CN1110355C - Method for producing polyamide reverse osmosis composite film - Google Patents
Method for producing polyamide reverse osmosis composite film Download PDFInfo
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- CN1110355C CN1110355C CN99125641A CN99125641A CN1110355C CN 1110355 C CN1110355 C CN 1110355C CN 99125641 A CN99125641 A CN 99125641A CN 99125641 A CN99125641 A CN 99125641A CN 1110355 C CN1110355 C CN 1110355C
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Abstract
The present invention provides relates to a method for making a polyamide reverse osmosis composite film having the properties of good osmosis quantity and desalination rate. A water solution of multifunctional amine containing more than polar compound, such as dipropylene glycol single alkyl ether, etc., and an organic solution containing an amine reaction compound selected from multifunctional base acyl halide, multifunctional base sulphonyl halide and multifunctional base isocyanic ester carry out reaction to form a polyamide film on a porous supporting layer.
Description
The invention relates in water for industrial use, agricultural water, domestic water, use, double salt solution or seawater desalinate employed reverse osmosis composite membrane when handling.
Utilize selective membranes such as secondary filter film, ultrafiltration membrane, reverse osmosis membrane, can make solute and separated from solvent.The so-called fresh water processing of using reverse osmosis membrane is that double salt solution or seawater apply the above pressure of osmotic pressure, by reverse osmosis membrane filter, the lewis' acid of separate dissolved, obtain the method for purifying waste water by film.Here said osmotic pressure is the pressure that acts in the other direction in above-mentioned filter process, and solute concentration is high more in the water source, and this osmotic pressure is also high more.
Use this reverse osmosis membrane, for jumbo half salt solution or seawater being carried out the fresh water processing with commercial size, require reverse osmosis membrane must possess the opposite characteristic of high infiltration capacity (that is, with the film of very low pressure) and so-called high desalination rate simultaneously by big water gaging.Except only paying attention to infiltration capacity, and do not require outside the special circumstances of high desalination rate, generally use when purifying waste water, require the desalination rate more than 97% with industrial level.For the requirement of infiltration capacity, during seawater, apply 800psi pressure, require at 10gfd (gallons/ft
2Day) more than, during half salt solution, apply 225psi pressure, require more than 15gfd.
Therefore, in reverse osmosis membrane,, generally use the composite membrane that on the porous supporting course, forms PA membrane as reverse osmosis membrane.As this typical PA membrane is the film that the interfacial polymerization by multi-functional yl amine and multiple functional radical acyl halide obtains.
To this; in No. the 4277344th, United States Patent (USP); Cadotte discloses the technology of making aromatic polyamide thin-film; that is, the aromatic series multiple functional radical acid halide that makes aromatic series multi-functional yl amine with two above primary amino radicals and have three above acyl halide functional groups carries out interfacial polymerization and makes.More particularly, to the record that obtains above-mentioned polyamide film be utilize coating process to be coated on m-phenylene diamine (MPD) (m-phenylenediamine) aqueous solution on the fine porous property polysulfones supporting mass after, remove superfluous m-phenylene diamine (MPD), react with the trimesic acid chloride solution that with " FREON " TF (trichorotrifluoroethane) is solvent again.
In the United States Patent (USP) No. 4872984 (in October, 1989 registration); Tomashke discloses a kind of manufacture method of reverse osmosis membrane; comprise following several stages: promptly (a) will contain (1) and have more than two amino; actual is the aromatic series polyamine of monomer; (2) aqueous solution of the amine salt compound of monomer; be coated on the stage that forms liquid level on the fine porous property supporting material; (b) make per 1 molecule contain multiple functional radical acyl halide or its mixture of 2.2 above acyl halide bases; actual is the organic solution that contains monomer aromatic series multiple functional radical acid halide compound; contact the stage of reacting with the aforesaid liquid layer, (c) product is carried out the dry stage.
In United States Patent (USP) No. 4983291 (in January, 1991 registration), Chau disclose a kind of on the porous supporting course and/or the layer in formation polymerization reactant film.More detailed saying; disclosed is that the polyamine aqueous solution that will contain non-proton property polar solvent, contain many hydroxide of acid acceptor is coated on the supporting course; after removing excess solution; the organic solution that is dissolved with the polyacyl halide thing is contacted on supporting course carry out polymerisation; resulting composite membrane; after processing such as hydroxyl polycarboxylic acids, poly-amino alkylidenyl polycarboxylic acids, sulfonic acid, amine salt, amino acid, polymer acid, inorganic acid, drying obtains reverse osmosis membrane.
And in United States Patent (USP) No. 5614099 (in March, 1991 registration); Hirose discloses a kind of reverse osmosis composite membrane; feature is that the average surface roughness (roughness) of polyamide surface layer is more than the 55nm, and this superficial layer is the halid reactant of multiple functional radical acid that has amino compound and have the acyl group acid functional group.More detailed saying, be to have proposed a kind of method that on supporting course, forms above-mentioned polyamide surface layer, promptly, with the m-phenylene diamine (MPD) solution coat after on the supporting course, organic solution with trimesic acid chloride (trimesicchloride) contacts again, by interface polymerization reaction, obtain film, carry out drying with high-temperature hot-air again and make.
People's such as above-mentioned Cadotte film though show that good penetration amount and desalination rate are arranged, in actual applications, for obtaining more economic film, is had higher requirement to the infiltration capacity and the desalination rate of polyamide reverse osmosis composite film.And also there is room for improvement in the variation of the chemical-resistance of film.
In view of above situation, the purpose of this invention is to provide a kind of polyamide reverse osmosis composite film, compare with above-mentioned existing method, can reach better infiltration capacity and desalination rate.
For achieving the above object; the manufacture method of relevant reverse osmosis membrane of the present invention; its main points are the aqueous solution that makes the amine that contains multiple functional radical and be selected from the polar compound in following the 1st group～the 3rd group; with contain be selected from multiple functional radical acyl halide, polyfunctional basic sulfonyl halide, the polyfunctional basic isocyanic ester, have and the organic solution of the amine reactive compound of amino reaction is reacted, and on the porous supporting course, form PA membrane.
The 1st group of compound: be selected from 1,2-alkane diol, 1,3-alkane diol, diethylene glycol (DEG) hexyl ether, diethylene glycol (DEG)-tert-butyl methyl ether, diethylene glycol dimethyl ether, DPG monoalky lether, triglyme, 1, X-cyclohexanedimethanol (X is 2～4 integer), in a kind or more than.
The 2nd group of compound: be selected from the alkyloxyalkanol a kind or more than.
The 3rd group of compound: be selected from alkoxyethanol and propane diols, alkoxyethanol and sulfoxide derivant, alkoxyethanol and urea, diethylene glycol (DEG) hexyl ether and propane diols, diethylene glycol (DEG) hexyl ether and sulfoxide derivant, diethylene glycol (DEG) hexyl ether and glycerine, 1, in 3-alkane diol and sulfoxide derivant, propane diols and the propylene-glycol monoalky lether a kind or more than.
As manufacture method of the present invention, preferably be coated in the above-mentioned aqueous solution on the porous supporting course after, contact with above-mentioned organic solution again, carry out interfacial polymerization.
Above-mentioned porous supporting course is selected from preferably that material in polysulfones, polyether sulfone, poly-imines, polyamide, polypropylene and the Kynoar makes.
Above-mentioned polar compound contains 0.01～8% (weight, as follows) in the preferably above-mentioned aqueous solution.
As polar compound, when using above-mentioned the 1st group of compound, preferably contain 0.1～4% in the above-mentioned aqueous solution, when using above-mentioned the 2nd group of compound, preferably contain 0.05～4% in the above-mentioned aqueous solution, when using above-mentioned the 3rd group of compound, preferably contain 3～4% in the above-mentioned aqueous solution.
In above-mentioned the 1st group of compound, when using the diethylene glycol (DEG) hexyl ether, preferably contain 0.1～3% in the above-mentioned aqueous solution.
Below be specifically described constituting main points of the present invention.
Reverse osmosis composite membrane among the present invention obtains by form PA membrane on the porous supporting course.Above-mentioned PA membrane is the aqueous solution that contains polar compound and polyfunctional basic amine by making, and contacts with the organic solution that contains amine reactive compound, carries out interface polymerization reaction and makes.
As above-mentioned porous supporting course, generally use fine porous property supporting course, there are not particular provisions, preferably the aperture of this supporting course can make infiltration water fully pass through.Yet when surpassing 300nm, extremely thin film can subside between the space, is difficult to obtain open and flat film, therefore, and 1～300nm preferably.
For the material of fine porous property supporting course, preferably use as polysulfones, polyether sulfone, gather the halogenation macromolecule of imines, polyacrylonitrile, polypropylene or Kynoar one class etc.
The thickness of fine porous property supporting course, though there is not special provision, preferably 25～125 μ m are more preferably 40～75 μ m.
The polyfunctional basic amine that uses among the present invention preferably has monomeric amines amino more than 2, has the better of 2～3 amino.And amino, preferably primary amino radical or secondary amino group, preferably primary amino radical.
As the example of polyfunctional basic amine, m-phenylene diamine (MPD), p-phenylenediamine (PPD) and their substitutive derivative are arranged, as substituting group, can comprise alkyl, alkoxyl, hydroxyalkyl, hydroxyl or the halogen atom etc. of methyl, ethyl etc.In addition, also has 1 of chain type alkane diamines, the 3-propane diamine, have 1 of N-alkyl or N-aryl, the N of the piperazine of the cyclohexane diamine of 3-propane diamine derivative, ring grease shape primary diamines, ring grease shape secondary diamine, piperazine alkyl derivative, aromatic series secondary diamine, N '-dimethyl-1,3-phenylenediamine, N, N '-diphenyl ethylene diamine or benzidine, dimethylphenylene diamine and its derivative etc.
Above-mentioned polyfunctional basic amine preferably is modulated into and contains 0.1～20% the above-mentioned aqueous solution, is more preferably to contain 0.5～8% the aqueous solution.
The above-mentioned aqueous solution preferably is adjusted to the scope of pH7～13.At this moment pH regulates, and is the aqueous solution interpolation acid acceptor with 0.001～5%.As acid acceptor, alkali-metal hydroxide, carboxylate, carbonate, borate, phosphate or trialkylamine etc. are arranged.
Above-mentioned polar compound uses to be selected from following the 1st group of compound～3rd group compound.Its concentration, the preferably above-mentioned aqueous solution contain 0.01～8% (better 0.1～4%).
As the 1st group of compound, have 1,2-alkane diol, 1,3-alkane diol, diethylene glycol (DEG) hexyl ether, diethylene glycol (DEG)-tert-butyl methyl ether, diethylene glycol dimethyl ether, DPG monoalky lether, triglyme, 1, X-cyclohexanedimethanol (X is the integer of 2-4).
As 1, the instantiation of 2-alkane diol has 1,2-butanediol, 1,2-pentanediol, 1,2-hexylene glycol, 1,2-ethohexadiol, as 1, the example of 3-alkane diol has 2-ethyl-1,3-hexylene glycol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,3-pentanediol, 2,2-diethyl-1, ammediol, 2,2-dimethyl-1, ammediol, as the example of DPG monoalky lether, dipropylene glycol methyl ether, DPG butyl ether, DPG-tert-butyl ether are arranged.In addition, also have propane diols propyl ether, propylene glycol butyl ether etc.
When using above-mentioned the 1st group of compound, contain 0.1～4% in the preferred above-mentioned aqueous solution.When using the diethylene glycol (DEG) hexyl ether, preferably 0.01～3%, be more preferably 0.1～3%.Use 2-ethyl-1, during the 3-hexylene glycol, preferably 0.1～1%.
As the alkyloxyalkanol of the 2nd group of compound, 2-methyl cellosolve, cellosolvo, 2-propoxyl group ethanol, butoxy ethanol etc. are arranged.
When using above-mentioned the 2nd group of compound, contain 0.05～4% in the preferred above-mentioned aqueous solution, it is 0.05～3%, 0.5～2% especially good to be more preferably.
As the 3rd group of compound, it is the polar compound that is used in combination more than 2 kinds, as the example, alkoxyethanol and propane diols, alkoxyethanol and sulfoxide derivant, alkoxyethanol and urea, diethylene glycol (DEG) hexyl ether and propane diols, diethylene glycol (DEG) hexyl ether and sulfoxide derivant, diethylene glycol (DEG) hexyl ether and glycerine, 1 are arranged, 3-alkane diol and sulfoxide derivant, propane diols and propylene-glycol monoalky lether.Here, as above-mentioned sulfoxide derivant, dimethyl sulfoxide (DMSO), butyl sulfoxide, methyl phenyl sulfoxide, tetramethylene sulfoxide etc. are arranged.In addition, also can use the composition of alkoxyethanol and urea derivative (urea derivative is the compound that its hydrogen more than 1 is replaced by alkyl), alkoxyethanol and glycerine etc.
When using above-mentioned the 3rd group of compound, contain 3～4% in the preferably above-mentioned aqueous solution.
Can infer, utilize the inventive method, can obtain to have the film of the good characteristic of high infiltration capacity, polar compound among the present invention is on porous supporting course surface, have the absorbefacient effect of the film of increasing, and have the effect that prevents from behind interface polymerization reaction, to produce film drying because of organic solvent evaporation.
Manufacture method as reverse osmosis composite membrane, the aqueous solution that preferably will contain polyfunctional basic amine and polar compound makes the organic solution that contains above-mentioned amine reactive compound contact with above-mentioned liquid phase film again and carries out interfacial polymerization after being coated in and forming the liquid phase film on the porous supporting course.
Above-mentioned amine reactive compound uses a kind or above compound being selected from multiple functional radical acyl halide, polyfunctional basic sulfonyl halide, the polyfunctional basic isocyanic ester.Above-mentioned amine reactive compound; be with the acyl halide of monomer, aromatic compound and multiple functional radical main points as necessity; satisfy the suitable compound of these main points; wherein, the trimesic acid chloride, isophathalic acid chloride, terephalic acid chloride or its composition that preferably have 2 or 3 carboxylic acid halides.
Above-mentioned amine reactive compound preferably contains 0.005～5% in above-mentioned organic solvent, better contain 0.01～0.5%.
Above-mentioned organic solvent must be water-insoluble, and preferably the halogen of the alkane of hexane, cyclohexane, heptane, 8～12 carbon atoms or freon (dicholorodifluoromethane) class replaces hydrocarbon etc.At aspect of performance,, good especially by the mixed organic solvents that the alkane of 8～12 carbon atoms forms.
Embodiment
Following listed examples is described more specifically the present invention, but the present invention is not limited by following embodiment, with scope that the context meaning is consistent in, also can suitably change and implement, but in any case, be included within the technical scope of the present invention.
Manufacture method
After being coated on the manual coating of above-mentioned aqueous solution utilization or series-operation on the porous supporting course, utilize suitable methods such as roll extrusion, wetting preshrunk or air knife coating again, the excess solution on the supporting course is removed.Subsequently, utilize dipping or spray-on process that above-mentioned organic solution is contacted with above-mentioned coating layer, kept 5 seconds～10 minutes, preferably kept 20 seconds～4 minutes, react.Reaction product, as an example, be through descending dry 1 minute, again with postprocessing working procedures such as alkaline aqueous solution washed 1 minute～30 minutes at 40 ℃.
Embodiment 1
On the thick nonwoven of 140 μ m, form the polysulfones supporting course, again this supporting course is flooded in the aqueous solution that contains 2.0% m-phenylene diamine (MPD) (MPD), 2.0%2-butyl cellosolve and 2.0% propane diols.After removing the excess solution on the supporting course, in イ ソ パ (EXXON society system) solvent, be dissolved with in the muriatic solution of 0.1% trimesic acid and flooded 1 minute, remove excess solution.The composite membrane that obtains after dry 1 minute at normal temperatures, is used 40～60 ℃ 0.1%Na again
2CO
3Solution washing is more than 30 minutes.Use the NaCl aqueous solution of 2000ppm, under the pressurized conditions of 225psi, measure the performance of gained reverse osmosis separating membrane, the result is, the desalination rate is 98.2%, and infiltration capacity is 27.5gfd.
Embodiment 2
Except using 1.0%2-butyl cellosolve, 1.0 urea as the polar compound, other are implemented with embodiment 1 the same method.Measure the rerum natura of gained film, the result is, the desalination rate is 98.8%, and infiltration capacity is 27.0gfd.
Embodiment 3
Except using 2.0%2-butyl cellosolve, 2.0% dimethyl sulfoxide (DMSO) as the polar compound, other are to implement with embodiment 1 identical method.Measure the rerum natura of gained film, the result is, the desalination rate is 96.4%, and infiltration capacity is 32.2gfd.
Embodiment 4～16 and Comparative examples A～X
Except the polar compound that uses following table 1, to implement, measure the rerum natura of gained film with embodiment 1 identical method, measurement result is shown in table 1.
Table 1
| Routine number | Polar compound | Concentration (weight %) | Transit dose (gfd) | Desalination rate (%) |
| Comparative examples A | - | 0 | 16 | 97 |
| Embodiment 4 | Butyl sulfoxide/butoxy ethanol | 1/2 | 39.0 | 91.9 |
| Embodiment 5 | Tetramethylene sulfoxide/butoxy ethanol | 1/2 | 29.3 | 94.7 |
| Comparative example B | Propane diols | 2 | 17.1 | 97.8 |
| Comparative example C | Propane diols | 8 | 18.8 | 95.8 |
| Embodiment 6 | Cellosolvo/propane diols | 2/2 | 30.4 | 98.2 |
| Embodiment 7 | 2-propoxyl group ethanol/propane diols | 2/2 | 27.2 | 99.0 |
| Embodiment 8 | Propylene glycol butyl ether/propane diols | 2/2 | 27.8 | 97.6 |
| Comparative Example D | Propylene glycol butyl ether | 4 | 3.0 | 90.0 |
| Comparative Example E | Propylene glycol butyl ether | 2 | 19.7 | 86.6 |
| Embodiment 9 | The propane diols propyl ether | 2 | 22.6 | 94.8 |
| Embodiment 10 | Propane diols propyl ether/propane diols | 2/2 | 23.3 | 98.7 |
| Comparative Example F | The N-methyl pyrrolidone | 2 | 18.6 | 97.4 |
| Embodiment 11 | Butoxy ethanol/glycerine | 1/2 | 31.8 | 96.5 |
| Comparative example G | 2-propoxyl group ethanol | 8 | 7.8 | 94.1 |
| Comparative Example H | Butoxy ethanol | 8 | 5.7 | 91.0 |
| Embodiment 12 | Butoxy ethanol | 4 | 18.4 | 96.1 |
| Embodiment 13 | Butoxy ethanol | 3 | 18.0 | 98.1 |
| Embodiment 14 | Butoxy ethanol | 2 | 22.3 | 98.9 |
| Embodiment 15 | Butoxy ethanol | 1 | 26.0 | 98.3 |
| Embodiment 16 | Butoxy ethanol | 0.5 | 25 | 97.7 |
| Comparative Example I | Diethylene glycol butyl ether/propane diols | 2/2 | 15.1 | 97.8 |
| Comparative Example J | Dimethyl sulfoxide (DMSO)/propane diols | 2/2 | 10.7 | 93.4 |
| Comparative example K | Dimethyl sulfoxide (DMSO)/glycerine | 2/2 | 8.7 | 94.4 |
| Comparative example L | Dimethyl sulfoxide (DMSO) | 2 | 20.1 | 96.5 |
| Comparative example M | The butyl sulfoxide | 1 | 29.3 | 94.4 |
| Comparative example N | The tetramethylene sulfone | 2 | 26.2 | 95.1 |
| Comparative example O | Tetramethylene sulfone/butoxy ethanol | 2/2 | 18.0 | 94.3 |
| Comparative example P | DGDE/propane diols | 2/2 | 21.2 | 98.1 |
| Comparative example Q | Diethylene glycol dimethyl ether | 2 | 20.7 | 97.0 |
| Comparative example R | Diethyl carbitol/propane diols | 2/2 | 20.5 | 97.8 |
| Comparative example S | Diethyl carbitol/propane diols | 2/2 | 17.8 | 97.6 |
| Comparative example T | DGDE | 2 | 17.7 | 96.7 |
| Comparative example U | DGDE/propane diols | 2/2 | 22.7 | 97.3 |
| Comparative example V | Diethylene glycol methyl ether | 2 | 14.4 | 95.1 |
| Comparative example W | Diethylene glycol methyl ether/propane diols | 2/2 | 15.4 | 97.5 |
| Comparative example X | Acetone/propane diols | 2/2 | 1/9 | 96.6 |
Embodiment 17～29 and comparative example Y～EE
Except the polar compound that uses following table 2, to implement, measure the rerum natura of gained film with embodiment 1 identical method, measurement result is shown in table 2.
Table 2
| Routine number | Polar compound | Concentration (weight %) | Infiltration capacity (gfd) | Desalination rate (%) |
| Comparative examples A | - | 0 | 16 | 97.0 |
| Embodiment 17 | Diethylene glycol (DEG)-t-butyl methyl ether | 2 | 26.2 | 98.6 |
| Comparative example Y | Diethyl carbitol | 2 | 20.7 | 97.0 |
| Embodiment 18 | The diethylene glycol (DEG) hexyl ether | 0.3 | 32.0 | 95.9 |
| Embodiment 19 | The diethylene glycol (DEG) hexyl ether | 0.2 | 29.4 | 97.5 |
| Embodiment 20 | The diethylene glycol (DEG) hexyl ether | 0.1 | 27.7 | 96.2 |
| Comparative example Z | Butyl carbitol | 2 | 13.6 | 97.4 |
| Comparative examples A A | Butyl carbitol | 1 | 23.1 | 95.3 |
| Comparative example BB | Butyl carbitol | 0.4 | 19.8 | 93.8 |
| Comparative example CC | Butyl carbitol | 0.3 | 19.3 | 95.5 |
| Comparative Example D D | Butyl carbitol | 0.2 | 20.0 | 95.3 |
| Comparative example T | DGDE | 2 | 17.7 | 96.7 |
| Comparative example V | Diethylene glycol methyl ether | 2 | 14.4 | 95.4 |
| Embodiment 21 | Triglyme | 2 | 28.5 | 97.5 |
| Comparative Example E E | Triethylene glycol | 2 | 18.8 | 96.7 |
| Embodiment 22 | 2-ethyl-1, the 3-hexylene glycol | 0.2 | 26.0 | 98.2 |
| Embodiment 23 | 1, the 4-cyclohexanedimethanol | 2 | 25.5 | 96.0 |
| Embodiment 24 | DPG | 2 | 25.2 | 96.8 |
| Embodiment 25 | Dipropylene glycol methyl ether | 2 | 27.0 | 96.0 |
| Embodiment 26 | Diethylene glycol (DEG) hexyl ether/propane diols | 0.2/2 | 31.3 | 97.1 |
| Embodiment 27 | Diethylene glycol (DEG) hexyl ether/glycerine | 0.2/2 | 31.1 | 97.4 |
| Embodiment 28 | Diethylene glycol (DEG) hexyl ether/dimethyl sulfoxide (DMSO) | 0.2/2 | 33.1 | 97.0 |
| Embodiment 29 | 2-ethyl-1,3-hexylene glycol/dimethyl sulfoxide (DMSO) | 0.2/2 | 28.2 | 97.0 |
The present invention is as above-mentioned formation, in the manufacturing of reverse osmosis membrane, added the aqueous solution of the polyfunctional basic amine of polar compound of the present invention by use, compare with PA membrane manufacture method of the prior art, can obtain to have the polyamide reverse osmosis composite film of better desalination rate and infiltration capacity two specific characters.
Claims (7)
1. the manufacture method of a polyamide reverse osmosis composite film; it is characterized in that; after the aqueous solution that will contain polyfunctional basic amine and be selected from the polar compound in following the 1st group～the 3rd group is coated on the porous supporting course; be selected from the multiple functional radical acyl halide with containing again; multiple functional radical sulfonyl halide; among the multifunctional isocyanate; have with the organic solution of amino reactive amine reactive compound and contact; carry out interface polymerization reaction; and on the porous supporting course, form PA membrane
The 1st group of compound: be selected from 1,2-alkane diol, 1,3-alkane diol, diethylene glycol (DEG) hexyl ether, diethylene glycol (DEG)-t-butyl methyl ether, diethylene glycol dimethyl ether, DPG monoalky lether, triglyme, 1, a kind or above compound in the X-cyclohexanedimethanol, wherein X is 2～4 integer
The 2nd group of compound: be selected from a kind or above compound in the alkyloxyalkanol,
The 3rd group of compound: be selected from alkoxyethanol and propane diols, alkoxyethanol and sulfoxide derivant, alkoxyethanol and urea, diethylene glycol (DEG) hexyl ether and propane diols, diethylene glycol (DEG) hexyl ether and sulfoxide derivant, diethylene glycol (DEG) hexyl ether and glycerine, 1,3-alkane diol and sulfoxide derivant, propane diols and propylene-glycol monoalky lether, in a kind or more than.
2. according to the manufacture method of the polyamide reverse osmosis composite film of claim 1 record, it is characterized in that above-mentioned porous supporting course is that the material that is selected from polysulfones, polyether sulfone, poly-imines, polyamide, polypropylene and the Kynoar is made.
3. according to the manufacture method of the polyamide reverse osmosis composite film of each record in the claim 1～2, it is characterized in that above-mentioned polar compound is to contain 0.01～8% (weight %, as follows) in the above-mentioned aqueous solution.
4. according to the manufacture method of the polyamide reverse osmosis composite film of record in the claim 3, it is characterized in that,, when using the 1st group of compound, contain 0.1～4% in the above-mentioned aqueous solution as above-mentioned polar compound.
5. according to the manufacture method of the polyamide reverse osmosis composite film of claim 4 record, it is characterized in that,, when using the diethylene glycol (DEG) hexyl ether, contain 0.1～3% in the above-mentioned aqueous solution as above-mentioned the 1st group of compound.
6. according to the manufacture method of the polyamide reverse osmosis composite film of claim 3 record, it is characterized in that,, when using above-mentioned the 2nd group of compound, contain 0.05～4% in the above-mentioned aqueous solution as above-mentioned polar compound.
7. according to the manufacture method of the polyamide reverse osmosis composite film of claim 3 record, it is characterized in that,, when using the 3rd group of compound, contain 3～4% in the above-mentioned aqueous solution as above-mentioned polar compound.
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| CN99125641A CN1110355C (en) | 1999-12-28 | 1999-12-28 | Method for producing polyamide reverse osmosis composite film |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4872984A (en) * | 1988-09-28 | 1989-10-10 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
| US5324538A (en) * | 1991-03-12 | 1994-06-28 | Toray Industries, Inc. | Process for producing composite semipermeable membrane employing a polyfunctional amine solution and high flash point - solvent |
| US5658460A (en) * | 1996-05-07 | 1997-08-19 | The Dow Chemical Company | Use of inorganic ammonium cation salts to maintain the flux and salt rejection characteristics of reverse osmosis and nanofiltration membranes during drying |
-
1999
- 1999-12-28 CN CN99125641A patent/CN1110355C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4872984A (en) * | 1988-09-28 | 1989-10-10 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
| US5324538A (en) * | 1991-03-12 | 1994-06-28 | Toray Industries, Inc. | Process for producing composite semipermeable membrane employing a polyfunctional amine solution and high flash point - solvent |
| US5658460A (en) * | 1996-05-07 | 1997-08-19 | The Dow Chemical Company | Use of inorganic ammonium cation salts to maintain the flux and salt rejection characteristics of reverse osmosis and nanofiltration membranes during drying |
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