CN110180409A - A kind of preparation method of the adjustable blended ultrafiltration membrane in aperture - Google Patents
A kind of preparation method of the adjustable blended ultrafiltration membrane in aperture Download PDFInfo
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- CN110180409A CN110180409A CN201910409905.7A CN201910409905A CN110180409A CN 110180409 A CN110180409 A CN 110180409A CN 201910409905 A CN201910409905 A CN 201910409905A CN 110180409 A CN110180409 A CN 110180409A
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- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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Abstract
The present invention provides a kind of preparation methods of the adjustable blended ultrafiltration membrane in aperture, it include: that the mixture of 65~82 mass parts solvents, 0~10 mass parts polyethylene glycol, 10~20 mass parts polyether sulfones and 0~10 mass parts polymer is added in container, a period of time is stirred with certain mixing speed under solution temperature, dissolve polyether sulfone and polymer, then the standing and defoaming under solution temperature, is made casting solution；On a support by casting solution coating, primary membrane is made；Primary membrane is immersed in coagulating bath, submergence solidification is carried out；Residual solvent is removed, dries later, obtains blended ultrafiltration membrane.Blended ultrafiltration membrane of the invention has high-throughput, high selection permeability and excellent mechanical property, can be applied in the purification and processing of water resource.
Description
Technical field
The present invention relates to technical field of membrane separation, more particularly, to a kind of preparation of the adjustable blended ultrafiltration membrane in aperture
Method.
Background technique
The membrane separation technique advanced technology emerging as 21 century, because its with it is easy to operate, without phase-change, without chemistry become
The advantages of conventional separation methods such as change, energy conservation, treatment effeciency height do not have, membrane separation technique are separated in gas-liquid and liquid liquid etc.
Field is widely used.Wherein ultrafiltration is a kind of important membrane separating process；The average pore size of ultrafiltration membrane is 0.01 micro-
Rice~0.1 micron, ultra-filtration process are to apply the power of 0.1-1Mpa or so according to aperture screening mechanism in film side, penetrate water
Film is mainly used to filter the solution containing fine particle or bigger molecule.Suspended material, the colloid in water can be effectively removed
Grain, microorganism, bacterial virus and some macromolecular dissolved organic matters, are widely used in drinking water treatment, have wide
Prospect.
In numerous polymeric film materials, polyether sulfone has good inoxidizability, thermal stability and excellent film forming
Property；Polyimides as a kind of aroma type polymer, unique structure make it have pressure-resistant high temperature resistant and chemicals-resistant corrosion
Performance has good resistance to toluene, hydrocarbon, pure and mild ketone etc., has been widely used in the preparation of ultrafiltration membrane material.
Life science, bioengineering, pharmaceuticals industry and food industry development, provide more attractive for ultrafiltration membrane
Application space, while higher requirements are also raised to ultrafiltration membrane material: (1) it is high-throughput；(2) have accurate adjustable aperture big
Small and relatively narrow pore-size distribution.Theoretically, the macroscopic property for being film-made liquid system determines finally at membrane structure and hole
Rate, solvent, non-solvent phase counterdiffusion dynamic process determine film pore size and pore-size distribution.
Summary of the invention
The present invention provides a kind of preparation method of adjustable interpenetrating networks bicontinuous structure blended ultrafiltration membrane in aperture, this method
It is simple and easy, aperture controllable, structure-controllable, the fluorine with high-throughput, highly selective and excellent mechanical property can be obtained
Carbon polymer microporous barrier.
The present invention provides a kind of methods for preparing blended ultrafiltration membrane, comprising: by 65~82 mass parts solvents, 0~10 matter
The mixture of amount part polyethylene glycol, 10~20 mass parts polyether sulfones and 0~10 mass parts polymer is added in container, is being dissolved
At a temperature of a period of time stirred with certain mixing speed, dissolve the polyether sulfone and the polymer, then in the dissolution
At a temperature of standing and defoaming, casting solution is made；On a support by casting solution coating, primary membrane is made；By the primary membrane
It is immersed in coagulating bath, carries out submergence solidification；Residual solvent is removed, dries later, obtains the blended ultrafiltration membrane.
In the above-mentioned methods, wherein the solvent includes dimethylformamide, dimethyl acetamide, N- crassitude
One of ketone, dimethyl sulfoxide, butyl acetate, butyrolactone are a variety of.
In the above-mentioned methods, wherein the polymer includes one of polyamide, polyimides and its derivative or more
Kind.
In the above-mentioned methods, wherein in the casting solution, the copolymer that is formed by the polyether sulfone and the polymer
Mass percentage be 16%~30%.
In the above-mentioned methods, wherein in the casting solution, the mass percentage of the solvent is 70%~82%.
In the above-mentioned methods, wherein the temperature of the coagulating bath is 25~80 DEG C.
In the above-mentioned methods, wherein the coagulating bath is the mixed solution of ethyl alcohol and water, and the ethyl alcohol is molten in the mixing
Mass percentage in liquid is 0~60%.
In the above-mentioned methods, wherein the solution temperature be 30 DEG C~65 DEG C, the mixing speed be 100 revs/min~
600 revs/min, the time of stirring is 8 hours~24 hours.
In the above-mentioned methods, wherein be immersed in the solidification after the primary membrane is made and by the primary membrane
Before in bath, controlling the aerial evaporation time of the primary membrane is 0~2h.
The present invention induces the method mutually separated using non-solvent, and it is double can to prepare a series of controllable interpenetrating networks in apertures
The section of the blended ultrafiltration membrane of continuous pore structure, the ultrafiltration membrane is uniform interpenetrating networks co-continuous pore structure, and passes through tune
Preparation condition is controlled, it is available with different pore size and with the ultrafiltration membrane of uniform interpenetrating networks co-continuous pore structure.This
The ultrafiltration membrane of invention has high-throughput, high selection permeability and excellent mechanical property, purification and place applied to water resource
In reason, it can be used for retaining the material of different molecular weight.
Detailed description of the invention
Fig. 1 is the cross section structure scanning electron microscope (SEM) photograph of blended ultrafiltration membrane prepared by embodiment 1.
Fig. 2 is the cross section structure scanning electron microscope (SEM) photograph of blended ultrafiltration membrane prepared by embodiment 5.
Fig. 3 is the cross section structure scanning electron microscope (SEM) photograph of blended ultrafiltration membrane prepared by embodiment 10.
Fig. 4 is blended ultrafiltration membrane pore-size distribution histogram prepared by embodiment 1.
Fig. 5 is blended ultrafiltration membrane pore-size distribution histogram prepared by embodiment 5.
Fig. 6 is blended ultrafiltration membrane pore-size distribution histogram prepared by embodiment 10.
Specific embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way
The present invention.
The present invention provides a kind of adjustable interpenetrating networks bicontinuous structure blended ultrafiltration membrane in aperture, preparation method includes
Following steps:
(1) by 65~82 mass parts solvents, 0~10 mass parts polyethylene glycol and 10~20 mass parts polyether sulfones and 0~
The mixture of 10 mass parts polymer is added in container, in certain solution temperature, certain mixing speed and certain mixing time
It inside dissolves various polymer, then casting solution is made within standing and defoaming 12~24 hours at the same temperature；Solution temperature is 30
DEG C~65 DEG C, mixing speed is 100 revs/min~600 revs/min, and mixing time is 8 hours~24 hours；Wherein, solvent packet
Include dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, butyl acetate, one in butyrolactone
Kind is a variety of, and polymer includes one of polyamide, polyimides and its derivative or a variety of；
(2) primary membrane, evaporation time of the control primary membrane in air is made in casting solution blade coating on a flat support object
For 0~2h, wherein flat support object can be made of any suitable materials such as plastics, metals；
(3) primary membrane is immersed in 0~90 DEG C of coagulating bath, carries out the submergence solidification of 24~48h；The coagulating bath
It is the mixed solution of ethyl alcohol and pure water, wherein mass percentage of the ethyl alcohol in mixed solution is 0%~60%；
(4) it is dried after removing residual solvent, obtains the adjustable interpenetrating networks bicontinuous structure blended ultrafiltration membrane in aperture.
It is illustrated below with reference to specific embodiment, so that those skilled in the art more fully understand the present invention.Flux
And retention test unification is carried out with 8010 ultrafiltration apparatus of Mi Libo Amicon stirring-type, the effective area of measuring device is
4.1cm2, test before water flux that precompressed 30min stablizes membrane flux under 0.15Mpa pressure, after survey it under 0.1Mpa pressure again
Water flux.Cutoff performance is evaluated with molecular cut off (MWCO:molecular weight cutoff).Film is to being trapped object
When the rejection of matter is greater than 90%, the cutoff performance of film, referred to as the retention molecule of film are just indicated with the molecular weight for being trapped substance
Amount.
Embodiment 1
By 76 mass parts butyrolactones, 8 mass parts polyethylene glycol and 12 mass parts polyether sulfones and 4 mass parts polyimides
Mixture be added in container, constant solution temperature, constant agitation speed keep various polymer molten in the constant agitation time
Solution, is then made casting solution in standing and defoaming 24 hours at the same temperature；Solution temperature is 60 DEG C, and mixing speed is 200 revs/min
Clock, mixing time are 12 hours；Primary membrane is made on a flat support object in casting solution blade coating, controls it in the evaporation of air
Time is 0min；Being immersed into temperature afterwards is in 60 DEG C of deionized water coagulating bath, is placed in film after film Automatic-falling clean
For 24 hours to be dried after the remaining solvent of removing in deionized water.Up to interpenetrating interpenetrating networks bicontinuous structure polyether sulfone/polyimides
Blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 688L/m after tested2H, molecular cut off 100KDa.
Embodiment 2
By 76 mass parts butyrolactones, 8 mass parts polyethylene glycol and 12 mass parts polyether sulfones and 4 mass parts polyimides
Mixture be added in container, constant solution temperature, constant agitation speed keep various polymer molten in the constant agitation time
Solution, is then made casting solution in standing and defoaming 24 hours at the same temperature；Solution temperature is 60 DEG C, and mixing speed is 200 revs/min
Clock, mixing time are 12 hours；Primary membrane is made on a flat support object in casting solution blade coating, controls it in the evaporation of air
Time is 0min；Being immersed into temperature afterwards is in 80 DEG C of deionized water coagulating bath, is placed in film after film Automatic-falling clean
For 24 hours to be dried after the remaining solvent of removing in deionized water.Up to interpenetrating interpenetrating networks bicontinuous structure polyether sulfone/polyimides
Blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 127L/m after tested2H, molecular cut off 43KDa.
Embodiment 3
By 76 mass parts butyrolactones, 8 mass parts polyethylene glycol and 12 mass parts polyether sulfones and 4 mass parts polyimides
Mixture be added in container, in constant solution temperature, constant agitation speed, keep various polymer molten in the constant agitation time
Solution, is then made casting solution in standing and defoaming 24 hours at the same temperature；Solution temperature is 60 DEG C, and mixing speed is 200 revs/min
Clock, mixing time are 12 hours；Primary membrane is made on a flat support object in casting solution blade coating, controls it in the evaporation of air
Time is 0min；It is immersed into the ethanol water coagulating bath that the mass fraction that temperature is 25 DEG C is 15%, is taken off automatically to film afterwards
Fall behind and is dried after film to be placed in in clean deionized water the solvent to remove remnants for 24 hours.Up to interpenetrating interpenetrating networks co-continuous
Structural polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 90L/m after tested2H, molecular cut off 22KDa.
Embodiment 4
By 76 mass parts butyrolactones, 8 mass parts polyethylene glycol and 12 mass parts polyether sulfones and 4 mass parts polyimides
Mixture be added in container, in constant solution temperature, constant agitation speed, keep various polymer molten in the constant agitation time
Solution, is then made casting solution in standing and defoaming 24 hours at the same temperature；Solution temperature is 60 DEG C, and mixing speed is 200 revs/min
Clock, mixing time are 12 hours；Primary membrane is made on a flat support object in casting solution blade coating, controls it in the evaporation of air
Time is 0min；It is immersed into the ethanol water coagulating bath that the mass fraction that temperature is 25 DEG C is 50%, is taken off automatically to film afterwards
Fall behind and is dried after film to be placed in in clean deionized water the solvent to remove remnants for 24 hours.Up to interpenetrating interpenetrating networks co-continuous
Structural polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 65L/m after tested2H, molecular cut off 10KDa.
Embodiment 5
By 74 mass parts butyrolactones, 8 mass parts polyethylene glycol and 14 mass parts polyether sulfones and 4 mass parts polyimides
Mixture be added in container, constant solution temperature, constant agitation speed keep various polymer molten in the constant agitation time
Solution, is then made casting solution in standing and defoaming 24 hours at the same temperature；The solution temperature is 60 DEG C, mixing speed 200
Rev/min, mixing time is 12 hours；Primary membrane is made on a flat support object in casting solution blade coating, controls it in air
Evaporation time be 0min；It is immersed into the deionized water coagulating bath that temperature is 60 DEG C, is placed in film afterwards after film Automatic-falling
For 24 hours to be dried after the remaining solvent of removing in clean deionized water.Up to interpenetrating interpenetrating networks bicontinuous structure polyether sulfone/poly-
Acid imide blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 108L/m after tested2H, molecular cut off 57KDa.
Embodiment 6
By 64 mass parts butyrolactones, 10 mass parts dimethylformamides, 8 mass parts polyethylene glycol and 14 mass parts are poly-
The mixture of ether sulfone and 4 mass parts polyimides is added in container, in constant solution temperature, constant agitation speed, constant is stirred
Mixing dissolves various polymer in the time, then casting solution is made within standing and defoaming 24 hours at the same temperature；Solution temperature is
60 DEG C, mixing speed is 200 revs/min, and mixing time is 12 hours；Casting solution blade coating is made just on a flat support object
Filming, controlling it in the evaporation time of air is 0min；It is immersed into the deionized water coagulating bath that temperature is 25 DEG C afterwards, certainly to film
It moves and is dried after film to be placed in in clean deionized water the solvent to remove remnants for 24 hours after falling off.It is double up to interpenetrating interpenetrating networks
Continuous structure polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 160L/m after tested2H, molecular cut off 67KDa.
Embodiment 7
By 64 mass parts butyrolactones, 10 mass parts dimethylformamides, 8 mass parts polyethylene glycol and 14 mass parts are poly-
The mixture of ether sulfone and 4 mass parts polyimides is added in container, in constant solution temperature, constant agitation speed, constant is stirred
Mixing dissolves various polymer in the time, then casting solution is made within standing and defoaming 24 hours at the same temperature；Solution temperature is
60 DEG C, mixing speed is 200 revs/min, and mixing time is 12 hours；Casting solution blade coating is made just on a flat support object
Filming, controlling it in the evaporation time of air is 0min；It is immersed into the deionized water coagulating bath that temperature is 40 DEG C afterwards, certainly to film
It moves and is dried after film to be placed in in clean deionized water the solvent to remove remnants for 24 hours after falling off.It is double up to interpenetrating interpenetrating networks
Continuous structure polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 108L/m after tested2H, molecular cut off 67KDa.
Embodiment 8
64 mass parts butyrolactones, 10 mass parts dimethylformamides, 8 mass parts polyethylene glycol and 14 mass parts are gathered
The mixture of ether sulfone and 4 mass parts polyimides is added in container, in constant solution temperature, constant agitation speed, constant is stirred
Mixing dissolves various polymer in the time, then casting solution is made within standing and defoaming 24 hours at the same temperature；The dissolution temperature
Degree is 60 DEG C, and mixing speed is 200 revs/min, and mixing time is 12 hours；Casting solution blade coating is made on a flat support object
At primary membrane, controlling it in the evaporation time of air is 0min；It is immersed into the second that the mass fraction that temperature is 25 DEG C is 15% afterwards
In alcohol solution coagulating bath, film is placed in after film Automatic-falling in clean deionized water for 24 hours to remove remaining solvent after
It dries.Up to interpenetrating interpenetrating networks bicontinuous structure polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 54L/m after tested2H, molecular cut off 4KDa.
Embodiment 9
It will be by 64 mass parts butyrolactones, 10 mass parts dimethylformamides, 8 mass parts polyethylene glycol and 14 mass parts
The mixture of polyether sulfone and 4 mass parts polyimides is added in container, in constant solution temperature, constant agitation speed, constant
It dissolves various polymer in mixing time, then casting solution is made within standing and defoaming 24 hours at the same temperature；Solution temperature
It is 60 DEG C, mixing speed is 200 revs/min, and mixing time is 12 hours；Casting solution blade coating is made on a flat support object
Primary membrane, controlling it in the evaporation time of air is 0min；It is immersed into the ethyl alcohol that the mass fraction that temperature is 25 DEG C is 50% afterwards
In aqueous coagulation bath, film is placed in clean deionized water for 24 hours to dry in the air after the remaining solvent of removing after film Automatic-falling
It is dry.Up to interpenetrating interpenetrating networks bicontinuous structure polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 40L/m after tested2H, molecular cut off 2KDa.
Embodiment 10
By 52 mass parts butyrolactones, 20 mass parts dimethylformamides, 8 mass parts polyethylene glycol and 16 mass parts are poly-
The mixture of ether sulfone and 4 mass parts polyimides is added in container, in constant solution temperature, constant agitation speed, constant is stirred
Mixing dissolves various polymer in the time, then casting solution is made within standing and defoaming 24 hours at the same temperature；Solution temperature is
60 DEG C, mixing speed is 200 revs/min, and mixing time is 12 hours；Casting solution blade coating is made just on a flat support object
Filming, controlling it in the evaporation time of air is 0min；It is immersed into the deionized water coagulating bath that temperature is 60 DEG C afterwards, certainly to film
It moves and is dried after film to be placed in in clean deionized water the solvent to remove remnants for 24 hours after falling off.It is double up to interpenetrating interpenetrating networks
Continuous structure polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 160L/m after tested2H, molecular cut off 43KDa.
Embodiment 11
By 82 mass parts dimethylformamides, 2 mass parts polyethylene glycol and 10 mass parts polyether sulfones and 6 mass parts polyamides
The mixture of imines is added in container, in constant solution temperature, constant agitation speed, makes various polymerizations in the constant agitation time
Object dissolution, is then made casting solution in standing and defoaming 24 hours at the same temperature；The solution temperature is 60 DEG C, and mixing speed is
200 revs/min, mixing time is 12 hours；Primary membrane is made on a flat support object in casting solution blade coating, controls it in sky
The evaporation time of gas is 0min；It is immersed into the 15% ethanol water coagulating bath that temperature is 25 DEG C afterwards, after film Automatic-falling
It is dried after film to be placed in in clean deionized water the solvent to remove remnants for 24 hours.Up to interpenetrating interpenetrating networks bicontinuous structure
Polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 700L/m after tested2H, molecular cut off 120KDa.
Embodiment 12
65 mass parts dimethyl acetamides, 10 mass parts polyethylene glycol and 15 mass parts polyether sulfones and 10 mass parts are gathered
Imido mixture is added in container, in constant solution temperature, constant agitation speed, makes various gather in the constant agitation time
Object dissolution is closed, then casting solution is made within standing and defoaming 24 hours at the same temperature；The solution temperature is 60 DEG C, mixing speed
It is 200 revs/min, mixing time is 12 hours；On a flat support object primary membrane is made in casting solution blade coating, control its
The evaporation time of air is 0min；It is immersed into the 50% ethanol water coagulating bath that temperature is 25 DEG C afterwards, to film Automatic-falling
It is dried after film to be placed in in clean deionized water the solvent to remove remnants for 24 hours afterwards.Up to interpenetrating interpenetrating networks co-continuous knot
Structure polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 90L/m after tested2H, molecular cut off 67KDa.
Embodiment 13
The mixture of 72 mass parts N-Methyl pyrrolidones, 20 mass parts polyether sulfones and 8 mass parts polyimides is added
Into container, dissolve polymer in the time in constant solution temperature, constant agitation speed, constant agitation, then in Xiang Tongwen
It spends lower standing and defoaming and casting solution is made in 24 hours；Solution temperature is 60 DEG C, and mixing speed is 200 revs/min, mixing time 12
Hour；Primary membrane is made on a flat support object in casting solution blade coating, controlling it in the evaporation time of air is 0min；After soak
Being less than temperature is in 60 DEG C of deionized water coagulating bath, film is placed in after film Automatic-falling in clean deionized water for 24 hours with
It is dried after removing remaining solvent.Up to interpenetrating interpenetrating networks bicontinuous structure polyether sulfone/polyimides blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 68L/m after tested2H, molecular cut off 43KDa.
Embodiment 14
72 mass parts dimethyl sulfoxides, 5 mass parts polyethylene glycol and 16 mass parts polyether sulfones and 4 mass parts polyamides are sub-
The mixture of amine is added in container, in constant solution temperature, constant agitation speed, keeps polymer molten in the constant agitation time
Solution, is then made casting solution in standing and defoaming 24 hours at the same temperature；Solution temperature is 60 DEG C, and mixing speed is 200 revs/min
Clock, mixing time are 12 hours；Primary membrane is made on a flat support object in casting solution blade coating, controls it in the evaporation of air
Time is 120min；It is immersed into the deionized water coagulating bath that temperature is 60 DEG C, is placed in film completely afterwards after film Automatic-falling
Deionized water in for 24 hours to dry after removing remaining solvent.It is sub- up to interpenetrating interpenetrating networks bicontinuous structure polyether sulfone/polyamides
Amine blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 150L/m after tested2H, molecular cut off 67KDa.
Embodiment 15
By 50 mass parts butyrolactones, 20 mass parts N-Methyl pyrrolidones, 10 mass parts polyethylene glycol and 16 mass
The mixture of part polyether sulfone and 4 mass parts polyamide is added in container, in constant solution temperature, constant agitation speed, constant
Polymer is dissolved in mixing time, then casting solution is made within standing and defoaming 24 hours at the same temperature；Solution temperature is 60
DEG C, mixing speed is 200 revs/min, and mixing time is 12 hours；Casting solution blade coating is made on a flat support object nascent
Film, controlling it in the evaporation time of air is 0min；It is immersed into the deionized water coagulating bath that temperature is 60 DEG C afterwards, it is automatic to film
Film is placed in clean deionized water for 24 hours to dry after the remaining solvent of removing after falling off.Up to interpenetrating interpenetrating networks doubly-linked
Continuous structural polyether sulfone/polyamide blended ultrafiltration membrane.
This blended ultrafiltration membrane water flux at 0.1MPa is 135L/m after tested2H, molecular cut off 67KDa.
It will be understood by those skilled in the art that above embodiments are only exemplary embodiments, without departing substantially from spirit of the invention
In the case where range, a variety of variations can be carried out, replaced and changed.
Claims (9)
1. a kind of method for preparing blended ultrafiltration membrane, comprising:
65~82 mass parts solvents, 0~10 mass parts polyethylene glycol, 10~20 mass parts polyether sulfones and 0~10 mass parts are gathered
The mixture for closing object is added in container, is stirred a period of time under solution temperature with certain mixing speed, is made the polyether sulfone
It is dissolved with the polymer, then the standing and defoaming under the solution temperature, is made casting solution；
On a support by casting solution coating, primary membrane is made；
The primary membrane is immersed in coagulating bath, submergence solidification is carried out；
Residual solvent is removed, dries later, obtains the blended ultrafiltration membrane.
2. according to the method described in claim 1, wherein, the solvent includes dimethylformamide, dimethyl acetamide, N- first
One of base pyrrolidones, dimethyl sulfoxide, butyl acetate, butyrolactone are a variety of.
3. according to the method described in claim 1, wherein, the polymer includes in polyamide, polyimides and its derivative
It is one or more.
4. according to the method described in claim 1, wherein, in the casting solution, by the polyether sulfone and the polymer shape
At copolymer mass percentage be 16%~30%.
5. according to the method described in claim 1, wherein, in the casting solution, the mass percentage of the solvent is
70%~82%.
6. according to the method described in claim 1, wherein, the temperature of the coagulating bath is 25~80 DEG C.
7. the ethyl alcohol exists according to the method described in claim 1, wherein, the coagulating bath is the mixed solution of ethyl alcohol and water
Mass percentage in the mixed solution is 0~60%.
8. the mixing speed is 100 according to the method described in claim 1, wherein, the solution temperature is 30 DEG C~65 DEG C
Rev/min~600 revs/min, the time of stirring is 8 hours~24 hours.
9. according to the method described in claim 1, wherein, being immersed in after the primary membrane is made and by the primary membrane
Before in the coagulating bath, controlling the aerial evaporation time of the primary membrane is 0~2h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910409905.7A CN110180409A (en) | 2019-05-16 | 2019-05-16 | A kind of preparation method of the adjustable blended ultrafiltration membrane in aperture |
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| CN201910409905.7A CN110180409A (en) | 2019-05-16 | 2019-05-16 | A kind of preparation method of the adjustable blended ultrafiltration membrane in aperture |
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| CN114405276A (en) * | 2021-12-27 | 2022-04-29 | 浙江易膜新材料科技有限公司 | Preparation method of high-temperature-resistant separation membrane material |
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