CN101228214A - Method of manufacturing for aromatic polyamide composite membrane - Google Patents
Method of manufacturing for aromatic polyamide composite membrane Download PDFInfo
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- CN101228214A CN101228214A CNA2006800270216A CN200680027021A CN101228214A CN 101228214 A CN101228214 A CN 101228214A CN A2006800270216 A CNA2006800270216 A CN A2006800270216A CN 200680027021 A CN200680027021 A CN 200680027021A CN 101228214 A CN101228214 A CN 101228214A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/20—Polymers characterized by their physical structure
- C08J2300/202—Dendritic macromolecules, e.g. dendrimers or hyperbranched polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
Abstract
The present invention provides a method of manufacturing an aromatic polyamide composite membrane comprising: coating an aqueous solution containing polyfunctional aromatic amine to a porous polymer substrate; and reacting the coated substrate with an organic solution containing polyfunctional aromatic acyl halide to lead to interfacial condensation polymerization between the polyfunctional aromatic amine and the polyfunctional aromatic acyl halide so that the reaction product resulting from the interfacial condensation polymerization is coated on the surface of the substrate, characterized in that either of the aqueous solution containing polyfunctional aromatic amine or the organic solution containing polyfunctional aromatic acyl halide has dendritic polymer as one of polyfunctional compounds added thereto. The resulting aromatic polyamide composite membrane which includes dendrimer as polyfunctional compound, exhibits high salt rejection rate and water flux.
Description
Technical field
The present invention relates to a kind of method for preparing aromatic polyamide composite membrane, and more specifically, relate to a kind of method for preparing new aromatic polyamide composite membrane, this new aromatic polyamide composite membrane contains as polyfunctional compound's branch-shape polymer and has high ratio of desalinization and water flux.
As everyone knows, aromatic polyamide composite membrane (or so-called sometimes reverse osmosis membrane) has excellent ratio of desalinization and water flux, and can be applied to wide range of application, comprise: be used for water purifier, industrial extra-pure water production, wastewater treatment, sea water desalinization of household application etc.In order to improve the performance of aromatic polyamide composite membrane, carrying out deep research and investigation now.
Background technology
As for example disclosed in the United States Patent (USP) 4,277,344, come applying porous polymer-based carbon surface by the interfacial polycondensation between multifunctional aromatic amine and the multifunctional aromatic acyl halides, with the preparation aromatic polyamide composite membrane in this area.
In order to improve the performance of aromatic polyamide composite membrane, it need have the high flow rate under reasonable transmembrane pressure, and has repelling characteristic from the dissolving of separated from solvent or the height of dispersive material.In order to realize these targets, recently exist the trial that multiple additives is applied to ordinary method, particularly, attempt using mphenylenediamine or triaminobenzene as multifunctional aromatic amine, and use pyromellitic trimethylsilyl chloride (trimesoyl chloride) or isophthalyl chloride as multifunctional aromatic acyl halides.
United States Patent (USP) 4,872,984 propose to add tertiary amine and strong acid or tetraalkylammonium hydroxide in the preparation of composite membrane, and United States Patent (USP) 6,723,241 discloses the adding phosphorus compound to improve film properties.Yet the problem that such additive has is that this additive remains on the composite membrane by physical adhesion, thereby causes dissolving in the use of reverse osmosis membrane.
Polyamidoamine (below be reduced to " PAMAM ") is star-like dendrimer (starburstdendrimer) representative, its constitutional features is to be combined with many reactive groups endways, and has the optional end group that is replaced by other group, thereby, be of value to life science biological example transmitter, and be suitable for chemical sensor, liquid or gas adsorption film, film, low-dielectric material or imprint lithography etc.
Korean Patent 10-0356282 has proposed a kind of method for preparing the film of surface modification, it is characterized in that, on the surface of coming modifying polymer film (film) or polymeric film (membrane) by plasma body or UV irradiation with after producing covalent linkage at membrane boundary, with branch-shape polymer or be coated with the surface of this polymeric film (film) or polymeric film (membrane) by the branch-shape polymer that active material replaces.But the shortcoming that this method has is, the inwardness of branch-shape polymer beyond expression of words because the combination between branch-shape polymer and the film is more as physical bond, and makes the desorption that is easy to of this branch-shape polymer.
Summary of the invention
(technical problem)
Therefore, be easy to break away from relevant above general issues in order to overcome from composite membrane with branch-shape polymer, the present invention is by adding the branch-shape polymer as one of polyfunctional compound in the combination reaction process of preparation aromatic polyamide composite membrane, have enhanced ratio of desalinization and water flux thereby provide, and between branch-shape polymer and film the new aromatic polyamide composite membrane of rigidity bonded.
(technological method of dealing with problems)
Below, will describe the present invention in detail.
The invention provides a kind of method for preparing aromatic polyamide composite membrane, described method comprises: the aqueous solution that will contain multifunctional aromatic amine is applied in the porous polymer substrate; With substrate that makes coating and the organic solution reaction that contains multifunctional aromatic acyl halides, to cause the interfacial polycondensation between multifunctional aromatic amine and the multifunctional aromatic acyl halides, thereby will be coated on from the reaction product that interfacial polycondensation produces on the substrate surface, it is characterized in that the organic solution that contains the aqueous solution of multifunctional aromatic amine or contain multifunctional aromatic acyl halides has the adding branch-shape polymer as one of polyfunctional compound wherein.
The branch-shape polymer that plays polyfunctional compound's effect comprises the branch-shape polymer of the end with amine replacement or has the branch-shape polymer of the end of carboxylic acid halides replacement.Particularly, branch-shape polymer comprises the PAMAM dendrimer with amine end and/or has the PAMAM dendrimer of the end that is replaced by carboxylic acid halides.
And as the polyfunctional compound, this branch-shape polymer can comprise the star-like dendrimer with the outer surface that surpassed for half generation.
Branch-shape polymer can have heteroatoms and/or functional group in dendritic structure.
Above heteroatoms comprises nitrogen or oxygen etc., and functional group comprises amide group, acetate groups (acetategroup) or ether.
And, the alternate example of branch-shape polymer can be the branch-shape polymer with nuclear compound, described nuclear compound is selected from any replacement in N-alkylamine, N-arylamines, alkyl diamine or the aryl diamine etc., rather than is replaced by common known ammonia.
More preferably, the aqueous solution that contains multifunctional aromatic amine has the adding branch-shape polymer that contains the end that amine replaces wherein.On the other hand, the organic solution that contains multifunctional aromatic acyl halides preferably has the adding branch-shape polymer that contains the end that carboxylic acid halides replaces wherein.
The multifunctional aromatic amine that uses among the present invention comprises mphenylenediamine, piperazine or triaminobenzene etc., and the multifunctional aromatic acyl halides of using among the present invention can be pyromellitic trimethylsilyl chloride or isophthalyl chloride etc.
In addition, above polyfunctional compound is that branch-shape polymer can have at least a in the group that the boron compound that is selected from the internal tree branched structure (branch part) that is introduced into this dendrimer, silicon compound, phosphorus compound and sulphur compound form.
And, in the method for synthetic dendrimer, reaction by dendrimer and boron compound, silicon compound, phosphorus compound or sulphur compound, part is introduced boron compound, silicon compound, phosphorus compound or sulphur compound in known dendrimer, thereby causes the synthetic and use of new dendrimer.
Wherein introduce when the dendrimer of another compound is arranged when using, the end of replacing this dendrimer with amine or carboxylic acid halides wholly or in part prepares the reverse osmosis composite membrane that contains this dendrimer.
Introduce silicon compound in the dendrimer chain and include but not limited to be selected from any in the group of forming by chlorosilane, alkyl silane, aryl-silane, organoalkoxysilane and amine silane.
Introduce phosphorus compound in the dendrimer and include but not limited to be selected from any in the group of forming by alkylphosphines, aryl phosphine, alkyl phosphate, aryl phosphate, alkoxyl group phosphine, alkyl phosphite, aryl phosphite, phosphoric acid alkoxy ester and phosphonitrile.
Introduce sulphur compound in the dendrimer chain and include but not limited to be selected from any in the group of forming by sulfide compound, sulphonate (salt) compound, sulfoxide compound.
Because the structural performance of dendrimer; Introduce the chemical property of wherein boron compound, silicon compound, phosphorus compound or sulphur compound; And the structural performance that obtains polymkeric substance, therefore compare with conventional aromatic polyamide composite membrane, wherein boron compound, silicon compound, phosphorus compound or sulphur compound are incorporated into the composite membrane that the branch-shape polymer in the dendrimer structure prepares and have shown enhanced ratio of desalinization and high flow rate by adding.
In addition, above branch-shape polymer can be alternative branch-shape polymer, and this alternative branch-shape polymer has and replaces normally used ammonia and as alternative amine, boron compound, silicon compound, phosphorus compound or the sulphur compound of centronucleus.
And, the porous polymer substrate is that the hole size that obtains is to receive-filter or the polymeric film of ultrafiltration level, and can be selected from any in the group of being made up of polysulfones, polyethersulfone, polymeric amide, polyethylene, polypropylene, poly-acetic ester (polyacetate), polyacrylonitrile and poly(vinylidene fluoride) or two kinds by use is prepared.
About the coating of the aqueous solution that contains polyfunctional amine, suitablely use common known method for example to flood or spray to the porous polymer substrate.After coating, can the aqueous solution that too much is coated on the porous polymer substrate surface be removed by using air knife, roller or sponge and other known means.
The content of multifunctional aromatic amine is at 0.1 to 25 weight % in the aqueous solution, and more preferably in the scope of 0.2 to 10 weight %.
If content is lower than 0.1 weight %, the aqueous solution that then contains multifunctional aromatic amine can not be evenly wetting in the porous polymer substrate.In addition, when content during greater than 25 weight %, then the thickness of the composite membrane of Chan Shenging increases, and causes that flow rate reduces.
And the preferred pH value of the aqueous solution that contains multifunctional aromatic amine is 7 to 12.
In addition, after being coated to the porous polymer substrate at the aqueous solution that will contain polyfunctional amine, make the porous polymer substrate to contact with the organic solution that contains multifunctional aromatic acyl halides, can use the porous polymer substrate is immersed in method in the organic solution, or on the porous polymer substrate, spray the method for organic solution.
The content of multifunctional aromatic acyl halides is at 0.01 to 10 weight % in the organic solution, and more preferably in the scope of 0.02 to 5 weight %.
If content is lower than 0.01 weight %, then do not carry out interfacial polycondensation fully.On the other hand, when content surpassed 10 weight %, then the thickness of the composite membrane of Chan Shenging increased, and causes that flow rate reduces.
With respect to the aqueous solution and organic solution gross weight separately, the content that is included in the aqueous solution that contains multifunctional aromatic amine or contains the branch-shape polymer in the organic solution of multifunctional carboxylic acid halides is at 0.001 to 5 weight %, and more preferably in the scope of 0.005 to 0.5 weight %.
In addition, the organic solvent that uses among the present invention includes but not limited to freonll-11, isoparaffins mixture, or the hydrocarbon of carbonatoms in 5 to 20 scopes.Interfacial polycondensation carries out 5 seconds to 10 minutes, and preferred 10 seconds to 2 minutes.If the reaction times is less than 5 seconds, then on the surface of polymeric substrates, does not carry out polymerization regularly, thereby cause that ratio of desalinization reduces.On the contrary, when the reaction times surpassed 10 minutes, then the thickness of composite membrane increased, thereby causes water flux to reduce.
Then, clean as the reverse osmosis composite membrane of above-mentioned preparation film that subsequent drying should clean with the ultrapure water or the aqueous solution that contains lower concentration carbonate.The temperature of rinse water is controlled in 20 to 50 ℃ the scope.
As described above shown in the specification sheets, because in the preparation of aromatic polyamide composite membrane, the branch-shape polymer Chemical bond that is used as additive is to film, therefore the reverse osmosis composite membrane by the present invention's preparation can overcome additive dissolved shortcoming, and owing to the primary characteristic of branch-shape polymer has excellent ratio of desalinization and high flow rate.
(beneficial effect)
As described in detail above, the invention provides the aromatic polyamide composite membrane that contains as the branch-shape polymer of additive, described branch-shape polymer in the preparation process of film Chemical bond to film, thereby solved the problems of dissolution of additive.
And, because the primary characteristic of branch-shape polymer, so aromatic polyamide composite membrane has improved ratio of desalinization and water flux significantly.
Implement best mode of the present invention
By following non-limiting examples and comparative example, the above feature of the present invention and other benefit will be expressly understood more.Yet, will be obvious that the particular content that the present invention is not limited to state in following examples for those skilled in the art.
Embodiment 1
Be the porous polysulfones substrate of 150 μ m dipping 1 minute in the aqueous solution of the polyamidoamine dendrimer (1 generation) of the mphenylenediamine of 2 weight % and 0.05 weight % with thickness, and the excessive aqueous solution removed from substrate by rubber rollers.The porous polymer substrate of handling like this is impregnated into once more in the organic solution of 0.2 weight % pyromellitic trimethylsilyl chloride about 1 minute.Finish after the reaction, the polysulfones substrate drying that under air, will be coated with 1 minute, and at room temperature use the carbonate aqueous solution of lower concentration to clean 30 minutes, thus form aromatic polyamide composite membrane.
Embodiment 2
With thickness is that the porous polysulfones substrate of 150 μ m was flooded 1 minute in the aqueous solution of the mphenylenediamine of 2 weight %, and by rubber rollers the excessive aqueous solution is removed from substrate.
The porous polymer substrate of handling like this is impregnated in the organic solution of polyamidoamine dendrimer (1 generation) that 0.2 weight % pyromellitic trimethylsilyl chloride and 0.05 weight % contain the end that carboxylic acid halides replaces about 1 minute once more.When finishing reaction, the polysulfones substrate drying that under air, will be coated with 1 minute, and at room temperature use the carbonate aqueous solution of lower concentration to clean 30 minutes, thus form aromatic polyamide composite membrane.
Embodiment 3 to 6
The polyamidoamine dendrimer species in changing the aqueous solution join mphenylenediamine solution shown in the following tabulation 1, by with embodiment 1 in identical step prepare aromatic polyamide composite membrane.
Table 1
| Project (section) | The dendrimer species |
| Embodiment 3 | Polyamidoamine dendrimer (0.5 generation) |
| Embodiment 4 | Polyamidoamine dendrimer (1.5 generation) |
| Embodiment 5 | Polyamidoamine dendrimer (2 generation) |
| Embodiment 6 | Polyamidoamine dendrimer (4 generation) |
Embodiment 7 to 10
The polyamidoamine dendrimer species in changing the organic solution join pyromellitic trimethylsilyl chloride shown in the following tabulation 2 with end that carboxylic acid halides replaces, by with embodiment 2 in identical step prepare aromatic polyamide composite membrane.
Table 2
| Project | The dendrimer species |
| Embodiment 7 | Polyamidoamine dendrimer (0.5 generation) |
| Embodiment 8 | Polyamidoamine dendrimer (1.5 generation) |
| Embodiment 9 | Polyamidoamine dendrimer (2 generation) |
| Embodiment 10 | Polyamidoamine dendrimer (4 generation) |
Embodiment 11
It with thickness the porous polysulfones substrate of 150 μ m dipping 1 minute in the aqueous solution of the star-like dendrimer (1 generation) of the mphenylenediamine of 2 weight % and 0.1 weight %, and by rubber rollers the excessive aqueous solution is removed from substrate, described star-like dendrimer has the phosphorus compound as the internal tree branched structure.The porous polysulfones substrate of handling like this is immersed in once more in the organic solution of 0.2 weight % pyromellitic trimethylsilyl chloride and reaches about 1 minute.Finish after the reaction, the polysulfones substrate drying that under air, will be coated with 1 minute, and at room temperature use the carbonate aqueous solution of lower concentration to clean 30 minutes, thus form aromatic polyamide composite membrane.
Embodiment 12
With thickness is that the porous polysulfones substrate of 150 μ m was flooded 1 minute in the mphenylenediamine aqueous solution of 2 weight %, and by rubber rollers the excessive aqueous solution is removed from substrate.
With the porous polysulfones substrate of handling like this be immersed in once more 0.2 weight % pyromellitic trimethylsilyl chloride and 0.05 weight % the organic solution of polyamidoamine dendrimer (1 generation) in reach about 1 minute, described dendrimer has as the phosphorus compound of internal tree branched structure and as the carboxylic acid halides of outer surface.Finish when reaction, with product under air dry 1 minute, and at room temperature cleaning 30 minutes, thereby form aromatic polyamide composite membrane with the carbonate aqueous solution of lower concentration.
Embodiment 13 to 17
The polyamidoamine dendrimer species in changing the aqueous solution join mphenylenediamine solution shown in the following tabulation 3, by with embodiment 11 in identical step prepare aromatic polyamide composite membrane.
Table 3
| Project | The dendrimer species |
| Embodiment 13 | Polyamidoamine dendrimer (0.5 generation) |
| Embodiment 14 | Polyamidoamine dendrimer (1.5 generation) |
| Embodiment 15 | Polyamidoamine dendrimer (2 generation) |
| Embodiment 16 | Polyamidoamine dendrimer (4 generation) |
| Embodiment 17 | Polyamidoamine dendrimer (5 generation) |
Embodiment 18 to 22
The polyamidoamine dendrimer species in changing the organic solution join pyromellitic trimethylsilyl chloride shown in the following tabulation 4 with end that carboxylic acid halides replaces, by with embodiment 12 in identical step prepare aromatic polyamide composite membrane.
Table 4
| Project | The dendrimer species |
| Embodiment 18 | Polyamidoamine dendrimer (0.5 generation) |
| Embodiment 19 | Polyamidoamine dendrimer (1.5 generation) |
| Embodiment 20 | Polyamidoamine dendrimer (2 generation) |
| Embodiment 21 | Polyamidoamine dendrimer (4 generation) |
| Embodiment 22 | Polyamidoamine dendrimer (5 generation) |
Embodiment 23
Be to reach 1 minute in the aqueous solution of the porous polysulfones substrate of the 150 μ m polyamidoamine dendrimer (1 generation) that is immersed in the mphenylenediamine of 2 weight % and 0.1 weight % with thickness, and by rubber rollers the excessive aqueous solution is removed from substrate, described dendrimer has the silicon compound as the internal tree branched structure.The porous polymer substrate of handling was like this flooded about 1 minute in the organic solution of 0.2 weight % pyromellitic trimethylsilyl chloride once more.Finish after the reaction, the polysulfones substrate drying that under air, will be coated with 1 minute, and at room temperature use the carbonate aqueous solution of lower concentration to clean 30 minutes, thus form aromatic polyamide composite membrane.
Embodiment 24
Be to reach 1 minute in the aqueous solution of the porous polysulfones substrate of the 150 μ m polyamidoamine dendrimer (1 generation) that is immersed in the mphenylenediamine of 2 weight % and 0.1 weight % with thickness, and by rubber rollers the excessive aqueous solution is removed from substrate, described dendrimer has the boron compound as the internal tree branched structure.The porous polysulfones substrate of handling was like this flooded about 1 minute in the organic solution of 0.2 weight % pyromellitic trimethylsilyl chloride once more.Finish after the reaction, the polysulfones substrate drying that under air, will be coated with 1 minute, and at room temperature use the carbonate aqueous solution of lower concentration to clean 30 minutes, thus form aromatic polyamide composite membrane.
Comparative example 1
With thickness is that the porous polysulfones substrate of 150 μ m is immersed in the mphenylenediamine aqueous solution of 2 weight % and reaches 1 minute, and by rubber rollers the excessive aqueous solution is removed from substrate.The porous polysulfones substrate of handling was like this flooded about 1 minute in the organic solution of 0.2 weight % pyromellitic trimethylsilyl chloride once more.
Finish when reaction, with the polysulfones substrate of this coating under air dry 1 minute, and at room temperature cleaned 30 minutes, thereby form aromatic polyamide composite membrane with the carbonate aqueous solution of lower concentration.
Under the constant voltage of 225psig, by using 2, the NaCl aqueous solution of 000ppm is at room temperature measured water flux and the ratio of desalinization according to the aromatic polyamide composite membrane of embodiment 1～24 and comparative example 1 preparation, and test result is shown in the table 5.
Table 5
| Project | Water flux (gallon/foot 2/ day) | Ratio of desalinization (%) |
| Embodiment 1 | 17.9 | 97.7 |
| Embodiment 2 | 18.4 | 98.0 |
| Embodiment 3 | 18.5 | 98.5 |
| Embodiment 4 | 20.1 | 98.9 |
| Embodiment 5 | 19.8 | 99.1 |
| Embodiment 6 | 17.6 | 98.6 |
| Embodiment 7 | 18.8 | 98.2 |
| Embodiment 8 | 19.5 | 98.5 |
| Embodiment 9 | 19.7 | 98.3 |
| Embodiment 10 | 18.3 | 98.0 |
| Embodiment 11 | 18.1 | 97.6 |
| Embodiment 12 | 18.0 | 97.9 |
| Embodiment 13 | 17.9 | 98.1 |
| Embodiment 14 | 18.6 | 98.5 |
| Embodiment 15 | 18.9 | 98.6 |
| Embodiment 16 | 17.4 | 97.1 |
| Embodiment 17 | 17.1 | 97.3 |
| Embodiment 18 | 17.8 | 98.3 |
| Embodiment 19 | 18.4 | 98.6 |
| Embodiment 20 | 18.8 | 98.5 |
| Embodiment 21 | 16.9 | 97.8 |
| Embodiment 22 | 16.8 | 97.5 |
| Embodiment 23 | 19.1 | 98.7 |
| Embodiment 24 | 17.9 | 99.1 |
| Comparative example 1 | 16.2 | 97.5 |
Industrial applicibility
As mentioned above, the present invention has realized having the preparation of the aromatic polyamide composite membrane of good salt rejection rate and water flux, and described aromatic polyamide composite membrane is preferred for comprising various devices such as ultra-pure water process units, sewage treatment equipment, desalination unit.
Claims (14)
1. method for preparing aromatic polyamide composite membrane, described method comprises: the aqueous solution that will contain multifunctional aromatic amine is applied in the porous polymer substrate; With, make the substrate and the organic solution reaction that contains multifunctional aromatic acyl halides of coating, to cause the interfacial polycondensation between multifunctional aromatic amine and the multifunctional aromatic acyl halides, thereby the reaction product that interfacial polycondensation is produced is coated on the substrate surface, it is characterized in that the organic solution that contains the aqueous solution of multifunctional aromatic amine or contain multifunctional aromatic acyl halides has the adding branch-shape polymer as one of polyfunctional compound wherein.
2. be the branch-shape polymer that has the branch-shape polymer of the end that amine replaces or have the end that carboxylic acid halides replaces wherein in accordance with the method for claim 1, as polyfunctional compound's described branch-shape polymer.
3. in accordance with the method for claim 1, the wherein said aqueous solution that contains multifunctional aromatic amine comprises the branch-shape polymer of the adding end with amine replacement wherein.
4. in accordance with the method for claim 1, the wherein said organic solution that contains multifunctional aromatic acyl halides comprises the branch-shape polymer of the adding end with carboxylic acid halides replacement wherein.
5. in accordance with the method for claim 1, wherein said branch-shape polymer as the polyfunctional compound is that outer surface is the star-like dendrimer at least 0.5 generation.
6. in accordance with the method for claim 1, wherein said branch-shape polymer comprises heteroatoms in dendritic structure.
7. in accordance with the method for claim 6, wherein said heteroatoms comprises nitrogen or oxygen.
8. in accordance with the method for claim 1, wherein said branch-shape polymer comprises in dendritic structure and is selected from least a in amide group, acetate groups and the ether.
9. in accordance with the method for claim 1, wherein said branch-shape polymer comprises the nuclear compound that is selected from the group of being made up of ammonia, N-alkylamine, N-arylamines, alkyl diamine and aryl diamine.
10. in accordance with the method for claim 1, wherein said branch-shape polymer as the polyfunctional compound comprises at least a compound that is selected from boron compound, silicon compound, phosphorus compound and the sulphur compound that is introduced in the dendroid polymeric chain.
11. in accordance with the method for claim 10, the wherein said silicon compound that is incorporated in the branch-shape polymer chain is to be selected from least a in the group of being made up of chlorosilane, alkyl silane, aryl-silane, organoalkoxysilane and amine silane.
12. in accordance with the method for claim 10, wherein being incorporated into phosphorus compound in the branch-shape polymer chain is to be selected from least a in the group of being made up of alkylphosphines, aryl phosphine, alkyl phosphate, aryl phosphate, alkoxyl group phosphine, alkyl phosphite, aryl phosphite, phosphorous acid alkoxy ester and phosphonitrile.
13. in accordance with the method for claim 10, wherein being incorporated into sulphur compound in the branch-shape polymer chain is to be selected from least a in the group of being made up of sulfide compound, sulphonate (salt) compound and sulfoxide compound.
14. in accordance with the method for claim 1, wherein with respect to the aqueous solution and organic solution gross weight separately, the amount that joins the aqueous solution that contains multifunctional aromatic amine or contain the described branch-shape polymer in the organic solution of multifunctional carboxylic acid halides is in the scope of 0.001 to 5 weight %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050072309A KR20070017740A (en) | 2005-08-08 | 2005-08-08 | Method of manufacturing for aromatic polyamide composite membrane |
| KR1020050072309 | 2005-08-08 | ||
| KR1020050121439 | 2005-12-12 |
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| CN101228214A true CN101228214A (en) | 2008-07-23 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140278A (en) * | 2010-09-30 | 2013-06-05 | 海绵股份有限公司 | Thin film composite membranes for forward osmosis, and their preparation methods |
| US9216391B2 (en) | 2011-03-25 | 2015-12-22 | Porifera, Inc. | Membranes having aligned 1-D nanoparticles in a matrix layer for improved fluid separation |
| US9227360B2 (en) | 2011-10-17 | 2016-01-05 | Porifera, Inc. | Preparation of aligned nanotube membranes for water and gas separation applications |
| US9636635B2 (en) | 2012-12-21 | 2017-05-02 | Porifera, Inc. | Separation systems, elements, and methods for separation utilizing stacked membranes and spacers |
| US9861937B2 (en) | 2013-03-15 | 2018-01-09 | Porifera, Inc. | Advancements in osmotically driven membrane systems including low pressure control |
| US10384169B2 (en) | 2014-10-31 | 2019-08-20 | Porifera, Inc. | Supported carbon nanotube membranes and their preparation methods |
| CN112387133A (en) * | 2019-08-13 | 2021-02-23 | 中国科学院大连化学物理研究所 | Preparation of polyamide composite membrane |
| US11541352B2 (en) | 2016-12-23 | 2023-01-03 | Porifera, Inc. | Removing components of alcoholic solutions via forward osmosis and related systems |
| US11571660B2 (en) | 2015-06-24 | 2023-02-07 | Porifera, Inc. | Methods of dewatering of alcoholic solutions via forward osmosis and related systems |
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| CN111841343B (en) * | 2020-07-30 | 2022-04-15 | 河南师范大学 | Asymmetric polyamide nano-film and preparation method thereof |
-
2005
- 2005-08-08 KR KR1020050072309A patent/KR20070017740A/en active Search and Examination
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140278A (en) * | 2010-09-30 | 2013-06-05 | 海绵股份有限公司 | Thin film composite membranes for forward osmosis, and their preparation methods |
| US9216391B2 (en) | 2011-03-25 | 2015-12-22 | Porifera, Inc. | Membranes having aligned 1-D nanoparticles in a matrix layer for improved fluid separation |
| US9227360B2 (en) | 2011-10-17 | 2016-01-05 | Porifera, Inc. | Preparation of aligned nanotube membranes for water and gas separation applications |
| US10464023B2 (en) | 2012-12-21 | 2019-11-05 | Porifera, Inc. | Separation systems, elements, and methods for separation utilizing stacked membranes and spacers |
| US9636635B2 (en) | 2012-12-21 | 2017-05-02 | Porifera, Inc. | Separation systems, elements, and methods for separation utilizing stacked membranes and spacers |
| US11090611B2 (en) | 2012-12-21 | 2021-08-17 | Porifera, Inc. | Separation systems, elements, and methods for separation utilizing stacked membranes and spacers |
| US11759751B2 (en) | 2012-12-21 | 2023-09-19 | Porifera, Inc. | Separation systems, elements, and methods for separation utilizing stacked membranes and spacers |
| US9861937B2 (en) | 2013-03-15 | 2018-01-09 | Porifera, Inc. | Advancements in osmotically driven membrane systems including low pressure control |
| US10500544B2 (en) | 2013-03-15 | 2019-12-10 | Porifera, Inc. | Advancements in osmotically driven membrane systems including multi-stage purification |
| US10384169B2 (en) | 2014-10-31 | 2019-08-20 | Porifera, Inc. | Supported carbon nanotube membranes and their preparation methods |
| US11571660B2 (en) | 2015-06-24 | 2023-02-07 | Porifera, Inc. | Methods of dewatering of alcoholic solutions via forward osmosis and related systems |
| US11541352B2 (en) | 2016-12-23 | 2023-01-03 | Porifera, Inc. | Removing components of alcoholic solutions via forward osmosis and related systems |
| CN112387133A (en) * | 2019-08-13 | 2021-02-23 | 中国科学院大连化学物理研究所 | Preparation of polyamide composite membrane |
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| KR20070017740A (en) | 2007-02-13 |
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