CN106621837A - Hydrophilically modified porous membrane containing network crosslinked polymer and preparation method of porous membrane - Google Patents
Hydrophilically modified porous membrane containing network crosslinked polymer and preparation method of porous membrane Download PDFInfo
- Publication number
- CN106621837A CN106621837A CN201611255685.XA CN201611255685A CN106621837A CN 106621837 A CN106621837 A CN 106621837A CN 201611255685 A CN201611255685 A CN 201611255685A CN 106621837 A CN106621837 A CN 106621837A
- Authority
- CN
- China
- Prior art keywords
- solvent
- preparation
- weight
- linked
- cross
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- B01D67/0011—Casting solutions therefor
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a hydrophilically modified porous membrane containing a network crosslinked polymer and a preparation method of the porous membrane. The preparation method comprises steps as follows: preparing a film casting liquid, adding the network crosslinked polymer, preparing the membrane and the like. The hydrophilically modified porous membrane containing the network crosslinked polymer solves the technical problems that the efficiency is low, the process is difficult to control, a waste liquid is difficult to treat, the pore size is reduced, the flux is decreased, the hydrophilia is not obvious in operation effect though the efficiency is high, the process is easy to operate and is improved and the like. Therefore, the preparation method is conducive to industrial application and promotion and has a very good application prospect.
Description
【Technical field】
The invention belongs to water-treatment technology field.More particularly it relates to a kind of hydrophilic modifying network cross-linked thing is more
Pore membrane, further relates to the preparation method of the hydrophilic modifying network cross-linked thing perforated membrane.
【Background technology】
Perforated membrane has sieve effect, belongs to pressure-driven, and its separative efficiency is controlled by the aperture of film and pore-size distribution,
It is widely used in the separation of the industries such as purification of water quality, food, pharmacy, biology special type small molecule.The membrane material of perforated membrane is mainly fibre
Dimension element and its derivative, Merlon, polyvinyl chloride, Kynoar, polysulfones, polyacrylonitrile, polyamide, polysulfonamides, sulphur
Change polysulfones, polyvinyl alcohol, the modified acrylic polymer of interlinkage etc..
The features such as existing perforated membrane requires selectivity, the hydrophily that mechanical strength is big, chemical stability is good, good.For example
Polyvinyl alcohol, modified acrylic polymer, polyamide, polysulfonamides, cellulose and its derivates, polyacrylonitrile etc. are existing hydrophilic
Material, although with good hydrophily, but its bad mechanical property, oxidation resistance is weak, perforated membrane silk short life.For example gather
The existing hydrophobic material such as vinyl chloride, Kynoar, polysulfones, although with mechanical strength it is big, chemical stability is good, selectivity is good
The features such as, but its hydrophobicity is strong, easily by protein, carbohydrate and organic humic acid class Substances Pollution, causes pressure in running
Rise, flux declines, operation energy consumption rises.
Hydrophobic membrane hydrophilic modification has become the focus of current porous membrane modifying, for example, make it have hydrophilic material and change
The method such as property, hydrophobic membrane surface modification, membrane material sheet be modifies.Make material body that there is hydrophily, development difficulty is big, the cycle
It is long.Hydrophobic membrane surface-modification method, image surface chemical treatment, chemical graft, surface coating etc., are inherently by some hydrophilic groups
Group or monomer are grafted on hydrophobic perforated film surface, these technology (such as plasma modification technology) difficulty are big, high cost, industry
Change is difficult to control to.Membrane material sheet is modifies actually to add some hydroaropic substances when membrane material is prepared, such as polyethylene glycol,
Polyvinylpyrrolidone etc., but hydroaropic substance is easy to be lost in during this kind of membrane material use, effect on driving birds is not good.
Network cross-linked polymers are added to form interpenetrating polymer networks structure in casting solution such that it is able to improve and divide
Subchain compatibility, increases network lattice density, makes phase constitution miniaturization, improves alternate adhesion.
CN 200910076285, CN 201110415045 propose the problem of application network cross-linked structure, but, they
Belong to porous film surface to be modified, this method efficiency is low, and process is difficult to control to, industrial production waste liquid is difficult to the problems such as processing, and
And the problems such as aperture reduces, flux declines, moreover, the hydrophily in During Process of Long-term Operation are being easily caused after surface-crosslinked
Though being improved, operational effect is improved not substantially, or even also deteriorates operational effect.
The present invention is dissolved in network cross-linked polymers in casting solution, and network cross-linked polymers form IPN with hydrophobic components
Polymer network hydrophiling structure, realizes the entanglement between molecule, makes perforated membrane have permanent hydrophilic and solvent resistant characteristic.
The pore-size distribution of hydrophilic modifying network cross-linked thing perforated membrane of the present invention, size, film silk flux are easier to control, efficiency high, it is easy to
Operation, is conducive to industrialized production..
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of hydrophilic modifying network cross-linked thing perforated membrane.
It is a further object to provide the preparation method of the hydrophilic modifying network cross-linked thing perforated membrane.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of preparation method of hydrophilic modifying network cross-linked thing perforated membrane.
The step of preparation method, is as follows：
A, prepare casting solution
0.1～30 parts by weight resin, 10～40 weight portion additives are well mixed with 50～80 parts by weight solvent, are obtained
Described casting solution；
Described resin is one or more selected from Kynoar, polyethylene, polypropylene, polysulfones, polyether sulfone or polychlorostyrene
Resin in ethene；
Described additive is one or more additive in the polyvinylpyrrolidone of different molecular weight；
Described solvent is one or more in dimethyl acetamide, dimethylformamide or methyl pyrrolidone
Solvent；
B, addition network cross-linked thing
According to the 0.1～10.0% of the casting solution weight, one or more selected from cross-linked polysulfones, cross-linked
Network cross-linked thing in polyether sulfone, cross-linked polyether ethersulfone, cross-linked polyether-ether-ketone or PVPP adds
In being added to the casting solution that step A is obtained, stir and evenly mix, vacuum defoamation, then using conventional non-solvent gel film-forming method masking,
Obtain described hydrophilic modifying network cross-linked thing perforated membrane.
A preferred embodiment of the invention, the polyvinylpyrrolidone of the different molecular weight be PVPk12,
PVPk15, PVPk17, PVPk25, PVPk30 or PVPk45.
Another kind of preferred embodiment of the invention, according to polyfunctional monomer and polynary acyl chloride monomer mole
Than 1：0.1～10., by one or more in ethylene glycol, glycerine, polyethylene glycol or the m-phenylene diamine (MPD) with cross-linking properties
Polyfunctional monomer and one or more polynary acyl in pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride
Chlorine class monomer, in being added to solvent, two of which total monomer weight compares 1 with the weight of solvent：20～100, it is well mixed, in acid
Property under the conditions of be crosslinked, until cross-linking products are not also precipitated, adopt the isolated product of rotary evaporation method and adding for described
Plus agent.
Another kind of preferred embodiment of the invention, according to the mol ratio of monomeric polyol and acid polynary aldehyde monomer
1：0.1～10, by one or more monomeric polyol and in ethylene glycol, glycerine, polyethylene glycol or polyvinyl alcohol
Plant or various acid polynary aldehyde monomers in glutaraldehyde, butanedial or MDA are added in solvent, two of which monomer
Gross weight compares 1 with the weight of solvent：20～100, it is well mixed, it is crosslinked in acid condition, until cross-linking products also do not have
There is precipitation, adopt the isolated product of rotary evaporation method for described additive.
Another kind of preferred embodiment of the invention, described solvent is one or more selected from dimethylacetamide
Solvent in amine, dimethylformamide or methyl pyrrolidone.
Another kind of preferred embodiment of the invention, described vacuum defoamation is in 30～130 DEG C of temperature and pressure
Deaeration is carried out under conditions of 0.01～0.10MPa, until bubble is removed completely.
Another kind of preferred embodiment of the invention, the weight ratio of the resin, additive and solvent is 5～24：
18～32：56～72.
Another kind of preferred embodiment of the invention, the addition of the network cross-linked thing is the casting solution weight
1.6～7.8%.
The invention further relates to the hydrophilic modifying network cross-linked thing perforated membrane that the preparation method is prepared.
The present invention is described in more detail below.
The present invention relates to a kind of preparation method of hydrophilic modifying network cross-linked thing perforated membrane.
The step of preparation method, is as follows：
A, prepare casting solution
0.1～30 parts by weight resin, 10～40 weight portion additives are well mixed with 50～80 parts by weight solvent, are obtained
Described casting solution；
In the present invention, the Main Function of the resin is the skeleton to form perforated membrane, is played a supporting role.
The resin that the present invention is used is one or more selected from Kynoar, polyethylene, polypropylene, polysulfones, polyether sulfone
Or the resin in polyvinyl chloride；
The resin that the present invention is used all is the product sold in the market.
In the present invention, the Main Function of the additive is, with hydrophily, to play non-solvent effect, induces split-phase.
Described additive is one or more additive in the polyvinylpyrrolidone of different molecular weight；
The polyvinylpyrrolidone of the different molecular weight be PVPk12, PVPk15, PVPk17, PVPk25, PVPk30 or
PVPk45。
The polyvinylpyrrolidone that the present invention is used all is the product sold in the market.
According to the invention, it is further possible to using the additive prepared using following two methods：
First method：According to the mol ratio 1 of polyfunctional monomer and polynary acyl chloride monomer：0.1～10, by a kind of or
It is various in ethylene glycol, glycerine, polyethylene glycol or m-phenylene diamine (MPD) with cross-linking properties polyfunctional monomer with it is a kind of or
Various polynary acyl chloride monomers in pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride, are added to solvent
In, two of which total monomer weight compares 1 with the weight of solvent：0.1～10, it is well mixed, it is crosslinked in acid condition, until handing over
Co-product is not also precipitated, and isolated product is described additive.
The solvent used when the additive is prepared be one or more selected from dimethyl acetamide, dimethylformamide or
Solvent in methyl pyrrolidone.
Described acid condition is pH 1～4；
Second method：According to the mol ratio 1 of monomeric polyol and acid polynary aldehyde monomer：0.1～10, will be a kind of or many
Plant the monomeric polyol in ethylene glycol, glycerine, polyethylene glycol or polyvinyl alcohol and one or more is selected from glutaraldehyde, fourth
Acid polynary aldehyde monomer in dialdehyde or MDA is added in solvent, the mol ratio 1 of two of which total monomer weight and solvent：
0.1～10, it is well mixed, it is crosslinked in acid condition, until cross-linking products are not also precipitated, using rotary evaporation method
Isolated product is described additive.
The solvent used when the additive is prepared be one or more selected from dimethyl acetamide, dimethylformamide or
Solvent in methyl pyrrolidone.
Described acid condition is pH1～4；
When casting solution is prepared, when the amount of additive and solvent is in the scope, if the amount of resin is less than 0.1,
Mechanical strength is low；If the amount of resin is more than 30, water permeability weakens, and water flux is low；Therefore, the amount of resin is 0.1～30
Be it is appropriate, preferably 5～24, more preferably 10～18；
When the amount of resin and solvent is in the scope, if the amount of additive is less than 10, phase separation is not obvious, end
Face structure hole is undeveloped；If the amount of additive is more than 40, casting solution stability is poor, can spinning properties reduction；Therefore, add
Plus the amount of agent be for 10～40 it is rational, preferably 18～32, more preferably 22～28；
When the amount of resin and additive is in the scope, if the amount of solvent is less than 50, resin is difficult to additive
Dissolving；If the amount of solvent is more than 80, casting film fluid viscosity is less, and perforated membrane mechanical performance is poor；Therefore, the amount of solvent is 50
～80 be it is rational, preferably 56～72, more preferably 60～68；
Preferably, the weight ratio of the resin, additive and solvent is 5～24：18～32：56～72.
It is highly preferred that the weight ratio of the resin, additive and solvent is 10～18：22～28：60～68.
B, addition network cross-linked thing
According to the 0.1～10.0% of the casting solution weight, one or more selected from cross-linked polysulfones, cross-linked
Network cross-linked thing in polyether sulfone, cross-linked polyether ethersulfone, cross-linked polyether-ether-ketone or PVPP adds
In being added to the casting solution that step A is obtained, stir and evenly mix, vacuum defoamation, then using conventional non-solvent gel film-forming method masking,
Obtain described hydrophilic modifying network cross-linked thing perforated membrane.
The basic role for adding network cross-linked thing in the casting solution is with good in perforated membrane running
Hydrophily, and be not lost in, while playing non-solvent effect in perforated membrane preparation process, induce split-phase.
The network cross-linked thing that the present invention is used is the network cross-linked thing for using in film applied technical field, and they are all
It is the product sold in the market.
According to the present invention, if the addition of the network cross-linked thing is less than 0.1%, hydrophilic interaction is not obvious；If
The addition of the network cross-linked thing is higher than 10.0%, then dissolubility is poor, and non-solvent effect is also relatively strong, and casting solution is unstable；Cause
This, the addition of the network cross-linked thing be 0.1～10.0% be it is appropriate, preferably 1.6～7.8%, more preferably
2.4～6.8%.
In the present invention, the basic role of vacuum defoamation is to remove the air brought in whipping process, reduces spinning process
In defect.
Described vacuum defoamation is a kind of customary technical operation method in the art.In the present invention, it is described
Vacuum defoamation is to carry out deaeration under conditions of 30～130 DEG C of temperature with 0.01～0.10MPa of pressure, until bubble takes off completely
Remove.The equipment that the present invention is used in vacuum defoamation is the product sold in the market.
The conventional non-solvent gel film-forming method that the present invention is adopted is referring to accompanying drawing 1.Its conventional non-solvent gel film-forming method
It is as follows：
The detailed preparation flow of seperation film is as follows：The preparation casting solution in storage tank 2 is mounted in by the first valve 3, filtration
Spinning head 6 is entered after device 4 and spinning pump 5.Spinning head 6 is generally made up of platinum tantalum alloy material, on spinning head 6 regularly
Arrange the eyelet that some apertures are 0.05～3mm.The casting solution thread extruded from spinneret orifice is entered and is mounted in gel bath 10
In coagulation bath in.The solvent of casting solution thread spreads in coagulation bath, and the precipitating reagent in coagulation bath is to casting solution
Spread in thread, this diffusion is referred to as double diffusion.Casting solution thread is set to reach critical concentration by diffusion, polymer is in coagulating bath
Separate out in liquid and form seperation film.
Separating the operation that includes of film preparation overall process is：(1) preparation of casting solution；(2) by casting solution from spinneret pore pressure
Go out to form thread；(3) stoste thread is frozen into as-spun fibre；(4) as-spun fibre package or directly post-processed.
The invention further relates to the hydrophilic modifying network cross-linked thing perforated membrane that the preparation method is prepared.
The hydrophilic modifying network cross-linked thing perforated membrane of the present invention keeps good hydrophily, hydrophilic in permanent running
The network-like molecular structure of component, the addition of hydrophilic component does not affect normal spinning process：Preparation method of the present invention is simple,
Production cost is suitable, is thus advantageous to large-scale production.
There is efficiency in existing porous film surface hydrophilic modifying field low, process is difficult control, in course of industrialization
Waste liquid is difficult to process, and the technical problems such as aperture reduces, flux declines are easily caused after surface-crosslinked, and in longtime running mistake
Cheng Zhong, though hydrophily is improved, the technical problem such as operational effect is not obvious, the present invention solves these technical problems.
The present invention is that network cross-linked polymers are dissolved in casting solution, efficiency high, and pore-size distribution, size, film silk flux are relatively easy to
Control, process operation easily, is thus advantageous to industrialized production.
[beneficial effect]
The invention has the beneficial effects as follows：The present invention is that network cross-linked polymers are dissolved in casting solution, efficiency high, aperture
Distribution, size, film silk flux are relatively easy to control, and easily, the efficiency for solving prior art presence is low, and process is difficult for process operation
Control, waste liquid is difficult, though aperture reduces, flux declines, hydrophily is improved, the technical problem such as operational effect is not obvious.
Therefore, preparation method of the present invention is conducive to industrial application, with very good application prospect.
【Description of the drawings】
Fig. 1 is conventional non-solvent gel film-forming method process chart；
In figure：
1- agitating devices；2- storage tanks；The valves of 3- first；4- filters；5- measuring pumps；6- spinning heads；7- core flow containers；8-
Second valve；9- spinner flowmeters；10- gel baths；11- guide wire apparatus；12- tanks；13- wrapping wire collection devices；14- nitrogen
Steel cylinder；The valves of 15- the 3rd；16- pressure gauges.
【Specific embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
5 weight portion polyvinylidene fluoride resins, 22 weight portion PVPk15 additives are molten with 68 weight portion dimethyl acetamides
Agent is well mixed, and obtains described casting solution；
B, addition network cross-linked thing
According to the 1.6% of the casting solution weight, cross-linked polysulfones network cross-linked thing is added to the casting that step A is obtained
In film liquid, stir and evenly mix, under conditions of 100 DEG C of temperature with pressure 0.01MPa vacuum defoamation is carried out, then using conventional non-molten
Agent gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Embodiment 2：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
24 weight account polyethylene resins, 28 weight portion PVPk17 additives and 50 weight portion solvent dimethylformamides are mixed
Close uniform, obtain described casting solution；
B, addition network cross-linked thing
According to the 7.8% of the casting solution weight, cross-linked polyether sulfone network cross-linked thing is added to what step A was obtained
In casting solution, stir and evenly mix, under conditions of 30 DEG C of temperature with pressure 0.08MPa vacuum defoamation is carried out, then using conventional non-
Sol gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Embodiment 3：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
By 0.1 parts by weight of polypropylene resin, 10 weight portion PVPk30 additives and 56 weight portion methyl pyrrolidone solvents
It is well mixed, obtains described casting solution；
B, addition network cross-linked thing
According to the 0.1% of the casting solution weight, cross-linked polyether ethersulfone network cross-linked thing is added to step A and is obtained
Casting solution in, stir and evenly mix, vacuum defoamation is carried out under conditions of 130 DEG C of temperature with pressure 0.10MPa, then using routine
Non-solvent gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Embodiment 4：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
30 weight portion polysulfone resins, 40 weight portion PVPk45 additives are mixed with 72 weight portion dimethylacetamide solvents
Uniformly, described casting solution is obtained；
B, addition network cross-linked thing
According to the 2.4% of the casting solution weight, cross-linked polyether-ether-ketone network cross-linked thing is added to step A and is obtained
Casting solution in, stir and evenly mix, vacuum defoamation is carried out under conditions of temperature 50 C and pressure 0.06MPa, then using routine
Non-solvent gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Embodiment 5：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
10 weight portion polyethersulfone resins, the additive of the following preparations of 18 weight portions is molten with 80 weight portion methyl pyrrolidones
Agent is well mixed, and obtains described casting solution；
Addictive preparation method is as follows：According to the mol ratio 1 of polyfunctional monomer and polynary acyl chloride monomer：3, by second two
Alcohol has cross-linking properties polyfunctional monomer and the polynary acyl chloride monomer of pyromellitic trimethylsilyl chloride, is added to methyl pyrrolidone solvent
In, two of which total monomer weight compares 1 with the weight of solvent：90, it is well mixed, it is crosslinked under the acid condition of pH4, until handing over
Co-product is not also precipitated, using the isolated described additive of rotary evaporation method；
B, addition network cross-linked thing
According to the 6.8% of the casting solution weight, PVPP network cross-linked thing is added to step A and is obtained
To casting solution in, stir and evenly mix, vacuum defoamation is carried out under conditions of temperature 70 C and pressure 0.04MPa, then using normal
Rule non-solvent gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Embodiment 6：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
By 18 weight portion Corvics, the additive of the following preparations of 32 weight portions and 60 weight portion dimethylformamides
Solvent is well mixed, and obtains described casting solution；
Addictive preparation method is as follows：According to the mol ratio 1 of monomeric polyol and acid polynary aldehyde monomer：2, by glycerine
The acid polynary aldehyde monomer of monomeric polyol and glutaraldehyde is added in solvent dimethylformamide, two of which total monomer weight with
The weight of solvent compares 1：80, it is well mixed, it is crosslinked under the acid condition of pH 3, until cross-linking products are not also precipitated,
Using the isolated described additive of rotary evaporation method.
B, addition network cross-linked thing
According to the 10.0% of the casting solution weight, cross-linked polyether sulfone network cross-linked thing is added to step A and is obtained
Casting solution in, stir and evenly mix, vacuum defoamation is carried out under conditions of 85 DEG C of temperature with pressure 0.02MPa, then using routine
Non-solvent gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Embodiment 7：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
By 14 weight portion Corvics, the additive of the following preparations of 36 weight portions and 64 weight portion dimethylformamides
Solvent is well mixed, and obtains described casting solution；
Addictive preparation method is as follows：According to the mol ratio 1 of polyfunctional monomer and polynary acyl chloride monomer：4.2, will be poly-
Ethylene glycol has cross-linking properties polyfunctional monomer and the polynary acyl chloride monomer of pyromellitic trimethylsilyl chloride, is added to dimethylformamide
In solvent, two of which total monomer weight compares 1 with the weight of solvent：90, it is well mixed, hand under the acid condition of pH 4.6
Connection, until cross-linking products are not also precipitated, using the isolated described additive of rotary evaporation method.
B, addition network cross-linked thing
According to the 4.8% of the casting solution weight, cross-linked polyether ethersulfone network cross-linked thing is added to step A and is obtained
Casting solution in, stir and evenly mix, vacuum defoamation is carried out under conditions of 40 DEG C of temperature with pressure 0.05MPa, then using routine
Non-solvent gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Embodiment 8：The preparation of hydrophilic modifying network cross-linked thing perforated membrane
The implementation steps of the embodiment are as follows：
A, prepare casting solution
26 weight portion polyether sulfones, the additive of the following preparations of 14 weight portions and 76 weight portion methyl pyrrolidone solvents are mixed
Close uniform, obtain described casting solution；
The preparation method of additive is as follows：According to the mol ratio 1 of monomeric polyol and acid polynary aldehyde monomer：2, by poly- second
Enol monomeric polyol is added in methyl pyrrolidone solvent with the acid polynary aldehyde monomer of MDA, two of which total weight of monomer
Amount compares 1 with the weight of solvent：90, it is well mixed, it is crosslinked under the acid conditions of pH 6, until cross-linking products also do not sink
Form sediment, using the isolated described additive of rotary evaporation method.
B, addition network cross-linked thing
According to the 3.4% of the casting solution weight, cross-linked polyether ethersulfone network cross-linked thing is added to step A and is obtained
Casting solution in, stir and evenly mix, vacuum defoamation is carried out under conditions of 48 DEG C of temperature with pressure 0.09MPa, then using routine
Non-solvent gel film-forming method masking, obtains described hydrophilic modifying network cross-linked thing perforated membrane.
Claims (9)
1. a kind of preparation method of hydrophilic modifying network cross-linked thing perforated membrane, it is characterised in that as follows the step of the method：
A, prepare casting solution
0.1～30 parts by weight resin, 10～40 weight portion additives are well mixed with 50～80 parts by weight solvent, obtain described
Casting solution；
Described resin is one or more selected from Kynoar, polyethylene, polypropylene, polysulfones, polyether sulfone or polyvinyl chloride
In resin；
Described additive is one or more additive in the polyvinylpyrrolidone of different molecular weight；
Described solvent is molten in dimethyl acetamide, dimethylformamide or methyl pyrrolidone one or more
Agent；
B, addition network cross-linked thing
According to the 0.1～10.0% of the casting solution weight, one or more cross-linked polysulfones, cross-linked polyethers are selected from
Network cross-linked thing in sulfone, cross-linked polyether ethersulfone, cross-linked polyether-ether-ketone or PVPP is added to
In the casting solution that step A is obtained, stir and evenly mix, vacuum defoamation, then using conventional non-solvent gel film-forming method masking, obtain
Described hydrophilic modifying network cross-linked thing perforated membrane.
2. preparation method according to claim 1, it is characterised in that the polyvinylpyrrolidone of the different molecular weight is
PVPk12, PVPk15, PVPk17, PVPk25, PVPk30 or PVPk45.
3. preparation method according to claim 1, it is characterised in that according to polyfunctional monomer and polynary acyl chloride monomer
Mol ratio 1：0.1～10., by one or more in ethylene glycol, glycerine, polyethylene glycol or the m-phenylene diamine (MPD) with friendship
Join performance polyfunctional monomer and one or more is selected from pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride
Polynary acyl chloride monomer is added in solvent, and two of which total monomer weight compares 1 with the weight of solvent：20～100., mixing is equal
It is even, it is crosslinked in acid condition, until cross-linking products are not also precipitated, the isolated product of rotary evaporation method is adopted for institute
The additive stated.
4. preparation method according to claim 1, it is characterised in that according to monomeric polyol and acid polynary aldehyde monomer
Mol ratio 1：0.1～10, by one or more polyalcohol list in ethylene glycol, glycerine, polyethylene glycol or polyvinyl alcohol
Body and one or more acid polynary aldehyde monomer in glutaraldehyde, butanedial or MDA are added in solvent, wherein two
Plant total monomer weight and compare 1 with the weight of solvent：20～100, it is well mixed, it is crosslinked in acid condition, until crosslinking is produced
Thing is not also precipitated, and adopts the isolated product of rotary evaporation method for described additive.
5. the preparation method according to claim 3 or 4, it is characterised in that described solvent is one or more selected from diformazan
Solvent in yl acetamide, dimethylformamide or methyl pyrrolidone.
6. preparation method according to claim 1, it is characterised in that described vacuum defoamation be 30～130 DEG C of temperature with
Deaeration is carried out under conditions of 0.01～0.10MPa of pressure, until bubble is removed completely.
7. preparation method according to claim 1, it is characterised in that the weight ratio of the resin, additive and solvent is 5
～24：18～32：56～72.
8. preparation method according to claim 1, it is characterised in that the addition of the network cross-linked thing is the casting film
The 1.6～7.8% of liquid weight.
9. the hydrophilic modifying network cross-linked thing perforated membrane that preparation method according to claim 1 or claim 2 is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611255685.XA CN106621837B (en) | 2016-12-30 | 2016-12-30 | A kind of hydrophilic modifying network cross-linked object perforated membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611255685.XA CN106621837B (en) | 2016-12-30 | 2016-12-30 | A kind of hydrophilic modifying network cross-linked object perforated membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106621837A true CN106621837A (en) | 2017-05-10 |
| CN106621837B CN106621837B (en) | 2018-11-30 |
Family
ID=58838862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611255685.XA Active CN106621837B (en) | 2016-12-30 | 2016-12-30 | A kind of hydrophilic modifying network cross-linked object perforated membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106621837B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862552A (en) * | 2019-11-26 | 2020-03-06 | 陕西科技大学 | Fluorocarbon modified humic acid micro-particles and preparation method and application thereof |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN113368704A (en) * | 2021-05-14 | 2021-09-10 | 科威天使环保科技集团股份有限公司 | High-performance ultrafiltration membrane for wastewater treatment and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014266A1 (en) * | 2003-08-08 | 2005-02-17 | Accord Partner Limited | Defect free composite membranes, method for producing said membranes and use of the same |
| CN104524993A (en) * | 2014-12-30 | 2015-04-22 | 张一琛 | Cross-linked sulfonated polysulfone/polyether sulfone-sulfonated polysulfone composite membrane and manufacturing method thereof |
| CN106188591A (en) * | 2016-07-11 | 2016-12-07 | 浙江工业大学义乌科学技术研究院有限公司 | The preparation method of photo-crosslinking SPSF ion exchange membrane |
-
2016
- 2016-12-30 CN CN201611255685.XA patent/CN106621837B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014266A1 (en) * | 2003-08-08 | 2005-02-17 | Accord Partner Limited | Defect free composite membranes, method for producing said membranes and use of the same |
| CN104524993A (en) * | 2014-12-30 | 2015-04-22 | 张一琛 | Cross-linked sulfonated polysulfone/polyether sulfone-sulfonated polysulfone composite membrane and manufacturing method thereof |
| CN106188591A (en) * | 2016-07-11 | 2016-12-07 | 浙江工业大学义乌科学技术研究院有限公司 | The preparation method of photo-crosslinking SPSF ion exchange membrane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862552A (en) * | 2019-11-26 | 2020-03-06 | 陕西科技大学 | Fluorocarbon modified humic acid micro-particles and preparation method and application thereof |
| CN110862552B (en) * | 2019-11-26 | 2021-08-10 | 陕西科技大学 | Fluorocarbon modified humic acid micro-particles and preparation method and application thereof |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN113083040B (en) * | 2021-04-23 | 2022-03-01 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN113368704A (en) * | 2021-05-14 | 2021-09-10 | 科威天使环保科技集团股份有限公司 | High-performance ultrafiltration membrane for wastewater treatment and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106621837B (en) | 2018-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7662212B2 (en) | Membrane post treatment | |
| CN106943899B (en) | Hydrophilic polysulfone membrane and preparation method thereof | |
| CN110314559A (en) | A kind of preparation method of interfacial polymerization composite membrane | |
| CN100562356C (en) | Hydrophilic polyvinyl chloride alloy doughnut filter membrane and preparation method thereof | |
| CN101837249A (en) | Composite polrvinyl chloride hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN105709616B (en) | A kind of preparation method of organic solvent-resistant ultrafiltration membrane, prepared film and its application | |
| CN106621837B (en) | A kind of hydrophilic modifying network cross-linked object perforated membrane and preparation method thereof | |
| CN112642305A (en) | Acid-resistant composite nanofiltration membrane and preparation method thereof | |
| CN109865501B (en) | Preparation method of composite membrane for adsorbing and removing organic dye in water | |
| CN101439269A (en) | Method for preparing thermoplastic polyurethane elastic hollow fiber membrane | |
| CN111495207A (en) | Hydrophilic modification method of polymer ultrafiltration membrane | |
| CN107638813B (en) | Preparation method and application of hollow fiber solvent-resistant nanofiltration membrane | |
| CN108499361A (en) | A kind of preparation method of the adjustable nano-porous polymer film in aperture | |
| CN109173753A (en) | Casting solution, ultrafiltration membrane, reverse osmosis composite membrane or Nano filtering composite membrane | |
| CN111974230B (en) | Preparation method of hydrophilic base membrane for preparing high-flux reverse osmosis membrane | |
| CN109248567B (en) | PIMs ultrathin layer composite hollow fiber membrane and preparation and application thereof | |
| JPH04176330A (en) | Production of charge type separation membrane | |
| CN115845616A (en) | COFs nano material mixed matrix ultrafiltration membrane based on Teleger base and preparation method thereof | |
| CN104801209A (en) | Ultralow-pressure nanofiltration membrane prepared from imidazole sulfonate grafted polyether sulfone | |
| CN108654395A (en) | A kind of formula and preparation method thereof of preparation of anti-fouling ultrafiltration membrane piece | |
| CN115487676B (en) | Preparation method of antibacterial modified hollow fiber ultrafiltration membrane | |
| WO2021074229A1 (en) | Method for the manufacture of a membrane system | |
| CN104998555A (en) | Preparing method of hydrophilia polyvinylidene fluoride filtering membrane | |
| CN115501765B (en) | Hollow fiber membrane, method for constructing hydrophilic network thereof, and use thereof | |
| CN107441936A (en) | A kind of Ag TiO2/ SPES mixing milipore filters and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 301800 No.10, Fuli Road, Baodi plastic products industrial zone, Baodi District, Tianjin Patentee after: Oseco membrane technology (Tianjin) Co.,Ltd. Address before: 301800 No.10, Fuli Road, Baodi plastic products industrial zone, Baodi District, Tianjin Patentee before: TIANJIN BISHUIYUAN MEMBRANE MATERIAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |