JPS5941335A - Preparation of composite membrane - Google Patents

Abstract

PURPOSE:To obtain a composite membrane suitable as an electrolytic membrane capable of keeping high current efficiency for a long period, by applying a thin film of a polymer compound and a vinyl monomer to the surface of a fluorine- containing cation exchange membrane, etc., and polymerizing monomer thereby bonding the polymer to the membrane. CONSTITUTION:A thin film of a polymer compound (e.g. ethylene, ethylene oxide, etc.) having a thickness of preferably 0.01-100mu and preferably 5-80wt% of a vinyl monomer (e.g. styrene) are applied to the surface of a polymeric membrane having fluorine atom and cation exchange group (e.g. sulfonic acid group) or a functional group (e.g. acid ester) to which a cation exchange group can be introduced easily, and the vinyl monomer is polymerized, and if necessary, ion exchange group is introduced to obtain the objective composite membrane.

Description

DETAILED DESCRIPTION OF THE INVENTION The object of the present invention is to obtain a composite ion-formed membrane of a sulfur-containing thread that can be maintained for a long period of time with extremely high current efficiency.

Ceramic ion exchange a (previously referred to as a fat film), which selectively permeates cations, has traditionally been used as a diaphragm in electrical separation screens made of alkali metals and other backings to stop Cheonghwa Emonoga. Today, a diaphragm for this caterpillar is called Naflon, a fluorine-containing cationic membrane obtained by copolymerizing fluorovinyl ether sulfonyl fluoride with tetrafluoroethylene.・It has excellent resistance to oxidation.However, when using a cationic exchange system containing fluorine as a diaphragm for the electrolysis of alkali gold salts, the frost and flow rate are low and unsatisfactory. .In addition, other polymers containing double-stranded polymers such as R compound K Noe-fluoro (alkyl vinyl nitrate sulfonyl fluoride), or II No. fluoro (alkyl vinyl ether sulfone In), etc.
A method of graft polymerization using 11°C radiative polymerization,
Similarly, fluorine-containing filamentous molecular film (perfluoro(alkyl vinyl ether carbon 6'R) at the snout)
A cation-exchange arm containing a polymer with a car+l' group and a fluorocarbon tether has been proposed as a method for grafting 1jIC radioactive compounds.

These carbon-containing double cation exchange agents have a strong oxidizing property and are highly effective in converting alkaline hydroxides (with fit efficiency).
f: We are aiming to develop a diaphragm for electrolysis to obtain. However, like general ion exchange membranes, when used continuously for a long period of time, the water content increases significantly even though the exchange capacity decreases slightly. As a result, the fixed ion concentration in the membrane decreases over time, resulting in a decrease in current efficiency. This is thought to be caused by the fact that ions permeate through the membrane due to IK during electrolysis, which causes loosening of polymer chains in the membrane over time due to heat generation and other factors. For this reason, it is desirable that the film has a crosslinked structure as uniform and highly as possible; however, it is unavoidable that the electrical resistance of the film becomes extremely low. Therefore, as a method for suppressing the above-mentioned loosening of the molecular chains of the diaphragm over time without causing a significant increase in electrical resistance, the present inventors have first bonded fluorine atoms and bonded cation exchange groups. Although it has been proposed to impregnate and polymerize a single vinyl into a molecular membrane, its durability in a high-temperature pig enclosure for a long period of time was still unsatisfactory.

Based on the above-mentioned intent, the inventors of the present invention have conducted further research into a film that exhibits significantly less decrease in f-1+14 even when exposed to a high-temperature atmosphere for a long period of time. As a result of the il-layering, we have developed a new method for producing a synthetic membrane. That is, in the present invention, the membrane-like polymer molecules in Table 011 are shown in Table 011 of the polymer film-like material which is bonded to the hydrogen atom and the functional Δ5 into which a field ion exchange group or a cation exchange group can be easily introduced in a post-treatment. This is a method for producing a composite membrane in which the following steps are taken: 1) polymerizing the vinyl 111M compound in the presence of a vinyl 4ii1 compound and introducing an ionic compound +y1ty as necessary.

The composite cation exchange membrane produced by the VC of the present invention exhibits extremely excellent performance, especially as a diaphragm for electrolysis. 7P; 1 liter of ions in the reef thick 'Kamenoke 1 Mizusumakinaka 9. When the constant ion resistance of Houji is low, K becomes VC so that the remaining ions also permeate the cation exchange membrane. Therefore, an ion exchange membrane with a low ion concentration is required, which uses an ion exchange membrane that is passed through a thick electric wire.

The inventors of the present invention have found that the efficiency of the electric field can be significantly improved by adding ion-exchanged dust (il-dehydration) to the lamp light.

Furthermore, this phenomenon shows that the fluorine atoms are fully bonded and have a negative effect on the fc electrophase diaphragm. For example, a co-11f combination of keto-2 fluoroethylene and perfluoro(3,6-soAgicercoumethyl-7-octensulfonyl fluoride) is converted into 1-hydrolysis L -C4rj fC/
"-7/l/orosulfone nz type cation exchange +1'
I n / , dry at 20"C g 114 V long no υ
) Open' and anotokarii σt1ノ: + tll, j
Water 1 (iJ 1, for example, the 11th eclipse J: l'bl water frost,
When used in the mood and fl, the power of θ force 1q-soda f is reduced to 9S%. Zuta,
Same II! t's 'a: J'll! When I boiled it in the water, I took 20% soda (iJ f,te'
tL's efficiency is only one in five. Such a drastic change in [j1=] is due to a change in hydrophobic bonding force.
It is presumed that this is because the water content h1- of the sample increases and the solid 5't ion concentration decreases. Of course, when electrolysis is applied to a diaphragm that has improved flow efficiency by applying 1 force to 1 pressure, the commercial efficiency gradually decreases (7) They become the same. This phenomenon can be seen even in the ion parent film which has a three-dimensional structure. From this point M, in the present invention, the cation exchange of the fluorine thread is carried out. By joining the cation exchange membrane with a membrane layer of a different polymer compound, the swelling II layer of the cation exchange membrane is suppressed and hardened.
The effect of stably maintaining the f-on weave is further enhanced by the polymerization of the vinyl state body impregnated with a thin film-like polymer compound and water.
l11 is done.

In the present invention, the cation exchange membrane made of Miyafluorocarbon fiber is easily coated with VC steel ion particles. ! Is there a specific method for bonding a thin film-like polymer compound onto the optical surface of a film-like object, impregnating it with VCC vinyl IT, and bonding it? , then 1+'letJ'
A one-place ion exchange membrane made of fluorine-containing threads is easily prepared and cation exchange groups are introduced. A method of bonding TiC together with a base and vinyl monomer. In addition, it is preferable that the film-like material formed from the ρj molecule compound has 6[ion exchange groups]. In the second chapter of ``History'', the ceramic ion exchange group B contains a positive ion': 9. An anus molded from a film-like material and a polymer material that introduces dust groups! After gluing the autumn items in advance with fusion glue, etc.
A preferable method is to impregnate vinyl monomers into the resin, combine them, and bond them together.

According to the present invention, it is preferable that a molecular compound (L-bond) be added to the cation exchange membrane of the fluorine-containing thread, thereby increasing the electrical resistance of the resulting cation exchange membrane. do not have.

[7 Therefore, in general, the present invention's flexible iono-converting IF,
The resistance of S is preferably the /θ culture of B11, which is a combination of polymer 11 compound I, and both yarns of the cation exchange membrane i:I.
It is safe to keep it to a level that does not exceed 7 cultures. Electricity of this conjugated IIhj ion exchange membrane 4jk 4
From the point of 't'+, VC is formed as a molecular compound that interferes with the polymerization of the vinyl monomers to be bonded. It's good to do that. It is preferable to form a layer as thin as possible on one side of the fluorine-containing cation exchange membrane rather than on the field side. In addition, when using the composite cation exchange membrane prepared as an electrolytic diaphragm, it is also possible to apply the rule 1, 4φ< i + a, where the PM layer resides. 1,000 is preferable for a thin layer of the compound τ.

h1 ratio rJ of thin BFA complex compound and vinyl sheep compound
Vinyl * m body or whole / ~ 90M
If the gθ plates'Ii% meet, there is an rC south effect.

A polymer 11f) having a fluorine atom used in the present invention and a cationic cross-functional group that can be easily introduced into a cationic cross-linking group 11f). 7.11, and any conventionally known method may be used. For example, tetrafluoroethylene and nozoichifluoro(,?, otsu-sookita-
A film-like copolymer of monofluoro (argyl vinyl ether sulfonyl fluoride) such as methyl-7-octensulfonyl fluoride), or a cationic conversion group that has been subjected to hydrolysis; rt treatment, etc. 0). That is, as a cation exchange membrane of fluorine-containing thread, one fluorine atom is uniformly bonded, and a functional group that can be easily introduced into the ion exchange group is uniformly bonded. One direction is 1114 autumn items over /ctn. One of the hydrogen atoms in the polymer membrane may be partially bonded to the polymer chain, or it may be a perfluorinated polymer, in particular to prevent IM of the polymer chain. 100, the ion exchange group is bonded in a completely stable manner (+7: A cation exchange membrane of /4'-fluoro thread in which a hydrogen atom is bonded to Jr:f is most preferable. As a cation or a substituent, One or more conventionally known cation conversion groups are used, and sulfone M
Base, Calbot! Nisglu group, phosphoric acid group, phosphorous acid ester group, diphosphoric acid ester group, thiolno, (, phenolic hydroxyl M, jl sulfuric acid bit "F' x Nr"i disordered acid amide group, 4-chelate compound on gold - (,° negative '11℃ loading?r (・M
``One God out of all things'': Good] Practice VC1H: I do. In addition, the fluorine atom can be easily converted into an ion exchange IC. It may be an rL polymer, and the functional groups include acid esters, acid anhydrides, acid halides, and the like. Furthermore, as a manufacturing method for the -Hiba [:shirc ceramic ion exchange membrane], any conventionally known manufacturing method may be used, and covalent bonds 1.
It can be anything, including those that form a crosslinked structure of q, those that are rendered unbathable by hydrophobic bonds, and those that are rendered insolubilized by the entanglement of a single duck molecule. If it has it in combination with the parent molecule, then it is the same as the one formed by forming an acid amide with ammonia. ,−
11) 4.F-on exchange membranes are treated at a temperature that does not deteriorate the 4-f-on exchange membrane, etc. KJ: improved. By using the cation exchange model of the present invention and making the r-shi combination of the present invention. That high 4! :l IIp can also be maintained safely for a long time over VC.

Next, 1 the above-mentioned 2 plain yarn 1 cedar ion exchange power monument polymer membrane VC bonded thin film polymer compound, If the molecular weight is within the range of 0θ, it may be a leg-like polymer, a branched polymer, or a cross-linked polymer.
For example, compounds such as ethylene, globylene, polyfins, globin oxide, ethylene oxide, etc. , vinyl monohalides such as vinyl chloride, vinyl bromide, vinyl iodide, vinyl buttomide, polyhalogenated vinyl such as vinylidene chloride, vinylidene fluoride, agglomerated ethylene trifluoride, enalene gfluoride, etc.
hestylene, chlormenalsterene, vinyltoluene,
Aromatic vinyl compounds such as enalvinylbenzene, sovinylpenvin, trivinylbenzene, vinylpyridine,
Heterocyclic vinyl compounds such as vinyl-veranone, vinyl ester compounds such as acrylic esters, vinyl acetate, methacrylic esters, styrene sulfonic esters, vinyl sulfonic esters, butanoene, isogrene, chlorogrene, par Fluorobutatsuene and other 110 allyl compounds, allylamine, allyl alcohol, allyl chloride, etc., perfluoro(alkyl vinyl ether), α-fluorostyrene, α, β, β'
- One or more selected from trifluorostyrene, α-fluoroacrylic acid esters, α, β, 79′-) polyvinyl monomers containing trifluoroacrylic acid esters, other buttomized carbon, etc. An fCl molecule compound obtained by polymerizing or copolymerizing a single fl is preferably used.

Thickness of the island molecular compound when the thin film of the island molecular compound is present on the surface of a cation exchange membrane or a polymer film having a functional group into which a cation exchange group can be easily introduced. Sa is 0. It is preferable that the thickness be as thin as possible with θ/~100μ. Although dissociative ion exchange groups may exist in the membrane layer in which these polymer compounds are fully bonded, it is best to reduce the number of cations and ion exchange groups in the membrane. It is.

On the other hand, the vinyl monomer in the present invention is not particularly limited, but may be one that swells the polymer compound bonded to the VC polymer film and polymerizes with 'I'J' 6M as described above. Furthermore, it is preferable to use a material that also swells the polymer blade Q-shaped material. Examples I, F, monovinyl monomers such as styrene, vinyl toluene esters, acrylic dispersion esters, acrylonitrile,
Vinylpyrinone Chlorstyrene, α-fluorostyrene, cr, β.

β-trifluorostyrene, α-methylstyrene, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chloromethylstyrene, esters of vinyl sulfonic acid, esters of styrene sulfonic acid, allyl sulfone (esters of 9, Vinylbos 7B acid esters 1, styrene phosphonic acid esters, styrene phosphonic acid esters 1, vinyl phosphinic acid esters 1, vinylphenolic acid Nisdel p:Q, vinyl acetate, polyfluorinated ethylene, Enaleno trifluoride, ethylvinylbenzenes, maleic fermentation ester fJJ % ichconic acid ester rtr, vinyl xide, polyvinyl compound (polyvinyl compound J) as m-, P-, 0-novinylbenzene, Sovinyl sulfone, butanoene, chloroglene, isogrene, trivinylbenzenes, sovinylnaphmelin,
Trihinylnaphthalene, noarylamine, triallylamine, divinyl sulfones, novinylchlorobenzene 4, and 1 alcohol 71? Reacrylate, 7J
``: One or more from link acrylates, novinyl ether, novinyl acetylene, divinyl sulfone, etc. In addition, vinyl sulfonic acid and salts, styrene sulfonic acid and salts, allyl sulfonic acid and salts (, vinyl sulfonic acid and salts, styrene phosphinic acid and tm M , vinyl phosphinic acid and tj @
acrylic acid, methacrylic acid, α-phenylacrylic acid, α-ethyl acrylic powder, α-halogenated acrylic powder, maleic acid, itaconic acid, α-butyl acrylic acid,
Vinyl benzoic acids, vinyl groups and cal+j in naphthalene base
? Xyl b'i and the like may also be used as long as S is frequently used in a mixture of one or more of the monomers. If many of these are used in the vinyl single phase mixture, a large amount of cation exchange groups will be introduced into the polymer compound layer, and the polymer compound layer will be significantly concentrated. Undesirable. In the present invention, in order to obtain a good composite membrane of the present invention, it is necessary to make one or more of these polyvinyl compounds and monovinyl compounds exist, and then polymerize the negative vinyl compound to make it into a polymer. . In order to form IQ molecules, radical polymerization initiators, X-rays, radiation, electron beams, discharge, light energy, etc. can be used. (Using a radical-opening TLH agent) ↓1 VC can be used as a radical-opening ρJR agent without any restrictions as long as it has a polarization of θC or more and a half-life of 70 hours or more. Examples include penzoyl peroxide, α, α′-azoisobutyronitrile, laurylnotone xai i″, tert-butylcumylperogine 1′, 190 peroxide on cumene, tert
-Butyl-Lauryl/P-Oxai) One example of this is Yuzuya j1, a polymer compound used here, and the processing blade T and VC. When a thin film-like IXIj molecular compound is layered and a vinyl compound is made to coexist at the same time and heated above the softening point, the thin film-like 1
Good results are obtained when using an initiator that produces a temperature above the softening point of the molecular compound when the vinyl monomer is coexisted with the vinyl monomer and impregnated after all of the compound is attached and heated above the softening point. bring about. Matakata>VCIH is here 1υ
Softening point of one molecule compound, -1: Next, using a cation exchange membrane, it is easily converted to cation exchange, and the ω of the #-like molecule is
(In the case of non-polymerization, which has an extremely high conversion point, depolymerization will occur if a vinyl compound is allowed to coexist with it and heat-treated to the softening point.In this case, an H molecule compound is attached to the coral in advance to bring it to the softening point.) It is effective to heat the vinyl compound at a pressure of 11 degrees and then allow the vinyl compound to adhere and permeate for polymerization.In this case, it is also effective to use a radical initiator as a method of combining the vinyl compound with PF, but it is not necessary to use radiation. ,X
Energy of ray, electron beam, >Y, knowledge; to pC,
You may also add 41 points. For example, when using a radial edge, the polymer compound i1 with fully bonded fluorine atoms is generally a degradable polymer, and the fraction I11 of this is 1;
It goes without saying that the composition of the vinyl compound should be determined by the composition of the vinyl compound if it is desirable to have a cross-linked structure.

In addition, in order to stably attach a polymeric film-like material that can easily be converted to a ceramic ion-exchange membrane or a cation-transformable film VC and a film-like polymeric compound, it is necessary to use not only vinylated adducts. F1? A compound having ion exchange properties such as an oxy compound and an amine may be used. For example, by impregnating a fine powder of a co-combination of -fluoro(alkylvinylneedle sulfone t') with NN' dimethylformamide, Spread it uniformly on the membrane and apply wind + i, then 2
Heat treated at around 00℃ and 10M! If you wear it, soak it with the ester power of acrylic acid.
&! k II@ radiation and combine to form a cross-linked structure in the polymer compound of the surface layer.
The ester of acrylic acid becomes viscous in the internal V of 7'L.
One example is how to do so.

J Sannoshita's implementation 1&jl V (Therefore, each of the same of the present invention is controlled by the control board σ. A two-chamber oven with an IU rating of θ and 5 cJm was heated using a 7-C titanium wire mesh coated with titanium oxide and ruthenium 112ide as a heating electrode. 1) J4 was used. 1! In the 1st frame room, put the 11th grade of alkaline water into the room? IjL, the total steady VC force of water [1 ent
In the gap between Olli Eile and 1 Togoku's appearance, I was on the 3rd and 3rd anniversary of Ruru, and I was on the VC for about a month. At the electrolysis temperature, θ ~ 0C, 'tl, m Wi, f 3θA / cl*
l -Cara fC. Oak? , Tora no'I [, fij
ia 4%: fl O, θN - in NaOH - c' g
o'c-c, 1000 cycle father Uii: kumquat and measured. (Measurement was carried out using the colorimetric method of 1/20θ in accordance with 1-1 JIS of the haloconide alkali in the ILi dihydrogenated alkali).

Example / Polymer membrane q/! made of a copolymer of tetrafluoroethylene and ramie-fluoro (3, otsu-sookitugou-methyl-7-octensulfonyl fluoride)! 1 piece of sulfone f'I'i type cation exchange membrane (for exchange capacity /, 200 EW) (with 3% N, N' The fc one was coated with somethylformamide, and the fc one was soaked in the same solution of VC and polyvinylidene buttonide was applied to both sides with PT 1t=4, and then air-dried. Vinylidene was used as a cationic exchange layer.The electrical resistance of these membranes and the diaphragm for salt electrolysis were used. The current efficiency is shown in Table 1.

Next, the 1-easy ion parenchymal membrane (J exchange 3) obtained above was immersed in VC in methyl nisder acrylate, immersed in light, and then put in MvK to extract r-gland from the C060 paddy 8 source -2#. O
When a cross-linked 4SI structure is formed on a thin layer of vinylidene with a height of 11" by injection, the result is 1111.
When a bond is formed between the cation and the parent body, the electrical resistance of this j dust r: I, 7, 0Ω-Cm
2, turn on the 11th saline solution and turn it on -N
By using aOH, I was rewarded with the efficiency of Denbyou C. After 3 months of doing this, I stopped and performed the electric folding board, and it was the same. Q N -NaOH is obtained and the current efficiency is 93-
Deat fc.

Example Ω A sheet of Oa 2 +ur11 of polyvinylidene fluoride was immersed in trimethylformamide V (soaked for 7 days, swollen for 1 month, and then t(
Then, chlorsulfone was added (it was then introduced with sulfonyl chloride &ffi [7, this was originally washed in 1c ethylene isochlorite to remove the chlorsulfonic acid of 5 + 1]) and dried in a dehydrated atmosphere. Then, sulfonyl chloride Δ and fluorine atoms were uniformly combined to form a molecule film-like material. Then, it was immersed in this film-like 11-button ethylenenoamine at VC 30° C. for g hours to react the sulfonyl chloride and the amine to form an acid amyl-' bond. This 111.1 directly immersed in ON-NaOH, hydrolyzed, 5A acid cautery, and a strongly acidic ion-exchange volume, and the sulfonylamide t1-
I found out that about 2 of the sulfonyl chloride groups are acid amide in the whole form bk city fc a Moon Q shape 1 that has this sulfonyl chloride, and of course the moon? Lichloroprene (
W type, I + Mortar No. 11 Chloroprene Co., Ltd. table) 3% benzene soap was evenly heated and air-dried, then 3% was added to 7g0C.
Heated for 0 minutes (7 minutes) to form a sulfonic acid amide crosslink on F'3, and to create a complete Ill K bond between the remaining amino groups in the coat layer and chloroprene. Styrene 30 on one side 11. Novinyl pen 70!0HII,'l-vinylpyrinoa
3 Q91 (Ni tert-Bunarurauriruno) Apply 100ml of the mixture evenly over the entire surface, cover with 100ml of cellophane, add 10L for 7 hours, add 1ml, and then add 6.0N.
- Hydrolysis of the sulfonyl chloride inside the membrane by soaking in KA OC in KOH was performed on the gold side.

The properties of this 11-dare pi extraction and the results obtained when it was used in electrolysis of saturated KC7 reduction are shown in the second column. In addition, do not perform ethylenediamine treatment or heat treatment. ON-KOH
The same procedure for υ was performed for the membrane containing only the hydrolyzed liquid)'/F L *.

Table d Example 3, Itsu 3 fluoride/packed ethylene powder was added to pJiiH.
A 70% benzene bath containing water and maleic acid was used to irradiate R 1til from a C060 source while uniformly dispersing the bath.
Maleic anhydride was bonded to ethylene.

After washing the prayed image powder with v4 separately, we measured the exchange arousal. g Mi IJ To M/f' It was dry dressing wood. This powder bed g l'ili VC7J t, te Daifroil +3
(manufactured by Ikin Co., Ltd.), and after uniformly mixing the two materials, the mixture was heated and pressed at 0° C. to form a molded product with il'41 molecules.

The resulting polymer membrane was thoroughly washed with methanol to extract and remove the fluoroyl, giving a carboxylic acid-type ceramic ion catalytic converter model. When I applied this to the saturated salt solution 'L', I found that ON -NaOH was exclusively used 'L'.
Turtle QI'i, the efficiency is 34%, 'I g % NaOH
In exchange, the fi value of Na1l in NaOH, 3
．． 200 pprn.

rKVcl Uniformly coat the p layer of this carboxylic acid type cation exchange membrane with a xylene preliquid of 10 pil/ton poly.
/ ,? IA with OC and heat! It was dressed up. Historically, this is 55% pure sovinylbenzene! 01'lIl, mekacrylic, was immersed in a uniform mixture of pensoylno-9-oxide/miyako and polymerized by heating at L//OU for g hours.

The obtained 'fc,'0 alloy was subjected to electrolysis in saturated saline solution in the same manner as above, resulting in B. Na when ON -NaOH is obtained and converted to ttg%NaOH at a current efficiency of 90%
There was only 17 I/20 ppl''n of NaCt in OH.

Example A molecular film-like material (thickness 0°, 2 rr
A thin layer of polyvinylidene fluoride was formed on one side of a sulfonic acid type ion-exchange membrane (produced by Hou Yong Li, 100 EW) prepared by hydrolyzing un) and subjected to the following treatment. That is,
B! between aluminum a fully glued to both sides of glass plates arranged with a gap of 0.2M! 7% scissors 1111
11J of the two glass plates on which the film is present by multiplying the intersection of θ0θθV by the θ cycle of
1, tetrafluoroethylene vapor diluted with hardwood gas is used as θILL[. Next, tetrafluoroethylene gas 11I:Iff is combined with a certain cation exchange membrane having a thin layer of polyvinylidene fluoride, and j? The bond between the vinylidene fluoride layer and the cation exchange IIQ layer was improved.

6. Electrolysis of saturated saline water was carried out using this IJ composite membrane. Obtain θN −NaOH and 'I
ff was 61+, the efficiency was 95chi, and the 6-month old bond was also 7Schi.

Example S: Apply 0CF20F2S02F noethelenetriamine to Katada 1 of a molecular film-like material (thickness: 0°2) having the following structural formula, apply a sulfonic acid amide bond, and bond soethylenetriamine. Then, 11 ml of 7J was added at 0°C for 70 minutes. This film n top tL history VC/%11? N, N of vinylidene fluoride
-A thin layer of methylformamide bath solution was applied and dried. rKVc This film is sandwiched between two aluminum plates with 3 gaps, and a thin layer of polyvinylidene fluoride is attached (1111 (After placing the VC on the tr, the two aluminum plates are A flow of V/θ00θ■ was applied, and tetrafluoroethylene gas was introduced onto the film surface to which vinylidene tetrifluoride was attached.ν
1) First, helium gas J&: was introduced into tetrafluoroethylene cooled in a '6M reactor, and tetrafluoroethylene was introduced using helium as a carrier gas. Monomarge J Yoshimen J: I worked on the discharge while soaking in VC and made 1 go. Tetrafluoroethylene vapor was sent over the treated membrane surface to cause discharge polymerization. By forming a thin layer of polyvinylidene butylene, the mold plate is increased by 1/2, and the weight of the crotch by discharge polymerization of tetrafluoroethylene is t + t J'
lf addition was % to θ.

The equated composite membrane was dissolved in l = 6 in ON-NaOH.
Soaked at 0°C (k(,,hydrolyzed 19 non-7X sulponylfluoride groups inside and on the surface of the model)!)! I: Then I changed it to sodium sulfonate. After this, Kim JlQ's father, Hou Guqi, was 0. g□m”k aim/y dry film, electrical resistance IR, riΩ-
It was cm. Using this composite membrane, electrolysis was carried out using the 11th saline solution as an anode and an IS' electrode made of iron and iron in the same way as in the f11 example, and 7, ON -NaO
It took 4 hours from Hk Yinli.

In addition, treatment! Electrolysis was applied to the surface of the membrane with one different pole facing each other.

Separately, untreated (replacement capacity 1110.3 mm Shang measure/2 dry capacity), 'City resistance is ohm, 3 ohm-cm)', even if the membrane r is stuck, electricity is ll/f')! = hfF.・The results are shown in the third column.

Part 3 Shishi

Claims (1)

[Claims] By combining atom and a cation-exchange group or a functional group into which a VC cation-exchange group can be easily introduced in post-treatment, a single-molecule compound with a V'C thin film on the surface of the polymer membrane and a vinyl monomer are formed. A method for producing a composite membrane characterized by: (f) polymerizing the vinyl monomer gold in the presence of the vinyl monomer and introducing an ion exchange group as necessary.