CN102188912A - Method for preparing chlorine-resistant polyamide reverse osmosis composite membrane - Google Patents
Method for preparing chlorine-resistant polyamide reverse osmosis composite membrane Download PDFInfo
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- CN102188912A CN102188912A CN201010125652XA CN201010125652A CN102188912A CN 102188912 A CN102188912 A CN 102188912A CN 201010125652X A CN201010125652X A CN 201010125652XA CN 201010125652 A CN201010125652 A CN 201010125652A CN 102188912 A CN102188912 A CN 102188912A
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- epoxide
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- osmosis composite
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Abstract
The invention belongs to a method for preparing a chlorine-resistant polyamide reverse osmosis composite membrane. The method comprises the following steps of: coating a layer of epoxy compound on the surface of a support bottom membrane; immersing the support bottom membrane of which the surface is coated with the epoxy compound in polyamine and polyacyl chloride solution in turn by a general composite process and performing interfacial polymerization reaction to obtain a polyamide reverse osmosis composite membrane; and performing heat treatment, and cleaning thoroughly, wherein the chlorine resistance of the obtained composite membrane is more than 10,000ppm.h.
Description
Technical field
The invention belongs to a kind of method of making the polyamide reverse osmosis composite film of anti-chlorine.At first will support counterdie surface-coated one deck epoxide, and then successively the counterdie of this surface-coated epoxide is immersed in through general combination process and carries out interface polymerization reaction in polyamines and the polynary solution of acid chloride and form polyamide reverse osmosis composite film, residue in Overheating Treatment and thorough cleaning film, gained composite membrane chlorine-resistant property is largely increased.
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.
Summary of the invention
The purpose of this invention is to provide a kind of method of making the polyamide reverse osmosis composite film of anti-chlorine.
To support the counterdie surface and at first apply one deck epoxide, and then successively the support counterdie of this surface-coated epoxide is immersed in through general combination process and carries out interface polymerization reaction in polyamines and the polynary solution of acid chloride and form polyamide reverse osmosis composite film, through Overheating Treatment and thoroughly washing, gained composite membrane chlorine-resistant property is largely increased at last.The epoxide on this counterdie surface plays two aspect effects: 1, and can improve the adhesive property between polyamide functional layer and counterdie, thereby improve the chemical-resistant stability at composite membrane interface; 2, this epoxide can be solidify to form netted compound by the amide groups/amido in the polyamide and polyamide molecule and epoxide molecular linkage are in the same place under heating condition, increase the interface bonding action, meanwhile, at the interface, by heat treatment, in the polyamide molecule easily by the free chlorine attack-the CONH base by with the epoxide that applies in epoxy reaction become high chlorine resistance-the CON-C-base, thereby improved the chlorine-resistant property of this composite membrane greatly.
Embodiment provided by the invention is as follows for the specific embodiment:
Comparative Examples: the polysulfones counterdie of the about 200A of average pore size immersed contain in 2.0% the m-phenylene diamine (MPD) aqueous solution 2 minutes, immerse the hexane solution 20 seconds of 0.2% pyromellitic trimethylsilyl chloride with squeegee press mold surface to half-dried back.Put into 110 ℃ oven 10 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, before counterdie immerses amine aqueous solution, with spray-on process with the cyclohexanone solution of the special solid F-05 epoxy glue of 0.5% peace to polysulfones counterdie surface spray 20 seconds, the vertical placement after 15 minutes, immersion contains in 2.0% the m-phenylene diamine (MPD) aqueous solution 2 minutes, other technology is identical with Comparative Examples, and 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 93.0%.
Embodiment 2, before counterdie immerses amine aqueous solution, with spray-on process with the cyclohexanone solution of the special solid F-05 epoxy glue of 5.0% peace to polysulfones counterdie surface spray 20 seconds, the vertical placement after 15 minutes, immersion contains in 2.0% the m-phenylene diamine (MPD) aqueous solution 2 minutes, other technology is identical with Comparative Examples, and 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 97.3%.
Table 1
Claims (5)
1. the invention belongs to a kind of method of making the polyamide reverse osmosis composite film of anti-chlorine, comprise support counterdie surface is at first applied one deck epoxide, and then successively the support counterdie of this surface-coated epoxide is immersed in through general combination process and carries out interface polymerization reaction in polyamines and the polynary solution of acid chloride and form polyamide reverse osmosis composite film, at last through Overheating Treatment and thoroughly clean and remove residue in the film.
2. as right 1 described method, surface-coated comprises the micromolecular compound that comprises one or more epoxide groups in the molecule with epoxide, oligomer and macromolecular compound.
3. as right 1 described method, surface-coated comprises the unification compound with epoxide, mixture and solution thereof.
4. as right 1 described method, surface-coated comprises the surface spraying with the coating method of epoxide.
5. as right 1 described method, the thickness of epoxide coating between 1 nanometer to 200 nanometers.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010125652XA CN102188912A (en) | 2010-03-16 | 2010-03-16 | Method for preparing chlorine-resistant polyamide reverse osmosis composite membrane |
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| CN201010125652XA CN102188912A (en) | 2010-03-16 | 2010-03-16 | Method for preparing chlorine-resistant polyamide reverse osmosis composite membrane |
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| CN102188912A true CN102188912A (en) | 2011-09-21 |
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| CN201010125652XA Pending CN102188912A (en) | 2010-03-16 | 2010-03-16 | Method for preparing chlorine-resistant polyamide reverse osmosis composite membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103736404A (en) * | 2014-01-06 | 2014-04-23 | 北京碧水源膜科技有限公司 | Basal membrane of reverse osmosis membrane and preparation method of reverse osmosis membrane |
| CN111495202A (en) * | 2020-04-16 | 2020-08-07 | 宁波水艺膜科技发展有限公司 | Preparation method of vacuum-assisted thin-layer composite membrane |
| CN112316752A (en) * | 2020-11-04 | 2021-02-05 | 天津工业大学 | Sulfonamide micromolecule surface modified polyamide composite membrane and preparation method thereof |
| CN114146566A (en) * | 2021-12-02 | 2022-03-08 | 万华化学集团股份有限公司 | Preparation method of high-performance polyolefin substrate reverse osmosis membrane, reverse osmosis membrane and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
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2010
- 2010-03-16 CN CN201010125652XA patent/CN102188912A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
Non-Patent Citations (1)
| Title |
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| 武少禹等: "超薄复合膜的截面控制", 《科学通报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103736404A (en) * | 2014-01-06 | 2014-04-23 | 北京碧水源膜科技有限公司 | Basal membrane of reverse osmosis membrane and preparation method of reverse osmosis membrane |
| CN111495202A (en) * | 2020-04-16 | 2020-08-07 | 宁波水艺膜科技发展有限公司 | Preparation method of vacuum-assisted thin-layer composite membrane |
| CN111495202B (en) * | 2020-04-16 | 2022-02-22 | 宁波水艺膜科技发展有限公司 | Preparation method of vacuum-assisted thin-layer composite membrane |
| CN112316752A (en) * | 2020-11-04 | 2021-02-05 | 天津工业大学 | Sulfonamide micromolecule surface modified polyamide composite membrane and preparation method thereof |
| CN114146566A (en) * | 2021-12-02 | 2022-03-08 | 万华化学集团股份有限公司 | Preparation method of high-performance polyolefin substrate reverse osmosis membrane, reverse osmosis membrane and application |
| CN114146566B (en) * | 2021-12-02 | 2024-05-03 | 万华化学集团股份有限公司 | Preparation method of high-performance polyolefin substrate reverse osmosis membrane, reverse osmosis membrane and application |
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Application publication date: 20110921 |