CN103243345A - Cation exchange film and electrolytic tank with the same - Google Patents
Cation exchange film and electrolytic tank with the same Download PDFInfo
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- CN103243345A CN103243345A CN2012103111011A CN201210311101A CN103243345A CN 103243345 A CN103243345 A CN 103243345A CN 2012103111011 A CN2012103111011 A CN 2012103111011A CN 201210311101 A CN201210311101 A CN 201210311101A CN 103243345 A CN103243345 A CN 103243345A
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Abstract
The subject of the invention is to provide a cation exchange film with high mechanical strength, such as high tearing strength, and an electrolytic tank with the cation exchange film. The cation exchange film is provided with the following components: a film body of fluorine-containing polymer with ion exchange groups, and a cation exchange film (1) of a reinforcing core material which is configured in the film body. The film body is provided with the following components: a first layer (2) which comprises fluorine-containing polymer with carboxylic acid groups, and a second layer (3) which comprises fluorine-containing polymer with sulfonic acid groups. In a section in a laminating direction of the first layer (2) and the second layer (3), when the distance between the center A of the reinforcing core material (4) to the film surface of the second layer (3) is a shortest line (L), the intersection between the line (L) and the film surface of the second layer (3) is set to B, the intersection between the line (L) and the film surface of the first layer (2) is set to C, and the intersection between the line (L) and the outer circumference of the reinforcing core material (4) next to B is set to D, distance (between B and D)/distance (between C and D) is 0.11-0.5.
Description
Technical field
The present invention relates to cationic exchange membrane and the electrolyzer that has used this cationic exchange membrane.
Background technology
Therefore excellences such as the thermotolerance of fluorine-containing cationic exchange membrane and chemical proofing, in the electricity decomposition (hereinafter being called electrolysis) of alkali metal chloride, are used as the electrolysis cationic exchange membrane for the manufacture of chlorine and alkali.In addition, also be used as ozone generation with various electrolysis such as barrier film, fuel cell, water electrolysis and electrolysis of hydrochloric acid with barrier film etc.Wherein, make at electrolytic brine etc. in the electrolysis of alkali metal chloride of caustic soda, chlorine and hydrogen, from the aspect of productivity, require the current efficiency height; From the aspect of economy, require electrolysis voltage low; Aspect from the quality of goods requires the common salt concn in the caustic soda low; Etc..
In these require, in order to show high current efficiency, usually use following cationic exchange membrane, this cationic exchange membrane by anion exclusion high with the carboxylic acid group as the carboxylic layer of ion-exchange group with low-resistancely constitute with the two-layer at least of sulphonic layer of sulfonic group as ion-exchange group.This cationic exchange membrane can directly contact with caustic soda with 80 ℃～90 ℃ chlorine when electrolysis, so the fluorinated polymkeric substance that chemical proofing is high is as the material of cationic exchange membrane.
But, when only utilizing the fluorinated polymkeric substance, not having sufficient mechanical as cationic exchange membrane, therefore, will be imbedded in the film as strengthening core by weaving cotton cloth of constituting such as polytetrafluoroethylene (PTFE) etc., strengthen with this etc.
In addition, not only imbed and strengthen core and strengthen, so for improve physical strength, further prolong product life, can more stably use, also carried out various researchs.
For example, patent documentation 1 has proposed the fluorine-containing cationic exchange membrane of a kind of electrolysis, it is the fluorine-containing cationic exchange membrane of electrolysis that comprises porous substrate, it has formed corresponding with the surface shape of porous substrate concavo-convex in the cathode plane side, put down in writing the content that film improves at the physical strength of bending in the document.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 04-308096 communique
Summary of the invention
The problem that invention will solve
But, the physical strength of disclosed cationic exchange membrane and insufficient in the patent documentation 1.Particularly, do not obtain the high cationic exchange membrane of the intensity of tearing (hereinafter being called tear strength) at film as yet.Tearing by the generation of cationic exchange membrane in electrolysis be full of cracks and this be full of cracks generation expansion of film causes, and its product that has that product life shortens or electrolysis produces is the influence that the common salt concn in the caustic soda uprises.Therefore, industrial community also extensively wishes to develop the higher cationic exchange membrane of physical strength.
The present invention In view of the foregoing carries out, and its purpose is to provide the high cationic exchange membrane of a kind of physical strength, particularly tear strength and the electrolyzer that has used this cationic exchange membrane.
Be used for solving the scheme of problem
In order to solve above-mentioned problem, the inventor has carried out repeatedly deep research, found that tearing by generation be full of cracks in film and this be full of cracks generation propagation of film causes, but dispose the cationic exchange membrane that strengthens core by the specific position that is formed in film inside, can suppress or block this propagation, can solve above-mentioned problem, finish the present invention thus.
That is, the present invention is as described below.
〔1〕
A kind of cationic exchange membrane, it is the cationic exchange membrane that has the film main body and strengthen core, and described film main body comprises the fluorinated polymkeric substance with ion-exchange group, and described enhancing core is disposed at the inside of described film main body, wherein,
Described film main body has layers 1 and 2, and described the 1st layer comprises the fluorinated polymkeric substance with carboxylic acid group, and described the 2nd layer comprises and have sulfonic fluoropolymer,
In described the 1st layer of cross section with described the 2nd layer lamination direction, in supposition from the center A of described enhancing core to the described distance that comprises the 2nd layer film surface with sulfonic fluoropolymer during for the shortest straight line,
On this straight line, will be made as B with the described intersection point that comprises the 2nd layer film surface with sulfonic fluoropolymer,
On this straight line, will be made as C with the described intersection point that comprises the 1st layer film surface of the fluoropolymer with carboxylic acid group,
On this straight line, will with the intersection point of the periphery of described enhancing core in be made as D near the intersection point of B, then be 0.11～0.5 apart from BD/ distance C D this moment.
〔2〕
As above-mentioned (1) described cationic exchange membrane, wherein, distance A B/ distance A C is 0.52～0.8.
〔3〕
As above-mentioned (1) or (2) described cationic exchange membrane, wherein, has the communicating aperture of tubulose in the inside of described film main body.
〔4〕
A kind of electrolyzer, its possess anode, negative electrode at least and be disposed at described anode and described negative electrode between above-mentioned (1)～(3) in each described cationic exchange membrane.
The invention effect
According to the present invention, can provide the high cationic exchange membrane of a kind of physical strength, particularly tear strength and the electrolyzer that has used this cationic exchange membrane.
Description of drawings
Fig. 1 is the schematic cross-section of wanting portion of an example of the cationic exchange membrane of present embodiment.
Fig. 2 is the schematic cross-section for the formation of an example of the cationic exchange membrane of explanation present embodiment.
Fig. 3 is the schematic cross-section for the formation of another example of the cationic exchange membrane of explanation present embodiment.
Fig. 4 is the schematic cross-section for the formation of another example of the cationic exchange membrane of explanation present embodiment.
Fig. 5 is the synoptic diagram for the percentage of open area of the cationic exchange membrane of explanation present embodiment.
Fig. 6 is another routine schematic cross-section of the cationic exchange membrane of present embodiment.
(a) of Fig. 7, (b) of Fig. 7 are the synoptic diagram for the method for the communicating aperture of the cationic exchange membrane of explanation formation present embodiment.
Fig. 8 is the synoptic diagram of an embodiment of the electrolyzer of present embodiment.
Fig. 9 is the synoptic diagram of the making method of the sample that uses for the observation in explanation film cross section.
Nomenclature
1 cationic exchange membrane
2 comprise the 1st layer of fluorinated polymkeric substance with carboxylic acid group
3 comprise the 2nd layer with sulfonic fluoropolymer
4 strengthen core
5 protuberances
11,12 coating layers
100 electrolyzers
200 anodes
300 negative electrodes
The 504a victim line
504 communicating apertures
Embodiment
Below, the specific embodiment of the present invention (hereinafter being called " present embodiment ") is elaborated.Need to prove that the present invention is not limited to following present embodiment, can in the scope of its main points, carry out various distortion and implement.Need to prove, only otherwise special declaration then waits the position relation to concern based on position shown in the drawings up and down in the accompanying drawing.And the dimension scale of accompanying drawing is not limited to illustrated ratio.
(cationic exchange membrane)
The cationic exchange membrane of present embodiment possesses the film main body and strengthens core, and described film main body comprises the fluorinated polymkeric substance with ion-exchange group, and described enhancing core is disposed at the inside of above-mentioned film main body.
Above-mentioned film main body has the 1st layer (hereinafter also the abbreviating the 1st layer or carboxylic layer sometimes as) that comprises the fluorinated polymkeric substance with carboxylic acid group and comprises the 2nd layer (hereinafter also abbreviating the 2nd layer or sulphonic layer sometimes as) with sulfonic fluoropolymer.
In above-mentioned the 1st layer of cross section with above-mentioned the 2nd layer lamination direction, when the distance of supposition from the center A of above-mentioned enhancing core to above-mentioned the 2nd layer film surface is the shortest straight line,
On this straight line, will be made as B with the intersection point on above-mentioned the 2nd layer film surface,
On this straight line, will be made as C with the intersection point on above-mentioned the 1st layer film surface,
On this straight line, will with the intersection point of the periphery of above-mentioned enhancing core in be made as D near the intersection point of B,
Then be 0.11～0.5 apart from BD/ distance C D this moment.
Need to prove, above-mentioned " the 2nd layer film surface ", " the 1st layer film surface " and do not mean that the 1st layer with the 2nd layer boundary member, and refer to surface with this boundary member opposition side.
(strengthening the position relation of core and film main body)
Below, based on accompanying drawing, the formation of the cationic exchange membrane of present embodiment is elaborated.
Fig. 1 is the schematic cross-section of the cationic exchange membrane of present embodiment.
When being used for electrolysis, the 1st layer of (carboxylic layer) 2 side are disposed at cathode side, the 2nd layer of (sulphonic layer) 3 side are disposed at anode side and carry out electrolysis.
Fig. 2 is the schematic cross-section of wanting portion of the cationic exchange membrane of present embodiment, and this figure is used for the formation of explanation cationic exchange membrane.
Use Fig. 2, the position of the enhancing core 4 in the cationic exchange membrane of present embodiment is described.
At first, in the cross section of cationic exchange membrane 1, the center that strengthens core 4 is made as A.The so-called center A that strengthens core 4 is under the situation of circle at the cross-sectional shape that strengthens core 4, refers to its center; Cross-sectional shape at enhancing core 4 is under the oval-shaped situation, refers to the intersection point of major diameter and minor axis; Cross-sectional shape at enhancing core 4 is under the rectangular situation, refers to intersection of diagonal.
And, suppose from the straight line L (dotted line Fig. 2) of the shortest distance on the film surface of 2 layers of (sulphonic layer) 3 of this A to the, according to the commit point B～D that gives a definition.
On this straight line L, will be made as B with the intersection point on the film surface of the 2nd layer of (sulphonic layer) 3.
On this straight line L, will be made as C with the intersection point on the film surface of the 1st layer of (carboxylic layer) 2.
On this straight line L, will with the intersection point of the periphery that strengthens core 4 in be made as D near the intersection point of above-mentioned B.
In the cationic exchange membrane 1 of present embodiment, be 0.11～0.5 apart from BD with respect to the ratio (BD/CD) of distance C D.From the aspect of electrolysis performance, be preferably 0.11～0.3, more preferably 0.11～0.2, more preferably 0.12～0.16.
Be more than 0.11 by making BD/CD, can fully guarantee from strengthening core 4 to the thickness on the film surface of the 2nd layer of (sulphonic layer) 3, thereby from the outside during to cationic exchange membrane 1 stress application, the stress that sulfonic fluoropolymer presses to the outside of cationic exchange membrane that comprises that strengthens that core 4 will have between BD obtains relaxing, and can prevent from strengthening core 4 and come off from cationic exchange membrane inside.Thus, even produce be full of cracks in the cationic exchange membrane, by comprising sulfonic fluoropolymer and strengthening core 4, also can suppress the propagation of (blocking-up) be full of cracks.Therefore, the tear strength height of the cationic exchange membrane of present embodiment can stably be used for electrolysis.
In addition, be below 0.5 by making BD/CD, abundant to the thickness on the film surface of the 1st layer of (carboxylic layer) 2 from strengthening core 4, thereby, according to above-mentioned same reason, the propagation that can suppress to chap.
Fig. 3 be present embodiment cationic exchange membrane another example want portion's schematic cross-section, this figure is used for the formation of explanation cationic exchange membrane.
Fig. 4 is the schematic cross-section of wanting portion of another example of the cationic exchange membrane of present embodiment, and this figure is used for the formation of explanation cationic exchange membrane.
Cationic exchange membrane shown in Figure 4 has formed protuberance 5 by concavo-convex processing is implemented on the surface of the 2nd layer of (sulphonic layer) 3.
Form under the irregular situation on the surface of the 2nd layer of (sulphonic layer) 3 as shown in Figure 4, can decide a B～D thus with concavo-convex height having been carried out average reference line as the film surface of the 2nd layer of (sulphonic layer) 3.
Need to prove that above-mentioned " concavo-convex height has been carried out average reference line " specifically can be obtained by ((height of the floorage * protuberance of protuberance)+(height of the area * recess of recess))/(area of the floorage+recess of protuberance).
In addition, the cationic exchange membrane preferred distance AB of present embodiment is 0.52～0.8 with respect to the ratio (AB/AC) of distance A C.Thus, tear strength further improves.More preferably 0.57～0.68.
(constituting the material of cationic exchange membrane)
The cationic exchange membrane of present embodiment possesses the film main body that comprises the fluorinated polymkeric substance with ion-exchange group.
See through cationic function and comprise the have ion-exchange group fluoropolymer of (carboxylic acid group or sulfonic group) as long as the film main body has optionally, its formation and material are not particularly limited, and can suit to select suitable formation and material.
Said fluorinated polymkeric substance with ion-exchange group fluorinated polymkeric substance that refers to have ion-exchange group or can form the ion-exchange based precursor of ion-exchange group by hydrolysis herein.
For example can enumerate following polymkeric substance: its main chain is made of fluorinated hydrocarbons, and the side chain that dangles has the functional group that can convert ion-exchange group by hydrolysis etc. to, and it can melt-processed.Below such fluorinated polymkeric substance is described.
About having carboxylic acid group's fluoropolymer, can be by making with the monomer copolymerization of following the 1st group monomer and the 2nd group or with the 2nd group monomer homopolymerization.
About having sulfonic fluoropolymer, can be by making with the monomer copolymerization of the 1st group monomer and the 3rd group or with the 3rd group monomer homopolymerization.
As the 1st group monomer, can enumerate for example fluorinated vinylether compound.As fluorinated vinylether compound, can enumerate for example ethylene fluoride, tetrafluoroethylene, R 1216, vinylidene fluoride, trifluoro-ethylene, trifluorochloroethylene, perfluor (alkyl vinyl ether) etc.Particularly, use under the situation of film as alkaline electrolysis at the cationic exchange membrane 1 that uses present embodiment, fluorinated vinylether compound is preferably perfluorinated monomers, is preferably the perfluorinated monomers that is selected from the group of being made up of tetrafluoroethylene, R 1216, perfluor (alkyl vinyl ether).
As the 2nd group monomer, can enumerate the vinyl compound that for example has the functional group that can convert the carboxylic acid type ion-exchange group to.As the vinyl compound with the functional group that can convert the carboxylic acid type ion-exchange group to, can enumerate for example CF
2=CF (OCF
2CYF)
s-O (CZF)
t(herein, s represents 0～2 integer to the monomers that-COOR represents etc., and t represents 1～12 integer, and Y and Z represent F or CF independently of one another
3, R represents low alkyl group).
Among these, preferred CF
2=CF (OCF
2CYF)
n-O (CF
2)
mThe compound that-COOR represents.(herein, n represents 0～2 integer, and m represents 1～4 integer, and Y represents F or CF
3, R represents CH
3, C
2H
5Perhaps C
3H
7).
Particularly, use under the situation of cationic exchange membrane as alkaline electrolysis at the cationic exchange membrane 1 that uses present embodiment, the preferred perfluorochemical that uses at least is as the 1st group monomer, but the alkyl of ester group (with reference to above-mentioned R) lost from polymkeric substance in the moment of hydrolysis, so alkyl (R) also can not be the perfluoroalkyl that whole hydrogen atoms are replaced by fluorine atom.Among these, for example, more preferably monomer shown below.
CF
2=CFOCF
2-CF(CF
3)OCF
2COOCH
3、
CF
2=CFOCF
2CF(CF
3)O(CF
2)
2COOCH
3、
CF
2=CF[OCF
2CF(CF
3)]
2O(CF
2)
2COOCH
3、
CF
2=CFOCF
2CF(CF
3)O(CF
2)
3COOCH
3、
CF
2=CFO(CF
2)
2COOCH
3、
CF
2=CFO(CF
2)
3COOCH
3。
As the 3rd group monomer, can enumerate the vinyl compound that for example has the functional group that can convert sulfone type ion-exchange group to.As the vinyl compound with the functional group that can convert sulfone type ion-exchange group to, for example, preferred CF
2=CFO-X-CF
2-SO
2The monomer that F represents (herein, X represents the perfluor base).As their concrete example, can enumerate monomer shown below etc.
CF
2=CFOCF
2CF
2SO
2F、
CF
2=CFOCF
2CF(CF
3)OCF
2CF
2SO
2F、
CF
2=CFOCF
2CF(CF
3)OCF
2CF
2CF
2SO
2F、
CF
2=CF(CF
2)
2SO
2F、
CF
2=CFO〔CF
2CF(CF
3)O〕
2CF
2CF
2SO
2F、
CF
2=CFOCF
2CF(CF
2OCF
3)OCF
2CF
2SO
2F。
Among these, more preferably CF
2=CFOCF
2CF (CF
3) OCF
2CF
2CF
2SO
2F and CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2F.
The multipolymer that is obtained by these monomers can be by developing at homopolymerization and the copolymerization of ethylene fluoride polymerization, particularly make at the employed general polymerization process of tetrafluoroethylene.For example, in non-aqueous method, using inert solvents such as perfluoroparaffin, cfc, in the presence of radical polymerization initiators such as perfluorocarbon superoxide or azo-compound, is that 0 ℃～200 ℃, pressure are to carry out polyreaction under the condition of 0.1MPa～20MPa in temperature.
In the above-mentioned multipolymer, kind and the ratio thereof of the combination of above-mentioned monomer is not particularly limited, the kind of the functional group that resulting fluorinated polymkeric substance is given according to hope and amount are selected and are determined.For example, form when only containing the fluorinated polymkeric substance of carboxylicesters functional group, select at least a monomer to carry out copolymerization respectively from above-mentioned the 1st group and the 2nd group and get final product.In addition, form when only containing the polymkeric substance of sulfonyl fluoride function, from the monomer of above-mentioned the 1st group and the 3rd group, select at least a monomer to carry out copolymerization respectively and get final product.In addition, form when having the fluorinated polymkeric substance of carboxylicesters functional group and sulfonyl fluoride function, from the monomer of above-mentioned the 1st group, the 2nd group and the 3rd group, select at least a monomer to carry out copolymerization respectively and get final product.In this case, also can make by above-mentioned the 1st group of multipolymer that becomes with the 2nd fabric and the multipolymer that becomes with the 3rd fabric by above-mentioned the 1st group polymerization respectively, mix then, thereby obtain target fluorinated polymkeric substance.And, the blending ratio of each monomer is not particularly limited, under the situation of the amount of the functional group that increases the unit polymkeric substance, as long as increase ratio by the monomer of above-mentioned the 2nd group and the 3rd group selection.
Total ion exchange capacity to the fluorinated multipolymer is not particularly limited, and is preferably 0.5mg equivalent/g～2.0mg equivalent/g in dry resin, more preferably 0.6mg equivalent/g～1.5mg equivalent/g.Herein, total ion exchange capacity refers to the equivalent of cation exchange groups of the per unit weight of dry resin, can be by mensuration such as neutralization titrations.
The film main body possesses the 1st layer of (carboxylic layer) 2 that comprises the fluorinated polymkeric substance with carboxylic acid group at least and comprises the 2nd layer of (sulphonic layer) 3 with sulfonic fluoropolymer.
Comprise the 2nd layer of (sulphonic layer) 3 with sulfonic fluoropolymer and be made of the low material of resistance, from the aspect of film toughness, preferred thickness is thicker.Comprise the 1st layer (carboxylic layer) of the fluorinated polymkeric substance with carboxylic acid group even the thin material that also has high anion exclusion of 2 preferred thickness.Said anion exclusion refers to hinder the character that negatively charged ion immerses and sees through to cationic exchange membrane 1 herein.By forming the film main body 10 of this layer structure, can further improve cationic selection perviousnesies such as sodium ion.
As used polymkeric substance in the 1st layer of (carboxylic layer) 2 that comprises the fluorinated polymkeric substance with carboxylic acid group, for example, in above-mentioned fluorinated polymkeric substance, preferred CF
2=CFOCF
2CF (CF
2) O (CF
2)
2COOCH
3
As comprising used polymkeric substance in the 2nd layer of (sulphonic layer) 3 with sulfonic fluoropolymer, for example, in above-mentioned fluorinated polymkeric substance, preferred CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2F.
(enhancing core)
The cationic exchange membrane 1 of present embodiment has the enhancing core 4 of the inside that is disposed at the film main body as described above.In the present embodiment, strengthen the parts that core 4 refers to strengthen physical strength and the dimensional stability of cationic exchange membrane.Be disposed at the inside of film main body by strengthening core 4, especially can be with the extension and contraction control of cationic exchange membrane in desired scope.This cationic exchange membrane 1 can be not flexible for more than the aequum because of hydrolysis or electrolysis etc., can long term maintenance excellent size stability.
The formation method that strengthens core 4 is not particularly limited, for example, can uses the line that will the be called as splicing thread material that forms that spins to form.Said splicing thread refers to constitute the parts that strengthen core 4 herein, can give cationic exchange membrane desired physical strength, and this line can stably exist in cationic exchange membrane 1.By using the enhancing core 4 that this splicing thread is spinned and forms, can give cationic exchange membrane 1 more excellent size stability and physical strength.
To strengthen core 4 and wherein the material of used splicing thread be not particularly limited, preferably bronsted lowry acids and bases bronsted lowry etc. is had the material of patience.Particularly, from long-term thermotolerance and the aspect of chemical proofing, more preferably comprise fluorine type polymer.As fluorine type polymer, can enumerate for example polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoraoethylene-hexafluoropropylene copolymer, chlorotrifluoroethylene-ethylene copolymer and vinylidene fluoride polymer (PVDF) etc.Among these, from the aspect of thermotolerance and chemical proofing, preferably polytetrafluoroethylene (PTFE).
Line for the splicing thread that strengthens core 4 directly is not particularly limited, is preferably 20 DENIER～300 DENIER, more preferably 50 DENIER～250 DENIER.In addition, the woven density of splicing thread (radical that beats up of unit length) is preferably 5 pieces/inch～50 pieces/inch.
Splicing thread can be monofilament, also can be multifilament.And, can also use they yarn, cut film silk etc.
As the form of the enhancing core 4 in the cationic exchange membrane 1, can use and utilize the weaving cotton cloth of above-mentioned splicing thread, non-woven fabrics, volume cloth.Among these, from the aspect of the easiness made, preferably weave cotton cloth.As the weave of weaving cotton cloth, the weave of preferred plain weave.The thickness of weaving cotton cloth is not particularly limited, is preferably 30 μ m～250 μ m, more preferably 30 μ m～150 μ m.
Weave and configuration to the enhancing core 4 in the film main body are not particularly limited, and can consider the size of cationic exchange membrane 1 and shape, to the desired rerum natura of cationic exchange membrane 1 and environment for use etc. and carry out suitable configuration aptly.For example, can strengthen core 4 along a direction configuration of the regulation of film main body, but from the aspect of dimensional stability, preferably the first direction configuration along regulation strengthens core 4, and along disposing other enhancing core 4 with the second direction of first direction approximate vertical.By at a plurality of enhancing cores of the almost parallel ground, inside of vertical film main body of film main body configuration, can be in multi-direction more excellent size stability and the physical strength of giving.For example, preferably inweaved the enhancing core 4 (warp) of configuration longitudinally and along the configuration of the enhancing core 4 (parallel) of landscape configuration on the surface of film main body.From the aspect of dimensional stability, physical strength and property easy to manufacture, the plain weave that the braiding of beating up while warp and parallel are alternately drifted along forms, twist two warps and inweave the doup weaving (Network body Woven り that forms with parallel), the parallel of the equal amts that beats up in the warp that disposes two or many being drawn respectively together and the square plain weave that weaves make (oblique sub-Woven り) etc.
Especially preferably strengthen core 4 along the MD direction (Machine Direction direction, vertical) of cationic exchange membrane 1 and the both direction configuration of TD direction (Transverse Direction direction, horizontal).That is, preferably at MD direction and TD direction plain weave.Herein, the MD direction refers to that film main body and various core are (for example in the manufacturing process of cationic exchange membrane described later, strengthen core 4, splicing thread, victim line described later etc.) delivery direction (flow direction), the TD direction refers to the direction with MD direction approximate vertical.And, will be called the MD line along the line that the MD direction is knitted, will be called the TD line along the line that the TD direction is knitted.Usually, the cationic exchange membrane 1 that is used for electrolysis is rectangle, and length direction mostly is the MD direction, and width mostly is the TD direction.By inweaving as the enhancing core 4 of MD line and enhancing core 4 as the TD line, can be in multi-direction more excellent size stability and the physical strength of giving.
The percentage of open area that strengthens core 4 is preferably more than 50% and below 90%.More preferably more than 60%, more preferably more than 65%.
Herein, percentage of open area refers to the ratio (B/A) of the total area (B) on the surface that the materials (electrolytic solution and the positively charged ion (for example sodium ion) that wherein contains) such as any surperficial area (A) intermediate ion in the film main body can pass through.
The total area on the surface that materials such as ion can pass through (B) refers to the total area in the zone that in cationic exchange membrane 1 positively charged ion and electrolytic solution etc. are not blocked by enhancing core 4 that cationic exchange membrane 1 contained and splicing thread etc.
Fig. 5 is the synoptic diagram for the percentage of open area of the enhancing core 4 of the cationic exchange membrane of explanation formation present embodiment.Among Fig. 5, the part of cationic exchange membrane 1 is amplified, in this zone, only illustrate the configuration that strengthens core 4, about miscellaneous part, omitted diagram.Herein, deduct the total area (C) that strengthens core 4 from the enhancing core 4 that comprises longitudinally configuration with along the shadow area (A) of the cationic exchange membrane of the enhancing core 4 of landscape configuration, thereby can obtain the total area (B) in the zone that the materials such as area (A) intermediate ion of aforementioned region can pass through.
That is, percentage of open area can be obtained by following formula (I).
Percentage of open area=(B)/(A)=((A)-(C))/(A) (I)
Concrete measuring method to percentage of open area describes.
Take the surface image of cationic exchange membrane (cationic exchange membranes before the coating coating etc.), obtain above-mentioned (B) by the area that does not have the part that strengthens core.And, obtain above-mentioned (A) by the area of the surface image of cationic exchange membrane, divided by above-mentioned (A), obtain percentage of open area with above-mentioned (B) thus.
As strengthening core 4, from chemical proofing and stable on heating aspect, particularly preferred form is the enhancing core that comprises PTFE, and from the aspect of intensity, particularly preferred form is flat filament or high oriented monofilament.Specifically, more preferably following enhancing core, its use will be cut into banded flat filament by high intensity, porous that PTFE constitutes or 50 DENIER～300 DENIER of the height-oriented monofilament that is made of PTFE, and be that woven density is 10 pieces/inch～50 pieces/inch plain weave, its thickness is the scope of 50 μ m～100 μ m.And above-mentioned percentage of open area is more preferably more than 60%.
Shape as splicing thread is not particularly limited, and can enumerate round line, stripline etc.
(communicating aperture)
The cationic exchange membrane 1 of present embodiment preferably has communicating aperture.
The hole of the positively charged ion that produces when communicating aperture refers to can be formed in electrolysis and the stream of electrolytic solution.
Communicating aperture refers to form by sacrifice core described later (or victim line) stripping in the hole of the tubulose of film body interior formation.The shape of communicating aperture and aperture etc. can be controlled by shape and the diameter selecting to sacrifice core (victim line).
By form communicating aperture in the inside of film main body, can guarantee the positively charged ion that when electrolysis, produces and the movability of electrolytic solution.
Shape to communicating aperture is not particularly limited.Utilizing method for making described later to make under the situation of cationic exchange membrane, owing to be dissolved in the communicating aperture that the victim line of acid or alkali forms the film main body, thereby the shape of communicating aperture becomes the shape of victim line.
In the cross section of cationic exchange membrane, communicating aperture is preferably alternately to form by the anode side (sulphonic layer side) of enhancing core and the mode of cathode side (carboxylic layer side).By being this structure, the electrolytic solution that flows and the positively charged ion (for example sodium ion) that wherein contains are shifted between the anode side of film main body and cathode side.Its result obtains relaxing for cationic mobile blocking during electrolysis, thereby can further reduce the resistance of cationic exchange membrane 1.
Communicating aperture can be only forms along a direction of the regulation of the film main body of the cationic exchange membrane 1 that constitutes present embodiment, but from the aspect of the more stable electrolysis performance of performance, and preferably the both direction at the vertical and horizontal of film main body forms.
(coating layer)
The aspect that gas is attached to cathode-side surface and anode-side surface when preventing electrolysis considers that as required, the cationic exchange membrane of present embodiment preferably also has the coating layer of any surperficial at least a portion of mulch film main body.
Fig. 6 is another routine schematic cross-section of the cationic exchange membrane of present embodiment.
11 covering of surface coated layer of the 1st layer of 2 side of film main body, 12 covering of surface coated layer of the 2nd layer of 3 side of film main body.
By utilizing the surface of coating layer 11,12 mulch film main bodys, the gas that produces in the time of can preventing electrolysis is attached to the film surface.Thus, cationic film perviousness can be further improved, thereby electrolysis voltage can be further reduced.
To constitute coating layer 11,12 material is not particularly limited, and from the aspect that prevents that gas from adhering to, preferably contains organic/inorganic substance.As inorganics, can enumerate for example zirconium white, titanium dioxide etc.
To form coating layer 11 in the film main body, 12 method is not particularly limited, and can use known method.For example, can enumerate by spraying etc. the subparticle with inorganic oxide is scattered in the method (spray method) that the liquid that forms in the binder polymer solution is coated with.As binder polymer, can enumerate vinyl compound that for example has the functional group that can convert sulfone type ion-exchange group to etc.Be not particularly limited for the coating condition, for example, can use spraying at 60 ℃.As the method beyond the spray method, for example can enumerate roller coat etc.
From preventing that gas from adhering to the aspect that the resistance that causes with thickness increases, coating layer 11,12 mean thickness are preferably 1 μ m～10 μ m.
In the cationic exchange membrane of Fig. 6, covered the surface of cationic exchange membrane shown in Figure 1 with coating layer 11,12, parts and formation about beyond the coating layer 11,12 can similarly adopt the parts and the formation that have illustrated as cationic exchange membrane 1.
(protuberance)
As shown in Figure 4, preferably to be formed with on the surface of film main body when cross-section highly be protuberance 5 more than the 20 μ m to the cationic exchange membrane of present embodiment.
Particularly, have protuberance 5 by making the 2nd layer of (sulphonic layer) 3, electrolytic solution is supplied to the film main body fully when electrolysis, thereby can further reduce the damage of film.
Usually, in order to reduce electrolysis voltage, cationic exchange membrane uses with the state with the anode driving fit.On the other hand, if cationic exchange membrane and anode driving fit, then the supply of electrolytic solution (salt solution etc.) is difficult to carry out, and the electrolysis of water takes place, and produces H+.It is known if then carboxylic layer is impaired for a large amount of generation H+.Thereby, form protuberance 5 by the surface at cationic exchange membrane, the driving fit of cationic exchange membrane and anode can be suppressed, thereby the supply of electrolytic solution can be successfully carried out.Its result can prevent that carboxylic layer is impaired.
Configuration density to protuberance 5 is not particularly limited, and from electrolytic solution being supplied to fully the aspect of film, is preferably 20/cm
2～1500/cm
2, 50/cm more preferably
2～1200/cm
2
Shape to protuberance 5 is not particularly limited, be preferably be selected from by in coniform, polygonal pyramid shape, round table-like, many terrace with edges shape, hemispherical, the dome-shaped group of forming more than a kind.In addition, the said hemispherical shape that is called as dome-shaped grade that also comprises herein.
The height of raised part 5, shape and configuration density can utilize following method to measure respectively and confirm.
At first, on the film surface of the square scope of 1000 μ m of cationic exchange membrane, with highly minimum point as benchmark.Then, will light from this benchmark highly is that part more than the 20 μ m is as protuberance.
As the measuring method of height, " the colored 3D laser microscope (VK-9710) " that use KEYENCE society to make carries out.Specifically, can at random cut out the part of 10cm * 10cm from the cationic exchange membrane of drying regime, with the fixing level and smooth plate of double sticky tape and the anode side of cationic exchange membrane, towards the mode of measuring lens the cathode side of cationic exchange membrane is arranged at the mensuration platform.In the film of each 10cm * 10cm, the shape on the square measurement range observation cationic exchange membrane surface of 1000 μ m as benchmark, is measured the height that rises from here with highly minimum point, observes protuberance thus.
In addition, about the configuration density of protuberance, at random cut out the film of the 3 10cm * 10cm of place, in the film of this each 10cm * 10cm, will measure the value that 9 places obtain in the square measurement range of 1000 μ m and average, resulting value is the configuration density of protuberance.
(manufacture method of cationic exchange membrane)
As the suitable manufacture method of the cationic exchange membrane of present embodiment, can enumerate the method for the operation with following (1)～(5).
(1) makes the operation of fluorinated polymkeric substance have ion-exchange group or can form the ion-exchange based precursor of ion-exchange group by hydrolysis.
(2) by inweaving the be enhanced operation of material of a plurality of enhancing cores; Perhaps, by inweaving character and the victim line that forms communicating aperture with the acid of being dissolved in or alkali and strengthening core, obtain disposing each other at adjacent enhancing core the operation of the strongthener of victim line thus.
(3) will have ion-exchange group or can obtain the operation of film by the above-mentioned fluorinated polymkeric substance membranization that hydrolysis forms the ion-exchange based precursor of ion-exchange group.
(4) in above-mentioned film, imbed above-mentioned strongthener, obtain having in internal configuration the operation of the film main body of above-mentioned strongthener.
(5) with acid or the above-mentioned victim line of alkali dissolution, form the operation (hydrolyzing process) of communicating aperture thus in the inside of film main body.
In the manufacture method of the cationic exchange membrane of present embodiment, by controlling temperature, pressure, time in the operation of the above-mentioned strongthener of imbedding of (4) and above-mentioned film, thereby the specific position that can be formed in film inside disposes the cationic exchange membrane that strengthens core.Below be elaborated.
(1) operation: the manufacturing process of fluorinated polymkeric substance
In the present embodiment, in order to control the loading capacity of fluorinated polymkeric substance, the ratio of mixture etc. of adjusting the monomer of raw material in its manufacturing process gets final product.
(2) operation: the operation of the material that is enhanced
Strongthener refers to weave that splicing thread forms weaves cotton cloth etc.By in film, imbedding strongthener, form and strengthen core.
When making the cationic exchange membrane with communicating aperture, victim line also inweaves together, forms strongthener.The mixed amount of knitting of victim line of this moment is preferably the 10 quality %～80 quality % of strongthener integral body, 30 quality %～70 quality % more preferably.Perhaps, polyvinyl alcohol that also preferably have the rugosity of 20 DENIER～50 DENIER, is constituted by monofilament or multifilament etc.Imbed victim line stripping in the operation of aftermentioned hydrolysis of film inside, thereby at the inner communicating aperture that forms of film.Need to prove, in (2) operation, by adjusting the configuration that strengthens core and victim line etc., can control the configuration of communicating aperture etc.
(3) operation: membranization operation
In (3) operation, use forcing machine with the fluoropolymer membranization that obtains in (1) operation.Film can be single layer structure, also can be the double-layer structure of sulphonic layer and carboxylic layer as mentioned above, can also be the multilayered structure more than three layers.
As the method for membranization, can enumerate following method.
At first, under the situation of double-layer structure that is sulphonic layer and carboxylic layer, can enumerate following method.
To form the fluoropolymer with carboxylic acid group of carboxylic layer and form the sulfonic fluoropolymer of having of the sulphonic layer method of membranization respectively.
To form the fluoropolymer with carboxylic acid group and the method that sulfonic fluoropolymer is made composite membrane that has that forms sulphonic layer of carboxylic layer by coextrusion.
Then, under the situation that is the multilayered structure more than three layers, can enumerate following method.
The method of the fluoropolymer difference membranization of each layer will be constituted.
To constitute specific two-layer fluoropolymer by coextrusion and make composite membrane, will constitute the method for the fluoropolymer difference membranization of other layers.
The fluoropolymer that will constitute each layer by coextrusion is made the method for composite membrane.
The coextrusion of plural layer helped to improve the bonding strength at interface, thus preferred.
(4) operation: the operation that obtains the film main body
In (4) operation, the strongthener that obtains in (2) operation is imbedded the inside of the film that obtains in (3) operation, obtain the film main body that there is strongthener in inside thus.
As the method for imbedding, can enumerate following method: have heating source and/or vacuum source and surface in inside and have on the flat board or cylinder of a large amount of pores, across the stable on heating release paper with ventilation property lamination strongthener, film successively, while it is integrated to remove the air of each interlayer by decompression under the temperature of the fluoropolymer melt of film.
At first, under the situation of double-layer structure that is sulphonic layer and carboxylic layer, can enumerate following method: on cylinder successively the film of lamination release paper, strongthener, formation sulphonic layer, constitute carboxylic layer film and integrated method; Perhaps successively lamination release paper, strongthener, sulphonic layer towards the composite membrane of strongthener side and integrated method; The film of lamination release paper, the film that constitutes sulphonic layer, strongthener, formation carboxylic layer and integrated method successively.
Secondly, under situation about making the long-pending multilayered structure that forms of the rete more than three, can enumerate following method: on cylinder successively lamination release paper, strongthener, constitute each layer the film of multi-disc and integrated method; On cylinder successively lamination release paper, the film that constitutes the multi-disc of each layer, strongthener, constitute each layer the film of multi-disc and integrated method; Etc..Under the situation of making the multilayered structure more than three layers, preferably to adjust so that constitute the rete of carboxylic layer and amass in distance cylinder position farthest, the rete that constitutes sulphonic layer amasss in the near position of distance cylinder.
More preferably on cylinder successively lamination release paper, the film that constitutes the sulfone layer, strongthener, sulphonic layer side towards the composite membrane of strongthener and integrated method.Utilize this method lamination and the cationic exchange membrane of integrated three-decker can increase the ratio with respect to distance C D apart from BD, thus preferred.
In addition, because strongthener is fixed in film inside, thereby can fully keep the physical strength of cationic exchange membrane.Need to prove that the variation of Shuo Ming lamination herein only is an example, can consider the suitable lamination patterns (for example, the combination of each layer etc.) of suitable selection such as the layer structure of desired film main body and rerum natura, carry out coextrusion then.
In the manufacture method of the cationic exchange membrane of present embodiment, under the temperature of each polymer melt by the decompression in the integrated operation of the air of removing each interlayer, by control temperature, the pressure of decompression, time, the position of enhancing core that can controlling diaphragm inside.
If improve temperature, polymer melt then, the mobile rising can increase apart from BD.As temperature, its strongthener and fluoropolymer during because of lamination is different, is preferably 210 ℃～260 ℃, controls in this temperature range with decompression degree, time.
If the pressure (decompression degree) when increasing decompression, polymer phase is embedded in easily for strengthening core, thereby can increase apart from BD.Decompression degree when attracting with cylinder, its strongthener and fluoropolymer during because of lamination is different, is preferably 65kPa～90kPa, controls in the scope of this decompression degree with temperature, time.
If time expand, polymer melt then, the mobile time is elongated, thereby can increase apart from BD.As the time that ion-exchange membrane is positioned over the machine of imbedding, its strongthener and fluoropolymer during because of lamination is different, is preferably 0.5 minute～5 minutes, controls in this time range with temperature, decompression degree.
In order further to improve the electric property of cationic exchange membrane, can also between sulphonic layer and carboxylic layer, further be mingled with and contain the two layer of carboxylicesters functional group and sulfonyl fluoride function, perhaps use the layer that contains carboxylicesters functional group and sulfonyl fluoride function to replace sulphonic layer.
The method that forms this layer both can also can be the method for this multipolymer of use after the monomer that will contain carboxylicesters functional group and the two copolymerization of monomer that contains sulfonyl fluoride function for making the polymkeric substance that contains carboxylicesters functional group respectively and containing the method for mixing behind the polymkeric substance of sulfonyl fluoride function.
To contain under the two the situation of mixolimnion as the formation of cationic exchange membrane of carboxylicesters functional group and sulfonyl fluoride function, can be with the co-extruded films moulding of carboxylic layer and this mixolimnion, sulphonic layer and its be membranization separately in addition differently, utilize aforesaid method to carry out lamination, can also utilize coextrusion with three layers of disposable membranization of carboxylic layer/mixolimnion/sulphonic layer.
Like this, can form the film main body that comprises the fluorinated polymkeric substance with ion-exchange group at strongthener.
As mentioned above, in the cationic exchange membrane of present embodiment, regulation be 0.11～0.5 apart from BD with respect to the ratio (BD/CD) of distance C D of regulation.
In addition, distance A B is preferably 0.52～0.8 with respect to the ratio (AB/AC) of the distance A C of regulation.
In order to control the relative position relation that strengthens core 4 and film main body, as mentioned above, in the operation that obtains the film main body, when integrated while the air of removing each interlayer by decompression under the temperature of each polymer melt, as long as control pressure, the time of temperature, decompression aptly, the position of the enhancing core of controlling diaphragm body interior gets final product.
In addition, in the cationic exchange membrane of present embodiment, the method that the surface in the film main body is formed protuberance is not particularly limited, and can adopt the known method that forms protuberance at resin surface.As the method that forms protuberance in the present embodiment on the surface of film main body, specifically, can enumerate on the surface of film main body and implement the embossing method for processing.For example, when above-mentioned composite membrane and strongthener etc. are integrated, the release paper that has carried out embossing processing in advance can be used, raised part can be formed thus.Be processed to form by embossing under the situation of protuberance, the height of protuberance and configuration density can be controlled by the embossing shape (shape of release paper) of control transfer printing.
(5) operation: the operation of hydrolysis
In (5) operation, with the film main body hydrolysis that obtains in above-mentioned (4) operation, make cationic exchange membrane with acid or alkali.Contain at strongthener under the situation of victim line, remove by using acid or alkali dissolution, thereby can form communicating aperture in the film main body.
Victim line has solvability for acid or alkali under the manufacturing process of cationic exchange membrane and electrolytic environments, by with acid or alkali stripping victim line, thereby form communicating aperture at this position.Like this, can obtain having formed in the film main body ion-exchange membrane of communicating aperture.
(5) used acid or alkali needs only the dissolving victim line in the operation, and its kind is not particularly limited.As acid, for example can enumerate hydrochloric acid, nitric acid, sulfuric acid, acetic acid, contain gifblaar poison.
As alkali, can enumerate for example potassium hydroxide, sodium hydroxide.
Herein, the operation that forms communicating aperture by the stripping victim line is described in detail.
Fig. 7 (a), Fig. 7 (b) are the synoptic diagram for the method for the communicating aperture of the cationic exchange membrane of explanation formation present embodiment.
Among Fig. 7 (a), only illustrate enhancing core 4 and victim line 504a (communicating aperture 504 of Xing Chenging thus), about miscellaneous parts such as film main bodys, omitted diagram.At first, inweave enhancing core 4 and victim line 504a, as strongthener.Then, victim line 504a stripping in above-mentioned (5) operation forms communicating aperture 504 and aperture portion (not shown) thus shown in Fig. 7 (b).
Based on aforesaid method, how to dispose according to the film body interior at cationic exchange membrane strengthen core 4, communicating aperture 504 is adjusted the method that inweaves that strengthens core 4 and victim line 504a and got final product, and is thereby very easy.Among Fig. 7 (a), example is illustrated in paper has longitudinally inweaved the plain weave that strengthens core 4 and victim line 504a with horizontal both direction strongthener, can change enhancing core 4 in the strongthener and the configuration of victim line 504a as required.
In addition, in (5) operation, the film main body hydrolysis that obtains in above-mentioned (4) operation can also be imported ion-exchange group to the ion-exchange based precursor.
Through after above-mentioned (1) operation～(5) operation, can form coating layer on the surface of resulting cationic exchange membrane.
Coating layer is not particularly limited, can utilizes known method to form.For example, can enumerate by spraying etc. the subparticle with inorganic oxide is scattered in the method (spray method) that the liquid that forms in the binder polymer solution is coated with.As binder polymer, can enumerate vinyl compound that for example has the functional group that to change sulfone type ion-exchange group into etc.The coating condition is not particularly limited, for example, can uses spraying at 60 ℃.As the method beyond the spray method, for example can enumerate roller coat etc.
(electrolyzer)
The cationic exchange membrane of present embodiment can use it to make electrolyzer.
Fig. 8 is the synoptic diagram of an embodiment of the electrolyzer of present embodiment.
The electrolyzer 100 of present embodiment possess anode 200, negative electrode 300 at least and be disposed at anode 200 and negative electrode 300 between cationic exchange membrane 1.
Herein, describe as an example with the electrolyzer 100 that possesses above-mentioned cationic exchange membrane 1, but be not limited thereto, can in the scope of the effect of present embodiment, various formations are out of shape to implement.This electrolyzer 100 can be used for various electrolysis, below, as typical example, the situation of the electrolysis that is used for aqueous alkali metal chloride is described.
Electrolytic condition is not particularly limited, can under known condition, carries out.
For example, can the anode chamber supplying with the aqueous alkali metal chloride of 2.5 equivalents (N)～5.5 equivalents (N), supply with the alkali metal hydroxide aqueous solution of water or dilution to cathode compartment, is that 50 ℃～120 ℃, current density are 5A/dm at electrolysis temperature
2～100A/dm
2Condition under carry out electrolysis.
Formation to the electrolyzer 100 of present embodiment is not particularly limited, and for example, can also can be multipole type for acyclic type.The material that constitutes electrolyzer 100 is not particularly limited, for example, as the material of anolyte compartment, preferably alkali metal chloride and chlorine is had the titanium etc. of patience, as the material of cathode compartment, preferably alkali metal hydroxide and hydrogen are had the nickel etc. of patience.About the configuration of electrode, can between cationic exchange membrane 1 and anode 200, proper spacing be set and be configured, even but be configured with the mode that cationic exchange membrane 1 contacts with anode 200, can not have any problem ground yet and use.And negative electrode usually arranges proper spacing with cationic exchange membrane and is configured, even but do not have the electrolyzer (zero space type electrolyzer) of the contact-type at this interval, do not use with can having any problem yet.
By using the cationic exchange membrane 1 of present embodiment, can runs steadily.In the past, in the salt solution of electrolysis, contained SiO
2Under the situation Deng impurity, the reduction of current efficiency may be occurred, but by using the cationic exchange membrane of present embodiment, the reduction of current efficiency can be suppressed.
Embodiment
Below, describe the present invention in detail by embodiment.Need to prove, the invention is not restricted to following examples.Need to prove, short of special declaration, then following unit is based on quality criteria.
(observation in film cross section)
In the cationic exchange membrane of embodiment 1～3 described later, comparative example 1～3, to each distance (BD, CD, AB, AC) following mensuration of the some A～D that links following definitions.
An A～D is following above-mentioned for point.
A point A～D determines comprising the 1st layer of fluorinated polymkeric substance with carboxylic acid group and comprise in the cross section of the 2nd layer lamination direction with sulfonic fluoropolymer.
A: the center that strengthens core
B: supposition is from above-mentioned some A to the distance that comprises the 2nd layer film surface with sulfonic fluoropolymer during for the shortest straight line, this straight line and the intersection point that comprises the 2nd layer film surface with sulfonic fluoropolymer
C: above-mentioned straight line and the intersection point that comprises the 1st layer film surface of the fluoropolymer with carboxylic acid group
D: the intersection point of close B in the intersection point of the periphery of above-mentioned straight line and above-mentioned enhancing core
For the composite membrane before being hydrolyzed, comprising the enhancing core of 16 MD directions, comprising the scope of the enhancing core of 16 TD directions, cut out 3 samples.
As shown in Figure 9, for the sample that cuts out, with the intersection point that link to strengthen core and the mode of crossing over the enhancing core 4 of three TD directions,, cut obliquely as the dotted line among Fig. 9 to the 16th from the 1st of the enhancing core of MD direction.
For the cross section of the sample after the cutting, use microscope (OLYMPUS BH-2) to carry out each Determination of distance.
About the value of each distance, in each sample, measure in the cross section at 5 places, will be in the value of the mean value that amounts to the value of measuring at 15 places as each distance.
(tear strength evaluation)
Following evaluation of tear strength for cationic exchange membrane.
The test pin (Homes て Needles) of tear tester (the smart machine elmendorf of Japan) is contacted with the pin switchboard, and mobile pendulum is adjusted the position of testing the pin switchboard, refers to zero of scale card subsidiary on its aligning pendulum.
Mobile No. three pendulums are confirmed scale card aligning zero really.
Then, after saponification (hydrolysis), with water reach the aftermentioned embodiment 1～3 of equilibrium state, the ion-exchange membrane of comparative example 1～3 cuts 7 respectively with the size of TD direction 75mm, MD direction 63mm and TD direction 63mm, MD direction 75mm, make fluoropolymer with carboxylic acid group layer the face side in the presence of, width be arranged at above-mentioned tear tester for the 75mm side and bind.
Be a side of 63mm side at width, use the cutter penetraction depth of tear tester to be the otch of 20mm, the test pin is contacted with the pin switchboard.
Press the switch of tear tester, mobile pendulum, the tear strength of mensuration film.
About evaluation result, for TD direction, MD direction, the maximum value in will having removed 7 respectively, 5 result's of minimum value mean value is as evaluation result.
(embodiment 1)
As strengthening core, use the flat filament of polytetrafluoroethylene (PTFE) system, 150 DENIER is twisted the thread (hereinafter being called the PTFE line) that forms with 900 times/m.
At first, with 22 pieces/inch the PTFE line is carried out plain weave, weaved cotton cloth (strongthener).
Then, use CF
2=CF
2And CF
2=CFOCF
2CF (CF
3) OCF
2CF
2COOCH
3Multipolymer make the polymer A of dry resin (loading capacity be 0.92mg equivalent/g), use CF
2=CF
2And CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2The multipolymer of F is made the polymer B of dry resin, and (loading capacity is 1.1mg equivalent/g).
Use these polymer A and B, obtain film X1 by coextrusion T modulus method.Among the film X1, the thickness of polymer A layer is that the thickness of 28 μ m, polymer B layer is 77 μ m.
In addition, use polymer B to obtain film X2.The thickness of film X2 is 51 μ m.
For above-mentioned strongthener, film X1 and X2, have on minute aperture and the inner cylinder with heating source and vacuum source lamination release paper, film X2, strongthener, film X1 successively on the surface, after the heating decompression, remove release paper, obtain composite membrane thus.
The processing temperature of this moment is that 223 ℃, decompression degree are that 77kPa, the time of imbedding are 2 minutes.
Resulting composite membrane 95 ℃ of hydrolysis after 1 hour, is washed, drying.
And then, the zirconium white that 1 particle diameter that adds 20 quality % in 5 quality % ethanolic solns of the acid-based polymer of polymer B is 1 μ m, concoct the suspension of its dispersion of sening as an envoy to, and utilize spray method this suspension of spraying on the two sides of above-mentioned composite membrane, surface at composite membrane forms coating layer, obtains cationic exchange membrane.
Utilize microscope that the cross section of resulting cationic exchange membrane is observed, the results are shown in following table 1.
The tear strength of the cationic exchange membrane that as above obtains is 5.6kg in the MD direction, be 5.6kg in the TD direction.
(embodiment 2)
As polymer A, use loading capacity as the polymkeric substance of 0.67mg equivalent/g, as polymer B, use loading capacity to be the polymkeric substance of 0.95mg equivalent/g.
Loading capacity is recently controlled by the mixing of adjusting monomer.
In addition, among the film X1, the thickness that makes the polymer A layer is 17 μ m, and the thickness that makes the polymer B layer is 53 μ m.
In addition, in the operation of each material of lamination, except processing temperature being changed to 221 ℃, will degree of decompression changing to the 77kPa, make cationic exchange membrane similarly to Example 1.
Utilize microscope that the cross section of resulting cationic exchange membrane is observed, the results are shown in following table 1.
The tear strength of the cationic exchange membrane that as above obtains is 5.3kg in the MD direction, be 6.0kg in the TD direction.
(comparative example 1)
Among the film X1, the thickness that makes the polymer A layer is 25 μ m, and the thickness that makes the polymer B layer is 38 μ m.In addition, in the operation of each material of lamination, except processing temperature being changed to 220 ℃, will degree of decompression changing to the 70kPa, make cationic exchange membrane similarly to Example 1.
Utilize microscope that the cross section of resulting cationic exchange membrane is observed, the results are shown in following table 1.
The tear strength of the cationic exchange membrane that as above obtains is 4.2kg in the MD direction, be 4.6kg in the TD direction.
(comparative example 2)
In the operation of each material of lamination, except processing temperature being changed to 223 ℃, will degree of decompression changing to the 70kPa, make cationic exchange membrane similarly to Example 2.
Utilize microscope that the cross section of resulting cationic exchange membrane is observed, the results are shown in following table 1.
The tear strength of the cationic exchange membrane that as above obtains is 4.7kg in the MD direction, be 5.4kg in the TD direction.
[table 1]
Among the embodiment 1 and 2, BD/CD is 0.11～0.5, and they are compared with 2 with comparative example 1, as can be known the tear strength height.
(embodiment 3)
As the splicing thread that constitutes strongthener, use used PTFE line among the embodiment 1.
As victim line, use the polyethylene terephthalate (PET) of 90 DENIER, 6 (filament) is twisted the line (hereinafter being called the PET line) that forms with 200 times/m.
And, carry out plain weave and weaved cotton cloth (strongthener), make that the PTFE line is 24 pieces/inch, configuration 2 victim line (with reference to Fig. 7) between the PTFE line.
Then, use CF
2=CF
2And CF
2=CFOCF
2CF (CF
3) OCF
2CF
2COOCH
3Multipolymer make the polymer A of dry resin (loading capacity be 0.85mg equivalent/g), use CF
2=CF
2And CF
2=CFOCF
2CF (CF
3) OCF
2CF
2SO
2The multipolymer of F is made the polymer B of dry resin, and (loading capacity is 1.0mg equivalent/g).
Use these polymer A and B, obtain film Y by coextrusion T modulus method.The thickness of polymer A layer is that the thickness of 15 μ m, polymer B layer is 104 μ m.
For the strongthener that obtains, film Y herein, have on minute aperture and the inner cylinder with heating source and vacuum source lamination release paper, strongthener, film Y successively on the surface, after the heating decompression, remove release paper, obtain composite membrane thus.The processing temperature of this moment is that 243 ℃, decompression degree are that 77kPa, the time of imbedding are 2 minutes.
, similarly to Example 1 make, obtain cationic exchange membrane thereafter.
Utilize microscope that the cross section of resulting cationic exchange membrane is observed, the results are shown in following table 2.
The tear strength of the cationic exchange membrane that as above obtains is 3.0kg in the MD direction, be 3.0kg in the TD direction.
(comparative example 3)
In the operation of each material of lamination, except processing temperature being changed to 235 ℃, will degree of decompression changing to the 77kPa, make cationic exchange membrane similarly to Example 3.
Utilize microscope that the cross section of resulting cationic exchange membrane is observed, the results are shown in following table 2.
The tear strength of the cationic exchange membrane that as above obtains is 2.6kg in the MD direction, be 2.6kg in the TD direction.
[table 2]
In embodiment 3 and the comparative example 3, victim line is imbedded in the strongthener together, is the cationic exchange membrane that is formed with communicating aperture in the film main body.
The BD/CD of embodiment 3 is 0.11～0.5, compares with comparative example 3, as can be known the tear strength height.
Industrial applicibility
Cationic exchange membrane of the present invention can suit as the cationic exchange membrane of alkali chloride electrolysis etc.
Claims (4)
1. cationic exchange membrane, it is the cationic exchange membrane that has the film main body and strengthen core, and described film main body comprises the fluorinated polymkeric substance with ion-exchange group, and described enhancing core is disposed at the inside of described film main body, wherein,
Described film main body has layers 1 and 2, and described the 1st layer comprises the fluorinated polymkeric substance with carboxylic acid group, and described the 2nd layer comprises and have sulfonic fluoropolymer,
In described the 1st layer of cross section with described the 2nd layer lamination direction, in supposition from the center A of described enhancing core to the described distance that comprises the 2nd layer film surface with sulfonic fluoropolymer during for the shortest straight line,
On this straight line, will be made as B with the described intersection point that comprises the 2nd layer film surface with sulfonic fluoropolymer,
On this straight line, will be made as C with the described intersection point that comprises the 1st layer film surface of the fluoropolymer with carboxylic acid group,
On this straight line, will with the intersection point of the periphery of described enhancing core in be made as D near the intersection point of B,
Then be 0.11～0.5 apart from BD/ distance C D this moment.
2. cationic exchange membrane as claimed in claim 1, wherein, distance A B/ distance A C is 0.52～0.8.
3. cationic exchange membrane as claimed in claim 1 or 2 wherein, has the communicating aperture of tubulose in the inside of described film main body.
4. electrolyzer, it possesses at least:
Anode,
Negative electrode and
Be disposed at each described cationic exchange membrane in the claim 1～3 between described anode and the described negative electrode.
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|---|---|---|---|
| JP2012028820A JP5774514B2 (en) | 2012-02-13 | 2012-02-13 | Cation exchange membrane and electrolytic cell using the same |
| JP2012-028820 | 2012-02-13 |
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Cited By (7)
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Also Published As
| Publication number | Publication date |
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| CN103243345B (en) | 2016-02-10 |
| JP2013163859A (en) | 2013-08-22 |
| JP5774514B2 (en) | 2015-09-09 |
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