CN107469639A - Composite nanometer filtering film and preparation method thereof - Google Patents

Composite nanometer filtering film and preparation method thereof Download PDF

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Publication number
CN107469639A
CN107469639A CN201710807196.9A CN201710807196A CN107469639A CN 107469639 A CN107469639 A CN 107469639A CN 201710807196 A CN201710807196 A CN 201710807196A CN 107469639 A CN107469639 A CN 107469639A
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composite nanometer
phase solution
filtering film
nanometer filtering
preparation
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苗晶
江志彬
廖海龙
蔡畅
唐浩林
涂凯
张玲
陈顺权
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Shenzhen Institute of Advanced Technology of CAS
Guangzhou Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
Guangzhou Institute of Advanced Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/54—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a kind of composite nanometer filtering film and preparation method thereof.The preparation method comprises the following steps：By in polyalcohol, binding agent, surfactant and the water of alkaline agent addition, stirring and dissolving, aqueous phase solution is obtained；Isocyanate-monomer is added into organic solvent, stirring and dissolving, obtains organic phase solution；Ultrafiltration membranes are soaked in the aqueous phase solution, then taken out, are dried；Ultrafiltration membranes after drying, which are soaked in the organic phase solution, to be reacted, and obtains NF membrane preform；The NF membrane preform is heat-treated in 50~70 DEG C；Produce the composite nanometer filtering film.Thus, composite nanometer filtering film made from above-mentioned preparation method has higher rejection and permeation flux.By the way of interfacial polymerization, operation is simplified compared with prior art, technique is easily controllable, can also overcome coating etc. method of modifying can cause active layer thickness homogeneity it is bad influence membrane separating property the defects of.

Description

Composite nanometer filtering film and preparation method thereof
Technical field
The present invention relates to technical field of membrane separation, more particularly to composite nanometer filtering film and preparation method thereof.
Background technology
UF membrane can operate, without phase transformation in a mild condition, be one of important technology of chemical field.The core of UF membrane The heart is film, and the structure and physical and chemical performance of membrane material are most important to separating property.Conventional membrane material have Kynoar, Polysulfones, polyether sulfone and polyacrylonitrile etc..These materials have excellent uvioresistant and ageing-resistant ability, and chemical stability It is good, do not corroded at room temperature by acid, alkali etc., while also there is preferable heat endurance and mechanical strength, it is the film forming of function admirable Material.However, weak point, which is them, is respectively provided with very strong hydrophobicity.The hydrophobic property of membrane material cause seperation film applied to The protein in water, oil droplet, colloid or other organic substances are easily adsorbed during water process and causes Pore Blocking, causes infiltration logical The dramatic decrease of amount, while these material modifications are difficult, greatly constrain the extensive use of film.In order to meet production requirement, Membrane material has to pass through functional modification.
Recent years, some seminars for PS membrane surface hydrophily and hole pollution capacity difference the problem of, to poly- Sulfone film surface has carried out study on the modification.Current study on the modification can substantially be divided into blending or organic/inorganic between organic matter Thing it is compound.Wherein, the modification of membrane material is carried out by the way of organic/inorganic thing is compound, in view of compatibility therebetween Difference, the problems such as easily causing flux depression or bad stability.
As for organic matter blend film and surface modified membrane, such as the blend film of polyacrylonitrile and polysulfones, with virgin pp nitrile film Or PS membrane is compared, the water flux of blend film significantly improves；Or by surface ionizing modified polysulfone film, using containing poly- methyl-prop The amphipathic nature block polymer of olefin(e) acid dimethylaminoethyl carries out solution blending with polysulfones, is prepared by immersion precipitation phase inversion process Composite membrane, after carrying out the quaternary ammoniated processing in surface with bromo acid solution, film surface carries anions and canons, the hydrophily and anti-soil of film Dye ability is significantly improved.Or use dopamine modified polysulfone film：Film forming again after being first modified with dopamine to polysulfones, can Flexibly and easily to need membrane structure according to use, prepared composite membrane has good backwash and resistance tocrocking Energy.But the above method is needed using preparation technologies such as casting solution blending phase inversion, modification or LBL self-assembly methods, its In, casting solution Blending Processes are not easily controlled, and the property of the dispersiveness and casting solution component of blended liquid has very big correlation；Table The less stable of method Modified Membrane is modified in face, and service life is short；It is not easy to operate and LBL self-assembly process is complicated.
The content of the invention
Summarized based on more than, it is necessary to provide a kind of preparation method of composite nanometer filtering film, the preparation method is simple to operate, work Skill is easily controllable, and obtained composite nanometer filtering film rejection and permeation flux are higher.
A kind of preparation method of composite nanometer filtering film, comprises the following steps：
Polyalcohol, binding agent, surfactant and alkaline agent are added to the water, stirring and dissolving, obtain aqueous phase solution；Wherein, institute The mass concentration for stating polyalcohol is 0.1~5%, and the mass concentration of binding agent is 0.1~5%, the mass concentration of surfactant For 0.01~1.5%, the mass concentration of alkaline agent is 0.01~1.5%；The molecular weight of the polyalcohol is no more than 2000 dalton (Da)；
Isocyanate-monomer is added into organic solvent, stirring and dissolving, obtains organic phase solution；Wherein, the isocyanic acid The mass concentration of ester monomer is 1~5%；
Ultrafiltration membranes are soaked in the aqueous phase solution, then takes out, dry；
Ultrafiltration membranes after drying, which are soaked in the organic phase solution, to be reacted, and obtains NF membrane preform；
The NF membrane preform is heat-treated in 50~70 DEG C；Produce the composite nanometer filtering film.
In one of the embodiments, the molecular weight of the polyalcohol is 200~1000Da.
In one of the embodiments, the polyalcohol is ethylene glycol, propane diols, diglycol, two three second two of contracting Alcohol, neopentyl glycol, glycerine, glycerine, trimethylolethane, trimethylolpropane, ethylenediamine pentaerythrite, pentaerythrite, wood Mixture more than one or both of sugar alcohol, sorbierite or polyethylene glycol (PEG).Preferably glycerine and polyethylene glycol.
In one of the embodiments, the temperature of the heat treatment is 55~65 DEG C.
In one of the embodiments, the isocyanate-monomer is hexamethylene diisocyanate, 4,4- dicyclohexyls Methane diisocyanate, trimethylhexane diisocyanate, durol XDI, isophorone diisocyanate Mixture more than one or both of ester, diphenyl methane -4,4 '-diisocyanate, toluene di-isocyanate(TDI).It is preferred that six Methylene diisocyanate, toluene di-isocyanate(TDI) and diphenyl methane -4,4 '-diisocyanate.
In one of the embodiments, by ultrafiltration membranes be soaked in soak time in the aqueous phase solution for 1~ 60min, preferably 20~40min；The time of the reaction is 1~60min, preferably 20~40min.
In one of the embodiments, the temperature of the drying is 20~40 DEG C.Drying time is preferably 20~40min.
In one of the embodiments, the organic solvent is n-hexane, hexamethylene, dodecane, heptane, octane, diformazan One kind in yl acetamide, N,N-dimethylformamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), trifluorotrichloroethane or two The mixture of the kind above.It is preferred that n-hexane and hexamethylene.
In one of the embodiments, the ultrafiltration membranes be polyether sulfone, it is sulfonated polyether sulfone, polysulfones, Kynoar, poly- Any one in acrylonitrile, polyvinyl chloride, polypropylene or polyimides.It is preferred that polysulfones.
In the present invention, the binding agent, surfactant and alkaline agent may be selected from binding agent commonly used in the art, preferably viscous Knot agent is sodium cellulose glycolate, and surfactant is lauryl sodium sulfate, alkaline agent be sodium hydroxide (potassium), organic base (such as Triethylamine) etc..
In the present invention, the composite nanometer filtering film can be tubular membrane, capillary-pipe film, spiral wound membrane, Flat Membrane or hollow fibre Tie up film.
The present invention also provides composite nanometer filtering film made from the preparation method of described composite nanometer filtering film.
The principle and advantage of the present invention is as follows：
The preparation method of the composite nanometer filtering film of the present invention, by the way that ultrafiltration membranes are soaked in including described in polyalcohol successively Aqueous phase solution and the organic phase solution including isocyanate-monomer, and promote two kinds of monomers to carry out interfacial polymerization, to realize super Filter composite polyurethane on basement membrane.
Wherein, by rationally controlling the concentration of each component in aqueous phase solution and organic phase solution, to promote the progress of polymerization And obtain and be adapted to rate of polymerization, while coordinated using polyalcohol of the molecular weight no more than 2000Da with isocyanate-monomer, The suitable polyurethane of compound molecule amount on ultrafiltration membranes, preferable molecule rejection and permeation flux can be obtained, and this is poly- Urethane contains substantial amounts of hydroxyl, and hydrophilicity is good.In addition, film is heat-treated at a certain temperature after completing to polymerize, to receiving Filter membrane active layer has batter effect, is further ensured that the rejection of composite nanometer filtering film.
Thus, composite nanometer filtering film made from above-mentioned preparation method has higher rejection and permeation flux.Using interface The mode of polymerization, operation is simplified compared with prior art, technique is easily controllable, can also overcome the method for modifying such as coating to cause activity Layer caliper uniformity it is bad influence membrane separating property the defects of.In addition, polyurethane has good biocompatibility and nonhazardous, It is good biomaterial, therefore the composite nanometer filtering film of the present invention has good separating property to macromolecular PEG.
Compared with prior art, the invention has the advantages that：
1st, the preparation method of composite nanometer filtering film of the invention, easy to operate, modified condition is gentle, and equipment requirement is low；
2nd, NF membrane made from the preparation method has higher rejection and permeation flux, and hydrophilicity is good, to big Molecule PEG has good separating property.Meanwhile the film layer of composite polyurethane has good mechanical performance, be advantageous to improve Film service life.
3rd, the preparation method covers the layer of polyurethane of one layer of lower molecular weight on the surface of ultrafiltration membranes, to ultrafiltration membranes knot Structure and performance are without destruction, and preparation technology is simple, energy-conserving and environment-protective, can build that stability is strong, the composite nanometer filtering film of form of diverse, fit For industrialized production and application.
Embodiment
Composite nanometer filtering film of the present invention and preparation method thereof is described in further detail below in conjunction with specific embodiment.
Composite nanometer filtering film prepared by the embodiment of the present invention is used to separate macromolecular organic polymer, rejection (R) and water Permeation flux (F) is two important parameters of evaluating combined NF membrane, shown in R calculation formula such as formula (1).
Wherein, R is rejection, cfIt is concentration of raw material, cpIt is penetrating fluid concentration.
Shown in F calculation formula such as formula (2).
Wherein, F is permeation flux (Lm-2·h-1), V is the volume (L) of penetrating fluid, and S is the effective area (m of film2), t It is time of penetration (h).
Separation macromolecular organic polymer concentration uses AAS, for the weak solution of organic polymer, its extinction Degree meets langbobier law.Its standard curve is first measured, concentration of raw material c is calculated further according to calibration curve equationfWith Penetrating fluid concentration cp, substitute into formula (1) and calculated.All films carry out 3 tests, and 3 test results are averaged.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
(1) PEG 1000 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g hexamethylene diisocyanates are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in insulating box after 60 DEG C of drying, rinsed with water dry Only, pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 1.
Comparative example 1：
(1) PEG 1000 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g hexamethylene diisocyanates are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is directly used into water rinsed clean, pre-molding, then carry out film Performance test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG 1000, PEG 6000, PEG 20000 rejection (R) and permeation flux (F), acquired results are shown in Table 1.
Comparative example 2
(1) PEG 1000 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g hexamethylene diisocyanates are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in insulating box after 80 DEG C of drying, rinsed with water dry Only, pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 1.
Table 1
It can be seen from the result of table 1, the heat treatment of proper temperature can further improve the rejection of film, obtain rejection more High composite nanometer filtering film.
Embodiment 2：
(1) PEG200 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g hexamethylene diisocyanates are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in insulating box after 60 DEG C of drying, rinsed with water dry Only, pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 2.
Embodiment 3：
(1) PEG600 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g hexamethylene diisocyanates are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in insulating box after 60 DEG C of drying, rinsed with water dry Only, pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 2.
Comparative example 3：
(1) PEG2000 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g hexamethylene diisocyanates are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in insulating box after 60 DEG C of drying, rinsed with water dry Only, pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 2.
Table 2
It can be seen from the result of table 2, use composite nanometer filtering film of the molecular weight for 2000Da polyalcohol, permeation flux (F) and Rejection (R) declines notable., can be with by adjusting the polyol molecule in aqueous phase solution in addition, in the range of certain molecular weight The composite nanometer filtering film of PSPP is obtained, the aperture of polyurethane interface polymeric modification composite nanometer filtering film is adjustable, prepares Journey is controllable.
Embodiment 4：
(1) PEG1000 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g toluene di-isocyanate(TDI)s are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in insulating box after 60 DEG C of drying, rinsed with water dry Only, pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 3.
Embodiment 5：
(1) PEG1000 (0.125g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 1.0g diphenyl methane -4 are measured, 4 '-diisocyanate is dissolved in 50ml hexane solutions, is obtained organic Phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in insulating box after 60 DEG C of drying, rinsed with water dry Only, pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 3.
Table 3
It can be seen from the result of table 3, interface polymerization reaction is carried out using different isocyanates, can be prepared with preferable The polyurethane-modified composite nanometer filtering film of cutoff performance.
Embodiment 6
(1) PEG 1000 (2.5g), sodium cellulose glycolate (0.125g), dodecyl sulphate acid sodium are weighed respectively (0.01g) and sodium hydroxide (0.05g) are added in 50ml deionized waters, and heating stirring is allowed to be completely dissolved, and is cooled to room Temperature, obtain aqueous phase solution；
(2) polysulfones ultrafiltration membranes are placed in aqueous phase solution and soak 30min；
(3) unnecessary aqueous phase solution is removed, then the film is placed in 30 DEG C of drying (about 30min) in insulating box；
(4) 2.5g hexamethylene diisocyanates are measured to be dissolved in 50ml hexane solutions, obtain organic phase solution；
(5) film after drying is placed in organic phase solution and soaks 30min；
(6) unnecessary organic phase solution is removed, reacted film is placed in baking oven after 60 DEG C of drying, with water rinsed clean, Pre-molding, then carry out film properties test.
Prepared film 0.6MPa pre-moldings, under 0.4MPa, room temperature condition, the film is tested respectively to 1000ppm PEG1000, PEG6000, PEG20000 rejection (R) and permeation flux (F), acquired results are shown in Table 4.
Table 4
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of preparation method of composite nanometer filtering film, it is characterised in that comprise the following steps：
Polyalcohol, adhesive, surfactant and alkaline agent are added into water, stirring and dissolving, obtain aqueous phase solution；Wherein, it is described The mass concentration of polyalcohol is 0.1~5%, and the mass concentration of binding agent is 0.1~5%, and the mass concentration of surfactant is 0.01~1.5%, the mass concentration of alkaline agent is 0.01~1.5%；The molecular weight of the polyalcohol is less than 2000Da；
Isocyanate-monomer is added into organic solvent, stirring and dissolving, obtains organic phase solution；Wherein, the isocyanates list The mass concentration of body is 1~5%；
Ultrafiltration membranes are soaked in the aqueous phase solution, then takes out, dry；
Ultrafiltration membranes after drying are soaked in the organic phase solution and reacted, obtain NF membrane preform；
The NF membrane preform is heat-treated in 50~70 DEG C；Produce the composite nanometer filtering film.
2. the preparation method of composite nanometer filtering film according to claim 1, it is characterised in that the molecular weight of the polyalcohol is 200~1000Da.
3. the preparation method of composite nanometer filtering film according to claim 2, it is characterised in that the polyalcohol be ethylene glycol, Propane diols, diglycol, triethylene-glycol, neopentyl glycol, glycerine, glycerine, trimethylolethane, trihydroxy methyl third Mixture more than one or both of alkane, ethylenediamine pentaerythrite, pentaerythrite, xylitol, sorbierite or polyethylene glycol.
4. the preparation method of composite nanometer filtering film according to claim 1, it is characterised in that the temperature of the heat treatment is 55 ~65 DEG C.
5. the preparation method of composite nanometer filtering film according to claim 1, it is characterised in that the isocyanate-monomer is six Methylene diisocyanate, 4,4- dicyclohexyl methyl hydride diisocyanates, trimethylhexane diisocyanate, durol diformazan In phenylene diisocyanate, IPDI, diphenyl methane -4,4 '-diisocyanate, toluene di-isocyanate(TDI) One or more kinds of mixtures.
6. the preparation method of the composite nanometer filtering film according to claim any one of 1-5, it is characterised in that soak ultrafiltration membranes It is 1~60min to steep the soak time in the aqueous phase solution；The time of the reaction is 1~60min.
7. the preparation method of the composite nanometer filtering film according to claim any one of 1-5, it is characterised in that the temperature of the drying Spend for 20~40 DEG C.
8. the preparation method of the composite nanometer filtering film according to claim any one of 1-5, it is characterised in that the organic solvent For n-hexane, hexamethylene, dodecane, heptane, octane, dimethyl acetamide, N,N-dimethylformamide, N- crassitudes Mixture more than one or both of ketone, dimethyl sulfoxide (DMSO), trifluorotrichloroethane.
9. the preparation method of the composite nanometer filtering film according to claim any one of 1-5, it is characterised in that the ultrafiltration membranes Material be polyether sulfone, sulfonated polyether sulfone, polysulfones, Kynoar, polyacrylonitrile, polyvinyl chloride, polypropylene or polyimides In any one.
10. composite nanometer filtering film made from the preparation method of the composite nanometer filtering film described in claim any one of 1-9.
CN201710807196.9A 2017-08-04 2017-09-08 Composite nanometer filtering film and preparation method thereof Pending CN107469639A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108905649A (en) * 2018-06-19 2018-11-30 杭州安诺过滤器材有限公司 A kind of preparation method of hydrophilic polyfluortetraethylemicroporous microfiltration membranes
CN109758929A (en) * 2019-01-23 2019-05-17 深圳清华大学研究院 Divide salt nanofiltration membrane and preparation method thereof
CN113509840A (en) * 2020-04-09 2021-10-19 中国石油化工股份有限公司 Composite nanofiltration membrane and preparation method and application thereof
CN113876817A (en) * 2020-07-03 2022-01-04 广州中国科学院先进技术研究所 Oil-soluble plant extract emulsion
CN116747715A (en) * 2023-04-14 2023-09-15 浙江大学 High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1973971A (en) * 2006-12-01 2007-06-06 北京工业大学 Prepn process of soiling resistant modified PVA film
CN103406027A (en) * 2013-06-18 2013-11-27 天津工业大学 Hydrophilic composite film containing ether groups in surface layer
CN104474910A (en) * 2014-12-11 2015-04-01 杭州水处理技术研究开发中心有限公司 Preparation method of organic-inorganic composite separation membrane
CN105797602A (en) * 2014-12-30 2016-07-27 普瑞奇科技（北京）股份有限公司 Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1973971A (en) * 2006-12-01 2007-06-06 北京工业大学 Prepn process of soiling resistant modified PVA film
CN103406027A (en) * 2013-06-18 2013-11-27 天津工业大学 Hydrophilic composite film containing ether groups in surface layer
CN104474910A (en) * 2014-12-11 2015-04-01 杭州水处理技术研究开发中心有限公司 Preparation method of organic-inorganic composite separation membrane
CN105797602A (en) * 2014-12-30 2016-07-27 普瑞奇科技（北京）股份有限公司 Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王永康等编著: "《纳米材料科学与技术》", 31 March 2002, 浙江大学出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108905649A (en) * 2018-06-19 2018-11-30 杭州安诺过滤器材有限公司 A kind of preparation method of hydrophilic polyfluortetraethylemicroporous microfiltration membranes
CN109758929A (en) * 2019-01-23 2019-05-17 深圳清华大学研究院 Divide salt nanofiltration membrane and preparation method thereof
CN113509840A (en) * 2020-04-09 2021-10-19 中国石油化工股份有限公司 Composite nanofiltration membrane and preparation method and application thereof
CN113509840B (en) * 2020-04-09 2023-01-03 中国石油化工股份有限公司 Composite nanofiltration membrane and preparation method and application thereof
CN113876817A (en) * 2020-07-03 2022-01-04 广州中国科学院先进技术研究所 Oil-soluble plant extract emulsion
CN116747715A (en) * 2023-04-14 2023-09-15 浙江大学 High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof
CN116747715B (en) * 2023-04-14 2024-01-23 浙江大学 High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof

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Application publication date: 20171215