CN105289321A - Composite nanofiltration membrane and preparation method thereof - Google Patents
Composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN105289321A CN105289321A CN201410350598.7A CN201410350598A CN105289321A CN 105289321 A CN105289321 A CN 105289321A CN 201410350598 A CN201410350598 A CN 201410350598A CN 105289321 A CN105289321 A CN 105289321A
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Abstract
The invention discloses a composite nanofiltration membrane, a preparation method thereof, and application of the composite nanofiltration membrane prepared by adopting the preparation method to the field of water treatment. The composite nanofiltration membrane comprises a supporting layer and a separating layer which are overlapped together, wherein the separating layer is a cross-linked net structure which is positioned on the surface of the supporting layer and formed through thermal crosslinking reaction of polymer containing hydroxyl and a silane coupling agent with a structure as shown in the formula (I) (shown in the description) through sol-gel; in the formula (I), Y is alkenyl or carbon functional group, the carbon functional group is alkyl carried with Cl, NH2, epoxy, SH, N3, (methyl) acrylyl or isocyanate group; X is one or more of Cl, OMe, OEt, OC2H4OCH3, OSiMe3 and OAc. According to the composite nanofiltration membrane and the preparation method thereof, provided by the invention, stable operation of the composite nanofiltration membrane in an aqueous solution with the PH of 0-14 is achieved, a higher salt removing rate and water permeability are achieved, higher acid and alkali resistance is further achieved; besides, the method is simple, and an industrial application prospect is further realized.
Description
Technical field
The present invention relates to a kind of composite nanometer filtering film and preparation method thereof.
Background technology
Nanofiltration is a kind of pressure-driven membrane separating process between counter-infiltration and ultrafiltration, the pore diameter range of NF membrane is at a few ran, organic matter monovalention and molecular weight being less than to 200 removes poor, and has higher removal efficiency to divalence or multivalent ion and the organic matter of molecular weight between 200 ~ 500.Can be widely used in that fresh water is softening, seawater softening, drink water purifying, water correction, water-oil separating, wastewater treatment and recycling, and the classification of the heavy chemicals such as dyestuff, antibiotic, polypeptide and polysaccharide, purifying and the field such as concentrated.
At present, commercial nanofiltration membrane greatly mainly with polysulphone super-filter membrane as supporting layer, carry out the interfacial polymerization of polyamine aqueous phase and polynary acyl chlorides organic phase in milipore filter upper surface original position, final product is composite nanometer filtering film.Common aqueous phase monomers is that piperazine or piperazine replace amine, organic phase is pyromellitic trimethylsilyl chloride or a kind of multifunctional carboxylic acid halides, as the content of report disclosed in patent No. US4769148 and US4859384, a large amount of unreacted acid chloride groups is hydrolyzed into carboxylic acid, make NF membrane surface band negative electricity, utilize charge effect, polypiperazine-amide composite nanometer filtering film has higher rejection to high-valence anion, has adjustable rejection to monovalent anion.In addition, patent No. US4765897, US4812270 and US4824574 additionally provide a kind of method how polyamide composite reverse osmosis membrane being transformed into NF membrane.But, due to the restriction of material self character, under extreme pH environments, particularly under basic conditions, traditional polyamide-based NF membrane can be degraded, because the use pH scope of polyamide nanofiltration membrane is generally 2 ~ 11, so neutral medium or the weak acid and weak base medium close to neutrality can only be used for.
In recent years, researchers develop multiple NF membrane, and occur multiple commercial product.In addition, a lot of new material, such as sulfonated polyether ketone, sulfonated polyether sulfone etc. are also applied to nanofiltration field.
Document " Acidstablethin-filmcompositemembranefornanofiltrationpre paredfromnaphthalene-1,3,6-trisulfonylchloride (NTSC) andpiperazine (PIP), J.Membr.Sci., 415-416,122-131,2012 " report in: sulfonamide material has very strong acid resistance, and the composite nanometer filtering film utilizing polynary sulfonic acid chloride monomer and piperazine to be obtained by interfacial polymerization can keep stable separating property in pH=0 environment.
Document " Sulfonatedpoly (etheretherketone) basedcompositemembranesfornanofiltrationofacidicandalkal inemedia, J.Membr.Sci., 381, 81-89, 2011 " report in: sulfonated polyether-ether-ketone both had acid resistance, there is again very strong alkali resistance, by the crosslinked NF membrane material that more can obtain cutoff performance excellence, and, polyetheretherketonematerials materials after crosslinked has very strong solvent resistance, dyestuff (Crosslinkingofmodifiedpoly (etheretherketone) membranesforuseinsolventresistantnanofiltration can be separated in isopropyl alcohol with acetone polar solvent, 447, 212-221, 2013).
" acid and alkali-resistance is high temperature resistant, and NF membrane HYDRACoRe70pHT is used for the recovery of sugar industry spent lye to document, membrane science and technology, 32,11-15,2006 " report in: commercial sulfonated polyether sulfone class composite nanometer filtering film is the HYDRACoRe series developed by day east electrician's Hydranautics company, can use in strong acid, strong base solution, be widely used in the recovery of salkali waste.
The acidproof NF membrane DuracidNF1812C that GE company develops is three-layer composite structure, can 20% hydrochloric acid, keep stable under sulfuric acid and phosphoric acid condition, and at 70 DEG C, still can keep stable under the sulfuric acid condition of 20% concentration.
Patent No. US5265734, the SelROMPS34 that KOCH company can be only had to develop in the NF membrane of pH=0 ~ 14 long-term stability operation is reported in EP0392982 (A3), it is developed by Israel scientist the earliest, and material is silicon rubber, is applied to infiltration evaporation the earliest.
Polyvinyl alcohol (PVA) is a kind of water-soluble polymer, has good film forming, cohesion, emulsibility, remarkable grease resistance and solvent resistance, and good acid-fast alkali-proof performance.Chemical crosslinking can reduce the degree of crystallinity of PVA, improves the mechanical strength of film, increases film to the rejection of salt ion, and has the performance of better acid and alkali-resistance and solvent.The eighties in last century, crosslinked PVA/PAN (polyacrylonitrile) composite membrane is used for ethanol dehydration by GFT company, makes infiltrating and vaporizing membrane obtain industrialized application.At present, commercial infiltrating and vaporizing membrane is mainly PVA film.The dissolubility good due to PVA and film forming, be applied to nanofiltration counter-infiltration field, is used for improving the resistance tocrocking of film.Its method is compound one deck PVA in polyamide functional layer mainly, then carries out heat cross-linking by crosslinking agent, and detailed process is shown in CN101462024.The composite nanometer filtering film utilizing crosslinked PVA functional layer to prepare also has bibliographical information, but because its poor salt-stopping rate is (generally to Na
2sO
4rejection lower than 90%) fail to realize industrialization.
Silane coupler is the silane that a class has organo-functional group, have in the molecule thereof simultaneously can and inanimate matter material (as glass, silica sand, metal etc.) chemically combined reactive group and with organic material (synthetic resin etc.) chemically combined reactive group.It is mainly used in adhesive field.
Therefore, how silane coupler is incorporated in PVA system and prepares a kind of acidproof composite nanometer filtering film and to need further R and D.
Summary of the invention
The object of the invention is the defect in order to overcome existing NF membrane acid resistance and alkali resistance difference, and a kind of composite nanometer filtering film and preparation method thereof is provided, and this composite nanometer filtering film and the application of composite nanometer filtering film in water treatment field that prepared by the method.
To achieve these goals, the invention provides a kind of composite nanometer filtering film, described composite nanometer filtering film comprises the supporting layer and separating layer that stack together, wherein, described separating layer is that polymer containing hydroxyl is dissolved in solvent react by sol-gel and heat cross-linking with the silane coupler containing structure shown in formula (I) and forms the cross-linked structure be positioned in described support layer surface afterwards;
formula (I),
Wherein, Y is alkenyl or carbon functional group, and described carbon functional group is with Cl, NH
2, epoxy, SH, N
3, (methyl) acryloxy or NCO alkyl; X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC
2h
4oCH
3, OSi (CH
2)
3(OSiMe
3) and acetoxyl group (OAc) in one or more; Preferably, Y is that carbon functional group is upper containing NH
2, epoxy, SH and (methyl) acryloxy alkyl in one or more, X is methoxyl group (OMe), ethyoxyl (OEt) and OC
2h
4oCH
3in one or more.
Present invention also offers a kind of preparation method of composite nanometer filtering film, the method comprises the following steps:
(1) polymer containing hydroxyl, silane coupler containing structure formula (I) Suo Shi are dissolved in solvent and are prepared into coating liquid;
(2) described coating liquid is coated on supporting layer forms initial film;
(3) supporting layer step (2) being formed with initial film immerses in the solution containing crosslinking agent and crosslinking catalyst and carries out cross-linking reaction, obtains the composite nanometer filtering film comprising supporting layer He be positioned at the cross-linked structure in described support layer surface;
formula (I),
Wherein, Y is alkenyl or carbon functional group, and described carbon functional group is with Cl, NH
2, epoxy, SH, N
3, (methyl) acryloxy or NCO alkyl; X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC
2h
4oCH
3, OSi (CH
2)
3(OSiMe
3) and acetoxyl group (OAc) in one or more; Preferably, Y is that carbon functional group is upper containing NH
2, epoxy, SH and (methyl) acryloxy alkyl in one or more, X is methoxyl group (OMe), ethyoxyl (OEt) and OC
2h
4oCH
3in one or more.
Present invention also offers the composite nanometer filtering film prepared by said method.
The application of composite nanometer filtering film in water treatment field that present invention also offers above-mentioned composite nanometer filtering film and prepared by said method.
The present inventor finds through further investigation, and on the one hand, the polymer containing hydroxyl of the present invention all has stronger resistance to acids and bases with the silane coupler containing structure shown in formula (I); On the other hand, cross-linked network structure is defined after polymer containing hydroxyl and the silane coupler containing structure shown in formula (I) are reacted by sol-gel and heat cross-linking, not only increase the mechanical property of film, and also increase the cutoff performance to inorganic salts and organic molecule.In sum, separating layer of the present invention is formed after being reacted by sol-gel and heat cross-linking by the polymer containing hydroxyl and the silane coupler containing structure shown in formula (I); Composite nanometer filtering film of the present invention can stable operation in the aqueous solution of pH=0-14, not only there is higher salt rejection rate and water penetration (water flux), also there is stronger resistance to acids and bases, and its preparation method is simple, has prospects for commercial application.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is forming process and the reaction mechanism of composite nanometer filtering film functional layer prepared by the present invention;
Fig. 2 be the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux with 4.9% H
2sO
4the change of soak time in the aqueous solution;
Fig. 3 is the change with soak time in the NaOH aqueous solution of 4% of the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux;
Fig. 4 is the change with soak time in the phosphate aqueous solution of 20% of the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux;
Fig. 5 is the change with soak time in the HCl aqueous solution of 5% of the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of composite nanometer filtering film, described composite nanometer filtering film comprises the supporting layer and separating layer that stack together, wherein, described separating layer is that polymer containing hydroxyl is dissolved in solvent react by sol-gel and heat cross-linking with the silane coupler containing structure shown in formula (I) and forms the cross-linked structure be positioned in described support layer surface afterwards;
formula (I),
Wherein, Y is alkenyl or carbon functional group, and described carbon functional group is with Cl, NH
2, epoxy, SH, N
3, (methyl) acryloxy or NCO alkyl; X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC
2h
4oCH
3, OSi (CH
2)
3(OSiMe
3) and acetoxyl group (OAc) in one or more; Preferably, Y is that carbon functional group is upper containing NH
2, epoxy, SH and (methyl) acryloxy alkyl in one or more, X is methoxyl group (OMe), ethyoxyl (OEt) and OC
2h
4oCH
3in one or more.
According to the present invention, the described polymer containing hydroxyl is one or more in polyethylene glycol, polyvinyl alcohol, shitosan, chitosan quaternary ammonium salt, PPG and PEPA; From the angle consideration that raw material is ready availability, preferably, the described polymer containing hydroxyl is one or more in polyethylene glycol, polyvinyl alcohol and shitosan.In the present invention, described shitosan (chitosan) is also known as chitosan, be that the chitin (chitin) extensively existed by nature obtains through deacetylation, chemical name is Chitosan (1-4)-2-amino-B-D glucose.
According to the present invention, the described silane coupler containing structure shown in formula (I) can be γ aminopropyltriethoxy silane (KH550), gamma-amino propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS (KH792), N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (DL602), γ-mercaptopropyl trimethoxysilane (KH590), gamma-mercaptopropyltriethoxysilane (KH580), vinyltrimethoxy silane, VTES, gamma-amino hydroxypropyl methyl diethoxy silane, gamma-amino hydroxypropyl methyl dimethoxysilane, dimethylaminopropyl trimethoxy silane, γ-glycydoxy ethyldimethoxysilane, γ-glycidoxypropyl ethyl trimethoxy silane, β-(3,4-epoxycyclohexyl) propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) ethyl-methyl dimethoxysilane, isocyanate group propyl-triethoxysilicane, isocyanate group hydroxypropyl methyl dimethoxysilane, beta-cyano ethyl trimethoxy silane, γ-acryloxypropyl trimethoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, amino-3, the 3-dimethylbutyl trimethoxy silanes of 4-, N-ethyl-3-trimethoxysilyl-2-methyl propylamine, dimethyl stearyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride, one or more in γ-methacryloxypropyl and vinyl three (2-methoxy ethoxy) silane.
Preferably, the described silane coupler containing structure shown in formula (I) is γ aminopropyltriethoxy silane (KH550), gamma-amino propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS (KH792), N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (DL602), one or more in γ-mercaptopropyl trimethoxysilane (KH590) and gamma-mercaptopropyltriethoxysilane (KH580),
More preferably, the described silane coupler containing structure shown in formula (I) is one or more in γ aminopropyltriethoxy silane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS (KH792), γ-mercaptopropyl trimethoxysilane (KH590) and gamma-mercaptopropyltriethoxysilane (KH580).
According to the present invention, the thickness of described supporting layer and separating layer is not particularly limited, it can be the routine selection of this area, but two-layerly can play better coordinated effect to make this, the composite nanometer filtering film obtained is enable to have excellent acid-proof alkaline, higher water flux and salt rejection rate better concurrently, under preferable case, the thickness of described supporting layer is 90-150 micron, and the thickness of described separating layer is 0.05-0.5 micron; More preferably in situation, the thickness of described supporting layer is 100-120 micron, and the thickness of described separating layer is 0.1-0.3 micron.
According to the present invention, described supporting layer is not particularly limited, can by existing various there is certain intensity and can be used in nanofiltration, the material of reverse osmosis membrane makes, usually can be made up of one or more in polyacrylonitrile, Kynoar, phenolphthalein type non-sulfonated polyether sulphone, polyether sulfone and bisphenol-a polysulfone, all can know these those skilled in the art, will repeat no more at this.
According to the present invention, the content of the present invention to the polymer containing hydroxyl in described separating layer and the silane coupler containing structure shown in formula (I) is not particularly limited, but mating reaction better can be played in order to make both, in the forming process of described separating layer, with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl is 0.1-50 weight portion, is preferably 0.25-25 weight portion; The consumption of the described silane coupler containing structure shown in formula (I) is 0.01-50 weight portion, is preferably 0.025-25 weight portion.
Present invention also offers a kind of preparation method of composite nanometer filtering film, the method comprises the following steps:
(1) polymer containing hydroxyl, silane coupler containing structure formula (I) Suo Shi are dissolved in solvent and are prepared into coating liquid;
(2) described coating liquid is coated on supporting layer forms initial film;
(3) supporting layer step (2) being formed with initial film immerses in the solution containing crosslinking agent and crosslinking catalyst and carries out cross-linking reaction, obtains the composite nanometer filtering film comprising supporting layer He be positioned at the cross-linked structure in described support layer surface;
formula (I),
Wherein, Y is alkenyl or carbon functional group, and described carbon functional group is with Cl, NH
2, epoxy, SH, N
3, (methyl) acryloxy or NCO alkyl; X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC
2h
4oCH
3, OSi (CH
2)
3(OSiMe
3) and acetoxyl group (OAc) in one or more; Preferably, Y is that carbon functional group is upper containing NH
2, epoxy, SH and (methyl) acryloxy alkyl in one or more, X is methoxyl group (OMe), ethyoxyl (OEt) and OC
2h
4oCH
3in one or more.
According to the present invention, the present invention in described coating liquid containing hydroxyl polymer, be not particularly limited containing the silane coupler of structure formula (I) Suo Shi and the consumption of solvent, as long as the NF membrane obtained can be enable to have excellent acid-proof alkaline, higher water flux and salt rejection rate concurrently, such as, in step (1), with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl can be 0.1-50 weight portion, is preferably 0.25-25 weight portion; The consumption of the described silane coupler containing structure shown in formula (I) can be 0.01-50 weight portion, is preferably 0.025-25 weight portion; In the present invention, the preparation process of described coating liquid is preferably carried out under the existence of the catalyst for sol-gel, the catalyst of described sol-gel is not particularly limited, can be one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, be preferably hydrochloric acid, and with the solvent of 100 weight portions for benchmark, the consumption of the catalyst of described sol-gel is 0.01-50 weight portion, be preferably 0.025-25 weight portion.In addition, in the present invention, the concentration of described hydrochloric acid is not particularly limited, and preferably, the concentration of described hydrochloric acid is 0.5-1.5mol/L, and more preferably, the concentration of described hydrochloric acid is 1mol/L.
According to the present invention, the pH value of the present invention to described coating liquid is not particularly limited, and preferably, the pH value of described coating liquid is 1-4.
According to the present invention, polymer containing hydroxyl, silane coupler containing structure formula (I) Suo Shi are being dissolved in the process of solvent by the present invention, preferably carry out under the condition stirred, the present invention is not particularly limited the condition of described stirring and the equipment of stirring, the mixing plant of the routine that can be well known to those skilled in the art carries out under suitable stirring condition, as long as can make the polymer containing hydroxyl, silane coupler containing structure formula (I) Suo Shi is fully dissolved in solvent.In addition, the process that the polymer containing hydroxyl, silane coupler containing structure formula (I) Suo Shi are being dissolved in solvent by the present invention is carried out at normal temperatures.
According to the present invention, the thickness of the present invention to described supporting layer is not particularly limited, it can be the routine selection of this area, but better coordinated effect can be played in order to make described supporting layer and described separating layer, enabling the composite nanometer filtering film obtained have excellent acid-proof alkaline, higher water flux and salt rejection rate better concurrently, under preferable case, the thickness of described supporting layer is 90-150 micron, is preferably 100-120 micron.
According to the present invention, the consumption of the present invention to described coating liquid is not particularly limited, but have excellent acid-proof alkaline, higher water flux and salt rejection rate better concurrently to enable the sodium filter membrane obtained, under preferable case, the consumption of described coating liquid makes the thickness of described separating layer be 0.05-0.5 micron, is preferably 0.1-0.3 micron.
According to the present invention, described coating liquid is being coated in the process of supporting layer, the described the present invention of being coated in is being not particularly limited, any one in the spraying that can be well known to those skilled in the art, blade coating, spin coating etc.
According to the present invention, coating liquid is evenly being coated in after on supporting layer, under preferable case, the supporting layer this being coated with coating liquid puts into baking oven with by solvent volatilization wherein completely, is not particularly limited, as long as can guarantee solvent volatilization completely its temperature and time in an oven in the present invention, under preferable case, being dry 20-40 minute in the baking oven of 50-70 DEG C in temperature, more preferably in situation, is dry 25-35 minute in the baking oven of 55-65 DEG C in temperature.
According to the present invention, the kind of the present invention to described solvent is not particularly limited, as long as the described polymer containing hydroxyl and the silane coupler containing structure shown in formula (I) can be dissolved, such as, in step (1), described solvent can be water, methyl alcohol, ethanol, acetone, glycol monoethyl ether, one or more in ethylene glycol and dimethyl sulfoxide (DMSO), preferably, described solvent is water, the mixed solvent of ethanol and dimethyl sulfoxide (DMSO), and in described mixed solvent, water, the weight ratio of ethanol and dimethyl sulfoxide (DMSO) can be 1-50:1-30:1, be preferably 1-25:1-20:1.The mixed solvent of water, ethanol and dimethyl sulfoxide (DMSO) is adopted more to be conducive to above-mentioned several substance dissolves, and the coating liquid of preparation can be made to be coated on supporting layer better, and the sodium filter membrane obtained can be enable to have excellent acid-proof alkaline, higher water flux and salt rejection rate better concurrently.
According to the present invention, in step (3), the condition of described cross-linking reaction can comprise: crosslinking temperature is 20-100 DEG C, and crosslinking time is 10 minutes-48 hours; Preferably, crosslinking temperature is 40-80 DEG C, and crosslinking time is 20 minutes-24 hours.
According to the present invention, the crosslinking agent contained in crosslinker solution of the present invention can be conventional aldehydes, as being one or more in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, MDA, butanedial and glutaraldehyde, be preferably in formaldehyde, acetaldehyde, propionic aldehyde and butyraldehyde one or more, be more preferably formaldehyde.
According to the present invention, a kind of crosslinking catalyst contained in crosslinker solution of the present invention can be customary acid class, as being one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, being preferably one or more in sulfuric acid, hydrochloric acid and acetic acid, being more preferably sulfuric acid; In addition, the another kind of crosslinking catalyst contained in crosslinker solution of the present invention can be Sulfates, as being one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate, being preferably one or more in sodium sulphate, sulphate of potash and magesium, being more preferably sodium sulphate.
According to the present invention, the consumption of the present invention to the crosslinking agent in described crosslinker solution and crosslinking catalyst is not particularly limited, as long as the composite nanometer filtering film obtained can be enable to have excellent acid-proof alkaline, higher water flux and salt rejection rate concurrently.In the present invention, with the gross weight of described solvent for benchmark, the consumption of described crosslinking agent is 1-100 % by weight, is preferably 5-50 % by weight; The consumption of described acids is 1-98 % by weight, is preferably 5-80 % by weight; The consumption of described Sulfates is 1-60 % by weight, is preferably 5-50 % by weight.
In a word, on the one hand, the polymer containing hydroxyl of the present invention all has stronger resistance to acids and bases with the silane coupler containing structure shown in formula (I); On the other hand, cross-linked network structure is defined after polymer containing hydroxyl and the silane coupler containing structure shown in formula (I) are reacted by sol-gel and heat cross-linking, not only increase the mechanical property of film, and the cutoff performance also increased inorganic salts and organic molecule, further increase the acid-proof alkaline of this composite nanometer filtering film, higher water flux and salt rejection rate.
According to the present invention, because the described polymer containing hydroxyl has higher molecular weight, it is difficult to dissolve completely in a solvent, therefore, in order to make the cross-linked structure that obtains more even, and improve the stability of described composite nanometer filtering film, under preferable case, the preparation method of described composite nanometer filtering film also comprises before being coated on supporting layer by described coating liquid, is filtered by described coating liquid.In specific operation process, first the described polymer containing hydroxyl and the silane coupler containing structure shown in formula (I) can be dissolved in solvent and to filter, obtaining the coating liquid of homogeneous transparent; In addition, described filtration is also not particularly limited, the filter method that can be well known to those skilled in the art and equipment.
According to the present invention, in order to make the composite nanometer filtering film that obtains more smooth, preferably, before the preparation method of composite nanometer filtering film provided by the invention is also included in and is coated on supporting layer by coating liquid, by fixing for described supporting layer on a glass or on film machine.
Present invention also offers the composite nanometer filtering film prepared by preparation method provided by the present invention.
Present invention also offers by composite nanometer filtering film of the present invention and the application of composite nanometer filtering film in water treatment field prepared by described preparation method of the present invention.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples:
(1) water flux of composite nanometer filtering film is tested by the following method and is obtained: composite nanometer filter permeable membrane loaded in membrane cisterna, under 1.2MPa, precompressed is after 0.5 hour, at the water transit dose that pressure is under 2.0MPa, temperature records described NF membrane in 1h under being 25 DEG C of conditions, and obtained by following formulae discovery:
J=Q/ (At), wherein, J is water flux, the effective film area (m of Q to be water transit dose (L), A be composite nanometer filtering film
2), t is the time (h);
(2) salt rejection rate of composite nanometer filtering film is tested by the following method and is obtained: loaded by composite nanometer filtering film in membrane cisterna, under 1.2MPa after precompressed 0.5h, in the change in concentration that pressure is under 2.0MPa, temperature records sodium sulphate in the former aqueous solution of sodium sulphate and permeate that initial concentration in 1h is 2000ppm under being 25 DEG C of conditions, and obtained by following formulae discovery:
R=(C
p-C
f)/C
p× 100%, wherein, R is salt rejection rate, C
pfor the concentration of sodium sulphate in stoste, C
ffor the concentration of sodium sulphate in permeate;
(3) the acid resistance test of composite nanometer filtering film: be that composite nanometer filtering film diaphragm is being contained 5 quality %H
2sO
4aqueous acid in soak one month, the then water flux of test compound NF membrane and the change of salt-stopping rate week about;
(4) the alkali resistance test of composite nanometer filtering film: be that composite nanometer filtering film diaphragm is soaked month in the aqueous solution of the alkali containing 4 quality %NaOH, the then water flux of test compound NF membrane and the change of salt-stopping rate week about.
In addition, in the following Examples and Comparative Examples:
Purchased from lark prestige Science and Technology Ltd., (alcoholysis degree is 95% to polyvinyl alcohol (PVA), weight average molecular weight is 95000), KH550, KH560, KH570, KH580, KH590 etc. are all purchased from lark prestige Science and Technology Ltd., and other chemical reagent is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
This embodiment is for illustration of composite nanometer filtering film provided by the invention and preparation method thereof.
Be dissolved in 100g deionized water by 0.5g polyvinyl alcohol (PVA), 0.3g γ aminopropyltriethoxy silane (KH550), then under agitation instill the watery hydrochloric acid of 1mol/L, the pH value regulating solution is 1.At normal temperatures, after stirring 24h, filter and obtain clarifying coating liquid;
Coating weak solution be coated in equably after on polysulfones counterdie, the baking oven then putting into 60 DEG C heats 30min, guarantees solvent volatilization completely; Again the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 30min, this composite nanometer filtering film is taken out, soak in deionized water after washing.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Fig. 1 gives the forming process of composite nanometer filtering film of the present invention, first be the silane coupler containing structure formula (I) Suo Shi is hydrolyzed and interacts with polyhydroxylated polymer polyethylene, then pass through in acid condition, utilize the reaction of formaldehyde and hydroxyl, silane coupler containing structure formula (I) Suo Shi and polyhydroxylated polymer are reacted and forms cross-linked network structure, obtain composite nanometer filtering film.
Embodiment 2
This embodiment is for illustration of composite nanometer filtering film provided by the invention and preparation method thereof.
Be dissolved in 100g deionized water by 0.5g polyvinyl alcohol (PVA), 0.1g γ aminopropyltriethoxy silane (KH550), then under agitation instill the watery hydrochloric acid of 1mol/L, the pH value regulating solution is 1.At normal temperatures, after stirring 24h, filter and obtain clarifying coating liquid;
Coating weak solution be coated in equably after on polysulfones counterdie, the baking oven then putting into 60 DEG C heats 30min, guarantees solvent volatilization completely; Again the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 30min, this composite nanometer filtering film is taken out, soak in deionized water after washing.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 3
This embodiment is for illustration of composite nanometer filtering film provided by the invention and preparation method thereof.
Be dissolved in 100g deionized water by 0.5g polyvinyl alcohol (PVA), 0.2g γ aminopropyltriethoxy silane (KH550), then under agitation instill the watery hydrochloric acid of 1mol/L, the pH value regulating solution is 1.At normal temperatures, after stirring 24h, filter and obtain clarifying coating liquid;
Coating weak solution be coated in equably after on polysulfones counterdie, the baking oven then putting into 60 DEG C heats 30min, guarantees solvent volatilization completely; Again the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 30min, this composite nanometer filtering film is taken out, soak in deionized water after washing.
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 4
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, adds 0.4g γ aminopropyltriethoxy silane (KH550);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Embodiment 5
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, adds 0.5g γ aminopropyltriethoxy silane (KH550);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Comparative example 1
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, does not add γ aminopropyltriethoxy silane (KH550);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Table 1
Embodiment 6
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 10min, this composite nanometer filtering film is taken out, soaks in deionized water after washing;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
Embodiment 7
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 20min, this composite nanometer filtering film is taken out, soaks in deionized water after washing;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
Embodiment 8
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 40min, this composite nanometer filtering film is taken out, soaks in deionized water after washing;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
Embodiment 9
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 50min, this composite nanometer filtering film is taken out, soaks in deionized water after washing;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
Embodiment 10
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, the composite nanometer filtering film obtained is immersed in the solution containing 100g water, the 10g concentrated sulfuric acid, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, after heating 60min, this composite nanometer filtering film is taken out, soaks in deionized water after washing;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 2.
Comparative example 2
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, is immersed in the solution containing water, the concentrated sulfuric acid, formaldehyde and sodium sulphate by the composite nanometer filtering film obtained, that is, does not carry out cross-linking reaction;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 1.
Table 2
Embodiment 11
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, is immersed in by the composite nanometer filtering film obtained in the solution containing 100g water, the 5g concentrated sulfuric acid, 5g formaldehyde and 10g sodium sulphate;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
Embodiment 12
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, is immersed in by the composite nanometer filtering film obtained in the solution containing 100g water, the 15g concentrated sulfuric acid, 15g formaldehyde and 20g sodium sulphate;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
Embodiment 13
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, is immersed in by the composite nanometer filtering film obtained in the solution containing 100g water, the 20g concentrated sulfuric acid, 20g formaldehyde and 25g sodium sulphate;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 3.
Table 3
Embodiment 14
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, γ aminopropyltriethoxy silane (KH550) is replaced with γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
Embodiment 15
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, γ aminopropyltriethoxy silane (KH550) is replaced with γ-methacryloxypropyl trimethoxy silane (KH570);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
Embodiment 16
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, γ aminopropyltriethoxy silane (KH550) is replaced with gamma-mercaptopropyltriethoxysilane (KH580);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
Embodiment 17
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, γ aminopropyltriethoxy silane (KH550) is replaced with γ-mercaptopropyl trimethoxysilane (KH590);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
Embodiment 18
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, γ aminopropyltriethoxy silane (KH550) is replaced with N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS (KH792);
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 4.
Table 4
Embodiment 19
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, polyvinyl alcohol (PVA) is replaced with shitosan;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
Embodiment 20
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, polyvinyl alcohol (PVA) is replaced with chitosan quaternary ammonium salt;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
Embodiment 21
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, polyvinyl alcohol (PVA) is replaced with polyether-tribasic alcohol;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
Embodiment 22
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, polyvinyl alcohol (PVA) is replaced with polyester trihydroxylic alcohol;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
Embodiment 23 (identical with embodiment 3 in material of telling somebody what one's real intentions are)
According to prepare the preparation method of composite nanometer filtering film identical with enforcement 1, institute's difference is, polyvinyl alcohol (PVA) is replaced with polyethylene glycol;
After the composite nanometer filtering film obtained is soaked 24 hours in water, then pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, by the H of this composite membrane at 5 quality %
2sO
4soak after one month in the aqueous solution, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
In addition, after this composite membrane is soaked one month in the NaOH aqueous solution of 4 quality %, pressure be 2.0MPa, temperature measures water flux and salt rejection rate under being 25 DEG C of conditions, result is as shown in table 5.
Table 5
As can be seen from the result of above embodiment 1-23, composite nanometer filtering film provided by the invention has excellent water flux and salt-stopping rate, and from before soda acid process and with 4.9 % by weight H
2sO
4process the result after 30 days can find out, composite nanometer filtering film provided by the invention there is acid-proof alkaline well, as can be seen from before soda acid process and by the result of 4 % by weight NaOH process after 30 days, composite nanometer filtering film provided by the invention there is alkaline resistance properties well, and preparation method is simple, has prospects for commercial application.Further, as can be seen from the comparing result of embodiment 1-23 and comparative example 1-2, the described polymer containing hydroxyl does not react with the silane coupler containing structure formula (I) Suo Shi, and water flux and the salt-stopping rate of prepared composite nanometer filtering film are lower, and acid-proof alkaline is poor.
Fig. 1-5 is the composite nanometer filtering films prepared with the preparation method described in embodiment 3 and post-treatment condition, the composite nanometer filtering film obtained is immersed in respectively the H of 4.9%
2sO
4the aqueous solution, the NaOH aqueous solution of 4%, the phosphate aqueous solution of 20% and 5% the HCl aqueous solution in one month, test the water flux of diaphragm and the change of salt-stopping rate week about, it the results are shown in Figure shown in 1-4.Wherein, Fig. 1 is forming process and the reaction mechanism of composite nanometer filtering film functional layer prepared by the present invention; Fig. 2 be the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux with 4.9% H
2sO
4the change of soak time in the aqueous solution; Fig. 3 is the change with soak time in the NaOH aqueous solution of 4% of the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux; Fig. 4 is the change with soak time in the phosphate aqueous solution of 20% of the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux; Fig. 5 is the change with soak time in the HCl aqueous solution of 5% of the salt-stopping rate of composite nanometer filtering film prepared of embodiment 3 and water flux.
As can be seen from Fig. 1-5, composite nanometer filtering film prepared by the present invention can keep water flux and salt-stopping rate substantially constant in the environment of pH=0-14.In addition, this composite nanometer filtering film can in the phosphate aqueous solution of 20%, retention be constant reaches 30 days or more of a specified duration, can reach a conclusion thus, such composite nanometer filtering film not only may be used for being separated multivalent ion or macromolecule in the environment of pH=0-14, being separated of phosphoric acid and hydrochloric acid can also be used for, and phosphoric acid is concentrated, has great commercial value.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a composite nanometer filtering film, described composite nanometer filtering film comprises the supporting layer and separating layer that stack together, it is characterized in that, described separating layer is that polymer containing hydroxyl is dissolved in solvent react by sol-gel and heat cross-linking with the silane coupler containing structure shown in formula (I) and forms the cross-linked structure be positioned in described support layer surface afterwards;
formula (I),
Wherein, Y is alkenyl or carbon functional group, and described carbon functional group is with Cl, NH
2, epoxy, SH, N
3, (methyl) acryloxy or NCO alkyl; X is Cl, methoxyl group, ethyoxyl, OC
2h
4oCH
3, OSi (CH
2)
3with one or more in acetoxyl group.
2. composite nanometer filtering film according to claim 1, wherein, the thickness of described supporting layer is 90-150 micron, is preferably 100-120 micron; The thickness of described separating layer is 0.05-0.5 micron, is preferably 0.1-0.3 micron.
3. composite nanometer filtering film according to claim 1, wherein, in the forming process of described separating layer, with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl is 0.1-50 weight portion, is preferably 0.25-25 weight portion; The consumption of the described silane coupler containing structure shown in formula (I) is 0.01-50 weight portion, is preferably 0.025-25 weight portion.
4. the composite nanometer filtering film according to claim 1 or 3, wherein, the described polymer containing hydroxyl is one or more in polyethylene glycol, polyvinyl alcohol, shitosan, chitosan quaternary ammonium salt, PPG and PEPA; Be preferably in polyethylene glycol, polyvinyl alcohol and shitosan one or more.
5. the composite nanometer filtering film according to claim 1 or 3, wherein, the described silane coupler containing structure shown in formula (I) is γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, vinyltrimethoxy silane, VTES, gamma-amino hydroxypropyl methyl diethoxy silane, gamma-amino hydroxypropyl methyl dimethoxysilane, dimethylaminopropyl trimethoxy silane, γ-glycydoxy ethyldimethoxysilane, γ-glycidoxypropyl ethyl trimethoxy silane, β-(3,4-epoxycyclohexyl) propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) ethyl-methyl dimethoxysilane, isocyanate group propyl-triethoxysilicane, isocyanate group hydroxypropyl methyl dimethoxysilane, beta-cyano ethyl trimethoxy silane, γ-acryloxypropyl trimethoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, amino-3, the 3-dimethylbutyl trimethoxy silanes of 4-, N-ethyl-3-trimethoxysilyl-2-methyl propylamine, dimethyl stearyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride, one or more in γ-methacryloxypropyl and vinyl three (2-methoxy ethoxy) silane.
6. a preparation method for composite nanometer filtering film, the method comprises the following steps:
(1) polymer containing hydroxyl, silane coupler containing structure formula (I) Suo Shi are dissolved in solvent and are prepared into coating liquid;
(2) described coating liquid is coated on supporting layer forms initial film;
(3) supporting layer step (2) being formed with initial film immerses in the solution containing crosslinking agent and crosslinking catalyst and carries out cross-linking reaction, obtains the composite nanometer filtering film comprising supporting layer He be positioned at the cross-linked structure in described support layer surface;
formula (I),
Wherein, Y is alkenyl or carbon functional group, and described carbon functional group is with Cl, NH
2, epoxy, SH, N
3, (methyl) acryloxy or NCO alkyl; X is Cl, methoxyl group, ethyoxyl, OC
2h
4oCH
3, OSi (CH
2)
3with one or more in acetoxyl group.
7. preparation method according to claim 6, wherein, in step (1), with the solvent of 100 weight portions for benchmark, the consumption of the described polymer containing hydroxyl is 0.1-50 weight portion, is preferably 0.25-25 weight portion; The consumption of the described silane coupler containing structure shown in formula (I) is 0.01-50 weight portion, is preferably 0.025-25 weight portion.
8. preparation method according to claim 6, wherein, the thickness of described supporting layer is 90-150 micron, and be preferably 100-120 micron, the consumption of described coating liquid makes the thickness of described separating layer be 0.05-0.5 micron, is preferably 0.1-0.3 micron.
9. preparation method according to claim 6, wherein, in step (1), described solvent is one or more in water, methyl alcohol, ethanol, acetone, glycol monoethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO), preferably, described solvent is the mixed solvent of water, ethanol and dimethyl sulfoxide (DMSO).
10. preparation method according to claim 9, wherein, in described mixed solvent, the weight ratio of water, ethanol and dimethyl sulfoxide (DMSO) is 1-50:1-30:1, is preferably 1-25:1-20:1.
11. preparation methods according to claim 6, wherein, in step (3), the condition of described cross-linking reaction comprises: crosslinking temperature is 20-100 DEG C, and crosslinking time is 10 minutes-48 hours; Preferably, crosslinking temperature is 40-80 DEG C, and crosslinking time is 20 minutes-24 hours.
12. preparation methods according to claim 6 or 11, wherein, in described cross-linking reaction, described crosslinking agent is one or more in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, MDA, butanedial and glutaraldehyde; Described crosslinking catalyst is one or more in acids and Sulfates; And with the gross weight of crosslinked fluid for benchmark, the consumption of described crosslinking agent is 1-100 % by weight, be preferably 10-50 % by weight; The consumption of described acids is 1-98 % by weight, is preferably 5-80 % by weight; The consumption of described Sulfates is 1-60 % by weight, is preferably 5-50 % by weight.
13. preparation methods according to claim 12, wherein, described acids is one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid; Described Sulfates is one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate.
14. composite nanometer filtering films prepared by the preparation method in claim 6-13 described in any one.
15. by the application of the composite nanometer filtering film described in claim 1 or 14 in water treatment field
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