CN104971631B - A kind of preparation method of high flux PVDF perforated membranes - Google Patents
A kind of preparation method of high flux PVDF perforated membranes Download PDFInfo
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- CN104971631B CN104971631B CN201510440731.2A CN201510440731A CN104971631B CN 104971631 B CN104971631 B CN 104971631B CN 201510440731 A CN201510440731 A CN 201510440731A CN 104971631 B CN104971631 B CN 104971631B
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Abstract
The invention discloses a kind of preparation method of high flux PVDF perforated membranes, Kynoar, high-hydrophilic polymer, pore-forming additive, deionized water, solvent and graphene powder are mixed, Jing after curing, stirring, standing and defoaming obtains casting solution, by casting solution striking film forming.In atmosphere after prevapourising, after being put in coagulating bath, immersion forms just film forming to wet film in deionized water.Just film forming is placed in heat-activated in deionized water, and soaks in absolute ethyl alcohol and n-butanol, dries in atmosphere., using the graphene nano particle with two-dimensional structure as additive, pure water flux is up to 800Lm for the present invention‑2·h‑1More than, to bovine serum albumin rejection up to more than 98%.Addition hydrophilic polymer is simultaneously activated to first film forming, is greatly improved the hydrophily of pvdf membrane, and film surface contact angle is up to 59.8 °.Using porous film material structure-controllable, pore diameter range can be controlled in 0.1 5 μm.
Description
Technical field
The present invention relates to a kind of preparation method of water treatment polymer film, belongs to field of environment protection.It is more particularly to a kind of right
Membrane for water treatment carries out the preparation method of blending and modifying.
Background technology
Membrane technology is one of modern high technology developed in recent years, is also Chemical waste-water and environmental project
Discipline development new growth point.As a kind of new separation method, compared with traditional isolation technics, membrane technology has separation
Efficiency high, selective high, energy consumption be low, without phase transformation, simple to operate, floor space it is few, it is pollution-free the advantages of, in many occasion fields
Can be integrated with other technologies, reach effective processing means.By developing rapidly for nearly more than ten years, membrane technology extensively has
The fields such as chemical industry, three-protection design, food processing, desalinization, medical science are applied to effect, portion of techniques is defined solely
Vertical complete new high-tech industry.
Kynoar is a kind of fluoropolymer of function admirable, and its mechanical strength is higher, with excellent rigid, hard
The excellent performance such as degree, creep resistant, abrasion performance and cut resistant, chemical stability are good, can antioxidant, acid, alkali, salt, halogen
The corrosion of element, aromatic hydrocarbons, fat and chlorinated solvent and swelling；Have excellent uvioresistant, gamma-rays and ageing-resistant performance concurrently.Cause
This is considered to prepare one of ideal material of various seperation films.But, as Kynoar membrane flux is relatively low, seriously restrict which
Application in terms of UF membrane.
Graphene be it is a kind of by the tightly packed two dimensional crystal for constituting of carbon atom, it is little with crystalline size, specific surface area compared with
Big the features such as.Since the self-existent Graphene of reported first in 2004, it is at aspects such as mechanics, calorifics, electricity, optics
Excellent properties, make the study hotspot in chemistry, material science and physics field in recent years.
The content of the invention
It is an object of the invention to provide a kind of preparation method of high flux PVDF perforated membranes, the method can be significantly improved
The water flux of polyvinylidene fluoride film.
By Kynoar, high-hydrophilic polymer, pore-forming additive, deionized water, the solvent that polymer can be dissolved, stone
Black alkene powder presses 1：（0.05-1）：（0.1-0.5）：（0.001-0.125）：（6.2-9.75）：（0.001-0.125）Ratio mix
After conjunction, 24-48h, stirring 12-36h are cured at 70 DEG C, and casting solution is obtained after standing and defoaming 8-48h at normal temperatures；By casting film
Liquid striking film forming；Wet film after prevapourising, is put into coagulating bath 1-30min in atmosphere, then soaks
Film forming；Just film forming is placed in heat-activated in deionized water, and 8-24h is soaked in absolute ethyl alcohol, takes out, and soaks in being put into n-butanol
Bubble 8-24h, dries in atmosphere, obtains high flux PVDF perforated membranes.
The solvent that polymer can be dissolved is dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, diformazan
One or more in base sulfoxide, triethyl phosphate.
The pore-forming additive be polyvinylpyrrolidone, polyethylene glycol, lithium chloride, one or more in sodium nitrate.
The high-hydrophilic polymer is polyvinyl alcohol, polyacrylic acid, polyether sulfone, the one kind in polymethyl methacrylate
Or it is various.
Pre-evaporation is -10 minutes 5 seconds to the wet film in atmosphere.
The coagulating bath is consisted of：Deionized water and dimethylformamide, dimethyl acetamide, N- crassitudes
One or more in ketone, dimethyl sulfoxide (DMSO), triethyl phosphate, deionized water content are 50%-80%.
The just film forming immersion time in deionized water is 1-10 days.
The just film forming heat-activated time is 0.5-8 hours, and heating-up temperature is 30-90 DEG C.
The present invention is prepared for a kind of PVDF blended porous membranes using the method for phase separation.With preparation method letter
Singly, the features such as properties of product are stable, membrane flux is high, separative efficiency is high, antifouling property is good.Specially：
1st, this technique adopts the graphene nano particle with two-dimensional structure as additive, Neng Gouxian in preparing membrane process
Write and improve water flux, pure water flux reaches as high as 800Lm-2·h-1More than, to bovine serum albumin, (BSA, molecular weight is 67000)
Rejection is up to more than 98%.
2nd, add hydrophilic polymer and first film forming is activated, be greatly improved the hydrophily of pvdf membrane, film surface
Contact angle meets the application request of milipore filter up to 59.8 °.
3rd, using porous film material structure-controllable, pore diameter range can be controlled in 0.1-5 μm, can prepare according to actual needs suitable
Close the porous diffusion barrier in aperture.
Description of the drawings
Fig. 1 is schemed for PVDF blend films cross section SEM；
Fig. 2 is schemed for PVDF blend films upper surface SEM；
Fig. 3 is schemed for PVDF blend film lower surfaces SEM.
Specific embodiment
The present invention is intended to further illustrate below in conjunction with case study on implementation, and the unrestricted present invention.
By Kynoar, high-hydrophilic polymer, pore-forming additive, deionized water, the solvent that polymer can be dissolved, stone
After the mixing of black alkene powder, Jing curings, stirring, and casting solution is obtained after standing and defoaming at normal temperatures；By casting solution striking film forming；It is wet
Film after prevapourising, is put into coagulating bath in atmosphere, then soaks；Just film forming is placed in deionization
Heat-activated in water, and soak in absolute ethyl alcohol, soak during n-butanol is put into after taking-up, dry in atmosphere, both.
Embodiment 1：By 8g polyvinyl alcohol, 8g Kynoar, 3g polyvinylpyrrolidones, 1g sodium nitrate, 1g go from
Sub- water, 38g dimethyl acetamides, 40g dimethylformamides and 1g graphene powders are well mixed in conical flask, at 70 DEG C
Curing 48h, 36h is stirred under the conditions of 70 DEG C, and standing and defoaming 48h obtains casting solution at normal temperatures.Casting solution is poured on into glass
Striking film forming on plate.Wet film is put into 1min in coagulating bath, preliminary replacement solvent, coagulating bath in atmosphere after prevapourising 5s, rapidly
It is the deionized water solution containing 20% dimethyl acetamide.Film Jing after preliminary displacement soaks 7 days in deionized water, is formed just
Film forming.Just film forming is placed in heat-activated 6h in 40 DEG C of deionized waters, and 12h is soaked in absolute ethyl alcohol, and taking-up is put into n-butanol
Middle immersion 12h, dries in atmosphere, both.Pure water flux of the resulting membrane material under 0.1MPa pressure is 536.2L
m-2·h-1, bovine serum albumin rejection is 98.37%, and tensile strength is 4.21MPa, and contact angle is 69.7 °.
Embodiment 2：By 0.5g polymethyl methacrylates, 10g Kynoar, 1g lithium chlorides, 0.5g deionized waters,
88g dimethyl sulfoxide (DMSO)s and 0.01g graphene powders are well mixed in conical flask, at 70 DEG C cure 18h, under the conditions of 70 DEG C
Stirring 24h, and standing and defoaming 24h obtains casting solution at normal temperatures.By casting solution striking film forming on a glass.Wet film is in sky
In gas after prevapourising 10min, be put into rapidly 30min in coagulating bath, preliminary replacement solvent, coagulating bath be containing 30% dimethyl sulfoxide (DMSO),
The deionized water solution of 20% dimethyl acetamide.Film Jing after preliminary displacement soaks 10 days in deionized water, formed just into
Film.Just film forming is placed in heat-activated 0.5h in 90 DEG C of deionized waters, and 24h is soaked in absolute ethyl alcohol, and taking-up is put into n-butanol
Middle immersion 24h, dries in atmosphere, both.Pure water flux of the resulting membrane material under 0.1MPa pressure is 576.2L
m-2·h-1, bovine serum albumin rejection is 92.43%, and tensile strength is 4.87MPa, and contact angle is 60.7 °.
Embodiment 3：By 5g polyether sulfones, 10g Kynoar, 1.5g polyethylene glycol, 1g polyether sulfones, 0.01g deionizations
Water, 82g dimethylformamides and 0.5g graphene powders are well mixed in conical flask, at 70 DEG C cure 8h, in 70 DEG C of bars
24h is stirred under part, and standing and defoaming 24h obtains casting solution at normal temperatures.By casting solution striking film forming on a glass.Wet film
In atmosphere after prevapourising 30s, 7min in coagulating bath, preliminary replacement solvent are put into rapidly, coagulating bath is containing 30% dimethyl formyl
The deionized water solution of amine.Film Jing after preliminary displacement soaks 7 days in deionized water, forms just film forming.Just film forming is placed in 30
Heat-activated 8h in DEG C deionized water, and 24h is soaked in absolute ethyl alcohol, taking-up soaks 12h in being put into n-butanol, in atmosphere
Dry, both.Pure water flux of the resulting membrane material under 0.1MPa pressure is 604.8Lm-2·h-1, bovine serum albumin
Rejection is 90.37%, and tensile strength is 3.96MPa, and contact angle is 59.8 °.
Embodiment 4：By 1g polyvinyl alcohol, 13g Kynoar, 5g polyvinylpyrrolidones, 0.1g deionized waters,
80.7g 1-METHYLPYRROLIDONEs and 0.2g graphene powders are well mixed in conical flask, at 70 DEG C cure 24h, at 70 DEG C
Under the conditions of stir 24h, and standing and defoaming obtains casting solution at normal temperatures.By casting solution striking film forming on a glass.Wet film
In atmosphere after prevapourising 30s, 10min in coagulating bath, preliminary replacement solvent are put into rapidly, coagulating bath is containing 30% N- methyl pyrroles
The deionized water solution of pyrrolidone.Film Jing after preliminary displacement soaks 1 day in deionized water, forms just film forming.Just film forming is put
Heat-activated 5h in 60 DEG C of deionized waters, and 12h is soaked in absolute ethyl alcohol, taking-up soaks 12h in being put into n-butanol, in sky
Dry in gas, both.Pure water flux of the resulting membrane material under 0.1MPa pressure is 803.9Lm-2·h-1, cow's serum
Retention rate of proteins is 88.31%, and tensile strength is 4.53MPa, and contact angle is 62.8 °.
Claims (7)
1. a kind of preparation method of high flux PVDF perforated membranes, it is characterised in that comprise the following steps：By Kynoar, high parent
Waterborne polymeric, pore-forming additive, deionized water, the solvent that can dissolve polymer, graphene powder are by 1：（0.05-1）：
（0.1-0.5）：（0.001-0.125）：（6.2-9.75）：（0.001-0.125）Ratio mixing after, cure 24- at 70 DEG C
48h, stirring 12-36h, and casting solution is obtained after standing and defoaming 8-48h at normal temperatures；By casting solution striking film forming；Wet film is in sky
In gas after prevapourising, coagulating bath 1-30min is put into, then soaks；Just film forming be placed in from
Heat-activated in sub- water, and 8-24h is soaked in absolute ethyl alcohol, take out, 8-24h is soaked in being put into n-butanol, is dried in the air in atmosphere
It is dry, obtain high flux PVDF perforated membranes；The high-hydrophilic polymer is polyvinyl alcohol, polyacrylic acid, polyether sulfone, poly- methyl-prop
One or more in e pioic acid methyl ester.
2. the preparation method of a kind of high flux PVDF perforated membranes according to claim 1, it is characterised in that：It is described to dissolve
The solvent of polymer is dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), triethyl phosphate
In one or more.
3. the preparation method of a kind of high flux PVDF perforated membranes according to claim 1, it is characterised in that：The pore-creating adds
Plus agent be polyvinylpyrrolidone, polyethylene glycol, lithium chloride, one or more in sodium nitrate.
4. the preparation method of a kind of high flux PVDF perforated membranes according to claim 1, it is characterised in that：The wet film exists
In air, pre-evaporation is -10 minutes 5 seconds.
5. the preparation method of a kind of high flux PVDF perforated membranes according to claim 1, it is characterised in that：The coagulating bath
Consist of：Deionized water and dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tricresyl phosphate
One or more in ethyl ester, deionized water content are 50%-80%.
6. the preparation method of a kind of high flux PVDF perforated membranes according to claim 1, it is characterised in that：The just film forming
The immersion time in deionized water is 1-10 days.
7. the preparation method of a kind of high flux PVDF perforated membranes according to claim 1, it is characterised in that：The just film forming
The heat-activated time is 0.5-8 hours, and heating-up temperature is 30-90 DEG C.
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| CN106129433B (en) * | 2016-07-20 | 2019-01-11 | 江南大学 | A kind of conduction microfiltration membranes and preparation method thereof |
| CN108172737B (en) * | 2016-12-07 | 2019-12-17 | 中南大学 | Preparation method of lithium ion battery polymer diaphragm |
| CN107519767B (en) * | 2017-09-25 | 2021-10-01 | 天津工业大学 | Method for preparing super-hydrophobic microporous membrane by phase separation under synergetic regulation of inorganic salt aqueous solution |
| WO2019111157A1 (en) * | 2017-12-04 | 2019-06-13 | King Abdullah University Of Science And Technology | Methods of making porous membranes |
| CN108159887A (en) * | 2018-01-11 | 2018-06-15 | 天津工业大学 | A kind of method for evaluating graphene oxide membrane nanochannel structural stability |
| CN108579697A (en) * | 2018-03-22 | 2018-09-28 | 天津工业大学 | The method that swelling-freezing system prepares blended porous membrane |
| CN108939930A (en) * | 2018-08-21 | 2018-12-07 | 烯膜科技（深圳）有限公司 | A kind of preparation method of graphene hybrid reinforcement polyvinylidene fluoride flat film |
| CN109012215A (en) * | 2018-08-21 | 2018-12-18 | 烯膜科技（深圳）有限公司 | A kind of preparation method of graphene hydridization Kynoar liner coating film |
| CN109173743B (en) * | 2018-10-17 | 2021-04-30 | 常州大学 | Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof |
| CN111755647A (en) * | 2019-03-27 | 2020-10-09 | 中南大学 | Preparation method of lithium-air battery composite diaphragm |
| CN111785892B (en) * | 2019-04-03 | 2021-10-08 | 中南大学 | Preparation method of lithium-sulfur battery composite diaphragm |
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