CN105289321B - A kind of composite nanometer filtering film and preparation method thereof - Google Patents
A kind of composite nanometer filtering film and preparation method thereof Download PDFInfo
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- CN105289321B CN105289321B CN201410350598.7A CN201410350598A CN105289321B CN 105289321 B CN105289321 B CN 105289321B CN 201410350598 A CN201410350598 A CN 201410350598A CN 105289321 B CN105289321 B CN 105289321B
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Abstract
A kind of composite nanometer filtering film and preparation method thereof, and application of the composite nanometer filtering film prepared by the composite nanometer filtering film and by the preparation method in water treatment field are disclosed the invention discloses one kind.The composite nanometer filtering film includes supporting layer and the separating layer stacked together, wherein, the separating layer is the cross-linked structure that the polymer containing hydroxyl is located at the silane coupler containing structure shown in formula (I) by formation after collosol and gel and heat cross-linking reaction in the support layer surface；Formula (I), wherein, Y is alkenyl or carbon functional group, and the carbon functional group is with Cl, NH2, epoxy, SH, N3, (methyl) acryloxy or NCO alkyl；X is Cl, OMe, OEt, OC2H4OCH3、OSiMe3With the one or more in OAc.The composite nanometer filtering film of the present invention can the stable operation in pH=0 14 aqueous solution, not only with higher salt rejection rate and water penetration, also with stronger resistance to acids and bases, method is simple, great prospects for commercial application.
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, and the pore diameter range of NF membrane exists
Several rans, the organic matter removing that 200 are less than to monovalention and molecular weight is poor, and to divalence or multivalent ion and molecule
The organic matter measured between 200~500 has higher removal efficiency.It can be widely used in fresh water softening, seawater softening, drinking water
Purification, water correction, water-oil separating, wastewater treatment and recycling, and the chemical industry system such as dyestuff, antibiotic, polypeptide and polysaccharide
The fields such as classification, purifying and the concentration of product.
At present, commercial nanofiltration membrane is carried out polynary mostly using polysulphone super-filter membrane as supporting layer in milipore filter upper surface original position
The interfacial polymerization of aqueous amine phase and polynary acyl chlorides organic phase, final product is composite nanometer filtering film.Common aqueous phase monomers are piperazine
Or piperazine substitution amine, organic phase be pyromellitic trimethylsilyl chloride or a kind of multifunctional carboxylic acid halides, such as patent No. US4769148 with
The content reported disclosed in US4859384, a large amount of unreacted acid chloride groups are hydrolyzed into carboxylic acid, bear NF membrane surface band
Electricity, using charge effect, polypiperazine-amide composite nanometer filtering film has higher rejection to high-valence anion, to monovalent anion
With adjustable rejection.In addition, the patent No. US4765897, US4812270 and US4824574 additionally provide a kind of how will
The method that polyamide composite reverse osmosis membrane is transformed into NF membrane.But, due to the limitation of material self character, in extreme pH environments
Under, particularly under basic conditions, traditional polyamide-based NF membrane can degrade, due to the use pH models of polyamide nanofiltration membrane
Generally 2~11 are enclosed, so being only used for neutral medium or the weak acid and weak base medium close to neutrality.
In recent years, researchers develop a variety of NF membranes, and the product of a variety of commercializations occur.In addition, many new
Material, such as sulfonated polyether ketone, sulfonated polyether sulfone etc. are also applied to nanofiltration field.
Document《Acid stable thin-film composite membrane for nanofiltration
Prepared from naphthalene-1,3,6-trisulfonylchloride (NTSC) and piperazine (PIP),
J.Membr.Sci.,415-416,122-131,2012》Middle report：Sulfonamide material has very strong acid resistance, using polynary
The composite nanometer filtering film that sulfonic acid chloride monomer is obtained with piperazine by interfacial polymerization can keep stable separation property in pH=0 environment
Energy.
Document《Sulfonated poly(etheretherketone)based composite membranes for
Nanofiltration of acidic and alkaline media, J.Membr.Sci., 381,81-89,2011》Middle report
Road：Sulfonated polyether-ether-ketone both has acid resistance, there is very strong alkali resistance again, can more obtain that cutoff performance is excellent to be received by crosslinking
Filter membrane material, moreover, the polyetheretherketonematerials materials after crosslinking have very strong solvent resistance, can be in isopropanol and acetone isopolarity
Dyestuff (Crosslinking of modified poly (etheretherketone) membranes for are separated in solvent
Use in solvent resistant nanofiltration, 447,212-221,2013).
Document《Acid and alkali-resistance high temperature resistant NF membrane HYDRACoRe70pHT for sugar industry spent lye reclaim, membrane science with
Technology, 32,11-15,2006》Middle report：The sulfonated polyether sulfone class composite nanometer filtering film of commercialization is by day eastern electrician Hai De
The HYDRACoRe series that energy company develops, can use in strong acid, strong base solution, be widely used in the recovery of salkali waste.
The acidproof NF membrane Duracid NF1812C that GE companies develop be three-layer composite structure, can 20% hydrochloric acid,
Keep stablizing under the conditions of sulfuric acid and phosphoric acid, and holding is remained under the conditions of 70 DEG C, the sulfuric acid of 20% concentration and stablize.
Receiving of can steadily in the long term being run in pH=0~14 is reported in the patent No. US5265734, EP0392982 (A3)
The SelRO MPS34 that filter membrane only KOCH companies develop, it is developed by Israel scientist earliest, and material is silicon
Rubber, earliest applied to infiltration evaporation.
Polyvinyl alcohol (PVA) is a kind of water-soluble polymer, remarkable with good film forming, cohesion, emulsibility
Grease resistance and solvent resistance, and good acid-fast alkali-proof performance.Chemical crosslinking can reduce PVA crystallinity, improve film
Mechanical strength, increase film is to the rejection of salt ion, and the performance with more preferable acid and alkali-resistance and solvent.Last century 80
PVA/PAN (polyacrylonitrile) composite membrane of crosslinking is used for ethanol dehydration by age, GFT companies, infiltrating and vaporizing membrane has been obtained work
The application of industry.At present, the infiltrating and vaporizing membrane of commercialization is mainly PVA film.Due to PVA good dissolubilities and film forming,
Nanofiltration counter-infiltration field is had been applied to, for improving the resistance tocrocking of film.Its method is multiple mainly in polyamide functional layer
Unify layer PVA, then heat cross-linking is carried out by crosslinking agent, detailed process is shown in CN101462024.Utilize the PVA functional layer systems of crosslinking
Standby composite nanometer filtering film also has a document report, but is due to its poor salt-stopping rate (typically to Na2SO4Rejection be less than
90%) fail to realize industrialization.
Silane coupler is the silane that a class has organo-functional group, has energy and inanimate matter material simultaneously in the molecule thereof
(such as glass, silica sand, metal) chemically combined reactive group and chemically combined anti-with organic material (synthetic resin etc.)
Answer group.It is mainly used in adhesive field.
Therefore, how silane coupler is incorporated into PVA systems and need to prepare a kind of acidproof composite nanometer filtering film
In further R and D.
The content of the invention
The invention aims to overcome the defect of existing NF membrane acid resistance and alkali resistance difference, and provide a kind of
Composite nanometer filtering film and preparation method thereof, and the composite nanometer filtering film and the composite nanometer filtering film that is prepared by this method are in water process
Application in field.
To achieve these goals, the present invention provides a kind of composite nanometer filtering film, and the composite nanometer filtering film includes being stacked in one
The supporting layer and separating layer risen, wherein, the separating layer is the polymer containing hydroxyl and the silane containing structure shown in formula (I)
Coupling agent is dissolved in solvent by forming the crosslinking being located in the support layer surface after sol-gel and heat cross-linking reaction
Network structure；
Formula (I),
Wherein, Y is alkenyl or carbon functional group, and the carbon functional group is with Cl, NH2, epoxy, SH, N3, (methyl)
The alkyl of acryloxy or NCO；X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC2H4OCH3、OSi(CH2)3
(OSiMe3) and acetoxyl group (OAc) in one or more；Preferably, Y is to contain NH on carbon functional group2, epoxy, SH and (first
Base) acryloxy alkyl in one or more, X be methoxyl group (OMe), ethyoxyl (OEt) and OC2H4OCH3In one
Plant or a variety of.
Present invention also offers a kind of preparation method of composite nanometer filtering film, this method comprises the following steps：
(1) silane coupler by the polymer containing hydroxyl, containing structure shown in formula (I), which is dissolved in solvent, is prepared into
Coating liquid；
(2) coating liquid is coated on supporting layer and forms initial film；
(3) step (2) is formed with solution of the supporting layer of the initial film immersion containing crosslinking agent and crosslinking catalyst
Row cross-linking reaction, obtains including the composite nanometer filtering film of supporting layer and the cross-linked structure in the support layer surface；
Formula (I),
Wherein, Y is alkenyl or carbon functional group, and the carbon functional group is with Cl, NH2, epoxy, SH, N3, (methyl)
The alkyl of acryloxy or NCO；X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC2H4OCH3、OSi(CH2)3
(OSiMe3) and acetoxyl group (OAc) in one or more；Preferably, Y is to contain NH on carbon functional group2, epoxy, SH and (first
Base) acryloxy alkyl in one or more, X be methoxyl group (OMe), ethyoxyl (OEt) and OC2H4OCH3In one
Plant or a variety of.
Present invention also offers the composite nanometer filtering film prepared by the above method.
The composite nanometer filtering film prepared present invention also offers above-mentioned composite nanometer filtering film and by the above method is in water process
Application in field.
The present inventor by further investigation find, on the one hand, the polymer of the present invention containing hydroxyl with
Silane coupler containing structure shown in formula (I) all has stronger resistance to acids and bases；On the other hand, the polymer containing hydroxyl with
Silane coupler containing structure shown in formula (I) forms cross-linked network structure after being reacted by sol-gel and heat cross-linking,
The mechanical property of film is not only increased, and also increases the cutoff performance to inorganic salts and organic molecule.In summary,
It is molten that separating layer of the present invention is that the silane coupler as the polymer containing hydroxyl and containing structure shown in formula (I) passes through
Formed after glue-gel and heat cross-linking reaction；Composite nanometer filtering film of the present invention can be steady in the pH=0-14 aqueous solution
Surely run, not only with higher salt rejection rate and water penetration (water flux), also with stronger resistance to acids and bases, and it is prepared
Method is simple, great prospects for commercial application.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
The forming process and reaction mechanism for the composite nanometer filtering film functional layer that Fig. 1 is prepared for the present invention；
Fig. 2 is the salt-stopping rate and water flux of composite nanometer filtering film prepared by embodiment 3 with the H 4.9%2SO4In the aqueous solution
The change of soak time；
Fig. 3 is that the salt-stopping rate and water flux of composite nanometer filtering film prepared by embodiment 3 soak with the 4% NaOH aqueous solution
The change of bubble time；
Fig. 4 is the salt-stopping rate and water flux of composite nanometer filtering film prepared by embodiment 3 with 20% phosphate aqueous solution
The change of soak time；
Fig. 5 is that the salt-stopping rate and water flux of composite nanometer filtering film prepared by embodiment 3 soak with 5% HCl/water solution
The change of bubble time.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of composite nanometer filtering film, the composite nanometer filtering film includes supporting layer and the separation stacked together
Layer, wherein, the separating layer is the polymer containing hydroxyl and is dissolved in solvent containing the silane coupler of structure shown in formula (I)
In pass through sol-gel and heat cross-linking reaction after formed be located at the support layer surface on cross-linked structure；
Formula (I),
Wherein, Y is alkenyl or carbon functional group, and the carbon functional group is with Cl, NH2, epoxy, SH, N3, (methyl)
The alkyl of acryloxy or NCO；X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC2H4OCH3、OSi(CH2)3
(OSiMe3) and acetoxyl group (OAc) in one or more；Preferably, Y is to contain NH on carbon functional group2, epoxy, SH and (first
Base) acryloxy alkyl in one or more, X be methoxyl group (OMe), ethyoxyl (OEt) and OC2H4OCH3In one
Plant or a variety of.
According to the present invention, the polymer containing hydroxyl is polyethylene glycol, polyvinyl alcohol, chitosan, chitosan quaternary ammonium
One or more in salt, PPG and PEPA；From the point of view of raw material is ready availability, it is preferable that described to contain
The polymer for having hydroxyl is the one or more in polyethylene glycol, polyvinyl alcohol and chitosan.In the present invention, the chitosan
(chitosan) chitosan is also known as, is that the chitin (chitin) being widely present by nature is obtained by deacetylation
Arrive, chemical name is Chitosan (1-4) -2- amino-B-D glucose.
According to the present invention, the silane coupler containing structure shown in formula (I) can be gamma-amino propyl triethoxy
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) epoxide silicon
Alkane (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- epoxycyclohexyls) propyl trimethoxy silicane, β-(3,4- epoxycyclohexyls) ethyl-methyl dimethoxysilane, isocyanide
Acidic group propyl-triethoxysilicane, isocyanate group hydroxypropyl methyl dimethoxysilane, beta-cyano ethyl trimethoxy silane, γ-
Acryloxypropyl trimethoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, 4- amino -3,3-
Dimethylbutyl trimethoxy silane, N- ethyl -3- trimethoxysilyl -2- methyl propylamine, dimethyl stearyl [3-
(trimethoxy silicon substrate) propyl group] ammonium chloride, γ-methacryloxypropyl and (the 2- methoxies of vinyl three
Base oxethyl) one or more in silane.
Preferably, the 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-first
Base acryloxypropyl trimethoxy silane (KH570), N- (β-aminoethyl)-γ-aminopropyl front three (second) TMOS
(KH792), N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (DL602), γ-mercaptopropyl trimethoxysilane
And the one or more in gamma-mercaptopropyltriethoxysilane (KH580) (KH590)；
It is highly preferred that the silane coupler containing structure shown in formula (I) is 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-mercapto propyl trimethoxy silicon
One or more in alkane (KH590) and gamma-mercaptopropyltriethoxysilane (KH580).
According to the present invention, the thickness of the supporting layer and separating layer is not particularly limited, and can be the routine of this area
Selection, but in order that can play more preferable coordinated effect for this two layers, so as to get composite nanometer filtering film can be preferably
Have concurrently under excellent acid-proof alkaline, higher water flux and salt rejection rate, preferable case, the thickness of the supporting layer is 90-150
Micron, the thickness of the separating layer is 0.05-0.5 microns；In the case of more preferably, the thickness of the supporting layer is micro- for 100-120
Rice, the thickness of the separating layer is 0.1-0.3 microns.
According to the present invention, the supporting layer is not particularly limited, can be by existing various with certain intensity and energy
It is enough in nanofiltration, the material of reverse osmosis membrane is made, generally can be by polyacrylonitrile, Kynoar, the poly- virtue of phenolphthalein type non-sulfonated
One or more in ether sulfone, polyether sulfone and bisphenol-a polysulfone are made, and this those skilled in the art can be known, herein will
Repeat no more.
According to the present invention, the present invention is to the polymer containing hydroxyl in the separating layer and contains knot formula (I) Suo Shi
The content of the silane coupler of structure is not particularly limited, but in order that preferably mating reaction can be played by obtaining both, in institute
In the forming process for stating separating layer, on the basis of the solvent of 100 parts by weight, the consumption of the polymer containing hydroxyl is 0.1-
50 parts by weight, preferably 0.25-25 parts by weight；The consumption containing the silane coupler of structure shown in formula (I) is 0.01-50
Parts by weight, preferably 0.025-25 parts by weight.
Present invention also offers a kind of preparation method of composite nanometer filtering film, this method comprises the following steps：
(1) silane coupler by the polymer containing hydroxyl, containing structure shown in formula (I), which is dissolved in solvent, is prepared into
Coating liquid；
(2) coating liquid is coated on supporting layer and forms initial film；
(3) step (2) is formed with solution of the supporting layer of the initial film immersion containing crosslinking agent and crosslinking catalyst
Row cross-linking reaction, obtains including the composite nanometer filtering film of supporting layer and the cross-linked structure in the support layer surface；
Formula (I),
Wherein, Y is alkenyl or carbon functional group, and the carbon functional group is with Cl, NH2, epoxy, SH, N3, (methyl)
The alkyl of acryloxy or NCO；X is Cl, methoxyl group (OMe), ethyoxyl (OEt), OC2H4OCH3、OSi(CH2)3
(OSiMe3) and acetoxyl group (OAc) in one or more；Preferably, Y is to contain NH on carbon functional group2, epoxy, SH and (first
Base) acryloxy alkyl in one or more, X be methoxyl group (OMe), ethyoxyl (OEt) and OC2H4OCH3In one
Plant or a variety of.
According to the present invention, the present invention to the polymer containing hydroxyl in the coating liquid, contain structure shown in formula (I)
The consumption of silane coupler and solvent is not particularly limited, if the NF membrane enabled to can have concurrently it is excellent acidproof
Alkaline energy, higher water flux and salt rejection rate, for example, in step (1), it is described on the basis of the solvent of 100 parts by weight
The consumption of polymer containing hydroxyl can be 0.1-50 parts by weight, preferably 0.25-25 parts by weight；It is described to contain formula (I) institute
The consumption for showing the silane coupler of structure can be 0.01-50 parts by weight, preferably 0.025-25 parts by weight；In the present invention,
The preparation process of the coating liquid carried out preferably in the presence of the catalyst for sol-gel, and the sol-gel is urged
Agent is not particularly limited, and can be the one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, preferably salt
Acid, and on the basis of the solvent of 100 parts by weight, the consumption of the catalyst of the sol-gel is 0.01-50 parts by weight, preferably
For 0.025-25 parts by weight.In addition, in the present invention, the concentration of the hydrochloric acid is not particularly limited, it is preferable that the hydrochloric acid
Concentration is 0.5-1.5mol/L, it is highly preferred that the concentration of the hydrochloric acid is 1mol/L.
According to the present invention, the present invention is not particularly limited to the pH value of the coating liquid, it is preferable that the pH of the coating liquid
It is worth for 1-4.
According to the present invention, the present invention is molten in the silane coupler by the polymer containing hydroxyl, containing structure shown in formula (I)
Solution is carried out during solvent preferably under conditions of stirring, condition and the equipment of stirring of the present invention to the stirring
It is not particularly limited, the conventional mixing plant that can be well known to those skilled in the art enters under appropriate stirring condition
OK, as long as the polymer containing hydroxyl, the silane coupler containing structure shown in formula (I) can be made to be completely dissolved in solvent i.e.
Can.In addition, the present invention is dissolved in solvent in the silane coupler by the polymer containing hydroxyl, containing structure shown in formula (I)
Process is carried out at normal temperatures.
According to the present invention, the present invention is not particularly limited to the thickness of the supporting layer, can be the routine of this area
Selection, but in order that more preferable coordinated effect can be played, make what is obtained to be combined by obtaining the supporting layer and the separating layer
NF membrane can be preferably had concurrently under excellent acid-proof alkaline, higher water flux and salt rejection rate, preferable case, the support
The thickness of layer is 90-150 microns, preferably 100-120 microns.
According to the present invention, the present invention is not particularly limited to the consumption of the coating liquid, but in order that obtained sodium filter
Film can be preferably had concurrently under excellent acid-proof alkaline, higher water flux and salt rejection rate, preferable case, the coating liquid
Consumption causes the thickness of the separating layer to be 0.05-0.5 microns, preferably 0.1-0.3 microns.
According to the present invention, during the coating liquid is coated in into supporting layer, do not have to the present invention that is coated in
It is specific to limit, in the spraying that can be well known to those skilled in the art, blade coating, spin coating etc. any one.
According to the present invention, after coating liquid is coated uniformly on supporting layer, under preferable case, this is coated with coating liquid
Supporting layer to be put into baking oven complete so that solvent therein to be volatilized, do not have to its temperature and time in an oven in the present invention
Body is limited, as long as being able to ensure that solvent volatilization is complete, under preferable case, 20- is dried in temperature is 50-70 DEG C of baking oven
40 minutes, more preferably in the case of, dried 25-35 minutes in temperature is 55-65 DEG C of baking oven.
According to the present invention, the present invention is not particularly limited to the species of the solvent, as long as described contain can be dissolved
The polymer of hydroxyl and the silane coupler containing structure shown in formula (I), for example, in step (1), the solvent can
Think the one or more in water, methanol, ethanol, acetone, glycol monoethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO), it is preferable that institute
The mixed solvent that solvent is water, ethanol and dimethyl sulfoxide (DMSO) is stated, and in the in the mixed solvent, water, ethanol and dimethyl sulfoxide (DMSO)
Weight ratio can be 1-50：1-30：1, preferably 1-25：1-20：1.Using the mixed solvent of water, ethanol and dimethyl sulfoxide (DMSO)
Above-mentioned several material dissolvings are more beneficial for, and the coating liquid of preparation can be made preferably to be coated on supporting layer, and can be made
Obtained sodium filter membrane can preferably have excellent acid-proof alkaline, higher water flux and salt rejection rate concurrently.
According to the present invention, in step (3), the condition of the cross-linking reaction can include：Crosslinking temperature is 20-100 DEG C,
Crosslinking time is -48 hours 10 minutes；Preferably, crosslinking temperature is 40-80 DEG C, and crosslinking time is -24 hours 20 minutes.
According to the present invention, the crosslinking agent contained in crosslinker solution of the present invention can be conventional aldehydes, such as can be
One or more in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, MDA, butanedial and glutaraldehyde, preferably first
One or more in aldehyde, acetaldehyde, propionic aldehyde and butyraldehyde, 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,
Such as can be the one or more in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, preferably in sulfuric acid, hydrochloric acid and acetic acid
One or more, more preferably sulfuric acid；In addition, another crosslinking catalyst contained in crosslinker solution of the present invention can
Think Sulfates, such as can be the one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate, preferably sodium sulphate,
One or more in sulphate of potash and magesium, more preferably sodium sulphate.
According to the present invention, the present invention is not special to the crosslinking agent and the consumption of crosslinking catalyst in the crosslinker solution
Ground is limited, as long as the composite nanometer filtering film enabled to can have excellent acid-proof alkaline, higher water flux and desalination concurrently
Rate.In the present invention, on the basis of the gross weight of the solvent, the consumption of the crosslinking agent is 1-100 weight %, preferably
For 5-50 weight %；The consumption of the acids is 1-98 weight %, preferably 5-80 weight %；The consumption of the Sulfates is
1-60 weight %, preferably 5-50 weight %.
In a word, on the one hand, the polymer of the present invention containing hydroxyl is with containing the silane coupled of structure shown in formula (I)
Agent all has stronger resistance to acids and bases；On the other hand, the polymer containing hydroxyl is with containing the silane coupled of structure shown in formula (I)
Agent not only increases the mechanical property of film by foring cross-linked network structure after sol-gel and heat cross-linking reaction, and
The cutoff performance to inorganic salts and organic molecule is also increased, the resistance to acids and bases of the composite nanometer filtering film is further increased
Energy, higher water flux and salt rejection rate.
According to the present invention, because the polymer containing hydroxyl has higher molecular weight, it is difficult in a solvent
It is completely dissolved, therefore, in order that obtained cross-linked structure is more uniformly distributed, and it is stable to improve the performance of the composite nanometer filtering film
Property, under preferable case, the preparation method of the composite nanometer filtering film also includes the coating liquid being coated on supporting layer into it
Before, the coating liquid is filtered.In specific operation process, by the polymer containing hydroxyl and formula first can be contained
(I) silane coupler of structure shown in is dissolved in solvent and filtered, and obtains the coating liquid of homogeneous transparent；In addition, for described
Filtering is also not particularly limited, the filter method and equipment that can be well known to those skilled in the art.
According to the present invention, in order that obtained composite nanometer filtering film is more smooth, it is preferable that the composite nanometer filter that the present invention is provided
The preparation method of film is additionally included in coating liquid is coated on supporting layer before, by the supporting layer fix on a glass or apply
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 as composite nanometer filtering film of the present invention and as the preparation method system described in the present invention
Application of the standby composite nanometer filtering film in water treatment field.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples：
(1) water flux of composite nanometer filtering film is tested by the following method obtains：Composite nanometer filter permeable membrane is fitted into membrane cisterna,
Under 1.2MPa after precompressed 0.5 hour, under pressure is 2.0MPa, temperature be water that the NF membrane in 1h is measured under the conditions of 25 DEG C
Transit dose, and obtained by below equation calculating：
J=Q/ (At), wherein, J is water flux, and Q is water transit dose (L), and A is effective membrane area of composite nanometer filtering film
(m2), t is the time (h)；
(2) salt rejection rate of composite nanometer filtering film is tested by the following method obtains：Composite nanometer filtering film is fitted into membrane cisterna,
Under 1.2MPa after precompressed 0.5h, under pressure is 2.0MPa, temperature be that to measure initial concentration in 1h under the conditions of 25 DEG C be 2000ppm
Sodium sulphate raw water solution and permeate in sodium sulphate change in concentration, and calculated and obtain by below equation：
R=(Cp-Cf)/Cp× 100%, wherein, R is salt rejection rate, CpFor the concentration of sodium sulphate in stoste, CfFor in permeate
The concentration of sodium sulphate；
(3) the acid resistance test of composite nanometer filtering film：It is containing 5 mass %H by composite nanometer filtering film diaphragm2SO4Sour water
Soaked one month in solution, the then change of the water flux and salt-stopping rate of test compound NF membrane week about；
(4) the alkali resistance test of composite nanometer filtering film：Be by composite nanometer filtering film diaphragm the alkali containing 4 mass %NaOH water
Soaked one month in solution, the then change of the water flux and salt-stopping rate of test compound NF membrane week about.
In addition, in the following Examples and Comparative Examples：
Polyvinyl alcohol (PVA) purchased from lark prestige Science and Technology Ltd. (alcoholysis degree is 95%, weight average molecular weight be 95000),
KH550, KH560, KH570, KH580, KH590 etc. are purchased from lark prestige Science and Technology Ltd., and other chemical reagent are purchased from
Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
The embodiment is used to illustrate composite nanometer filtering film of the invention provided and preparation method thereof.
0.5g polyvinyl alcohol (PVA), 0.3g γ aminopropyltriethoxy silanes (KH550) are dissolved in 100g deionizations
In water, 1mol/L watery hydrochloric acid is then instilled under agitation, the pH value of regulation solution is 1.At normal temperatures, after stirring 24h, filtering
Obtain clarifying coating liquid；
After coating weak solution is uniformly coated on polysulfones counterdie, 30min is heated in the baking oven for being then placed in 60 DEG C, really
Protect solvent volatilization complete；Obtained composite nanometer filtering film is immersed in containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g again
In the solution of sodium sulphate, at 60 DEG C, after heating 30min, the composite nanometer filtering film is taken out, deionized water is immersed in after washing
In.
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 1.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
Fig. 1 gives the forming process of the composite nanometer filtering film of the present invention, is by the silane containing structure shown in formula (I) first
Coupling agent is hydrolyzed simultaneously to interact with polyhydroxylated polymer polyethylene, then by acid condition, using formaldehyde and
The reaction of hydroxyl so that react to form cross-linked network knot containing the silane coupler of structure shown in formula (I) and polyhydroxylated polymer
Structure, obtains composite nanometer filtering film.
Embodiment 2
The embodiment is used to illustrate composite nanometer filtering film of the invention provided and preparation method thereof.
0.5g polyvinyl alcohol (PVA), 0.1g γ aminopropyltriethoxy silanes (KH550) are dissolved in 100g deionizations
In water, 1mol/L watery hydrochloric acid is then instilled under agitation, the pH value of regulation solution is 1.At normal temperatures, after stirring 24h, filtering
Obtain clarifying coating liquid；
After coating weak solution is uniformly coated on polysulfones counterdie, 30min is heated in the baking oven for being then placed in 60 DEG C, really
Protect solvent volatilization complete；Obtained composite nanometer filtering film is immersed in containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g again
In the solution of sodium sulphate, at 60 DEG C, after heating 30min, the composite nanometer filtering film is taken out, deionized water is immersed in after washing
In.
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 1.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
Embodiment 3
The embodiment is used to illustrate composite nanometer filtering film of the invention provided and preparation method thereof.
0.5g polyvinyl alcohol (PVA), 0.2g γ aminopropyltriethoxy silanes (KH550) are dissolved in 100g deionizations
In water, 1mol/L watery hydrochloric acid is then instilled under agitation, the pH value of regulation solution is 1.At normal temperatures, after stirring 24h, filtering
Obtain clarifying coating liquid；
After coating weak solution is uniformly coated on polysulfones counterdie, 30min is heated in the baking oven for being then placed in 60 DEG C, really
Protect solvent volatilization complete；Obtained composite nanometer filtering film is immersed in containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g again
In the solution of sodium sulphate, at 60 DEG C, after heating 30min, the composite nanometer filtering film is taken out, deionized water is immersed in after washing
In.
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 1.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
Embodiment 4
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, adds 0.4g γ-ammonia
Base propyl-triethoxysilicane (KH550)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 1.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
Embodiment 5
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, adds 0.5g γ-ammonia
Base propyl-triethoxysilicane (KH550)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 1.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
Comparative example 1
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, does not add γ-ammonia
Base propyl-triethoxysilicane (KH550)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 1.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
Table 1
Embodiment 6
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, heating
After 10min, the composite nanometer filtering film is taken out, soaked after washing in deionized water；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 2.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
Embodiment 7
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, heating
After 20min, the composite nanometer filtering film is taken out, soaked after washing in deionized water；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 2.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
Embodiment 8
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, heating
After 40min, the composite nanometer filtering film is taken out, soaked after washing in deionized water；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 2.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
Embodiment 9
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, heating
After 50min, the composite nanometer filtering film is taken out, soaked after washing in deionized water；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 2.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
Embodiment 10
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 10g concentrated sulfuric acids, 10g formaldehyde and 15g sodium sulphate, at 60 DEG C, heating
After 60min, the composite nanometer filtering film is taken out, soaked after washing in deionized water；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 2.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 2.
Comparative example 2
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, not by answering for obtaining
Close NF membrane to be immersed in the solution containing water, the concentrated sulfuric acid, formaldehyde and sodium sulphate, i.e. do not carry out cross-linking reaction；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 1.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 1.
Table 2
Embodiment 11
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 5g concentrated sulfuric acids, 5g formaldehyde and 10g sodium sulphate；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 3.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 3.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 3.
Embodiment 12
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 15g concentrated sulfuric acids, 15g formaldehyde and 20g sodium sulphate；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 3.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 3.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 3.
Embodiment 13
According to implement 1 prepare composite nanometer filtering film preparation method it is identical, institute's difference is, compound is received what is obtained
Filter membrane is immersed in the solution containing 100g water, the 20g concentrated sulfuric acids, 20g formaldehyde and 25g sodium sulphate；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 3.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 3.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 3.
Table 3
Embodiment 14
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by gamma-amino propyl group
Triethoxysilane (KH550) replaces with γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 4.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
Embodiment 15
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by gamma-amino propyl group
Triethoxysilane (KH550) replaces with γ-methacryloxypropyl trimethoxy silane (KH570)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 4.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
Embodiment 16
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by gamma-amino propyl group
Triethoxysilane (KH550) replaces with gamma-mercaptopropyltriethoxysilane (KH580)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 4.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
Embodiment 17
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by gamma-amino propyl group
Triethoxysilane (KH550) replaces with γ-mercaptopropyl trimethoxysilane (KH590)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 4.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
Embodiment 18
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by gamma-amino propyl group
Triethoxysilane (KH550) replaces with N- (β-aminoethyl)-γ-aminopropyl front three (second) TMOS (KH792)；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 4.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 4.
Table 4
Embodiment 19
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by polyvinyl alcohol
(PVA) chitosan is replaced with；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 5.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
Embodiment 20
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by polyvinyl alcohol
(PVA) chitosan quaternary ammonium salt is replaced with；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 5.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
Embodiment 21
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by polyvinyl alcohol
(PVA) polyether-tribasic alcohol is replaced with；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 5.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
Embodiment 22
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by polyvinyl alcohol
(PVA) polyester trihydroxylic alcohol is replaced with；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 5.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
Embodiment 23 (same as Example 3 in material of telling somebody what one's real intentions are)
Identical according to the preparation method that composite nanometer filtering film is prepared with implementation 1, institute's difference is, by polyvinyl alcohol
(PVA) polyethylene glycol is replaced with；
Obtained composite nanometer filtering film is soaked after 24 hours in water, is then that 2.0MPa, temperature are 25 DEG C of bars in pressure
Water flux and salt rejection rate are determined under part, as a result as shown in table 5.
In addition, by the composite membrane 5 mass % H2SO4It is 2.0MPa, temperature in pressure after being soaked one month in the aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
In addition, being 2.0MPa, temperature in pressure after the composite membrane is soaked one month in the 4 mass % NaOH aqueous solution
Spend to determine water flux and salt rejection rate under the conditions of 25 DEG C, as a result as shown in table 5.
Table 5
Can be seen that the composite nanometer filtering film of the invention provided from above example 1-23 result has excellent water flux
And salt-stopping rate, and from soda acid before processing and with 4.9 weight %H2SO4Result after handling 30 days can be seen that the present invention and carry
The composite nanometer filtering film of confession has acid-proof alkaline well, from soda acid before processing and with 4 weight %NaOH processing 30 days
Result afterwards can be seen that the alkaline resistance properties well that has for the composite nanometer filtering film that the present invention is provided, and preparation method is simply,
Great prospects for commercial application.Further, it can be seen that from embodiment 1-23 and comparative example 1-2 comparing result and described contain hydroxyl
The polymer of base does not react with the silane coupler containing structure shown in formula (I), and the water of prepared composite nanometer filtering film leads to
Amount and salt-stopping rate are relatively low, and acid-proof alkaline is poor.
Fig. 1-5 is the composite nanometer filtering film prepared with the preparation method and post-treatment condition described in embodiment 3, will
Obtained composite nanometer filtering film is separately immersed in 4.9% H2SO4The aqueous solution, the 4% NaOH aqueous solution, 20% phosphate aqueous solution
And 5% HCl/water solution in one month, the change of the water flux and salt-stopping rate of diaphragm is tested week about, its result is shown in
Shown in Fig. 1-4.Wherein, the forming process and reaction mechanism for the composite nanometer filtering film functional layer that Fig. 1 is prepared for the present invention；Fig. 2 is real
The salt-stopping rate and water flux of the composite nanometer filtering film of the preparation of example 3 are applied with the H 4.9%2SO4The change of soak time in the aqueous solution；
Fig. 3 is the salt-stopping rate and water flux of composite nanometer filtering film prepared by embodiment 3 with the soak time in the 4% NaOH aqueous solution
Change；Fig. 4 is that the salt-stopping rate and water flux of composite nanometer filtering film prepared by embodiment 3 soak with 20% phosphate aqueous solution
The change of time；Fig. 5 is the salt-stopping rate and water flux of composite nanometer filtering film prepared by embodiment 3 with 5% HCl/water solution
The change of soak time.
The composite nanometer filtering film that it can be seen from Fig. 1-5 prepared by the present invention can keep water to lead in pH=0-14 environment
Amount and salt-stopping rate are basically unchanged.In addition, the composite nanometer filtering film can in 20% phosphate aqueous solution retention property it is constant up to 30
It is more long, from this it can be concluded that such composite nanometer filtering film can be not only used for separating in pH=0-14 environment
Multivalent ion or macromolecule, can be also used for the separation of phosphoric acid and hydrochloric acid, and phosphoric acid concentration, with great business valency
Value.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (24)
1. a kind of composite nanometer filtering film, the composite nanometer filtering film includes supporting layer and the separating layer stacked together, it is characterised in that
The separating layer is the polymer containing hydroxyl with being dissolved in containing the silane coupler of structure shown in formula (I) in solvent by molten
The cross-linked structure being located in the support layer surface is formed after glue-gel and heat cross-linking reaction；
Wherein, Y is alkenyl or carbon functional group, and the carbon functional group is with Cl, NH2, epoxy, SH, N3, (methyl) propylene
The alkyl of acyloxy or NCO；X is Cl, methoxyl group, ethyoxyl, OC2H4OCH3、OSi(CH2)3In acetoxyl group
It is one or more.
2. composite nanometer filtering film according to claim 1, wherein, the thickness of the supporting layer is 90-150 microns；Described point
The thickness of absciss layer is 0.05-0.5 microns.
3. composite nanometer filtering film according to claim 2, wherein, the thickness of the supporting layer is 100-120 microns；Described point
The thickness of absciss layer is 0.1-0.3 microns.
4. composite nanometer filtering film according to claim 1, wherein, in the forming process of the separating layer, with 100 parts by weight
Solvent on the basis of, the consumption of the polymer containing hydroxyl is 0.1-50 parts by weight；It is described to contain structure shown in formula (I)
The consumption of silane coupler is 0.01-50 parts by weight.
5. composite nanometer filtering film according to claim 4, wherein, in the forming process of the separating layer, with 100 parts by weight
Solvent on the basis of, the consumption of the polymer containing hydroxyl is 0.25-25 parts by weight；It is described to contain structure shown in formula (I)
Silane coupler consumption be 0.025-25 parts by weight.
6. the composite nanometer filtering film according to claim 1 or 4, wherein, the polymer containing hydroxyl is polyethylene glycol, gathered
One or more in vinyl alcohol, chitosan, chitosan quaternary ammonium salt, PPG and PEPA.
7. composite nanometer filtering film according to claim 6, wherein, the polymer containing hydroxyl is polyethylene glycol, poly- second
One or more in enol and chitosan.
8. the composite nanometer filtering film according to claim 1 or 4, wherein, the silane coupler containing structure shown in formula (I)
For γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy
Silane, γ-methacryloxypropyl trimethoxy silane, N- (β-aminoethyl)-γ-aminopropyl front three (second) epoxide silicon
Alkane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, γ-mercaptopropyl trimethoxysilane, the γ-second of mercapto propyl group three
TMOS, vinyltrimethoxy silane, VTES, gamma-amino hydroxypropyl methyl diethoxy silane,
Gamma-amino hydroxypropyl methyl dimethoxysilane, dimethylaminopropyl trimethoxy silane, γ-glycydoxy second
Base dimethoxysilane, γ-glycidoxypropyl ethyl trimethoxy silane, β-(3,4- epoxycyclohexyls) propyl trimethoxy
Silane, β-(3,4- epoxycyclohexyls) 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, 4- amino -3,3- dimethylbutyls trimethoxy silane, N- ethyls -
3- trimethoxysilyl -2- methyl propylamine, dimethyl stearyl [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, γ -
One or more in methacryloxypropyl and vinyl three (2- methoxy ethoxies) silane.
9. a kind of preparation method of composite nanometer filtering film, this method comprises the following steps：
(1) silane coupler by the polymer containing hydroxyl, containing structure shown in formula (I), which is dissolved in solvent, is prepared into coating
Liquid；
(2) coating liquid is coated on supporting layer and forms initial film；
(3) step (2) is formed with solution of the supporting layer of the initial film immersion containing crosslinking agent and crosslinking catalyst and handed over
Connection reaction, obtains including the composite nanometer filtering film of supporting layer and the cross-linked structure in the support layer surface；
Wherein, Y is alkenyl or carbon functional group, and the carbon functional group is with Cl, NH2, epoxy, SH, N3, (methyl) propylene
The alkyl of acyloxy or NCO；X is Cl, methoxyl group, ethyoxyl, OC2H4OCH3、OSi(CH2)3In acetoxyl group
It is one or more.
10. preparation method according to claim 9, wherein, in step (1), on the basis of the solvent of 100 parts by weight,
The consumption of the polymer containing hydroxyl is 0.1-50 parts by weight；It is described to contain the silane coupler of structure shown in formula (I)
Consumption is 0.01-50 parts by weight.
11. preparation method according to claim 10, wherein, in step (1), on the basis of the solvent of 100 parts by weight,
The consumption of the polymer containing hydroxyl is 0.25-25 parts by weight；It is described to contain the silane coupler of structure shown in formula (I)
Consumption is 0.025-25 parts by weight.
12. preparation method according to claim 9, wherein, the thickness of the supporting layer is 90-150 microns, the coating
The consumption of liquid causes the thickness of separating layer to be 0.05-0.5 microns.
13. preparation method according to claim 12, wherein, the thickness of the supporting layer is 100-120 microns, described to apply
The consumption of covering liquid causes the thickness of separating layer to be 0.1-0.3 microns.
14. preparation method according to claim 9, wherein, in step (1), the solvent is water, methanol, ethanol, third
One or more in ketone, glycol monoethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO).
15. preparation method according to claim 14, wherein, in step (1), the solvent is water, ethanol and diformazan
The mixed solvent of base sulfoxide.
16. preparation method according to claim 15, wherein, in the in the mixed solvent, water, ethanol and dimethyl sulfoxide (DMSO)
Weight ratio be 1-50：1-30：1.
17. preparation method according to claim 16, wherein, in the in the mixed solvent, water, ethanol and dimethyl sulfoxide (DMSO)
Weight ratio be 1-25：1-20：1.
18. preparation method according to claim 9, wherein, in step (3), the condition of the cross-linking reaction includes：Hand over
It is 20-100 DEG C to join temperature, and crosslinking time is -48 hours 10 minutes.
19. preparation method according to claim 18, wherein, in step (3), the condition of the cross-linking reaction includes：
Crosslinking temperature is 40-80 DEG C, and crosslinking time is -24 hours 20 minutes.
20. the preparation method according to claim 9 or 18, wherein, in the cross-linking reaction, the crosslinking agent is first
One or more in aldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, MDA, butanedial and glutaraldehyde；The crosslinking is urged
Agent is the one or more in acids and Sulfates；And on the basis of the gross weight of crosslinked fluid, the consumption of the crosslinking agent
For 1-100 weight %；The consumption of the acids is 1-98 weight %；The consumption of the Sulfates is 1-60 weight %.
21. preparation method according to claim 20, wherein, on the basis of the gross weight of crosslinked fluid, the crosslinking agent
Consumption is 10-50 weight %；The consumption of the acids is 5-80 weight %；The consumption of the Sulfates is 5-50 weight %.
22. preparation method according to claim 20, wherein, the acids be sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and
One or more in nitric acid；The Sulfates is the one or more in sodium sulphate, potassium sulfate, magnesium sulfate and ammonium sulfate.
23. the composite nanometer filtering film prepared as the preparation method described in any one in claim 9-22.
24. by application of the composite nanometer filtering film described in claim 1 or 23 in water treatment field.
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| CN108176259A (en) * | 2018-01-17 | 2018-06-19 | 浙江工业大学 | A kind of modified polyamide reverse osmosis membrane and its manufacturing method |
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