CN102284254B - Method for manufacturing chlorine-resistant polyamide reverse osmosis composite film - Google Patents
Method for manufacturing chlorine-resistant polyamide reverse osmosis composite film Download PDFInfo
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- CN102284254B CN102284254B CN 201110154645 CN201110154645A CN102284254B CN 102284254 B CN102284254 B CN 102284254B CN 201110154645 CN201110154645 CN 201110154645 CN 201110154645 A CN201110154645 A CN 201110154645A CN 102284254 B CN102284254 B CN 102284254B
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Abstract
The invention discloses a method for manufacturing a chlorine-resistant polyamide reverse osmosis composite film. The method comprises the following steps of: 1, preparing a supporting bottom film by a general phase inversion method, wherein an additive is added into bottom film casting liquid in advance and the additive is one or a mixture of more than one of a curing agent of an adhesive containing an epoxide group, a curing agent of an adhesive containing a silica group, and a curing agent of an adhesive containing an isocyanate group; 2, treating the surface of the supporting bottom film by using liquid of the adhesive containing the epoxide group, the silica group or the isocyanate group; and 3, compounding a layer of polyamide reverse osmosis composite film on the surface of the supporting bottom film by an interface polymerization method. The chlorine resistance performance of the polyamide reverse osmosis composite film manufactured by the method is greatly improved.
Description
Technical field
The present invention relates to a kind of method of making the polyamide reverse osmosis composite film of anti-chlorine, belong to preparation method's technical field of pellicle.
Background technology
Nanofiltration and reverse osmosis membrane are because of the separating property to the brilliance of organic molecule and inorganic ion, and safety, environmental friendliness, the advantage such as easy to operate and become one of key technology of water treatment.Its application comprises seawater and the bitter degree of saltiness, water softening, and middle water reclaims, Industrial Wastewater Treatment, the wide spectrums such as ultra-pure water preparation.Wherein composite membrane can be with the rejection of film because of it, water flux, stability wait performance optimization and become current development the fastest, use maximum film kinds, surpassing in the market 90% nanofiltration and reverse osmosis membrane is composite membrane.Composite membrane refers to that on the support counterdie of porous compound one deck is very thin, different materials fine and close, that the special separation function is arranged.Compare with integrated film, the surface compact layer thickness of composite membrane is thinner, thereby makes film have simultaneously high solute separation rate and the transmission rates of water, and optimizable physical chemistry structure, can satisfy various Selective Separation demand.The current composite membrane that is widely used in water treatment field is mainly taked the mode of interfacial polymerization, polyamide film is compound to micropore support counterdie surperficial.Common technical process has detailed introduction at the United States Patent (USP) 4277344 of initiative.At first the micropore counterdie that polysulfones is coated on polyester non-woven fabric and forms, be immersed in diamines or the polyamines aqueous solution, then drench by wind, the methods such as roll-in are removed the unnecessary amine aqueous solution in film surface, be immersed in again in organic non-polar solution of polynary acyl chlorides and acyl chlorides generation interface polymerization reaction, thereby form the fine and close polyamide ultrathin active layer with separation function on the surface, after film forming, fully washing and suitable heat cure are processed and can be increased film properties.The chemical constitution of polyamide makes the chlorine-resistant property of such composite membrane very weak, and all commercial polyamide composite films are almost nil to the permission of free chlorine, thereby has increased the pretreatment cost of film and reduced service life.In order to improve the chlorine resistance of polyamide composite film, do a lot of work both at home and abroad, mainly concentrate on by adopting different monomers to change the chemical constitution of polyamide or increase the chemical-resistant stability of film by the post processing means such as oxidation/chlorination on film surface, but these class methods tend to lose other performance as reducing rejection or water flux.Chinese patent 95116419.8 " Interface Control prepares the method for the aromatic polyamides of anti-chlorine reverse osmosis composite membrane " makes the generation of interfaces cross-linked structure by the Chemical Physics modification, thereby has greatly improved the chlorine-resistant property of polyamide reverse osmosis composite film.Aspect water flux improved, except using widely various additives, in polyamines or polynary solution of acid chloride, gained composite membrane water flux can significantly improve US Patent No. 20100062156 with nanoparticulate dispersed.
Summary of the invention
The present invention wants the technical solution problem to be: overcome the shortcoming of above-mentioned prior art, a kind of method of making the polyamide reverse osmosis composite film of anti-chlorine is provided.
In order to solve above technical problem, a kind of method of making the polyamide reverse osmosis composite film of anti-chlorine of the present invention is characterized in that comprising:.
The first step, the general phase inversion of process are made the support counterdie, wherein, be added with in advance additive in the counterdie casting solution, described additive be the bonding agent of the curing agent that contains the bonding agent of epoxide group, siliceous oxygen groups curing agent, contain one or more the mixing in the curing agent of bonding agent of isonitrile acid groups;
The solution-treated of second step, the surperficial bonding agent with containing epoxide group or silica group or isonitrile acid groups of support counterdie;
The 3rd step, supporting counterdie surface recombination one deck polyamide reverse osmosis composite film through interfacial polymerization.
Further, described curing agent is one or more micromolecular compound or oligomer or the macromolecular compound that comprises in molecule in nitrogen-atoms, hydroxyl, carboxyl, anhydride group, phenolic hydroxyl group, mercapto.
In the present invention, the described bonding agent that contains epoxide group is one or more that contain at least in the oligomer that contains at least an epoxide group in the micromolecular compound that contains at least an epoxide group in molecule, molecule, molecule in the macromolecular compound of an epoxide group; The bonding agent of described siliceous oxygen groups is one or more that contain at least in the oligomer that contains at least a silica group in the micromolecular compound that contains at least a silica group in molecule, molecule, molecule in the macromolecular compound of a silica group; The described bonding agent that contains the isonitrile acid groups is one or more that contain at least in the oligomer that contains at least an isonitrile acid groups in the micromolecular compound that contains at least an isonitrile acid groups in molecule, molecule, molecule in the macromolecular compound of an isonitrile acid groups.
Further, the concentration that the curing agent that adds in counterdie casting solution of the present invention accounts for the bed die casting solution is 0.01-10%.
Further, in second step of the present invention, the counterdie surface treatment is 0.01-50% with the solution concentration of bonding agent.In second step, be a kind of during two-sided dip-coating, surface spraying, surface are brushed to supporting counterdie surface-treated method.
Contained epoxy in this counterdie surface, silica and isonitrile acid compounds function as follows: 1, can improve the adhesive property between polyamide functional layer and counterdie, thereby improve the chemical-resistant stability at composite membrane interface; 2, this compounds can be under heating condition be solidified by the curing agent in the group such as the amide groups/amido in polyamide/carboxyl and counterdie, forms netted compound in reaching at the interface the counterdie body, thereby has greatly improved the chlorine-resistant property of this composite membrane; 3, amide groups at the interface be subject to that free chlorine attacks-the CONH base will become with the epoxy on counterdie surface or isonitrile acid-base reaction be not subject to that free chlorine attacks-the CON-group, improved like this chlorine-resistant property of this composite membrane from the chemical constitution aspect.
Through the polyamide reverse osmosis composite film that the inventive method is made, its chlorine-resistant property is greatly improved.
The specific embodiment
Comparative Examples: the polysulfones of 16% (mass percent) is dissolved in the solvent dimethylformamide of 84% (mass percent), after filtration, after deaeration, on pulling, scrapes in glass the counterdie of restriction 60 micron thickness with scraper, after pure water thoroughly cleans 4 hours as coagulating bath and with the pure water that flows, be immersed in the m-phenylene diamine (MPD) aqueous solution that contains 2.0% (mass percent) 2 minutes, with squeegee press mold surface to the hexane solution of the pyromellitic trimethylsilyl chloride of half-dried rear immersion 0.2% 20 seconds.Put into the oven 20 minutes of 110 ℃ after taking-up, then use successively aqueous slkali, test membrane performance after acid solution, alcoholic solution and pure water thoroughly clean.The composite membrane of this Comparative Examples gained is at 25 ℃, the 1500ppm NaCl aqueous solution, and under the 1.5MPa pressure test conditions, to the rejection 98.6% of NaCl, water flux is 0.82M
3/ M
2.d.This film drops to respectively 85.0% and 35.5% to the rejection of NaCl at room temperature after 1000ppm NaClO aqueous solution soaking is processed 1 hour and 10 hours.
Embodiment 1,3% PEI (GE Ultem 1000) and 13% polysulfones are dissolved in 84% solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, with the special solid F-05 epoxy glue of 3% peace/positive hexanone solution-treated counterdie surface 5 minutes, drench use after doing with Comparative Examples in identical combination process composite membrane-forming.Test condition is identical with Comparative Examples, and result is listed table 1 in.After 1000ppm NaClO aqueous solution soaking is processed 10 hours, to the rejection of NaCl still up to 96.3%.
Embodiment 2,1% poly acrylic anhydride and 15% polysulfones are dissolved in 84% solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, with the special solid F-05 epoxy glue of 3% peace/positive hexanone solution-treated counterdie surface 5 minutes, drench use after doing with Comparative Examples in identical combination process composite membrane-forming.Test condition is identical with Comparative Examples, and result is listed table 1 in.After 1000ppm NaClO aqueous solution soaking is processed 10 hours, to the rejection of NaCl still up to 96.2%.
Embodiment 3,5% poly-(N-ketene imine carbonyl) and 11% polysulfones are dissolved in 84% solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, with the special solid F-05 epoxy glue of 3% peace/positive hexanone solution-treated counterdie surface 5 minutes, drench use after doing with Comparative Examples in identical combination process composite membrane-forming.Test condition is identical with Comparative Examples, and result is listed table 1 in.After 1000ppm NaClO aqueous solution soaking is processed 10 hours, to the rejection of NaCl up to 98.5%.
Embodiment 4,5% polyvinyl alcohol-20000 and 11% polysulfones are dissolved in 84% solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, processed the counterdie surface 5 minutes with 1%A-186 coupling agent/ethanolic solution, drench use after doing with Comparative Examples in identical combination process composite membrane-forming.Test condition is identical with Comparative Examples, and result is listed table 1 in.After 1000ppm NaClO aqueous solution soaking is processed 10 hours, to the rejection of NaCl up to 96.4%.
Embodiment 5,3% PEI and 13% polysulfones are dissolved in 84% solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, processed the counterdie surface 5 minutes with 3% toluene di-isocyanate(TDI)/aqueous isopropanol, drench use after doing with Comparative Examples in identical combination process composite membrane-forming.Test condition is identical with Comparative Examples, and result is listed table 1 in.After 1000ppm NaClO aqueous solution soaking is processed 10 hours, to the rejection of NaCl up to 96.5%.
Embodiment 6,1% poly acrylic anhydride and 15% polysulfones are dissolved in 84% solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, processed the counterdie surface 5 minutes with 3% toluene di-isocyanate(TDI)/aqueous isopropanol, drench use after doing with Comparative Examples in identical combination process composite membrane-forming.Test condition is identical with Comparative Examples, and result is listed table 1 in.After 1000ppm NaClO aqueous solution soaking is processed 10 hours, to the rejection of NaCl up to 96.1%.
Embodiment 7,5% poly-(N-ketene imine carbonyl) and 11% polysulfones are dissolved in 84% solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, processed the counterdie surface 5 minutes with 3% toluene di-isocyanate(TDI)/aqueous isopropanol, drench use after doing with Comparative Examples in identical combination process composite membrane-forming.Test condition is identical with Comparative Examples, and result is listed table 1 in.After 1000ppm NaClO aqueous solution soaking is processed 10 hours, to the rejection of NaCl up to 98.4%.
Table 1
As can be known, utilize the reverse osmosis composite membrane of the inventive method manufacturing from table, chlorine-resistant property is significantly improved.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (8)
1. method of making the polyamide reverse osmosis composite film of anti-chlorine is characterized in that comprising:
The first step, the general phase inversion of process are made the support counterdie, wherein, be added with in advance additive in the counterdie casting solution, described additive be the bonding agent of the curing agent that contains the bonding agent of epoxide group, siliceous oxygen groups curing agent, contain one or more the mixing in the curing agent of bonding agent of isonitrile acid groups;
The solution-treated of second step, the surperficial bonding agent with containing epoxide group or silica group or isonitrile acid groups of support counterdie;
The 3rd step, supporting counterdie surface recombination one deck polyamide reverse osmosis composite film through interfacial polymerization.
2. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1 is characterized in that: described curing agent is one or more micromolecular compound or oligomer or the macromolecular compound that comprises in molecule in nitrogen-atoms, hydroxyl, carboxyl, anhydride group, phenolic hydroxyl group, mercapto.
3. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1 is characterized in that: the bonding agent that contains epoxide group is one or more that contain at least in the oligomer that contains at least an epoxide group in the micromolecular compound that contains at least an epoxide group in molecule, molecule, molecule in the macromolecular compound of an epoxide group.
4. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1 is characterized in that: the bonding agent of siliceous oxygen groups is one or more that contain at least in the oligomer that contains at least a silica group in the micromolecular compound that contains at least a silica group in molecule, molecule, molecule in the macromolecular compound of a silica group.
5. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1 is characterized in that: the bonding agent that contains the isonitrile acid groups is one or more that contain at least in the oligomer that contains at least an isonitrile acid groups in the micromolecular compound that contains at least an isonitrile acid groups in molecule, molecule, molecule in the macromolecular compound of an isonitrile acid groups.
6. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1, it is characterized in that: the concentration that the curing agent that adds in the counterdie casting solution accounts for the bed die casting solution is 0.01-10%.
7. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1, it is characterized in that: in second step, the counterdie surface treatment is 0.01-50% with the solution concentration of bonding agent.
8. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1 is characterized in that: in second step, be a kind of during two-sided dip-coating, surface spraying, surface are brushed to supporting counterdie surface-treated method.
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| CN112210102A (en) * | 2020-10-27 | 2021-01-12 | 银金达(上海)新材料有限公司 | High-barrier PETG (polyethylene terephthalate glycol) aluminized composite film and preparation method thereof |
| CN113828174A (en) * | 2021-10-09 | 2021-12-24 | 苏州苏瑞膜纳米科技有限公司 | Reverse osmosis membrane with double-layer composite structure and preparation method thereof |
| CN114146567A (en) * | 2021-12-02 | 2022-03-08 | 万华化学集团股份有限公司 | Preparation process of epoxy modified reverse osmosis membrane, reverse osmosis membrane and application of reverse osmosis membrane |
Citations (3)
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| CN1054200A (en) * | 1989-12-14 | 1991-09-04 | 联合信号股份有限公司 | Dry high flux semipermeable membranes |
| CN1468649A (en) * | 2002-07-16 | 2004-01-21 | 世韩工业株式会社 | Method for producing selective diffusion barrier with excellent pollution resistibility |
| CN101244367A (en) * | 2007-02-13 | 2008-08-20 | 世韩工业株式会社 | Selective membrane having a high fouling resistance |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054200A (en) * | 1989-12-14 | 1991-09-04 | 联合信号股份有限公司 | Dry high flux semipermeable membranes |
| CN1468649A (en) * | 2002-07-16 | 2004-01-21 | 世韩工业株式会社 | Method for producing selective diffusion barrier with excellent pollution resistibility |
| CN101244367A (en) * | 2007-02-13 | 2008-08-20 | 世韩工业株式会社 | Selective membrane having a high fouling resistance |
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| 武少禹等.超薄复合膜的界面控制.《科学通报》.1996,(第4期),383. |
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Application publication date: 20111221 Assignee: NANJING AQUACUP TECHNOLOGY CO., LTD. Assignor: Nanjing Co., Ltd. Royal membrane water purification materials development Contract record no.: 2017320000091 Denomination of invention: Method for preparing chlorine-resistant polyamide reverse osmosis composite membrane Granted publication date: 20130619 License type: Exclusive License Record date: 20170324 |
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Effective date of registration: 20201105 Address after: 239300, Anhui, Chuzhou province Tianchang Development Zone on the south side of latitude three road, west side of the four road Patentee after: Anhui encote Film Technology Co.,Ltd. Address before: 210046, No. 25, Heng Jing Road, Xingang Development Zone, Qixia District, Jiangsu, Nanjing Patentee before: NANJING DELNAMEM TECHNOLOGY Co.,Ltd. |