CN1036052C - Cation exchange membrane and manufacturing method thereof - Google Patents
Cation exchange membrane and manufacturing method thereof Download PDFInfo
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- CN1036052C CN1036052C CN94115229A CN94115229A CN1036052C CN 1036052 C CN1036052 C CN 1036052C CN 94115229 A CN94115229 A CN 94115229A CN 94115229 A CN94115229 A CN 94115229A CN 1036052 C CN1036052 C CN 1036052C
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- 239000012528 membrane Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000005341 cation exchange Methods 0.000 title abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 239000004744 fabric Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000003440 styrenes Chemical class 0.000 claims abstract description 12
- -1 alkyl styrene Chemical compound 0.000 claims abstract description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 210000004379 membrane Anatomy 0.000 claims description 30
- 125000002091 cationic group Chemical group 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000012745 toughening agent Substances 0.000 claims description 19
- 210000002469 basement membrane Anatomy 0.000 claims description 18
- 238000006277 sulfonation reaction Methods 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004800 polyvinyl chloride Substances 0.000 claims description 13
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229920002681 hypalon Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000004902 Softening Agent Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000007581 slurry coating method Methods 0.000 abstract 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 13
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000009172 bursting Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005862 Whey Substances 0.000 description 1
- 102000007544 Whey Proteins Human genes 0.000 description 1
- 108010046377 Whey Proteins Proteins 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to a cation exchange membrane and a method for producing the same. The cation exchange membrane is polymerized by monomer styrene or alkyl styrene, aromatic diene compound as a cross-linking agent, benzoyl peroxide or azodiisobutyronitrile as an initiator, and a reinforcing softening agent and a reinforcing fabric of a non-ionic linear high molecular compound soluble in styrene and alkyl substituted styrene. The enhanced flexibilizer adopted by the invention has the advantages of high exchange capacity of the obtained cation exchange membrane, good electrochemical performance, high flexibility and strength, strong acid and strong alkali resistance, homogeneous slurry in the preparation process, easy slurry coating and greatly improved process. The cation membrane can be widely applied to national economic departments such as food industry, electronic industry, semiconductor industry, medical industry, printing and dyeing industry, chemical industry and the like.
Description
The present invention relates to a kind of only with carbon one carbon unsaturated double-bond react polymkeric substance and manufacture method thereof, particularly a kind of cationic exchange membrane of aromatic series type and manufacture method thereof.
Day Bender mountain Cao Da company has invented a kind of coating method and has prepared styrene type sulfonic acid cationic exchange membrane.[Bull，Chem.SOC.Japan，36，(4)361，(1963)]。This film is to be polymerized by vinylbenzene (monomer), divinylbenzene (linking agent), polyvinyl chloride powder (toughener), dioctyl phthalate (DOP) (softening agent) and benzoyl peroxide (initiator).The preparation method of this film is mixed with slurries to said components, slurries are coated on the polyvinyl chloride cloth (Terlorn cloth), the heating and pressurizing polymerization gets basement membrane, then basement membrane is heated sulfonation in the vitriol oil, then get cationic exchange membrane, this film has certain flexibility, non-frangibility, and its preparation method is also simple, operation is also easy.But there are following shortcoming in this film and method: (1) is used in the slurries system, and system film critical material---toughener is the polyvinyl chloride powder, it is insoluble in vinylbenzene (monomer) and the divinylbenzene (linking agent), can only swelling, so the slurries of gained are a kind of nonhomogeneous systems, and also rarer.Because the high molecular polymer of polyvinyl chloride powder is owing to the existence of chlorine atom, intermolecular attraction is big, and molecular rigidity is big simultaneously, not increasing gentle effect so the polyvinyl chloride powder itself has.Must add softening agent such as dioctyl phthalate (DOP) just can make polyvinyl chloride play to strengthen and increase gentle purpose.In order to obtain submissive book film, polyvinyl chloride powder and dioctyl phthalate (DOP) shared ratio in slurries is very big in this film, is roughly equal to 45%, and main ingredient vinylbenzene only accounts for about 50%, and content is not high.The loading capacity of the cationic exchange membrane that makes like this is not high.Only be 1.1-1.2 milligramequivalent/gram dry film, thereby influenced chemical property that its face resistance height is 5-6 Ω cm
2(2) contain dioctyl phthalate (DOP) in basement membrane, dioctyl phthalate (DOP) can be destroyed by the vitriol oil during basement membrane sulfonation, causes and stays micropore in the film.Can reduce the chemical property of film so again, as reducing cationic transport number, the transport number of this film is 0.86-0.88.(3) the toughener polyvinyl chloride powder in this film is insoluble to vinylbenzene, only can swelling, and therefore the slurries of gained are homogeneous systems not in film-forming process, prepared film sees it is discontinuous from microcosmic angle, still belongs to heterogeneous film category.In addition, in film-forming process, the gained slurries are difficult for being attached on the reinforced fabric, and the film that makes is easy to generate pin hole.
The purpose of this invention is to provide a kind of exchange capacity height, chemical property is good, snappiness is good homogeneous phase cation exchange film and manufacture method thereof.
The present invention implements like this.Cationic exchange membrane of the present invention is made up of monomer, toughener, flexibilizing agent, linking agent, initiator and reinforced fabric; monomer is vinylbenzene or ring-alkylated styrenes; linking agent is aromatic series double vinyl compound such as divinylbenzene; initiator is benzoyl peroxide or Diisopropyl azodicarboxylate; feature of the present invention is that toughener and flexibilizing agent are a kind of linear polymers of non-ionic type, and this compound dissolves in vinylbenzene or the alkyl-substituted styrene.As chlorosulfonated polyethylene, chlorinatedpolyethylene, ethylene-propylene rubber(EPR), the weight percent proportioning of its membrane component is a monomer: linking agent: increase gentle toughener: initiator=50-80%: 2-30%: 6-22%; 0.2-2%.Reinforced fabric of the present invention is glasscloth, polypropylene cloth and polyvinyl chloride cloth.
The process that the present invention makes cationic exchange membrane is:
(1) slurrying: with monomer, linking agent, increase soft toughener, initiator is mixed in proportion, and is stirred into the homogeneous phase slurries under 10～40 ℃ of temperature.Monomer is vinylbenzene or ring-alkylated styrenes; linking agent is aromatic series double vinyl compound such as divinylbenzene; increasing soft toughener is the linear polymer that dissolves in the non-ionic type in vinylbenzene or the alkyl-substituted styrene; initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, and its proportioning is by following per-cent: monomer: linking agent: increase gentle toughener: initiator=50-80%: 2-30%: 6-22%: 0.2-2%.
(2) system film: slurries are coated on the reinforced fabric, the pressurized, heated polymerization, pressure is 0.5-25 * 10 during polymerization
5Pa, Heating temperature is 60-120 ℃, basement membrane is taken out after cooling, the release in polymerization time 〉=3 hour.Reinforced fabric is glasscloth, polypropylene cloth and polyvinyl chloride cloth.
(3) basement membrane sulfonation: the basement membrane that takes out is carried out sulfonation with sulphonating agent, and sulphonating agent is the vitriol oil, and sulfonation temperature is 60～100 ℃, sulfonation time 〉=4 hour.
Its structure of monomer styrene of the present invention or ring-alkylated styrenes is:
(R=H ,-CH
3,-C
2H
5,-C
3H
7,-C
4H
9).
Of the present invention to increase soft toughener be the linear non-ionic macromolecule compound that can be dissolved in the monomer, and as chlorosulfonated polyethylene, its structure is:
Chlorinatedpolyethylene
Ethylene rubber
Cationic exchange membrane of the present invention and preparation method thereof has following advantage:
(1) component of film of the present invention is few, has only 4 components, and without the plasticizer phthalic acid dioctyl ester, cost has reduced; (2) the present invention's linear polymeric plastics elastic body of adopting non-ionic type to dissolve in vinylbenzene or the ring-alkylated styrenes makes to increase gentle toughener, the slurries of gained are homogeneous system, the film that makes like this is a homogeneous phase cation exchange film, and it is low to increase gentle toughener proportion in slurries, only 6～22%, and the ratio of styrene comprise is big, thereby the cationic exchange membrane loading capacity height that makes is generally 2.0～2.6 milligramequivalents/gram dry film.Face resistance is low to be 1-3 Ω cm
2Film has snappiness and higher-strength, the film alternating bending do not ruptured, and ability strong acid, highly basic.In addition, this kind slurries have very high viscosity, easily attached on the reinforced fabric, can operate continuously, easily realize the production of industry rule film, and the film free of pinholes of producing.(3) do not have dioctyl phthalate (DOP) in the basement membrane of the present invention, so in the vitriol oil after the sulfonation, resulting cationic exchange membrane does not have micropore, the selection perviousness of the cationic exchange membrane of gained is good, and promptly the transport number height is generally 0.95～0.99.(4) coating method of the present invention is homogeneous phase slurries coating methods, is not heterogeneous slurries coating method.
Table 1 has been listed cationic exchange membrane of the present invention and Japanese cationic exchange membrane properties data.
Table 1 performance relatively
| Film thickness (mm) | Loading capacity [milligramequivalent/gram dry film] | Face resistance [Ω .cm 2] | Transference number of ions | |
| The present invention | 0.16-0.20 | 2.0-2.6 | 1-3 | 0.95-0.99 |
| Japan | 0.23-0.24 | 1.1-1.2 | 5-6 | 0.86-0.88 |
The cationic exchange membrane of making according to the present invention can be used for electrodialytic desalting prepare tap water, sea water desaltination, seawater concentrate salt manufacturing, milk whey electrodialysis desalination, D-pectinose desalting and purifying, in, the low pressure boiler water treatment, make electrolytic film and contain acid to contain alkali waste water processing and recycling etc.Therefore can be widely used in sectors of the national economy such as foodstuffs industry, electronic industry, semi-conductor industry, medicine industry, printing and dyeing industry and chemical industry.
The embodiment of the invention is as follows
Example 1. is with 100 gram vinylbenzene, 14 gram divinylbenzenes, 12 gram chlorosulfonated polyethylenes and 0.5 gram benzoyl peroxide stir together, at room temperature make the homogeneous phase slurries, be that (area is bigger slightly than aluminium sheet to spread out polyester film on 200 millimeters * 100 millimeters * 2 millimeters the smooth aluminum panel a specification.), again on the polyester film upper berth with polyvinyl chloride cloth (thick 0.1 millimeter), sizing liquor equably inclines, cover a polyester film again, even with the rubber roll roller coat, squeeze and remove unnecessary slurries, get a uniform coating, repave thereon with polyvinyl chloride cloth (size is the same), the sizing liquor that inclines covers polyester film, again with the rubber roll roller coat evenly and squeeze and remove unnecessary slurries, a uniform coating again, 20 layers of coating of pasting so repeatedly, the last smooth aluminum panel that goes up the same specification of another piece that covers thereon, this whole coating is placed on the pressing machine, pressurization, pressure is 2.7 * 10
5Pa, temperature is 80 ℃, polymerization 6 hours, cooling, membrane stack is taken out in release, peels off and promptly gets evenly smooth basement membrane.Then with a basement membrane, a woven fiber glass alternately is superimposed together totally 20 layers, and it is 300 * 200 * 50 millimeters rectangular vessel that this membrane stack is placed specification, add the vitriol oil, add-on must can be flooded membrane stack, keeps 16 hours down at 70 ℃, gets the black cationic exchange membrane, cationic exchange membrane with gained is immersed in 10% sodium chloride aqueous solution at last, add hydrochloric acid and regulate about PH=2, left standstill 24 hours, take out film, wash with water to neutrality, promptly getting can be for practical sodium type cationic exchange membrane.
Performance: 0.18 millimeter of thickness, loading capacity 2.0 milligramequivalents/gram dry film, water content 26%, face resistance 3.0 ohm-cms
2, transport number 95%, bursting strength 2.0 * 10
5Pa, strong acid, strong base solutions such as anti-sulfuric acid and sodium hydroxide.
Example 2. is with 100 gram vinylbenzene, and 4 restrain divinylbenzenes, and 22 gram chlorosulfonated polyethylenes and 1 gram Diisopropyl azodicarboxylate stir together, make the homogeneous phase slurries at ambient temperature.Pasting and converging operation are with example 1, but when polymerization, condition is a pressure 0.5 * 10
5Pa, 60 ℃ of temperature, polymerization 20 hours makes basement membrane.Basement membrane is sulfonation in the vitriol oil, 80 ℃ of temperature, and 8 hours time, aftertreatment gets the black cationic exchange membrane with example 1.Performance: 0.20 millimeter of thickness, loading capacity 2.6 milligramequivalents/gram dry film, water content 30%, face resistance 1.0 ohm-cms
2, transport number 99%, anti-strong acid, highly basic, bursting strength 1.51 * 10
5Pa.
Example 3, with 100 gram vinylbenzene, 20 gram divinylbenzenes, 6 gram chlorinatedpolyethylenees and 0.2 gram benzoyl peroxide at room temperature stir together makes the homogeneous phase slurries.Pasting operation and converging operation are glasscloth all with example 1 but strengthen screen cloth, and condition is a pressure 10 * 10 during polymerization
5Pa, temperature is 120 ℃, 6 hours time, gets basement membrane.The sulfonation operation of basement membrane and aftertreatment are all with example 1, but the sulfonation condition is 100 ℃ of sulfonation temperatures, 8 hours time.
Performance: 0.20 millimeter of thickness, loading capacity 2.2 milligramequivalents/gram dry film, water content 25%, face resistance 2.6 ohm-cms
2, transport number 96%, ability strong acid, bursting strength 4.5 * 10
5Pa.
Example 4, with 100 gram vinylbenzene, 16 gram divinylbenzenes, 16 gram chlorosulfonated polyethylenes, 2 gram benzoyl peroxides stir together, at room temperature make the homogeneous phase slurries.Pasting operation and converging operation are all with example 1, but polymerizing condition is: 100 ℃ of temperature, pressure 25 * 10
5Pa gets its film.The basement membrane sulfurization is with example 1, and condition is 85 ℃ of temperature, 8 hours time, gets the black cationic exchange membrane.
Performance: 0.16 millimeter of thickness, loading capacity 2.57 milligramequivalents/gram dry film, water content 28%, face resistance 1.53 ohm-cms
2, transport number 99%, bursting strength 2.32 * 10
5Pa, anti-strong acid, highly basic.
Example 5, with 100 gram vinylbenzene, 20 gram divinylbenzenes, 10 gram ethylene-propylene rubber(EPR) and 0.5 gram benzoyl peroxide at room temperature stir into homogeneous slurry together, and pasting and converging operation are all with example 1 but to strengthen screen cloth be polypropylene cloth, and polymerizing condition is a pressure 10 * 10
5Pa, temperature is 80 ℃, 12 hours time, gets basement membrane.The sulfonation operation of basement membrane and aftertreatment be all with example 1, but the sulfonation condition is, 60 ℃ of temperature, 24 hours time, make catalyzer with 0.5% Sulfuric acid disilver salt, the black cationic exchange membrane.
Performance: 0.20 millimeter of thickness, loading capacity 2.4 milligramequivalents/gram dry film.Water content 28.5%, face resistance 2.48 ohm-cms
2, transport number 97%, bursting strength 2.35 * 10
5Pa, anti-strong acid, highly basic.
Claims (6)
1. cationic exchange membrane; it is by monomer, linking agent, increases gentle toughener, initiator and reinforced fabric and be polymerized; monomer is vinylbenzene or alkyl-substituted styrene; linking agent is the aromatic series double vinyl compound; initiator is benzoyl peroxide or Diisopropyl azodicarboxylate; it is characterized in that increasing soft toughener is the linear polymer that non-ionic type dissolves in vinylbenzene or alkyl-substituted styrene, and the per distribution ratio of cationic exchange membrane component is a monomer: linking agent: increase gentle toughener: initiator=50-80%: 2-30%: 6-22%: 0.2-2%.
2. cationic exchange membrane as claimed in claim 1, it is characterized in that non-ionic type dissolve in vinylbenzene or alkyl-substituted styrene linear polymer to increase gentle toughener be chlorosulfonated polyethylene, chlorinatedpolyethylene, ethylene-propylene rubber(EPR).
3. cationic exchange membrane as claimed in claim 1 is characterized in that the aromatic series double vinyl compound is a divinylbenzene.
4. cationic exchange membrane as claimed in claim 1 is characterized in that reinforced fabric is glasscloth, polypropylene cloth and polyvinyl chloride cloth.
5. the manufacture method of a cationic exchange membrane as claimed in claim 1 is characterized in that this method technological process is as follows:
(1) slurrying: with monomer, linking agent, increase gentle toughener and initiator is mixed in proportion, under 10-40 ℃ of temperature, stir into homogeneous slurry, monomer is vinylbenzene or alkyl-substituted styrene, linking agent is the aromatic series double vinyl compound, increasing gentle toughener is the non-ionic type linear polymer that dissolves in vinylbenzene or the alkyl-substituted styrene, initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, and its per distribution ratio is: monomer: linking agent: increase gentle toughener: initiator=50-80%: 2-30%: 6-22%: 0.2-2%;
(2) system film: slurries are coated on the reinforced fabric, the pressurized, heated polymerization, during polymerization, pressure is 0.5-25 * 10Pa, Heating temperature is 60～120 ℃, polymerization time 〉=3 hour, cooling is taken out basement membrane, and is carried out sulfonation with sulphonating agent after the release.
6. preparation method as claimed in claim 5 is characterized in that sulphonating agent is the vitriol oil, 60～100 ℃ of sulfonation temperatures, sulfonation time 〉=4 hour.
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|---|---|---|---|
| CN94115229A CN1036052C (en) | 1994-09-27 | 1994-09-27 | Cation exchange membrane and manufacturing method thereof |
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|---|---|---|---|
| CN94115229A CN1036052C (en) | 1994-09-27 | 1994-09-27 | Cation exchange membrane and manufacturing method thereof |
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| CN1036052C true CN1036052C (en) | 1997-10-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352657B (en) * | 2008-02-29 | 2011-07-20 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
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| CN102585254B (en) * | 2011-01-07 | 2013-10-09 | 通用电气公司 | Crosslinking method and product obtained by using same |
| CN103623713A (en) * | 2012-08-28 | 2014-03-12 | 上海乐泽环境工程有限公司 | One-step homogeneous cation exchange membrane and molding technology thereof |
| CN103910897A (en) * | 2013-01-06 | 2014-07-09 | 中国科学院宁波材料技术与工程研究所 | Method for making cation exchange membrane through photocuring |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5203982A (en) * | 1989-10-16 | 1993-04-20 | Ionics, Incorporated | Cation exchange membranes |
-
1994
- 1994-09-27 CN CN94115229A patent/CN1036052C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5203982A (en) * | 1989-10-16 | 1993-04-20 | Ionics, Incorporated | Cation exchange membranes |
Non-Patent Citations (1)
| Title |
|---|
| BULL CHEM.SOC.JAPAN,36,(4) 1963.1.1 Yukio Mizutani,eeal * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352657B (en) * | 2008-02-29 | 2011-07-20 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1104556A (en) | 1995-07-05 |
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