer containing π carboxyl group-containing pendant side chains and 0 to 60% sulfonyl group-containing pendant side chains,
Provides outstanding current efficiency. Polymers in which 100% of the functional groups are carboxyl groups, ie, r in the structural formula is zero, give the best current efficiency.

However, an equally important criterion in chlor-alkali electrolysers is the power requirement per unit of chlorine and caustic. Honmei wholesale 1 book.

The closure polymer described therein allows a suitable combination of operating requirements to achieve an excellent and unexpected reduction in power. Since the power requirement (which can be expressed in Watts per hour) is a function of both electrolysis voltage and current efficiency, a low electrolytic 4 iM voltage is desirable and necessary. However, 1F combinations that do not have high current efficiency cannot function effectively from an industrial point of view, even at very low voltages. Moreover, polymers with inherent high current efficiencies are suitable for grammeters such as in the processing of films and/or in the operation of electric Wr tanks to achieve a theoretical reduction in the potential power. combinations are allowed. For example, polymers can be processed at low equivalent weights, which can result in greater losses in current efficiency than can be compensated for by voltage drops. 150-95% carboxyl group-containing pendant side 4
1! i and Qj polymers with a sulfonyl group-containing pendant side chain of 5 to 50π, with a brightness of 4≦, have low power consumption.

Book “J” by Ming, Polymer Pendant Till 3
t', l: 1 surface in the carboxyl form or in the carboxyl and sulfonyl form, and 111
It is also possible to produce films and membranes giving a 4+1q structure with other surfaces where the pendant side chains of the merging are completely in the sulfonyl form.
Is the pendant 'i = 1 chain of the polymer a Cull sequence? Xyl type 'F
, %9, ”:l: Take carboxyl and sulfonyl shape 7 (, is both surfaces and polymer bending NU!I
Even if films and membranes are produced with structures such that the inner layer is completely in the sulfonyl form - it is still T+J capable.

If only one surface of the structure contains carboxyl groups, the thickness of the carboxyl layer is usually the total thickness of C7).
'0.01 to 80%. For cation 3 in which both surfaces contain carboxyl groups, @the thickness of the surface layer is +:'ii
Smaller than the thick part of the structure, usually 001 in thickness
40>g. The thickness of the layer containing carboxyl groups is: IF! 1S is at least 200 angstroms. Ai-layer materials can be manufactured by melting and pressing a layer of the desired composition into a single layer. When only one surface of the structure contains cal/xyl groups, the narrow surface is l'g'i l in the electrolytic cell.
! t < t or the cathode, it is usually placed facing the cathode 7' (2).

) (part of JC'!, currently has a ridge-like (i),
The carboxyl group-containing layer has a thickness of about 4 to 5 mils, and the base layer (which usually contains sulfonyl groups) has a thickness of about 1 to 1 r) mils. ? Well, it is, and it has a structure! The total thickness of the snout is such that it is approximately 2-20 mils. 1- The thickness listed is the effective film thickness, i.e.
This is the thickness excluding the sleeve reinforcing fibers and other members that do not contain ion exchange groups.

Polymers according to the invention containing either carboxyl groups, carboxyl groups or tosulfonyl groups have functional utility for ion exchange. Therefore, the general utility of 111 coalescence in ion exchange reservoirs is directly anticipated. For example, cation permselectivity is directly involved.

One method of measuring cation exchangeability is the measurement of permselectivity at a fraction of the same but different concentrations of cations in solution. This involves the transport of cations and Voltage-free permselectivity measurements indicate that the polymer is nonfunctional for ion exchange.

Specific uses for the polymers of the present invention containing carboxyl groups, both carboxyl groups and sulfonyl groups, may be found in IrJ:, 1973, 4 Jl.
West German Patent No. A2,251,660 published on the 26th and Dutch Patent Order No. 72.1 published on June 29, 1973
7598, in chlor-alkali electrolysers. Similar to these descriptions, f'! of a polymeric film used to separate the anode and cathode sections of the cell which produce chlorine and caustic, respectively, from the salt water flowing in the anode section of the electrolytic cell. T! However, the tank itself can be a normal chlor-alkali electrolyzer. Although the West German and Dutch patent applications are for use in chlor-alkali electrolysers, the use of alkali or alkaline earth metal salts with total dielectric hydroxides, such as chlorine, from solutions of alkali or alkaline earth metal salts is It is within the scope of this invention to produce halogens such as Current efficiency and power consumption? The operating conditions of the electrolyzer are similar to those noted for sodium chloride, although the conditions are different.

Carboxyl 4 , f k Ice: By means of fluorinated polymers of the type of the invention having pendant groups present as either carboxyl or tosulfonyl groups,
Significant benefits were observed in terms of current efficiency in chlor-alkali electrolyzers.

The following examples are presented to further illustrate the novel features of the invention.

Example 1 Tetrafluoroethylene and CIl', = CF OC
I', Cfi'330nd! Stainless steel surface] CF2-CFOCF2CF(CF3)O of 322f/
CF2CF2COOCH3,20r of tetrafluoroethylene and 15Fl! 1.1.2-trichloro-1
,2,2-) 0.05% NOZO in refluoroethane
A solution containing fluoropropionyl peroxide was charged.

After heating at 50°C for 3 hours, unreacted gas was evacuated,
The liquid and solid products were evaporated to dryness. After thoroughly washing the solid polymer product with aqueous acetone, it was dried in a vacuum dryer to obtain 3.9 tons of white solid. The product was pressed at 240°C to give a clear 5~
A 6 mil film was formed, reacted with a mixture of methyl sulfoxide and water, dried and treated with tetrafluoroethylene and CF2. =C'FOCI? 2C
I? (CF3) A copolymer with + in OCR'2CF2COO- was obtained. The infrared spectrum showed the presence of a modest amount of carboxylate. /By high determination, the final product carboxylate salt is 0.9 s milliequivalent/? , this (6:
Heavy phase: was found to be 1020.

KO-treated film (thickness 6 after KO, IL treatment)
~7 mils) with a 4-inch diameter sample at 2.0 amperes 7
/in2 after testing for 6 hours in a laboratory chlor-alkali electrolyzer operating at 1/29.05 93.2 3.912
28, 76 92.6 3.955
23.06 90.9
3966 24.5087.6 4.08
Example 2 Tetrafluoroethylene and CF2C'p'O(,
'F2C/I'330ml stainless steel pressure tube,
40 inside? CF2=(,'FOCF2CF (C'
l:,)OCF2CII', C'00CH,, 26
2 of 1,1.2-) dichloro-1+2+2-trifluoroethane, 207 of tetrafluoroethylene and 20
1,,1'+ 2-trichloro-1,2゜2-) of scrap I. J 0.05% NOZO in fluoroethane
A solution containing fluoroprobionyl peroxide was charged. After heating at 50° C. for 3 hours, unreacted gas was vented and the liquid and solid products were evaporated to dryness. The solid polymer product was thoroughly washed with aqueous acetone and then dried in a vacuum oven to obtain 552 as a white solid. The star product was pressed at 240° C. into a clear I-6 mil film, reacted with a mixture of Koji, dimethyl sulfoxide 9 and water, and dried to form tetrafluoroethylene and CF2CFOCF2CF (CF
3) A copolymer with + in OCF, CF, and COO- was obtained.

The infrared spectrum shows the presence of a certain amount of carboxylate salt, while the titration shows that the carboxylate content of the product is
, s 38 milliequivalent/7, and the equivalent weight is 119
Show that it is 0. The final film had a resistivity of 1.15 ohms.

A 4-inch diameter 5-6 mil thick film was installed in a laboratory chlorine-Irekali electrolyzer operating at 2.0 amps/in., current efficiency of 89-97%, 35.
5-37% sodium hydroxide, 4.4
The cell was operated for 14 days at a voltage of ~5.1 delt. The biL amount of water to the cathode chamber was then increased to decrease the sodium hydroxide concentration.

After a few days of some erratic operation of the electrolyzer, the electrolyzer was operated at a current efficiency of 90-94%, a sodium hydroxide concentration of 27-30% and a voltage of 4.2-4.6 volts.
I drove for days.

Example 3 Tetrafluoroethylene and CF2=CFO[CF, CF(CF,)O']2CF2
(?/l'2COOC (1°330me stainless steel pressure vessel, 313 CF, = CFO [CF2CF
(CFs) 0 ]2CF2CF2COOC/i,,2
Of tetrafluoroethylene and 15 of 1.1.
A solution containing 0.05% perfluoropropionyl peroxide in 2-trichloro-1,2,2-trifluoroethylene was charged.

After heating at 50° C. for 3 hours, unreacted gases were vented and the liquid and solid products were evaporated to dryness.

The solid polymerization product was thoroughly washed with aqueous acetone and then dried in a vacuum dryer to obtain 432 as a white solid. When a small portion of the product was pressed into a thin film, its infrared spectrum showed the presence of significant carbomethoxy groups with an absorption at 5.6 microns.

Example 4 Tetrafluoroethylene, CI'', -CFOCF, CF (CF3)OCF2CF
2SO2F and CF2=CFOCF2C11(CF3
) OCF2CF2COOCII, copolymerization 330rnI! 25.4y in stainless steel pressure tube
CF2. ,,CFOCF2CF (CF, ) OC
F, CF25o2F.

8.11 CF2: CFOCF, CF (ClF3)
0CF2CF2So2F.

202 of tetrafluoroethylene and 1 of 15ηr/
．． A solution containing 0.05% nosaefluoroprobionyl peroxide in 1,2-trichloro-1,2,2-trifluoroethylene was charged.

After heating at 50°C for 3 hours, unreacted gas was exhausted,
Thoroughly wash the remaining product with aqueous acetone,
Filter and dry in a vacuum oven.

The 5,3 f white solid polymerization product was pressed at 280°C into a 5-6 mil film. The infrared spectrum of this material showed the significant presence of carbomethoxy and fluorinated sulfonyl groups with absorptions at 56 and 68 microns, respectively. After reaction with a mixture of trimethyl sulfoxide, Koji and water, infrared spectra showed that all of the sulfonyl fluoride and carbomethoxy groups were converted to sulfonate and carboxylate groups, respectively.

Tetrafluoroethylene, CF2=CFOCF2CF (
C'F,) OCF2CF, 5O3K and CF2.
=CFOCF2CF(CF3) OCF,, CF2C
00K (7) Copolymerized IXo, 4 inch diameter, 5-6
The film of the mill was installed in a laboratory salt-alkaline electrolyzer operating at 20 amps/in2 for 12
The following 21 results were obtained for the 2-day test.

1 43.0 71.0 4.73
2 31.5' 60.3 4.656
34.0 63.4 4.577
34.0 63.8 4.6012
32.0? 1.0 4.60 In this table, the current efficiency is low when the ion exchange capacity is 1.3 m
Indicates that e q/W has been exceeded, that is, the normal range has been exceeded.

Example 5 A piece of 5 mil film of a co-10 combination of tetrafluoroethylene and perfluoro(3,6-thioxer-4-methyl-7-octensulfonyl fluoride) having an equivalent weight of 1100 was placed in a press and 1 Tetrafluoroethylene with an equivalent weight of 980 and monofluoro(4,7-thioxal-5-methyl-8-)monic acid) having an equivalent weight of 980
It was covered with methyl copolymer powder 1F. After heating this material at 200℃ for 4 minutes without applying pressure, 30.0
Heated at 200°C for 2 minutes under a pressure of 00p8i. The obtained film was treated with a mixture of trimethyl sulfoxide, water and potassium hydroxide at 900 °C for 1 hour, washed and dried to obtain a transparent film. The infrared spectrum of the 8-85 mil thick film thus obtained was 5.
．． It showed very strong carboxylate absorption at 95 microns. The film was mounted in a chlor-alkali electrolyzer operating at 20 amps/in2 with the carboxylate side facing the catholyte, and an aqueous sodium chloride solution was added to the electrolyte M1, c, 3. 85~ at electrolytic sliding voltage of s~4.0 volts
29.5-37.8% A at 91% current efficiency
'a Got OH.

Example 6 Tetrafluoroethylene and perfluoro(3,6-dioxa-4-methyl-
octenesulfonyl fluoride), with one embedded Teflon T-12 cloth mesh and with the sulfonyl fluoride groups converted to a corresponding potassium sulfonate salt to a depth of 0.8 mils. A piece of 7 mil film having one surface layer was placed into the press with the sulfonyl fluoride side up. - 1 side was coated with a powder of a copolymer of tetrafluoroethylene and methyl pernonenoate having an equivalent weight of 996 - 0 This material was heated without pressure at 210"C for 4 minutes, then 30" ，
Heated at 210°G for 1 minute under a pressure of 1,000 psi.

The laminate thus obtained was treated with a mixture of trimethyl sulfoxide, water and potassium hydroxide at 90°C for 1 hour and washed with water to convert the remaining sulfonyl fluoride groups and ester groups into sulfonate and carbonyl j-fl, respectively.
converted into salt. This laminate was installed in a chlor-alkali electrolytic cell operating at 20 amperes/inch with the carboxylate side facing the catholyte, and an aqueous sodium chloride solution was electrolyzed to produce 4.6 to 4.8 port. 9 at an electrolytic sliding voltage of
At current efficiency from 0 to 96, 392 to 3 B, 2
．． 5% Na'OE was obtained.

Example 7 32.2F perfluoro(4,7-soxar 2.5
-dimethyl-8-nonenenitrile), 20V of tetrafluoroethylene and 15 ml of 1°ll 2-F
A 0.05.9(i) solution of perfluoropropionyl peroxide in dichloro-1,2,2-trifluoroethane was heated in a stainless steel MU 1fjl pressure tube at 50°C for 3 hours. The contents were removed and diluted with aqueous acetone. After washing, filtering, and drying, a white polymer 591 was obtained.The infrared spectrum of the film of this polymer was 10
．． Strong ether absorption at 2 microns and 4.4
It showed the presence of absorption by the nitrile at 0 microns. By differential thermal analysis, this polymer was found to be 182 mol%
(Estimated to contain 527% by weight of nitrile comonomer.

Example 8 Noguichi fluoro(3,6-thioxer 4
-methyl-7-octensulfonyl fluoride), 8
．． 11 nog-fluoro(4,7-dioxa-2,5-
of a 0.05% solution of noso-fluoropropionyl peroxide in 8-nonenenitrile), 202% tetrafluoroethylene and 15 m/1.1.2-)lichloro-1,2,2-)lifluoroethane. The mixture was heated in a stainless steel pressure tube at 50" for 3 hours. The contents were removed and washed with aqueous acetone.
After filtering and drying, a white polymer 591 was obtained.

The infrared spectrum of this polymer film is 6
．． It showed the presence of sulfonyl fluoride and nitrile groups with absorptions at 8 and 4.4 microns.

A film of this terpolymer is made of trimethyl sulfoxide,
2 at 90°0 with potassium hydroxide and water
Time processed. The infrared spectrum of the film thus obtained showed no presence of sulfonyl fluoride or nitrile absorptions. 5,9 corresponding to the potassium salt of carnic acid
A new absorption of 5 microns was observed. Infrared and titration results indicate that 0.16 my+) equivalents/
′? This shows that there are 83 m + ) equivalents of carboxylate salts and sulfonate salts.

Example 9 92! i'ノC'F2-CFOCF2CP' (CF
3) OCF2CF, C00II3.1029 1.1.
2-trichloro-1,2,2-trifluoroethane, 2
0me's 1.1.2-) Lichlorol, 2, 2-
) 1.1 /ξ fluorozolopionyl peroxide 005g in fluoroethanol and 1257
18i of tetrafluoroethylene was heated at 50° C. for 3 hours while the pressure was maintained at 125 psi by addition of tetrafluoroethylene. Excess gas was vented and the colorless, shell-like product was heated under vacuum to remove unreacted monomer and solvent. The solid residue and official substances were washed once with aqueous acetone and twice with acetone, filtered, and dried at 100°C in a vacuum dryer to obtain 132
A white solid of 2 was obtained. The infrared spectrum of the copolymer product showed strong absorptions at 34 and 56 microns, indicative of the presence of esters of fluorocarboxylic acids.

This monthly film was pressed at 220℃ and ester j
water, dimethyl sulfoxide, potassium hydroxide and/or
The mixture was hydrolyzed at 90°C for 1 hour.

Titration of this material showed it to have a weight of 1115.

A 5-6 mil thick film was installed in a Salt Qin alkaline electrolyzer to electrolyze an aqueous sodium chloride solution at 2 amps per square foot for 35 days to give a current efficiency of 88-97 kidneys and a current efficiency of 4.1-59 ports. At electrolysis + git pressure, 2
#aO11 of 7-369 was obtained.

Example 10 828? CF2-Cl? 0C11',, CF (C
F3) 0CF2CF.

C00C111,112,41i' 1,1,2-trichloro-1,2,2-)lifluoroethane, 20rnl
A 005% solution of zR-fluoropropionyl peroxide and 170 psi of tetrafluoroethylene in 1.2.2-trinofluoro-1.2.2-trinofluoroethylene and 170 psi of tetrafluoroethylene was added while maintaining the pressure at 170 psi K by addition of tetrafluoroethylene. Heat at 50' for 3 hours. Excess gas was vented and the dense glue-like product was heated under vacuum to remove unreacted single pieces and lubricant. The solid residue was washed twice with acetone and dried in a vacuum dryer at 100° C. to give the product 11.81. A film of this material was pressed at 1750C and the ester groups were replaced with a mixture of trimethyl sulfoxide, potassium hydroxide and 4+3'q
The mixture was hydrolyzed for 1 hour at 90° C. in

The infrared spectrum of the hydrolyzed i & Jj L product is 5,
9 microns exhibits a very strong acoustic absorption of the -''-fluorocarboxylic acid salt and the titration is 980 equivalent tons] f
It showed L.

Alkaline electric f'i'f with 6-7 mil thick film
Attached to the tank shell, the sodium chloride solution was applied at 2 amps/sq. ft. for 18 days, with a current efficiency of 87-95% and a current efficiency of 87-95%.
g, at an electrolytic sliding voltage of ~40 volts, 25-34
°d)V a, 0 /, / were obtained.

Example (,4) COOJI C'J" 1 CFCI"OCF'C'F0CF=C"F Crude 11. C00CCF2CF"20C of 152 in separatory funnel
'F' (CIC,) C/I'20CF, -=CP'
, was shaken with 25me of 10% Na01i aqueous solution at room temperature.

The aqueous layer was separated and made acidic using cold foundation 11C1.

Remove the lower layer with a small amount of F20. Distilled from
107g of 3- r 2- () trifluoroethenoxy)-1-(toIJ fluoromethyl) trifluoroethoxy 1 tetrafluoroprodione R1 boiling point 5 a ”c
lo,25ru,,n'','; = 1.3078, was obtained.

Calculation value for C811F, 04: C, 23, 54
;11, 0.25 iF, 6 tl, 53 neutralization, ;-1408 analysis iXj: C”, 23.80;ノ/
, 0. 5 2 i1 ノ, 61.71; 1 equivalent of medium oxide:, 407.7 (B) ■ F2 P'CCF'3CF2C7i'2CO011 8,82 3-[2-()lifluoroethenoxy) -1
-C)! J fluoromethyl) trifluoroethoxy 1
Tetrafluoropropion (1.1. of 13n+r)
2-) Lichlorotrifluoroethane and 0.01 m
A glass tube containing a 6% solution of perfluoropropionyl peroxide in 1.1.2-trichlorotrifluoroethane of F was sealed and rotated for 60 minutes at room temperature. The gas was purged and a 6% solution of perfluoropropionyl peroxide in 32 me of tetrafluoroethylene and 0.01 me of 1.1.2-trichlorotrifluoroethane was added. The tube was sealed and rotated overnight at room temperature before being opened. After filtration and washing in ether, a copolymer 232 of the above repeat units was obtained. The pressed film showed strong infrared absorption for -'C00Il.

Example 12 F2 F’(,’ CI’.

cp, c)-'2(,'00 // 8.82 of 3- [2-(trifluoroethenoxy)-
1-()lifluoromethyl)trifluoroethoxy 1-tetrafluoroproproionic acid, 2.2 f of tetrafluoroethylene, 13ηe of 1,1,2-trichlorotrifluoroethane and 0.01 ml of 1.1.
2-) A glass tube containing a 6% bath of A-fluorozoropionyl peroxide in dichlorotrifluoroethane was sealed and rotated for 60 hours at room temperature. After discharging the gas, 32 tetrafluoroethylene and 0.0
1,1°2-) of 17g + 6% of 7-fluoropropionyl peroxide in
Add the solution. The tube was sealed and rotated overnight at room temperature before being opened. After filtration and washing in ether, copolymer 2.32 of the above repeat units was obtained. The pressed film showed strong infrared absorption for -COO,H.

Example 13 (,4) 3-[ of 1267IP (0,031 mol)
2-()Lifluoroethenoxy)-1-(1-Lifluoromethyl)trifluoroethenoxyj Tetrafluoropropionic acid up to the point of neutralization with 1554γl/0,2N sodium hydroxide (indication rate phenolfretane) Titration of showed a neutralization equivalent of 407.69 (calc. 408) 1 nl/excess of 0.2N NaO11 was added and the solution was frozen in a 50me Carius tube. Then 0252 ammonium persulfate in 10 me water, 1
027 Na2S2O3・s in o-waste g water 71,0
solution and 3.11 i' of tetrafluoroethylene were added separately with freezing and then the tube was sealed. The tubes were rotated overnight at room temperature to form a clear solution and a small amount of solid polymer. The solution was filtered and acidified to give a gel that was mostly soluble in ether. Removal of ether and drying under vacuum at 100°C gave a 3.2y copolymer. it at 100℃/10,000 psi
It was then pressed and made into a film. This copolymer 1
'i -COOIf (broad 3μ and 57μ)
showed strong infrared absorption.

CB) F2 FCCF.

CF2CF2COONa Using the general procedure for (,4) of this example,
6f (0,015 mol) of 3-r 2-()lifluoroethenoxy)-1-()lifluoromethyl)trifluoroethoxy]tetra, diluted with a slight excess of 0.2 N sodium hydroxide. Fluoroglobionic acid, 10tne
0.259 ammonium persulfate in water, 10'ml
A 200 g Carius tube containing 0.029 Na2S, 03.5II, 0 and 10 f tetrafluoroethylene in water was rotated overnight at room temperature and then opened after cooling. The glue-like polymer (IJ salt) was collected by filtration and dried under vacuum at 100°C to obtain a copolymer of 651 (neutralized by titration: 41,976
,) was obtained. The acidic copolymer obtained by acidifying the furnace liquor was collected by filtration and dried under vacuum at 100°C (weight 5.111").

Example 14 The following layers: (1) 51 microns of a copolymer of tetrafluoroethylenetomethyl perfluoro (4,'7-yoxa-5-methyl-8-nonenoate) with an equivalent weight of 1050 (
(2) a copolymer of tetrafluoroethylenetohafluoro(3,e-sooxa-4-methyl-7-octensulfonyl fluoride) having an equivalent weight of 1100; a 102 micron (4 mil) layer of +31/e-fluorocarbon reinforcing fabric; and (4) a 51 micron (2 mil) layer of the same copolymer described in (2) above on the anode side. The membrane was created by thermally bonding the surface layers together under pressure.

The resulting membrane was treated with 30% trimethyl sulfoxide and 11
%', was hydrolyzed for 20 minutes at 90°C in an aqueous bath containing OIJ. The membrane was then cleaned and installed in a wet state in a small polyalkali electrolytic cell with an effective area of 45 d between the dimensionally stable anode and the mild extracted ground metal cathode. This electrolytic cell was heated to 31°C at 90°C.
The anolyte solution was 305fNaC1/I) liters of high purity salt water.Water was added to the cathode solution to reduce the concentration of the resulting caustic soda to 32±1%. These conditions were the optimum conditions for chloralkali electrolysis using this membrane.

The average current efficiency during the first 10 days of operation was 956%. The average 10-day flow efficiency on the 400th day of operation was 96.1%. On the 828th day of operation, the 10-day average current efficiency was 956%.

Although the invention has been described in terms of particular embodiments, it is not intended that the invention be limited to these embodiments. As will be apparent to those skilled in the art, many embodiments can be made without departing from the spirit of the invention or the scope of the appended claims.

Claims (1)

[Claims] 1. A method for producing alkali metal hydroxide in a cathode chamber by electrolyzing alkali metal chloride in an electrolytic cell divided into an anode chamber and a cathode chamber by an ion exchange membrane, The membrane has a fluorinated ion-exchanged sulfonyl polymer on one surface and -0-CF2C'12C'00J? on the other surface. 'Gi [Here, /? 1 is if, low range, ammonium or quaternary ammonium, and is the valence of tldAi], each polymer having between 08 and 1.3 milliequivalents/ A method for electrolyzing alkali metal chloride, characterized in that the membrane is a fluorinated ion exchange polymer membrane having an ion exchange capacity of that of f-polymer, and the other surface thereof is arranged to face the cathode chamber. 2. The m is the one tD surface K −C/”2C/”2
sOR2 group, where R2 is I?, C7 or R3, is an alkali metal, ammonium or is quaternary ammonium, and the valence of tl'iM is 1
a fluorinated ion exchange polymer having pendant side chains containing a repeating unit on the other surface (wherein ?L is 2, p is 1 to 10, and , q is 3 to 15, r is 0 to 1 (l, S is 0, 1.2- or 3, and X is 4 fluorine or 3 fluorine and 1
)' is the Ii' total (r or CF, and Z is 1=' or
H is CJ・□, R111'i is lower alkyl72 or AI(-t), lze21d: p, C1 is OR3, R3 is 1
1-1: or M(1), M (d alkali metal,
11' milk, which is a membrane comprising a polymer having ammonium or quaternary ammonium, t being the valence of M;'1 - The method according to claim 1. 3. The membrane has a fluorinated ion-exchanged sulfonyl polymer on one surface, and a fluorinated sulfonyl polymer on the other surface; 1 to 10, q is 3 to 15, and X is 4 fluorine or 3 fluorine and 1
chlorine, M is alkali metal, ammonium, or Shirin ammonium, and t is the valence of M, i.
t6 or the method described for the second. 4 positive electrode, anode installed in the anode chamber, a cathode chamber, the negative electrode, a cathode installed in the gap chamber, and separate these chambers;
It consists of a cation-exchange membrane that has a fluorinated ion-exchange sulfonyl vehicle on one surface and a 10-CI? , CP',, C00/<1 group, AI is an alkali metal, ammonium or quaternary ammonium, and t is the valence of each polymer has 0.8-13 meq/9t
An electrochemical cell characterized in that it is a fluorinated ion exchange polymer membrane having an ion exchange capacity of fi combination, and is arranged so that the other surface faces the cathode chamber side. 5 The film has -Cl='2c/-' on the one surface,
, SO, R2 group [here, l? 2 is p゛, C2 or (nod°3), alkali metal, ammonium or quaternary ν is ammonium, and t is the valence of AI.Fluorinated ion exchange with a pendant thin containing 1 21f association 9. 14 other power table (rl)
The polymer has a repeating degree (where n is 1 rE or 2, p is 1-10, q is 3-15, rlj:0-1O, and S is 0.1. 2 or 3, and X is 4 fluorine or 3 fluorine and 1
)' is F's CF, Z is p' is C12, No2 is F', C1 or 01 (3, M is the range of alkali, ammonium or 5. The tank according to claim 4, which is a membrane comprising a polymer having quaternary ammonium, t is the valence of M. 6 When loading and unloading, one surface has a fluorinated ion exchanger 41H'>
has a sulfonyl polymer and &”ts 11 on the other surface.
In the formula, n is 12, p is 1 to 10, q is 3 to 15, and X is 4 fluorine or 3 fluorine in total. Fluorine and 1
1 is chlorine, qf is an alkali metal, ammonium is quaternary ammonium, and t is a film containing a polymer with H valence of -1! 1 request for permission σ) 1
It1) Hinoki cypress according to item 4 or 5.