CN103877876B - A kind of hybrid inorganic-organic polyamide nanofiltration membrane and preparation method thereof - Google Patents
A kind of hybrid inorganic-organic polyamide nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN103877876B CN103877876B CN201210566283.7A CN201210566283A CN103877876B CN 103877876 B CN103877876 B CN 103877876B CN 201210566283 A CN201210566283 A CN 201210566283A CN 103877876 B CN103877876 B CN 103877876B
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Abstract
The present invention relates to a kind of novel organic-inorganic hybrid polyamide nanofiltration membrane and preparation method thereof.The present invention is on porous support layer, carries out interfacial polycondensation by between the aqueous solution of the caged silsesquioxane containing polynary amino and the organic solution containing polynary acyl chlorides monomer, forms the ultra-thin function separating layer of one deck.Film obtained by the present invention is the hybrid organic-inorganic film of hydridization on a molecular scale, there is good oxidative resistance, heat-resisting quantity and solvent resistance, and preparation method is simple, process conditions better control, and have broad application prospects at aqueous solution separation, organic matter separation field.
Description
Technical field
The present invention relates to a kind of novel organic-inorganic hybrid polyamide nanofiltration membrane and preparation method thereof
Background technology
Nanofiltration is a kind of new membrane isolation technics grown up phase late 1980s, there is due to it advantages such as high efficiency, low energy consumption, high selectivity, be used widely in desalinization, wastewater treatment, bioproduct separation, environmental project, food, medicine and other fields.
The core of nanofiltration is NF membrane, composite membrane is the primary structure form of current NF membrane, composite membrane one deck ultrathin functional layer is deposited to the porous support membrane surface with suitable aperture, depositional mode mainly contains surface coating, interfacial polymerization and in-situ polymerization etc., and composite membrane can make the performance of every layer reach optimization.Aromatic polyamides is the main material of current NF membrane, is widely used because it has the advantages such as salt rejection rate is high, flux is large, chemical stability is good, the pH scope of application is wide, operating pressure requirement is low, but its not resistance to oxidation, easily by Active Chlorine chlorizating depolymerization.Research finds that the chlorine resistance order of polyamide prepared by amine is: aromatic diamine < alicyclic diamine < aliphatic diamine, only there is the chlorination of reversible amido link in the polyamide that alicyclic ring or aliphatic diamine monomer prepare, and there is not the chlorination of irreversible aromatic rings, replace aromatic amine to prepare PA membrane with alicyclic ring or fatty amine and improve chlorine resistance, but after introducing alicyclic ring or fatty amine, the mechanical strength of film can be reduced, should not use under the condition that pressure is higher.At present, the application mainly water solution system of NF membrane, but the very major part that actual industrial flow process relates to is organic solvent system, along with the development of NF membrane and the needs of practical application, solvent resistant NF membrane is arisen at the historic moment, the following aspects is depended in the selection of membrane material: film forming characteristics, heat endurance, pressure tightness and solvent inertia, the development of solvent resistant NF membrane is also in the starting stage.
In recent years, hybrid organic-inorganic film combines the premium properties of traditional organic film and inoranic membrane, has become one of the study hotspot in film field.Research shows, under the prerequisite keeping the advantages such as traditional organic film good toughness, density are low, hydridization film strength and chemical stability have had raising.Current hybrid organic-inorganic film mainly contains two classes, and a class is inorganic particle filled type hybridized film, and namely inorganic particulate is as wild phase, be dispersed in organic main body mutually in and formed a class hybridized film, the polyamide blended film of such as zeolite molecular sieve; Another kind of for organic matrix and inorganic precursor (metal alkoxide) react in film-forming process (dehydrating condensation) form covalent bond or ionic bond, be prepared into the homogeneous phase hybrid film of molecular level, such as SiOxCyHz film.Hybridized film is in composite nanometer filtering film field, and mainly filled-type at present, and there is the problem such as particle dispersion, film defect, if can obtain the NF membrane of molecular level hydridization, not only above problem can improve, and its intensity and chemical stability have larger raising.
Summary of the invention
The object of the invention is the method adopting interfacial polymerization, prepare a kind of novel organic-inorganic hybrid polyamide nanofiltration membrane of molecular level hydridization.
The present invention is achieved by the following technical solutions:
A kind of novel organic-inorganic hybrid polyamide nanofiltration membrane and preparation method thereof, porous support layer side or two side surfaces are attached with a layer function separating layer, and function separating layer is formed in the polycondensation of porous support membrane surface interface by the aqueous solution containing polynary amino caged silsesquioxane and the organic solution containing polynary acyl chlorides monomer.
Above-mentioned hybrid inorganic-organic polyamide nanofiltration membrane, is characterized in that:
Described polynary amino caged silsesquioxane, can be water-soluble, typical cage structure is (a) cube, (b) triangular prismatic type, two five-membered ring, two six annulus of complete hydrolysis condensation, and one or two or more kinds in (c) incomplete hydrolytic condensation structure;
The R be connected with cage structure is-R
1nH
2,-R
1nH
3+,-R
1nHR
2,-R
1n (CH
2cH
2)
2nH ,-R
1cONH
2in one or more, R
1, R
2for the chain hydrocarbon containing 2 to 7 C atoms, or phenyl ring, or the combination of chain hydrocarbon and phenyl ring, chain hydrocarbon or phenyl ring contain 0 to 10-OH ,-COOH ,-SO
3one or more in H.
Above-mentioned hybrid inorganic-organic polyamide nanofiltration membrane, is characterized in that: described polynary amino caged silsesquioxane is (d) octa-aminopropyl caged silsesquioxane.
Above-mentioned hybrid inorganic-organic polyamide nanofiltration membrane, is characterized in that:
Described polynary acyl chlorides monomer is the monomer containing acyl chlorides or isocyanide ester group, more than on monomer, group has two or three.
Above-mentioned hybrid inorganic-organic polyamide nanofiltration membrane, is characterized in that:
Described polynary acyl chlorides monomer is one or two or more kinds in pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, 5-isocyanide ester-isophthaloyl chlorine, 5-oxygen formyl chloride-isophthaloyl chlorine.
The preparation method of above-mentioned hybrid inorganic-organic polyamide nanofiltration membrane, is characterized in that:
First be mixed with the aqueous phase of the above-mentioned monomer containing polynary amino caged silsesquioxane and the organic phase solution containing polynary acyl chlorides monomer respectively, by supporting layer side one side or two sides are two-sided is immersed in the aqueous solution, taking-up is after its surface water is dry, be immersed in organic phase solution, 2-15 minute, dry in the shade in air 1-3 minute, 60-100 DEG C of heat treatment 5-10 minute, afterwards with water rinse;
The described aqueous phase containing polynary amino caged silsesquioxane, the mass concentration that solute contains polynary amino caged silsesquioxane is 0.5-4wt%;
The described organic phase solution containing polynary acyl chlorides monomer, solute is 0.05-0.3wt% containing the mass concentration of polynary acyl chlorides monomer.
Above-mentioned preparation method, is characterized in that:
The described aqueous phase containing polynary amino caged silsesquioxane, the aqueous solution of both simple above-mentioned polynary amino caged silsesquioxane, may also be above-mentioned polynary amino caged silsesquioxane and the blended aqueous solution of multi-element organic amine;
Described multi-element organic amine is m-phenylene diamine (MPD), p-phenylenediamine (PPD), sulfonation m-phenylenediamine, all benzene triamine, piperazine, ethylenediamine, diethylenetriamine, 1, one or two or more kinds in 6 hexamethylene diamines;
The mass fraction of multi-element organic amine in itself and the blended solute of polynary amino caged silsesquioxane is 0-100%, and blended solute mass fraction in water is 0.5-4wt%
The solvent that the described organic phase solution containing polynary acyl chlorides monomer adopts is can dissolve polynary acyl chlorides monomer but the liquid immiscible with water.
Above-mentioned preparation method, is characterized in that:
Described solvent is one or more in n-hexane, normal heptane, hendecane, trifluorotrichloroethane.
Above-mentioned preparation method, is characterized in that:
Described porous support layer is the blend of one or two or more kinds in the polymer such as polysulfones, polyacrylonitrile, Merlon, polyamide, polyimides, PEI, polybenzimidazoles, PAEK, Kynoar, polytetrafluoroethylene (PTFE).
Obtained film can be Flat Membrane, hollow-fibre membrane or tubular membrane; Separating layer is attached to side or two side surfaces of Flat Membrane; Separating layer is attached to the outer surface of hollow-fibre membrane or tubular membrane or inner surface or inside and outside two side surfaces.
The invention provides a kind of novel organic-inorganic hybrid polyamide nanofiltration membrane and preparation method thereof, the cage-type silsesquioxane and acyl chlorides that contain polynary amino are passed through interfacial polycondensation, forms the polyamide nanofiltration membrane of hydridization on molecular level.The method preparation condition is gentle, and process is simple, is applicable to large-scale industrial production.The amino of this film amide moieties is fatty amine, and reversible substitution reaction can only occur for the hydrogen on amine and Active Chlorine, and non-degradable; Due to containing inorganic caged silsesquioxane, this film has good intensity, pressure tightness and heat-resisting quantity; This film degree of cross linking is higher, has good solvent resistance, has broad application prospects at aqueous solution separation, organic matter separation field.
Specific implementation method
Embodiment 1
Porous support layer used is polysulphone super-filter membrane, and molecular cut off is 20,000; By soluble in water for eight ammonium chloride propyl group cage-type silsesquioxanes, be configured to the aqueous solution that mass fraction is 0.5wt%, drip the triethylamine of solute 1.5 times of molar equivalents; Organic phase is the hexane solution of mass fraction 0.1wt% pyromellitic trimethylsilyl chloride; Polysulfones support membrane to be immersed in aqueous phase 15 minutes, to take out after its surface water is dry, immerse organic phase 5 minutes, take out and dry in the shade in atmosphere 1 minute, put into 80 DEG C of baking ovens 10 minutes, to immerse in cold water test performance after the night; Pure water flux is under 0.34L/m2hatm, 0.8MPa be 69% to 1000ppmNaCl rejection.
Embodiment 2
Porous support layer used is polysulphone super-filter membrane, and molecular cut off is 10,000; By soluble in water for eight ammonium chloride propyl group cage-type silsesquioxanes, be configured to the aqueous solution that mass fraction is 2wt%, drip the triethylamine of solute 1.5 times of molar equivalents; Organic phase is the hexane solution of mass fraction 0.3wt% pyromellitic trimethylsilyl chloride; Wetting polysulfones support membrane to be immersed in aqueous phase 20 minutes, to take out after its surface water is dry, immerse organic phase 10 minutes, take out and dry in the shade in atmosphere 1 minute, put into 90 DEG C of baking ovens 5 minutes, to immerse in cold water test performance after the night; Pure water flux is 0.21L/m
2be 70% to 1000ppmNaCl rejection under hatm, 0.8MPa.
Embodiment 3
Porous support layer used is polysulphone super-filter membrane, and molecular cut off is 30,000; By eight ammonium chloride propyl group cage-type silsesquioxanes and m-phenylene diamine (MPD) soluble in water, be configured to the aqueous solution that mass fraction is 1wt%, eight ammonium chloride propyl group cage-type silsesquioxanes and m-phenylene diamine (MPD) mass ratio are 7:3, drip the triethylamine of solute 1.5 times of eight ammonium chloride propyl group cage-type silsesquioxane molar equivalent; Organic phase is the hexane solution of mass fraction 0.15wt% pyromellitic trimethylsilyl chloride; Wetting polysulfones support membrane to be immersed in aqueous phase 5 minutes, to take out after its surface water is dry, immerse organic phase 2 minutes, take out and dry in the shade in atmosphere 1 minute, put into 70 DEG C of baking ovens 10 minutes, to immerse in cold water test performance after the night; Pure water flux is 2.03L/m
2be 90% to 1000ppmNaCl rejection under hatm, 0.8MPa.
Claims (9)
1. one kind has machine ?inorganic hybridization polyamide nanofiltration membrane, it is characterized in that: on porous support layer side or two side surfaces, be attached with a layer function separating layer, function separating layer is formed in the polycondensation of porous support membrane surface interface by the aqueous solution containing polynary amino caged silsesquioxane and the organic solution containing polynary acyl chlorides monomer.
2. according to You Ji according to claim 1 ?inorganic hybridization polyamide nanofiltration membrane, it is characterized in that: described polynary amino caged silsesquioxane, can be water-soluble, typical cage structure is (a) cube, (b) triangular prismatic type, two five-membered ring, two six annulus of complete hydrolysis condensation, and one or two or more kinds in (c) incomplete hydrolytic condensation structure;
The R Wei be connected with cage structure ?R
1nH
2, ?R
1nH
3 +, ?R
1nHR
2, ?R
1n (CH
2cH
2)
2nH, ?R
1cONH
2in one or more, R
1, R
2for containing the chain hydrocarbon of 2 to 7 C atoms, or phenyl ring, or the combination of chain hydrocarbon and phenyl ring, chain hydrocarbon or phenyl ring contain 0 to 10 Ge ?OH, ?COOH, ?SO
3one or more in H.
3. according to the You Ji described in claim 1 or 2 ?inorganic hybridization polyamide nanofiltration membrane, it is characterized in that: described polynary amino caged silsesquioxane is (d) octa-aminopropyl caged silsesquioxane
4. according to You Ji according to claim 1 ?inorganic hybridization polyamide nanofiltration membrane, it is characterized in that:
Described polynary acyl chlorides monomer is the monomer containing acyl chlorides or isocyanide ester group, more than on monomer, group has two or three.
5. according to the You Ji described in claim 1 or 4 ?inorganic hybridization polyamide nanofiltration membrane, it is characterized in that:
Described polynary acyl chlorides monomer be pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, 5 ?Yi nitrile Suan Zhi ?isophthaloyl chlorine, 5 ?oxygen formyl Lv ?one or two or more kinds in isophthaloyl chlorine.
6. claim 1 ?5 arbitrary described in have the preparation method of machine ?inorganic hybridization polyamide nanofiltration membrane, it is characterized in that:
First be mixed with the aqueous phase of the above-mentioned monomer containing polynary amino caged silsesquioxane and the organic phase solution containing polynary acyl chlorides monomer respectively, by supporting layer side one side or two sides are two-sided is immersed in the aqueous solution, taking-up is after its surface water is dry, be immersed in organic phase solution, 2 ?15 minutes, dry in the shade in air 1 ?3 minutes, 60 ?100 DEG C of heat treatment 5 ?10 minutes, afterwards with water rinse;
The described aqueous phase containing polynary amino caged silsesquioxane, the mass concentration that solute contains polynary amino caged silsesquioxane be 0.5 ?4wt%;
The described organic phase solution containing polynary acyl chlorides monomer, solute containing the mass concentration of polynary acyl chlorides monomer be 0.05 ?0.3wt%.
7., according to preparation method according to claim 6, it is characterized in that:
The described aqueous phase containing polynary amino caged silsesquioxane, both the aqueous solution of polynary amino caged silsesquioxane described in simple claim 2, or may also be polynary amino caged silsesquioxane described in claim 2 and the blended aqueous solution of multi-element organic amine;
Described multi-element organic amine is m-phenylene diamine (MPD), p-phenylenediamine (PPD), sulfonation m-phenylenediamine, all benzene triamine, piperazine, ethylenediamine, diethylenetriamine, 1, one or two or more kinds in 6 hexamethylene diamines;
The mass fraction of described multi-element organic amine in itself and the blended solute of polynary amino caged silsesquioxane is less than 100% for being more than or equal to 0, blended solute mass fraction in water be 0.5 ?4wt%;
The solvent that the described organic phase solution containing polynary acyl chlorides monomer adopts is can dissolve polynary acyl chlorides monomer but the liquid immiscible with water.
8., according to preparation method according to claim 7, it is characterized in that:
Described solvent is one or more in n-hexane, normal heptane, hendecane, trifluorotrichloroethane.
9., according to preparation method according to claim 6, it is characterized in that:
Described porous support layer is the blend of one or two or more kinds in polysulfones, polyacrylonitrile, Merlon, polyamide, polyimides, PEI, polybenzimidazoles, PAEK, Kynoar, polytetrafluoroethylene (PTFE).
Obtained film can be Flat Membrane, hollow-fibre membrane or tubular membrane; Separating layer is attached to side or two side surfaces of Flat Membrane; Separating layer is attached to the outer surface of hollow-fibre membrane or tubular membrane or inner surface or inside and outside two side surfaces.
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| CN105617888B (en) * | 2014-11-05 | 2018-11-06 | 天津大学 | A kind of preparation method of high flux and high retention ratio composite nanometer filtering film |
| CN105601935B (en) * | 2015-12-25 | 2018-06-05 | 吉林省聚科高新材料有限公司 | The poly aryl ether ketone polymer of structure containing polysilsesquioxane and preparation method |
| CN105617879B (en) * | 2016-02-23 | 2018-07-20 | 天津大学 | Pegylation Polyhedral Oligomeric silsesquioxane/sodium alginate hybridization compounding film and preparation and application |
| CN107376674B (en) * | 2017-08-09 | 2020-05-26 | 哈尔滨工业大学 | Modification method for improving antibacterial property of POSS armored polyamide reverse osmosis membrane surface |
| CN110935334A (en) * | 2019-12-04 | 2020-03-31 | 哈尔滨工业大学（威海） | Inorganic-organic hybrid material modified membrane and preparation and application method thereof |
| CN112221362A (en) * | 2020-10-21 | 2021-01-15 | 天津大学 | Quaternized polysulfone homogeneous membrane with ion cluster structure, and preparation and application thereof |
| CN113363541B (en) * | 2021-06-03 | 2023-11-14 | 大连理工大学 | POSS covalent hybridization polybenzimidazole ion exchange membrane and preparation method thereof |
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| CN102151499A (en) * | 2011-02-28 | 2011-08-17 | 浙江理工大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
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| US8431220B2 (en) * | 2009-06-05 | 2013-04-30 | Xerox Corporation | Hydrophobic coatings and their processes |
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| CN101945696A (en) * | 2008-03-11 | 2011-01-12 | 东丽株式会社 | Composite separation membrane |
| CN101530748A (en) * | 2009-03-17 | 2009-09-16 | 郑州大学 | Method for preparing composite charged mosaic membrane via interfacial polymerization |
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