CN101773788B - Fluorine-containing ion exchange membrane with reinforced sacrificial fiber mesh cloth - Google Patents
Fluorine-containing ion exchange membrane with reinforced sacrificial fiber mesh cloth Download PDFInfo
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- CN101773788B CN101773788B CN 200910231445 CN200910231445A CN101773788B CN 101773788 B CN101773788 B CN 101773788B CN 200910231445 CN200910231445 CN 200910231445 CN 200910231445 A CN200910231445 A CN 200910231445A CN 101773788 B CN101773788 B CN 101773788B
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Abstract
The invention relates to a fluorine-containing ion exchange membrane with reinforced sacrificial fiber mesh cloth, which comprises a fluorine-containing ion exchange resin base membrane, mesh cloth with sacrificial fiber and a hydrophilic coating, wherein the fluorine-containing ion exchange resin base membrane comprises a perfluorocarboxylic acid resin membrane layer of 5-10 micrometers, a perfluorosulfonic acid resin membrane layer of 90-120 micrometers, and a perfluorosulfonic acid/perfluorocarboxylic acid copolymerization or blending resin membrane layer of 0-40 micrometers, which is positioned between the perfluorocarboxylic acid membrane layer and the perfluorosulfonic acid membrane layer; and the mesh cloth with the sacrificial fiber comprises reinforced fiber and sacrificial fiber. In the invention, the fluorine-containing ion exchange membrane with the reinforced sacrificial fiber mesh cloth can improve the electrochemical properties of the membrane and can effectively reduce the resistance of the membrane.
Description
Technical field
The invention belongs to functional fluoropolymer polymer composite field, particularly fluoride ion exchange multilayer film of band sacrificial fiber mesh cloth enhancing and preparation method thereof.
Background technology
The perfluorinated ion-exchange membrane material has purposes very widely, can be used to comprise the barrier film of the various electrolytic preparation devices of chlorine industry machine, in addition, also demonstrate excellent serviceability at aspects such as electrodialysis, chemical catalysis, gas separation, gas drying, sewage disposal, desalinizations.
Amberplex is the core of ionic membrane method alkali-chloride electrolytic cell, and the residing electrolytic condition of membrane material is harsh in electrolytic process, and a side of film is the acid brine and the chlorine of high-temperature high concentration, and opposite side then is the alkali lye of high-temperature high concentration.Therefore, be to adapt to electrolytic condition, ionic membrane must have good chemistry and heat endurance, superior chemical property and low film resistance, and has excellent mechanical intensity.The fluoride ion film of chlor-alkali industry use now is owing to the stability of C-F bond structure, and the fluoride ion film can satisfy the electrolysis requirement under common electrolytic condition.But the development along with chlor-alkali industry and ionic membrane research requires ionic membrane to have higher current density and low membrane voltage, will have higher mechanical strength and dimensional stability simultaneously and have the favorable mechanical processing characteristics.
Prior art adopts the composite membrane of sulfonic acid polymer and carboxylic acid polyalcohol composition usually or introduces the chemical property that functional inorganic matter improves ionic membrane.Obtain high current density and keep certain mechanical strength and dimensional stability simultaneously for solving ionic membrane, adopt the mechanical strength of materials enhancing ionic membranes such as fiber, cloth, fabric usually, keep the dimensional stability of membrane material.European patent EP 0875524B1 discloses and has utilized the glass fibre membrane of glass fibre non-woven technology preparation to strengthen Du Pont
The technology of series membranes is mentioned oxides such as silica simultaneously in this patent document.But non-woven glass fibre cloth is the base material that must use in this patent document, and this will limit the scope of application of film greatly.
U.S. Pat 6692858 discloses the technology that polytetrafluoroethylene fibre strengthens perfluorinated sulfonic resin, be with perfluor sulfonyl fluororesin and polytetrafluoroethylene fibre mix, extrude, to make the transition make fibre-reinforced perfluorinated sulfonic resin.This method can not be produced continuously because transformation process is consuming time, does not also have functional inorganic matter to improve the electric conductivity of film simultaneously.
The perfluorinated ion-exchange membrane that is used for chlor-alkali industry need satisfy: good electro-chemical properties, low membrane voltage, high mechanical properties and dimensional stability.Generally speaking, when the perfluorinated ion-exchange membrane ion exchange capacity became big, film resistance can reduce, but mechanical strength can reduce.
Summary of the invention
At the deficiency that technology is arranged now, the purpose of this invention is to provide fluorine-containing multilayer amberplex that screen cloth that a kind of usefulness that has better electro-chemical properties and mechanical strength simultaneously contains sacrificial fiber strengthens and preparation method thereof, is the perfluorinated ion-exchange membrane that is applicable to chlor-alkali industry.
Technical scheme of the present invention is as follows:
A kind of exchange membrane containing fluorine with the sacrificial fiber mesh cloth enhancing, this film is by ion exchange fluoro resin basement membrane, the screen cloth of band sacrificial fiber and the multilayer complex films that hydrophilic coating is formed; Wherein the ion exchange fluoro resin basement membrane comprises perfluorinated carboxylic acid resin's rete of 5-10 micron, the perfluorinated sulfonic resin rete of 90-120 micron, and the perfluorinated sulfonic acid/carboxyl acid copolymer of the 0-40 micron between perfluorocarboxylic acid rete and perfluorinated sulfonic acid rete or blending resin rete, the screen cloth of band sacrificial fiber is formed by fortifying fibre and sacrificial fiber braiding.
Above-mentioned ion exchange fluoro resin basement membrane gross thickness between the 95-170 micron, preferred 95-130 micron.
Above-mentioned fortifying fibre is selected from: one or more in glass fibre, polytetrafluoroethylene (PTFE) fiber, perfluoroethylene-propylene fiber, ion exchanging function fiber (CN101003588), poly-perfluoro propyl vinyl ether fiber, tetrafluoroethene-perfluoroalkyl vinyl ether copolymer fibre fluorocarbon polymer fiber, polyphosphazene fiber, polyphenylene sulfide fibre, nylon, ceramic fibre, quartz fibre, mineral fibres, oxide fibre or the silicon carbide fibre.
Above-mentioned sacrificial fiber is selected from polyester fiber, cellulose, artificial silk or Fypro.
Above-mentioned hydrophilic coating is by the ZrO that contains the 3-5wt% perfluorinated sulfonic resin
2Drying formed after-alcohol dispersion liquid was coated in the ion exchange resin membrane surface.
ZrO
2-alcohol dispersion liquid is the ZrO that adds 10-15wt% particle diameter 3-5 micron in absolute ethyl alcohol
2The aaerosol solution that forms.
Preferably, perfluorocarboxylic acid film ion exchange capacity is 0.8～1.0mmol/g, and thickness is between the 8-10 micron; The perfluoro sulfonic acid membrane ion exchange capacity is 0.9～1.0mmol/g, and thickness is between the 100-110 micron.
The main chain of ion exchange fluoro resin involved in the present invention is to form by Fluorine containing olefine, one or more fluorine-containing alkene monomer copolymerization that contain functional group.Described Fluorine containing olefine is selected from tetrafluoroethene, CTFE, trifluoro-ethylene, hexafluoropropene or vinylidene, preferred tetrafluoroethene, CTFE or hexafluoropropene, more preferably tetrafluoroethene.
The fluorine-containing alkene monomer of functional group that contains that uses is general formula (I), (II) one or more in (III):
Wherein, a, b, c can be respectively 0 or than 0 big integer, but can not be zero simultaneously;
D be 0 or than 0 big integer
N be 0 or than 0 big integer;
R
F1, R
F2And R
F3Can from perfluoroalkyl or dichlorodifluoromethan base, choose respectively;
X can be from F, Cl, and Br chooses one or more among the I;
Y
1, Y
2, Y
3Can be the identical or different functional group of structure, comprise SO
2M, M can be from F, Cl, OR (R is C1～C20 alkyl, aryl, also can be H, metal ion or ammonium root), COOR
4(R
4=be C1～C20 alkyl, aryl, also can be H, metal ion or ammonium root).
Preferably containing the fluorine-containing alkene monomer of functional group is general formula (I), and n=1～2, X=F, b=c=0, a=1～5, Y
1=SO
2M or n=0, b=c=0, a=1～5, Y
1=SO
2M.
Work as Y
1, Y
2, Y
3All select SO
2During M, adopt this type of monomer copolymerization to make perfluorinated sulfonic resin,
Work as Y
1, Y
2, Y
3All select COOR
4The time, adopt this type of monomer copolymerization to make the perfluorinated carboxylic acid resin,
Work as Y
1, Y
2, Y
3Be selected from SO respectively
2M and COOR
4The time, adopt this type of monomer copolymerization to make perfluorinated sulfonic acid/carboxyl acid copolymer resin.
The preparation method of the exchange membrane containing fluorine that band sacrificial fiber mesh cloth of the present invention strengthens, step is as follows:
A, the copolymer that adopts described perfluorinated sulfonic resin, perfluorinated carboxylic acid resin, perfluorinated sulfonic resin and perfluorinated carboxylic acid resin or blend are by melt extruding or the technology of lamination hot pressing prepares the ion exchange fluoro resin basement membrane;
B, the enhancing screen cloth that adopts the continous vacuum combination process will have sacrificial fiber are inserted inner formation of ion exchange fluoro resin basement membrane and are strengthened ionic membrane;
C, with the processing that makes the transition in hydrolysis 10-15 hour in 90 ℃ the 25wt%KOH aqueous solution of step b gained ionic membrane; With the ZrO that contains the 3-5wt% perfluorinated sulfonic resin
2-alcohol dispersion liquid is carried out double-face spray painting to the ionic membrane after making the transition, and dry back forms hydrophilic coating;
Among the above-mentioned steps b, preferably strengthening screen cloth has the thickness of 1-10% to expose the surface that fluoride ion exchanges basement membrane, forms screen cloth profile roughness in membrane surface.
The part that the fortifying fibre screen cloth exposes fluoride ion exchange basement membrane also applies hydrophilic coating.
The present invention also provides the weaving method of the enhancing screen cloth of band sacrificial fiber, and step is as follows:
Select above-mentioned fortifying fibre monofilament or multifilament for use, tow fineness is that 80-100 danier and filament diameter are that the sacrificial fiber tow of 10-20 μ m alternately is woven into plain weave structure.The count of fortifying fibre is 3-40 root/cm, and per two bundles have 2 groups of sacrificial fiber between the fortifying fibres, and the sacrificial fiber tiling is arranged in groups, is made up of 8-10 root monofilament for every group.
Excellent results of the present invention is as follows:
1. the exchange membrane containing fluorine that band sacrificial fiber mesh cloth of the present invention strengthens can improve the electro-chemical properties of film, effectively reduces film resistance.
2. the arrangement because sacrificial fiber tiles, the duct of retaining after molten the removing is shallow, and is low to the damage of basement membrane itself, makes amberplex have high mechanical properties, uniform thickness, and good at the use initial performance, and long-term stability.
3. the segment thickness of band sacrificial fiber mesh cloth exposes outside the fluoride ion exchange base rete, thereby the hydrophilic coating on surface with contain the sulfonic fluoropolymer rete antidetonation of having avoided deviating from of screen cloth, this structure to help significantly to improve amberplex of combining closely and swing performance, prolong service life of amberplex.
Description of drawings
Fig. 1 is the fragmentary cross-sectional view of fluoride ion film in the embodiment of the invention 4,
Fig. 2 is the fragmentary cross-sectional view of fluoride ion film in the Comparative Examples 8 of the present invention,
Fig. 3 is the fragmentary cross-sectional view of fluoride ion film in the embodiment of the invention 10,
Wherein, 1 hydrophilic coating, 2 sacrificial fiber, 3 fortifying fibres, 4 sulfonate resin layers, 5 carboxylic acid resin's layers, 6 sulfonate resins and carboxylic acid resin's blended layer.
The specific embodiment
By the following examples the present invention is further specified, but the present invention is not limited only to following embodiment.
Used perfluorinated carboxylic acid resin's structure is as follows among the embodiment:
Ion exchange capacity=0.88mmol/g;
Used perfluorinated sulfonic resin structure is as follows among the embodiment:
Repetitive is
Ion exchange capacity=0.92mmol/g;
Percentage composition among the embodiment is mass percent.
The polytetrafluoroethylene (PTFE) film is stretched fast, and the film that will stretch is cut into the monofilament that fineness was 90 dawn then; PET (PET) fabric integer that is 10 μ m with 8 diameters is tiled into one group of yarn.Order with 2 groups of PET yarns of a PTFE line alternately is made into plain weave type fabric, and establishment density is 15 lines/cm.
Adopt fusion-film extrusion technology and heat pressing process to prepare fluorine resin monofilm and composite membrane.
At first preparing thickness with above-mentioned perfluorinated carboxylic acid resin A is 8 microns film A; Preparing thickness with above-mentioned perfluorinated sulfonic resin B is 80 microns film B; Perfluorinated carboxylic acid resin A and perfluorinated sulfonic resin B are mixed with 1: 1 mass ratio, and preparation thickness is 6 microns film C.Then, with various films by A C the order of B stack that to carry out hot pressing laminated and obtain multilayer film.
The order of pressing screen cloth, multilayer film (the B film is that the sulfonate film side is to screen cloth) and the release liners of band sacrificial fiber stacks combination and is placed on the laminator heating plate.Then, it is laminated to carry out hot pressing under the effect of vacuum and heating, will strengthen the scrim layer envelope and be embedded in the perfluorinated sulfonic resin film.Then release liners is peelled off, promptly got the exchange membrane containing fluorine that sacrificial fiber mesh cloth strengthens.
With the hydrolysis after 12 hours in 90 ℃ the 25%KOH aqueous solution of this film, will contain 13% mean particle size and be 5 microns ZrO
2-alcohol dispersion liquid is sprayed on the both sides of this film, and perfluorinated sulfonic resin content is 5wt% in this dispersion liquid.Measure its hot strength, cubical expansivity and electrolysis performance then.Current density is 4.5kA/m when carrying out electrolysis
2, temperature is 85 ℃, will strengthen film and be placed in the electrolytic cell, the side antianode of film B.Its test result is listed in table 1 and the table 2 with other embodiment result.
Embodiment 2
Strengthen screen cloth with the method preparation identical with embodiment 1, PET (PET) fabric integer that different is is 10 μ m with 10 diameters when making is tiled into one group yarn and weaves.
Utilize with embodiment 1 in identical multilayer film and lamination, transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.And measure its hot strength, cubical expansivity and electrolysis performance with embodiment 1 identical method.
Strengthen screen cloth with the method preparation identical with embodiment 1, PET (PET) fabric integer that different is is 10 μ m with 9 diameters when making is tiled into one group yarn and weaves.
Utilize with embodiment 1 in identical multilayer film and lamination, transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.And measure its hot strength, cubical expansivity and electrolysis performance with embodiment 1 identical method.
Strengthen screen cloth with the method preparation identical with embodiment 3, PET (PET) fabric integer that different is is 15 μ m with 9 diameters when making is tiled into one group yarn and weaves.
Utilize with embodiment 1 in identical multilayer film and lamination, transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.Screen cloth in this film has 8% thickness to be exposed at resin basement membrane outside, sees accompanying drawing 1.Measure its hot strength, cubical expansivity and electrolysis performance with embodiment 1 identical method.
Strengthen screen cloth with the method preparation identical with embodiment 3, PET (PET) fabric integer that different is is 20 μ m with 9 diameters when making is tiled into one group yarn and weaves.
Utilize with embodiment 1 in identical multilayer film and lamination, transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.And measure its hot strength, cubical expansivity and electrolysis performance with embodiment 1 identical method.
Embodiment 6
Strengthen screen cloth with the method preparation identical with embodiment 3, different is when making with fineness is that the PTFE monofilament at 80 dawn weaves.
Utilize with embodiment 1 in identical multilayer film and lamination, transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.And measure its hot strength, cubical expansivity and electrolysis performance with embodiment 1 identical method.
Embodiment 7
Utilize perfluorinated sulfonic resin B, to prepare thickness be 6 microns film D by melt extruding film-forming process.The order combination that enhancing screen cloth that will be identical with embodiment 4 and multilayer film strengthen screen cloth/multilayer film/release liners according to D/ stacks and is placed on that to carry out hot pressing on the laminator heating plate laminated.Then, release liners is peeled off, promptly got the amberplex that strengthens.
Utilize with embodiment 1 in identical transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.And measure its electrolysis performance with embodiment 1 identical method.
Comparative Examples 8
Utilize enhancing screen cloth and the various resin molding identical with embodiment 7, the order that strengthens screen cloth/multilayer film/release liners according to release liners/D/ makes up to stack and is placed on that to carry out hot pressing on the laminator heating plate laminated.Then, release liners is peeled off, promptly got the amberplex that strengthens.
Utilize with embodiment 1 in identical transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.Screen cloth all is embedded in resin basement membrane inside in this film, sees accompanying drawing 2.Measure its electrolysis performance with embodiment 1 identical method.
Embodiment 9
Adopt fusion-film extrusion technology and heat pressing process to prepare fluorine resin monofilm and composite membrane.
At first preparing thickness with perfluorinated carboxylic acid resin A is 10 microns film E; Preparing thickness with perfluorinated sulfonic resin B is 110 microns film F; Perfluorinated carboxylic acid resin A and perfluorinated sulfonic resin B are mixed with 2: 1 mass ratio, and preparation thickness is 6 microns film G.Then, with various films by E G the order of F stack that to carry out hot pressing laminated and obtain multilayer film.
Utilize the enhancing screen cloth identical, make up to stack according to the order that strengthens screen cloth, multilayer film (F film one side is to strengthening screen cloth) and release liners and place that to carry out vacuum hotpressing on the laminator heating plate laminated with embodiment 4.Then, release liners is peeled off, promptly got the amberplex that strengthens.
Utilize with embodiment 1 in identical transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.And measure its electrolysis performance with embodiment 1 identical method.
Embodiment 10
Adopt perfluorinated carboxylic acid resin A and perfluorinated sulfonic resin B to be coextruded into membrane process and prepare the double-layered compound film that thickness is respectively 30 microns and 60 microns by fusion.
Adopt the identical enhancing screen cloth of embodiment 4 then, the order combination that strengthens screen cloth/double-layered compound film/release liners according to film D/ stacks and places that to carry out vacuum hotpressing on the laminator heating plate laminated.Then, release liners is peeled off, promptly got the amberplex that strengthens.Screen cloth has 5% thickness to be exposed at resin basement membrane outside in this film, sees accompanying drawing 3.
Utilize with embodiment 1 in identical transition and the coating processes exchange membrane containing fluorine that obtains the sacrificial fiber mesh cloth enhancing.And measure its electrolysis performance with embodiment 1 identical method.
Table 1
Table 2
Claims (3)
1. be with the preparation method of the exchange membrane containing fluorine of sacrificial fiber mesh cloth enhancing, step is as follows:
A, adopt perfluorinated sulfonic resin, perfluorinated carboxylic acid resin and perfluorinated sulfonic resin and perfluorinated carboxylic acid resin's copolymer or blend, by melt extruding or the technology of lamination hot pressing prepares the ion exchange fluoro resin basement membrane;
B, the screen cloth that adopts the continous vacuum combination process will have sacrificial fiber are inserted inner formation of ion exchange fluoro resin basement membrane and are strengthened ionic membrane; The screen cloth of band sacrificial fiber is made up of fortifying fibre and sacrificial fiber;
C, with the processing that makes the transition in hydrolysis 10-15 hour in 90 ℃ the 25wt%KOH aqueous solution of step b gained ionic membrane; With the ZrO that contains perfluorinated sulfonic resin
2-alcohol dispersion liquid is carried out double-face spray painting to the enhancing ionic membrane after making the transition, and dry back forms hydrophilic coating; Wherein, described ZrO
2The content of perfluorinated sulfonic resin is the 3-5wt% of dispersion liquid weight in the-alcohol dispersion liquid.
2. the preparation method of the exchange membrane containing fluorine that band sacrificial fiber mesh cloth as claimed in claim 1 strengthens, wherein the screen cloth that has sacrificial fiber among the step b has the surface that the thickness of 1-10% exposes fluoride ion exchange basement membrane, forms screen cloth profile roughness in membrane surface.
3. the preparation method of the exchange membrane containing fluorine that band sacrificial fiber mesh cloth as claimed in claim 1 strengthens, wherein the braiding step with the enhancing screen cloth of sacrificial fiber is as follows:
Select fortifying fibre monofilament or multifilament for use, tow fineness is the 80-100 danier, with filament diameter be that the sacrificial fiber tow of 10-20 μ m is woven into plain weave structure at interval; The count of fortifying fibre is 3-40 root/cm, and per two bundles have 2 groups of sacrificial fiber between the fortifying fibres, and the sacrificial fiber tiling is arranged in groups, is made up of 8-10 root monofilament for every group.
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