CN102284254A - 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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- CN102284254A CN102284254A CN2011101546457A CN201110154645A CN102284254A CN 102284254 A CN102284254 A CN 102284254A CN 2011101546457 A CN2011101546457 A CN 2011101546457A CN 201110154645 A CN201110154645 A CN 201110154645A CN 102284254 A CN102284254 A CN 102284254A
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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, advantage such as easy to operate and become one of key technology of water treatment.Its application comprises the seawater and the bitter degree of saltinessization, water softening, and middle water reclaims, Industrial Wastewater Treatment, wide spectrums such as ultra-pure water preparation.Wherein composite membrane can be with the rejection of film because of it, water flux, performance optimization such as stability and become current with fastest developing speed, use maximum film kinds, surpassing 90% nanofiltration and reverse osmosis membrane in the market is composite membrane.Composite membrane is meant very thin, the different materials fine and close, that the special separation function is arranged of compound one deck on the support counterdie of porous.Compare with integrated film, the surface compact layer thickness of composite membrane is thinner, thereby makes film have the high solute separation rate and the transmission rates of water simultaneously, and optimizable physical chemistry structure, can satisfy various Selective Separation demand.The current composite membrane that is widely used in the water treatment field is mainly taked the mode of interfacial polymerization, polyamide film is compound to micropore supports the counterdie surface.Common technical process has detailed introduction at the United States Patent (USP) 4277344 of initiative.The micropore counterdie that at first polysulfones is coated on the polyester non-woven fabric and forms, be immersed in the diamines or the polyamines aqueous solution, drench by wind then, 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 the film forming, fully washing and suitable heat cure are handled 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 preliminary treatment 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, but these class methods tend to lose other performance as reducing rejection or water flux by the post processing means such as oxidation/chlorination on film surface.Chinese patent 95116419.8 " Interface Control prepares the method for the aromatic polyamides of anti-chlorine reverse osmosis composite membrane " makes the interface produce cross-linked structure by the Chemical Physics modification, thereby has improved the chlorine-resistant property of polyamide reverse osmosis composite film greatly.Aspect water flux improved, except using various additives widely, in polyamines or polynary solution of acid chloride, gained composite membrane water flux can significantly improve U.S. Pat 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 additive in the counterdie casting solution in advance, 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;
Second step, the support counterdie surface solution-treated of the bonding agent that contains epoxide group or silica group or isonitrile acid groups;
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 the molecule in nitrogen-atoms, hydroxyl, carboxyl, anhydride group, phenolic hydroxyl group, the mercapto.
Among the present invention, the described bonding agent that contains epoxide group is to contain in the macromolecular compound of an epoxide group one or more in the oligomer that contains an epoxide group in the micromolecular compound that contains an epoxide group in the molecule at least, the molecule at least, the molecule at least; The bonding agent of described siliceous oxygen groups is to contain in the macromolecular compound of a silica group one or more in the oligomer that contains a silica group in the micromolecular compound that contains a silica group in the molecule at least, the molecule at least, the molecule at least; The described bonding agent that contains the isonitrile acid groups is to contain in the macromolecular compound of an isonitrile acid groups one or more in the oligomer that contains an isonitrile acid groups in the micromolecular compound that contains an isonitrile acid groups in the molecule at least, the molecule at least, the molecule at least.
Further, to account for the concentration of bed die casting solution be 0.01-10% to the curing agent that is added in the counterdie casting solution of the present invention.
Further again, 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 group such as the amide groups/amido in the polyamide/carboxyl and the counterdie, forms netted compound in reaching the counterdie body at the interface, thereby has improved the chlorine-resistant property of this composite membrane greatly; 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 the chlorine-resistant property of this composite membrane like this 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 the 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, and immersed the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride with squeegee press mold surface to half-dried back.Put into 110 ℃ oven 20 minutes after the taking-up, use aqueous slkali then successively, acid solution, alcoholic solution and pure water thoroughly clean back test membrane performance.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 85.0% and 35.5% respectively to the rejection of NaCl at room temperature after 1000ppm NaClO aqueous solution soaking is handled 1 hour and 10 hours.
Embodiment 1,3% PEI (GE Ultem 1000) and 13% polysulfones be dissolved in 84% the 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 the result lists table 1 in.After 1000ppm NaClO aqueous solution soaking is handled 10 hours, to the rejection of NaCl still up to 96.3%.
Embodiment 2,1% poly acrylic anhydride and 15% polysulfones be dissolved in 84% the 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 the result lists table 1 in.After 1000ppm NaClO aqueous solution soaking is handled 10 hours, to the rejection of NaCl still up to 96.2%.
Embodiment 3,5% poly-(N-vinyl imines carbonyl) and 11% polysulfones be dissolved in 84% the 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 the result lists table 1 in.After 1000ppm NaClO aqueous solution soaking is handled 10 hours, to the rejection of NaCl up to 98.5%.
Embodiment 4,5% polyvinyl alcohol-20000 and 11% polysulfones be dissolved in 84% the solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, handled 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 the result lists table 1 in.After 1000ppm NaClO aqueous solution soaking is handled 10 hours, to the rejection of NaCl up to 96.4%.
Embodiment 5,3% PEI and 13% polysulfones be dissolved in 84% the solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, handled 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 the result lists table 1 in.After 1000ppm NaClO aqueous solution soaking is handled 10 hours, to the rejection of NaCl up to 96.5%.
Embodiment 6,1% poly acrylic anhydride and 15% polysulfones be dissolved in 84% the solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, handled 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 the result lists table 1 in.After 1000ppm NaClO aqueous solution soaking is handled 10 hours, to the rejection of NaCl up to 96.1%.
Embodiment 7,5% poly-(N-vinyl imines carbonyl) and 11% polysulfones be dissolved in 84% the solvent dimethylformamide, with with Comparative Examples in identical counterdie manufacturing process make counterdie, handled 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 the result lists table 1 in.After 1000ppm NaClO aqueous solution soaking is handled 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 additive in the counterdie casting solution in advance, 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;
Second step, the support counterdie surface solution-treated of the bonding agent that contains epoxide group or silica group or isonitrile acid groups;
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 the molecule in nitrogen-atoms, hydroxyl, carboxyl, anhydride group, phenolic hydroxyl group, the 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 to contain in the macromolecular compound of an epoxide group one or more in the oligomer that contains an epoxide group in the micromolecular compound that contains an epoxide group in the molecule at least, the molecule at least, the molecule at least.
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 to contain in the macromolecular compound of a silica group one or more in the oligomer that contains a silica group in the micromolecular compound that contains a silica group in the molecule at least, the molecule at least, the molecule at least.
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 to contain in the macromolecular compound of an isonitrile acid groups one or more in the oligomer that contains an isonitrile acid groups in the micromolecular compound that contains an isonitrile acid groups in the molecule at least, the molecule at least, the molecule at least.
6. the method for the manufacturing polyamide reverse osmosis composite film of anti-chlorine according to claim 1 is characterized in that: the concentration that the curing agent that is added 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 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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| CN 201110154645 CN102284254B (en) | 2011-06-10 | 2011-06-10 | Method for manufacturing chlorine-resistant polyamide reverse osmosis composite film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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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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| 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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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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. |
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