CN1027897C - Method for manufacturing aliphatic anion exchange membrane - Google Patents
Method for manufacturing aliphatic anion exchange membrane Download PDFInfo
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- CN1027897C CN1027897C CN90103412A CN90103412A CN1027897C CN 1027897 C CN1027897 C CN 1027897C CN 90103412 A CN90103412 A CN 90103412A CN 90103412 A CN90103412 A CN 90103412A CN 1027897 C CN1027897 C CN 1027897C
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- -1 alkylene acrylate Chemical compound 0.000 claims abstract description 53
- 239000004744 fabric Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000005576 amination reaction Methods 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- 210000002469 basement membrane Anatomy 0.000 claims description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 19
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 16
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 15
- 150000005690 diesters Chemical class 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000012745 toughening agent Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 150000002924 oxiranes Chemical group 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 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 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920004935 Trevira® Polymers 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000004902 Softening Agent Substances 0.000 abstract 1
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000010612 desalination reaction Methods 0.000 abstract 1
- 239000003651 drinking water Substances 0.000 abstract 1
- 235000020188 drinking water Nutrition 0.000 abstract 1
- 238000000909 electrodialysis Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 26
- 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 20
- 239000010408 film Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000007265 chloromethylation reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012805 post-processing Methods 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 3
- 210000004379 membrane Anatomy 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002821 Modacrylic Polymers 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical class CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FKSLYSSVKFYJKE-UHFFFAOYSA-N n,n-diethylethanamine;methanol Chemical compound OC.CCN(CC)CC FKSLYSSVKFYJKE-UHFFFAOYSA-N 0.000 description 1
- BWZVWVOEWUSVMS-UHFFFAOYSA-N n,n-dimethylmethanamine;methanol Chemical compound OC.CN(C)C BWZVWVOEWUSVMS-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A process for preparing the anionic exchange membrane of aliphatic series includes such steps as preparing slurry from the alkylene acrylate or alkyl acrylate as monomer, aliphatic or aromatic diene compound as cross-linking agent, trigger, reinforcing agent and softening agent, coating the slurry on the reinforcing fabric, polymerizing to become basic membrane, and aminating. The anion exchange membrane prepared by the method has flexibility, excellent mechanical property and electrochemical property, and is convenient for industrial production. The anion exchange membrane can be used for preparing drinking water by electrodialysis desalination, treating water for medium and low pressure boilers, performing metal electrolytic reduction, recovering acid-containing and alkali-containing wastewater and the like.
Description
The present invention relates to a kind of manufacture method of only reacting the polymkeric substance that obtains, particularly a kind of manufacture method of anion-exchange membrane of aliphatics type with the carbon-to-carbon unsaturated double-bond.
The manufacture method of anion-exchange membrane, generally be to be monomer with vinylbenzene, divinylbenzene is a linking agent, in the presence of initiator, contain method by soaking, basement membrane is made in coating method or the polymerization of casting method elder generation, then basement membrane is carried out chloromethylation with chloromethyl ether in the presence of the catalyzer Zinc Chloride Anhydrous and obtain the chloromethylation film, last chloromethylation film carries out quaterisation with Trimethylamine 99 and obtains anion-exchange membrane.
Set out as monomer with vinylbenzene and to carry out the manufacturing of anion-exchange membrane, must pass through this step of chloromethylation, and chloromethylation must be used the highly toxic substance chloromethyl ether, aborning human body there is serious harm, chloromethyl ether heavy corrosion production unit causes serious environmental to pollute simultaneously.For this reason, United States Patent (USP) 4,374,206 propose acrylic acid epoxy propyl ester class or glytidyl methacrylate class are reacted the quaternary ammonium salt of generation vinylformic acid N-Hydroxyproyl Trimethyl amine ester or the quaternary ammonium salt of methacrylic acid N-Hydroxyproyl Trimethyl amine ester with the Trimethylamine hydrochloride in ethanol, add water and make into aqueous ethanolic solution, then in solution, add the two vinylformic acid second diester of linking agent or methacrylate second diester and initiator benzoyl peroxide, then this solution is placed a groove, Modacrylic cloth is clipped between the sheet glass, be stacked in from level to level in the groove, heated polymerizable obtains anion-exchange membrane.Yet, still there are many shortcomings in this method: two vinylformic acid second diester of (1) vinylformic acid N-Hydroxyproyl Trimethyl amine ester or methacrylic acid N-Hydroxyproyl Trimethyl amine ester and linking agent or the resulting cross-linked polymer of methacrylate second diester polyreaction are hard solids, although add reinforced fabric Modacrylic cloth, but the cross-linked polymer that has strengthened remains hard, there is not snappiness, as add the external force bending, film is with regard to embrittlement, the flexural strength of film and flexible very poor, do not reach practical requirement, (2) film that makes is very thick, and about 1 millimeter, chemical property is relatively poor, (3) in film-forming process, solution in the whole groove is all with polymerization, and it is very difficult to peel off and take out each film, is difficult to realize that serialization produces large-area film.
The objective of the invention is to provide a kind of technology simple, the novel method of preparation aliphatics anion-exchange membrane easy and simple to handle, the film of making has excellent electrochemical properties, and strong acid, highly basic, flexibility, flexural strength is good and be easy to realize industrialization.
Main points of the present invention are when the preparation film making solution, at first make film making solution become slurry, and slurry is coated on the reinforced fabric easily and can be attached to securely on the reinforced fabric like this, does not need to add any solvent during slurrying.When the preparation slurry; except acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class will be arranged is monomer; aliphatics double vinyl compound or aromatic series double vinyl compound are linking agent; benzoyl peroxide or Diisopropyl azodicarboxylate are outside the initiator; in order to make the anion-exchange membrane that makes have snappiness and very high physical strength, must add toughener and flexibilizing agent.Toughener is that linear polymer is vinyl chloride-vinyl acetate alkene copolymer or Vinyl Acetate Copolymer.It can increase snappiness, elasticity and the intensity of film, make the film alternating bending and do not rupture, in addition, toughener can make film making solution have very high viscosity and become slurry, slurry can be easily attached on the reinforced fabric like this, the pasting operation can intermittently or be carried out continuously, can realize plant-scale production.Flexibilizing agent is that high boiling organic compound is the bialkyl ortho phthalate class, and it can increase the flexibility of film.
The slurry of making is coated in aggregates into basement membrane on the reinforced fabric earlier, then basement membrane carries out amination with aminated compounds, makes anion-exchange membrane.
System pleurodiaphragmatic in terspace reason of the present invention is: the structure of acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class is
(in the formula, R is H ,-CH
3,-C
2H
5Or-C
3H
7Deng, n=1-6).In the molecular structure of this compounds, has very active epoxide group
, this epoxide group can react with the fatty amine compounds, and this moment, the epoxide group open loop generated new aminated compounds.
Earlier acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class are then become polymkeric substance with the two vinylformic acid second diester of linking agent or two vinylformic acid one diethyl diester or methacrylate second diester or the methacrylate one diethyl diester that contracts that contracts with initiator benzoyl peroxide or Diisopropyl azodicarboxylate reacting by heating.Resulting polymkeric substance promptly gets the strong basicity quaternary ammonium compound with the aminated compounds reaction.
The process that the present invention makes anion-exchange membrane is (1) slurrying: with monomer; linking agent; initiator; toughener; flexibilizing agent is mixed in proportion; under 10-40 ℃ of temperature, be stirred into slurry; monomer is acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class; linking agent is aliphatics double vinyl compound or aromatic series double vinyl compound; toughener is the linear polymer that dissolves in acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class; flexibilizing agent is a phthalic acid dialkyl class; initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, and its proportioning is a monomer: linking agent: toughener: flexibilizing agent: initiator=45-80%: 4-20%: 5-20%: 5-20%: 0.2-2%.(2) system film: slurry is coated on the reinforced fabric, the pressurized, heated polymerization, pressure is 0.5-25 * 10 during polymerization
5Pa, Heating temperature is 60-120 ℃, polymerization time is equal to or greater than 3 hours, takes out basement membrane after the cooling release, and carries out amination with aminating agent.Aminating agent is the fatty amine compounds, and its structure is
, R in the formula
1For-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
2H
4OH, R
2For-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
2H
4OH, R
3For-CH
3,-C
2H
5,-C
3H
7, C
4H
9,-C
5H
11,-C
6H
13,-C
2H
4OH, amine concentration is not less than 25%, and the mol ratio of the epoxide group in amine and the monomer is 20: 1-10: 1, amine is 15-45 ℃ than temperature, the amination time is more than 4 hours or 4 hours.
The said monomer acrylic acid epoxy of the present invention alkane ester class or alkyl acrylic oxirane ester class, its structure is
, R is H in the formula ,-CH
3,-C
2H
5,-C
3H
7, n=1-6.
The said aliphatics double vinyl compound of the present invention linking agent is two vinylformic acid second diester, two vinylformic acid one diethyl diester that contracts, methacrylate second diester, the methacrylate one diethyl diester that contracts; Fragrance same clan double vinyl compound linking agent is a divinylbenzene.
The said toughener of the present invention is the linear polymer that can be dissolved in the monomer, and this family macromolecule compound of preferentially selecting for use is Vinyl Acetate Copolymer or vinyl chloride-vinyl acetate copolymer.
The structure of the said flexibilizing agent phthalic acid of the present invention dialkyl class is
R is-CH in the formula
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15,-C
8H
17
The said reinforced fabric of the present invention is glasscloth (woven fiber glass), trevira cloth (woven dacron), nylon cloth, polypropylene fibre cloth (Polypropylene), non-woven fabrics and thermovyl cloth (polyvinyl chloride fibre cloth).
Anion-exchange membrane according to the present invention's preparation has following advantage: (1) thin film thickness, be generally 0.16 millimeter-0.22 millimeter, and (2) chemical property is good, and face resistance is low, generally at the 4.5-8 ohm-cm
2, (3) transport number height, generally at 88-95%, (4) ability strong acid, highly basic.(5) film is flexible and do not rupture.The anion-exchange membrane of making according to the present invention can be used for electrodialytic desalting and prepares tap water, in, the low pressure boiler water treatment, electrolytic etching of metal reduction and contain acid, contain alkali waste water and reclaim and use etc.
Specific embodiments of the invention are as follows:
Example 1, with 315 gram glytidyl methacrylate, 20 gram methacrylate second diester, 35 gram vinyl chloride-vinyl acetate copolymers, 20 gram dioctyl phthalate (DOP)s and 2 gram benzoyl peroxides stir together, make even slurry at ambient temperature, be on 900 millimeters * 500 millimeters * 2 millimeters the smooth aluminum panel, to spread polyester film (area is bigger slightly than aluminium sheet) a specification, again on the polyester film upper berth with (thick 0.15 millimeter of thermovyl cloth, area is 900 * 500 millimeters), incline equably and go up slurry, cover a polyester film again, even with the rubber roll roller coat, squeeze and remove unnecessary slurry, get a uniform coating.Repave thereon with thermovyl cloth (size is the same), incline and go up slurry, cover polyester film, evenly also squeeze with the rubber roll roller coat again and remove unnecessary slurry, a uniform coating again, 8 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 press (the press bed area is 900 * 500 millimeters), pressurization, and pressure is 2.7 * 10
5Pa, heating, temperature is 120 ℃ of polyase 13s hour, cooling, membrane stack is taken out in release, peel off promptly get evenly, smooth basement membrane.It is 800 * 400 millimeters that basement membrane is cut into specification, then with a basement membrane, a polypropylene fibre screen cloth (or woven fiber glass) alternately is superimposed together, totally 8 layers, it is 900 * 500 * 100 millimeters rectangular vessel that this membrane stack is placed specification, add 5 liters of content and be no less than 25% trimethylamine aqueous solution, the trimethylamine aqueous solution amount of adding must can be flooded membrane stack.Kept 16 hours down at 25 ℃, get the black anion-exchange membrane.Anion-exchange membrane with gained is immersed in 10 liter of 10% sodium chloride aqueous solution at last, adds hydrochloric acid and regulates about pH=2, leaves standstill 24 hours, takes out film, washes with water to neutrality, and promptly getting can be for practical chlorine type anion-exchange membrane.
Example 2, with 180 gram glytidyl methacrylate, 20 gram methacrylate second diester, 25 gram vinylchlorid-vinyl acetate multipolymers, 20 gram dioctyl phthalate (DOP)s and 2 gram benzoyl peroxides, at room temperature make even slurry together, pasting and converging operation are all with example 1, but when polymerization, condition is a pressure 0.5 * 10
5Pa, 80 ℃ of temperature, polymerization 10 hours.Amination and processing operation are with example 1, but the amination condition is 15 ℃ of temperature, 24 hours time.
Example 3,140 gram glytidyl methacrylate, the 50 gram methacrylates one diethyl diester that contracts, 60 gram vinyl chloride-vinyl acetate copolymers, 55 gram dibutyl phthalates, 4 gram benzoyl peroxides at room temperature stir together and make slurry.Pasting operation and converging operation are all with example 1, but polymerizing condition is: pressure 10 * 10
5Pa, temperature is 100 ℃, 8 hours time.The amination operation of basement membrane and post-processing operation are all with example 1, but the amination condition is: 8 tunics are immersed in 10 liter of 25% trimethylamine aqueous solution, and the amination temperature is 40 ℃, 4 hours time.
Example 4, with 270 gram glytidyl methacrylate, the two vinylformic acid second diester of 100 grams, 80 gram Vinyl Acetate Copolymer, 25 gram dibutyl phthalates and 5 gram benzoyl peroxides stir (room temperature) together, make even slurry.Pasting operation and converging operation are all with example 1.During pasting, strongthener polypropylene fibre cloth (0.15 millimeter thickness), polymerizing condition: pressure 25 * 10
5Pa, temperature is 100 ℃, 10 hours time.The amination operation of basement membrane and post-processing operation are all with example 1, and the amination condition is: 8 tunics are immersed in 6 liter of 25% trimethylamine aqueous solution, 30 ℃ of temperature, 8 hours time.
Example 5, with 250 gram acrylic acid epoxy propyl ester, the two vinylformic acid one of the 100 grams diethyl diester that contracts, 95 gram vinyl chloride-vinyl acetate copolymers, 25 gram dioctyl phthalate (DOP)s and 4 gram benzoyl peroxides are mixed together in stirring at room and make slurry.Pasting operation and converging operation are all with example 1, and when pasting, used enhancing screen cloth is thermovyl cloth (0.15 millimeter of a thickness), polymerizing condition: pressure 8 * 10
5Pa, 100 ℃ of temperature, 10 hours time.The amination operation of basement membrane and aftertreatment are all with example 1, but the amination condition is: 8 tunics are immersed in 5 liters and are not less than in 30% the trimethylamine aqueous solution 30 ℃ of temperature, 6 hours time.
Example 6, with 250 gram acrylic acid epoxy butyl esters, the two vinylformic acid second diester of 100 grams, 25 gram vinyl chloride-vinyl acetate copolymers, 95 gram dioctyl phthalate (DOP)s, 4 gram benzoyl peroxides are mixed together, and at room temperature stir and make slurry.Pasting operation and converging operation be all with example 1, but make strongthener with glasscloth (0.15 millimeter of thickness) in pasting.Polymerizing condition: pressure is 10 * 10
5Pa, 100 ℃ of temperature, 8 hours time.The amination operation of basement membrane and aftertreatment are immersed in 5 liter of 25% TMA (TriMethylAmine) methanol solution but the amination condition is 8 tunics all with example 1,25 ℃ of temperature, 10 hours time.
Example 7, with 300 gram glytidyl methacrylate, 80 gram content are 46% divinylbenzene, 50 no Vinyl Acetate Copolymer, 45 gram dioctyl phthalate (DOP)s and 11 gram benzoyl peroxides are mixed together and at room temperature stir into even slurry.Pasting operation and converging operation are all with example 1.But when pasting, make strongthener with thermovyl cloth (0.15 millimeter of thickness), polypropylene film makes to cover the barrier coat film.Polymerizing condition is: pressure is 10 * 10
5Pa, 100 ℃ of temperature, 8 hours time.Basement membrane amination operation and aftertreatment are all with example 1, but the amination condition is: 8 tunics are immersed in 5 liter of 25% Trimethylamine 99 methanol solution, 25 ℃ of temperature, 12 hours time.
Example 8, with 300 gram glytidyl methacrylate, 45 gram divinylbenzenes (content 46%), 40 gram vinyl chloride-vinyl acetate copolymers, 25 gram dioctyl phthalate (DOP)s, 1 gram benzoyl peroxide stirs into even slurry together, then slurry is coated on the glasscloth (0.15 millimeter of thickness), makes to cover barrier coat with polyester film and uses.Converging operation is with example 1, and polymerizing condition is: pressure 10 * 10
5Pa, 100 ℃ of temperature, 8 hours time.Basement membrane amination operation and post-processing operation are all with example 1, but the amination condition is: 8 layers of basement membrane are immersed in 5 liter of 30% trolamine methanol solution, 40 ℃ of temperature, 8 hours time.
Example 9, with 300 gram glytidyl methacrylate, 50 grams, 46% divinylbenzene, 40 gram vinyl chloride-vinyl acetate copolymers, 45 gram dioctyl phthalate (DOP)s and 3 gram Diisopropyl azodicarboxylates stir together makes even slurry.Slurrying is at room temperature carried out.Pasting operation and condition are all with example 1.Converging operation is with example 1.Polymerizing condition is: pressure 10 * 10
5Pa, 60 ℃ of temperature, polymerization 48 hours, cooling, release is peeled off, and obtains smooth basement membrane.The amination operation of basement membrane and post-processing operation are all with example 1, and the amination condition is: 8 tunics are immersed in 5 liter of 25% trimethylamine aqueous solution, 30 ℃ of temperature, 8 hours time.
Example 10, with 300 gram glytidyl methacrylate, the divinylbenzene of 50 grams 46%, 80 gram vinyl chloride-vinyl acetate copolymers, 30 gram dioctyl phthalate (DOP)s and 3 gram benzoyl peroxides at room temperature stir together makes even slurry, and pasting operation and condition are all with example 1.Converging operation is with example 1.But polymerizing condition is: pressure 10 * 10
5Pa, 80 ℃ of temperature, 20 hours time, the every operation after the polymerization is all with example 1, and basement membrane amination operation and aftertreatment are all with example 1, and the amination condition is: 8 tunics are immersed in 5 liters and are not less than in 30% trimethylamine aqueous solution, 30 ℃ of temperature, 10 hours time.
Example 11, with 300 gram methacrylic acid epoxy fourth vinegar, 50 gram methacrylate diethyl esters, 60 gram vinyl chloride-vinyl acetate copolymers, 60 gram dioctyl phthalate (DOP)s and 3 gram benzoyl peroxides at room temperature stir into even slurry together, pasting operation and condition are all with example 1, and converging operation is with example 1, but polymerizing condition is: pressure 25 * 10
5Pa, 100 ℃ of temperature, 6 hours time, the every operation after the polymerization is all with example 1, and basement membrane amination operation and aftertreatment are all with example 1, and the amination condition is: 8 tunics are immersed in 5 liters and are not less than in 30% trimethylamine aqueous solution, 35 ℃ of temperature, 8 hours time.
Example 12, with 300 gram glytidyl methacrylate, the divinylbenzene of 80 grams 46%, 60 gram vinyl chloride-vinyl acetate copolymers, 90 gram dioctyl phthalate (DOP)s and 4 gram benzoyl peroxides are mixed together at room temperature to stir makes slurry, pasting operation and condition be all with example 1, and converging operation is with example 1, polymerizing condition: pressure 10 * 10
5Pa, 100 ℃ of temperature, 8 hours time.Basement membrane amination operation and aftertreatment are all with example 1, but the amination condition is: 8 layers of basement membrane are immersed in 5 liters and are no less than in the 30% triethylamine methanol solution, and the amination temperature is 30 ℃, 10 hours time.
Example 13, according to the prescription of example 12, pasting, polymerization, amination and aftertreatment etc. are operated all with example 1, and polymerizing condition is with example 12, but the amination condition is: 8 layers of basement membrane are immersed in 8 liters and are no less than in the 30% trolamine methanol solution, and temperature is 40 ℃, 10 hours time.
The snappiness of the anion-exchange membrane of the foregoing description gained, intensity, electrochemical properties all is better than United States Patent (USP) 4,374,206 anion-exchange membrane greatly.
Claims (7)
1, a kind of manufacture method of anion-exchange membrane is characterized in that this method technological process is as follows:
(1) slurrying: with monomer; linking agent; initiator; toughener; flexibilizing agent is mixed in proportion; under 10-40 ℃ of temperature, be stirred into slurry; monomer is acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class; linking agent is aliphatics double vinyl compound or aromatic series double vinyl compound; toughener is the linear polymer that dissolves in acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class, and flexibilizing agent is a phthalic acid dialkyl class, and initiator is benzoyl peroxide or Diisopropyl azodicarboxylate; its proportioning is a monomer: linking agent: toughener: flexibilizing agent: initiator=45-80%: 4-20%: 5-20%: 5-20%: 0.2-2%
(2) system film: slurry is coated on the reinforced fabric, the pressurized, heated polymerization, pressure is 0.5-25 * 10 during polymerization
5Pa, Heating temperature is 60-120 ℃, polymerization time is equal to or greater than 3 hours, take out basement membrane after the cooling release, and aminating agent carries out amination.
2, manufacture method as claimed in claim 1 is characterized in that the structure of acrylic acid epoxy alkane ester class or alkyl acrylic oxirane ester class is
, in the formula, R is H ,-CH
3,-C
2H
5,-C
3H
7, n=1-6.
3, preparation method as claimed in claim 1, it is characterized in that aliphatics double vinyl compound linking agent is two vinylformic acid second diester, two vinylformic acid one diethyl diester that contracts, methacrylate second diester, the methacrylate one diethyl diester that contracts, fragrant same clan double vinyl compound linking agent is a divinylbenzene.
4, preparation method as claimed in claim 1 is characterized in that linear polymer is Vinyl Acetate Copolymer or vinyl chloride-vinyl acetate copolymer.
5, preparation method as claimed in claim 1 is characterized in that the structure of phthalic acid dialkyl class is
, R is-CH in the formula
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15,-C
8H
17
6, preparation method as claimed in claim 1 is characterized in that reinforced fabric is glasscloth (woven fiber glass), trevira cloth (being coated with synthetic fibre cloth), nylon cloth, polypropylene fibre cloth (Polypropylene), non-woven fabrics and thermovyl cloth (polyvinyl chloride fibre cloth).
7, preparation method as claimed in claim 1 is characterized in that aminating agent is the fatty amine compounds, and its structure is
, R in the formula
1For-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
2H
4OH, R
2For-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
2H
4OH, R
3For-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
2H
4OH, amine concentration is not less than 25%, and the mol ratio of the epoxide group in amine and the monomer is 20: 1-10: 1, amine is 15-45 ℃ than temperature, the amination time is more than 4 hours or 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90103412A CN1027897C (en) | 1990-07-09 | 1990-07-09 | Method for manufacturing aliphatic anion exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90103412A CN1027897C (en) | 1990-07-09 | 1990-07-09 | Method for manufacturing aliphatic anion exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1058030A CN1058030A (en) | 1992-01-22 |
| CN1027897C true CN1027897C (en) | 1995-03-15 |
Family
ID=4878049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90103412A Expired - Fee Related CN1027897C (en) | 1990-07-09 | 1990-07-09 | Method for manufacturing aliphatic anion exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027897C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978038B (en) * | 2005-12-09 | 2010-05-05 | 中国科学技术大学 | Method for preparing homogeneous-phase anion exchange film |
| CN101012315B (en) * | 2006-04-06 | 2012-08-01 | 浙江千秋环保水处理有限公司 | Method of manufacturing low permeation ion exchange membrane |
| GB0813227D0 (en) * | 2008-07-18 | 2008-08-27 | Fuji Film Mfg Europ B V | Process for preparing membranes |
| CN102926197B (en) * | 2012-11-15 | 2014-05-07 | 杭州水处理技术研究开发中心有限公司 | Manufacturing method of support cloth for preparation of ion exchange membrane |
| CN103910898A (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 anion exchange membrane through photocuring |
| CN111992259A (en) * | 2020-09-01 | 2020-11-27 | 中国海洋大学 | Side chain type anion exchange membrane and preparation method thereof |
| CN112546873A (en) * | 2020-12-31 | 2021-03-26 | 山东天维膜技术有限公司 | Bipolar membrane and preparation method thereof |
-
1990
- 1990-07-09 CN CN90103412A patent/CN1027897C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1058030A (en) | 1992-01-22 |
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Correction item: Character Correct: Nai Qiangsuan False: Er Qiangsuan Page: 3 Correction item: Character Correct: An Hua False: An Bi Page: 3 Correction item: Character Correct: 50 grams of vinegar False: 50 without vinegar Page: 4 Correction item: Character Correct: An Hua False: An Bi Page: 2 |
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