CN109745874A - A kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane - Google Patents
A kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane Download PDFInfo
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Abstract
The present invention relates to technical field of membrane, and in particular to a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane.This method is using chloromethyl polyether-ketone as basal lamina material, it is dissolved in organic solvent and forms casting solution by standing and defoaming, chloromethyl polyether-ketone plate basement membrane is prepared using phase inversion, reselection is grafted obtained plate membrane with the big molecular modification agent of hydrophilic radical, then it is further introduced into amphoteric ion group and achievees the effect that surface hydrophilic modification, obtain chloromethyl polyether-ketone antipollution ultrafiltration membrane.The disadvantage that simple chloromethyl polyether-ketone ultrafiltration membrane hydrophily and contamination resistance difference can be made up using the method for the present invention is obtained the chloromethyl polyether-ketone ultrafiltration membrane with appropriate water flux and good antifouling property, extends the service life of ultrafiltration membrane.
Description
Technical field
The present invention relates to technical field of membrane, and in particular to a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane.
Background technique
Compared to other isolation technics, membrane separation technique is simple with operating process, does not generate secondary pollution, phase does not occur
The advantages that change, energy saving is the important new and high technology for solving the problems, such as the contemporary energy, resource and environment.Currently, membrane separation technique
Micro-filtration (MF), ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO) etc. are broadly divided into according to pore size.
As described above, ultrafiltration membrane is the major class in membrane separation technique.Ultrafiltration membrane is that a kind of aperture specification is consistent, specified hole
Diameter range is 0.01 micron of micropore filtering film below.Appropriate pressure is imposed in the side of film, can be sifted out molten less than aperture
Matter molecule.Ultrafiltration membrane has wide practical use in fields such as food industry, pharmaceuticals industries, can be used for drug, fruit juice, dairy products
Deng concentration purification, pure water, mineral spring Water warfare etc..
Although being considered as most promising technology, there are this main problems of fouling membrane in application, i.e., in feed liquid
Macromolecules adsorption is deposited on film surface, causes Pore Blocking, causes flux that irreversible decaying occurs, and separating effect decline shows
As.Currently, membrane pollution problem seriously restricts the development and application of ultrafiltration membrane, is urgent problem to be solved in UF membrane application, such as
The stain resistance what improves ultrafiltration membrane is also one of hot spot of current research.Studies have shown that most pollutants macromolecular is hydrophilic
For the degree of absorption on property surface well below hydrophobic surface, hydrophilic surface has excellent antifouling property.Therefore, pass through enhancing
The hydrophily of ultrafiltration membrane surface, the antifouling property of Lai Tigao film play important work to expanding application field, saving operating cost
With.
As CN102626595A discloses formula and its preparation side of the industrial high-intensitive ultrafiltration polyether sulfone plate membrane of one kind
Method is coated with the casting of the polyether sulfone, Hydrophilic Nanofibrous cellulose crystal, pore-foaming agent of certain mass ratio on high strength non-woven fabric substrate
Film liquid passes through a series of process preparation film forming such as vacuum outgas, air bath, sizing bath.The deficiency of the technology is film build method
Complexity and uncertainty, cause the antipollution effect of ultrafiltration membrane not ideal enough.
If CN104667768A discloses a kind of preparation method of novel antipollution polysulfone ultrafiltration membrane, by polysulfones and pore-foaming agent
It is dissolved in solvent and prepares casting solution, be coated on non-woven fabrics supporting layer and prepare basement membrane using phase inversion, then ultraviolet/red
Surface grafting is carried out using cladding process under the conditions of outer, hydrophilic layer is formed in ultrafiltration membrane surface, improves antifouling property.The technology is not
Foot is that the method being modified to basement membrane is complex, and influence factor is more, such as light intensity, light application time, more difficult to modified result
Control.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of chloromethyl polyether-ketone antipollution ultrafiltration membrane, carry out to basement membrane
Surface hydrophilic modification is to solve the membrane pollution problem in existing membrane separation technique.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane, comprising the following steps: by chloromethyl polyether-ketone and pore
Agent is dissolved in organic solvent, and stirring obtains flat plate ultrafiltration membrane casting solution after standing and defoaming；Then the casting solution is existed
Film on matrix prepares chloromethyl polyether-ketone plate basement membrane using phase inversion in coagulating bath；By the plate basement membrane band
There is the big molecular modification agent of hydrophilic radical to carry out hydrophilic modifying, obtains modified chloromethyl polyether-ketone antipollution ultrafiltration membrane；It will
The Modified Membrane carries out second step hydrophilic modifying, introduces amphoteric ion group, and it is super to obtain final chloromethyl polyether-ketone antipollution
Filter membrane.
The chloromethyl polyether-ketone is the chloromethyl substituent of polyether-ketone, and structure is,
Wherein x=10-70%.
The pore-foaming agent is polyethylene glycol or polyvinylpyrrolidone.
The organic solvent is N-Methyl pyrrolidone or N,N-dimethylformamide.
The mass concentration of chloromethyl polyether-ketone is 10-20wt% in the casting solution, and pore-foaming agent mass concentration is 2-10wt%,
Mixing time is 4-10h, and the standing and defoaming time is 12-24h.
The phase inversion specifically: casting solution is taken on a glass it is appropriate, using being soaked after manual knifing cutter painting film
Enter in deionization water-bath, film forming Automatic-falling from glass plate is fully cured to casting solution and obtains chloromethyl polyether-ketone plate base
Film, wherein deionized water bath temperature is 10-25 DEG C, and gained wet-film thickness is 50-100 μm；The plate basement membrane be stored in from
In sub- water.
The hydrophilic modifying method particularly includes: chloromethyl polyether-ketone plate basement membrane is immersed in modifier solution, is controlled
Temperature and time makes modified molecules carry out graft reaction in membrane surface, obtains chloromethyl polyether-ketone antipollution ultrafiltration membrane；
The big molecular modification agent is polyethyleneimine, structural formula are as follows:
For the modifier solution using water, ethyl alcohol or methanol as solvent, the mass concentration of modifying agent is 3-10wt%；Graft reaction temperature
Degree is 20-70 DEG C；The reaction time is 1-5h；The modified chloromethyl polyether-ketone antipollution ultrafiltration membrane be stored in from
In sub- water；Modified chloromethyl polyether-ketone antipollution ultrafiltration membrane structure are as follows:。
Wherein x=10-70%.
The modified modifying agent of the second step is propane sultone, structural formula are as follows:;
For the modifier solution using ethyl alcohol as solvent, modifying agent mass concentration is 3-10wt%；The reaction temperature is 20-70 DEG C；
The reaction time is 1-6h；The final chloromethyl polyether-ketone antipollution ultrafiltration membrane is stored in deionized water.It is described final
Chloromethyl polyether-ketone antipollution ultrafiltration membrane structure are as follows:。
Wherein x=10-70%.
The advantages and positive effects of the present invention are:
1. film build method of the invention is easy to operate and is easy to control, it can guarantee that the film-formation result of basement membrane under the same terms is consistent
And it is good, be conducive to carry out hydrophilic modifying.
2. the present invention carries out hydrophilic modifying, reaction process letter to chloromethyl polyether-ketone ultrafiltration membrane using chemical surface treatment method
Single, mild condition, modified effect is stablized, and has good economy and the feature of environmental protection.Poly- second of the selection with a large amount of amidos first
For alkene imines as modifying agent, amido reactivity is high, easily reacts with the benzyl chloride group in chloromethyl polyether-ketone, completes in film surface
Crosslinking, guarantees the presence of hydrophilic radical.Second step is modified to introduce amphoteric ion group, makes its surrounding water molecules by electrostatic interaction
Electrostatic-dipole effect is generated, and combines closely hydrone to form hydrated sheath, effectively improves the hydrophilicity of film surface.
3. comparing simple chloromethyl polyether-ketone ultrafiltration membrane, chloromethyl polyether-ketone antipollution ultrafiltration membrane parent prepared by the present invention
Aqueous to significantly improve, flux recovery rate is up to 99.7%.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to work of the present invention
Process is described further, but protection scope of the present invention is not limited to the following examples.
Embodiment 1
It takes 15g chloromethyl polyether-ketone and 5g Macrogol 4000 to be dissolved in 80gN- methyl pyrrolidone, 5h is stirred after sealing,
Standing and defoaming 12h obtains the casting solution of 15wt%；Appropriate casting solution is taken on a glass, is 150 μm of scraper with intermembrane space is scraped
It is immersed in 15 DEG C of deionization water-baths after hand coatings, film forming is fully cured from glass plate after Automatic-falling, by base after casting solution
Film collection saves in deionized water.
The performance test of gained basement membrane is as follows: water contact angle is 79.3 °, pure water flux 439LMH, and flux recovery rate is
57.5%。
It takes 30g polyethyleneimine to be dissolved in 560g deionized water and obtains the modifier solution of 5.08wt%, it will be at 30 DEG C
The chloromethyl polyether-ketone basement membrane that 2d is saved in deionized water impregnates 3h in the solution and is modified, and obtains chloromethyl polyether-ketone anti-pollution
Ultrafiltration membrane is contaminated, is saved in deionized water.
The performance test of the modified chloromethyl polyether-ketone antipollution ultrafiltration membrane of gained is as follows: water contact angle is 56.6 °, pure
Water flux is 384LMH, and flux recovery rate is 86.8%.It is good that test result shows that ultrafiltration membrane prepared in the present embodiment has
Good antifouling property.
Embodiment 2
It takes 17g propane sultone to be dissolved in 402g ethyl alcohol and obtains the modifier solution of 4.06wt%, it will be in deionized water at 40 DEG C
The middle modified chloromethyl polyether-ketone antipollution ultrafiltration membrane of embodiment 1 for saving 2d impregnates 3h in the solution and is modified, and obtains
Final chloromethyl polyether-ketone antipollution ultrafiltration membrane saves in deionized water.
The performance test of gained chloromethyl polyether-ketone antipollution ultrafiltration membrane is as follows: water contact angle is 43.6 °, and pure water flux is
362LMH, flux recovery rate are 96.5%.Test result shows that ultrafiltration membrane prepared in the present embodiment has good anti-pollution
Metachromia energy.
Embodiment 3
It takes 12g chloromethyl polyether-ketone and 8g Macrogol 4000 to be dissolved in 79gN- methyl pyrrolidone, 5h is stirred after sealing,
Standing and defoaming 12h obtains the casting solution of 12wt%；Appropriate casting solution is taken on a glass, is 150 μm of scraper with intermembrane space is scraped
It is immersed in 15 DEG C of deionization water-baths after hand coatings, film forming is fully cured from glass plate after Automatic-falling, by base after casting solution
Film collection saves in deionized water.
The performance test of gained basement membrane is as follows: water contact angle is 78.3 °, pure water flux 558LMH, and flux recovery rate is
58.1%。
It takes 18.2g polyethyleneimine to be dissolved in 504g deionized water and obtains the modifier solution of 3.45wt%, it will at 40 DEG C
The chloromethyl polyether-ketone basement membrane for saving 2d in deionized water impregnates 1h in the solution and is modified, and it is anti-to obtain chloromethyl polyether-ketone
Ultrafiltration membrane is polluted, is saved in deionized water.
The performance test of the modified chloromethyl polyether-ketone antipollution ultrafiltration membrane of gained is as follows: water contact angle is 68.9 °, pure
Water flux is 459LMH, and flux recovery rate is 78.7%.
It takes 28.6g propane sultone to be dissolved in 382g ethyl alcohol and obtains the modifier solution of 6.97wt%, will gone at 30 DEG C
The chloromethyl polyether-ketone Modified Membrane that 2d is saved in ionized water is impregnated 2h in the solution and is modified, and final chloromethyl polyethers is obtained
Ketone antipollution ultrafiltration membrane saves in deionized water.
The performance test of gained chloromethyl polyether-ketone antipollution ultrafiltration membrane is as follows: water contact angle is 51.7 °, and pure water flux is
416LMH, flux recovery rate are 92.1%.Test result shows that ultrafiltration membrane prepared in the present embodiment has good anti-pollution
Metachromia energy.
Embodiment 4
It takes 20g chloromethyl polyether-ketone and 8g Macrogol 4000 to be dissolved in 72gN- methyl pyrrolidone, 10h is stirred after sealing,
Standing and defoaming 12h obtains the casting solution of 20wt%；Appropriate casting solution is taken on a glass, is 150 μm of scraper with intermembrane space is scraped
It is immersed in 15 DEG C of deionization water-baths after hand coatings, film forming is fully cured from glass plate after Automatic-falling, by base after casting solution
Film collection saves in deionized water.
The performance test of gained basement membrane is as follows: water contact angle is 77.8 °, pure water flux 352LMH, and flux recovery rate is
58.4 %。
It takes 39.3g polyethyleneimine to be dissolved in 381g deionized water and obtains the modifier solution of 9.29wt%, it will at 50 DEG C
The chloromethyl polyether-ketone basement membrane for saving 2d in deionized water impregnates 4h in the solution and is modified, and it is anti-to obtain chloromethyl polyether-ketone
Ultrafiltration membrane is polluted, is saved in deionized water.
The performance test of the modified chloromethyl polyether-ketone antipollution ultrafiltration membrane of gained is as follows: water contact angle is 53.2 °, pure
Water flux is 267LMH, and flux recovery rate is 91.0%.
It takes 20.4g propane sultone to be dissolved in 460g ethyl alcohol and obtains the modifier solution of 4.17wt%, will gone at 35 DEG C
The chloromethyl polyether-ketone Modified Membrane that 2d is saved in ionized water is impregnated 2h in the solution and is modified, and final chloromethyl polyethers is obtained
Ketone antipollution ultrafiltration membrane saves in deionized water.
The performance test of gained chloromethyl polyether-ketone antipollution ultrafiltration membrane is as follows: water contact angle is 43.2 °, and pure water flux is
241LMH, flux recovery rate are 95.1%.Test result shows that ultrafiltration membrane prepared in the present embodiment has good anti-pollution
Metachromia energy.
Embodiment 5
It takes 17g chloromethyl polyether-ketone and 8g Macrogol 4000 to be dissolved in 76gN- methyl pyrrolidone, 8h is stirred after sealing,
Standing and defoaming 12h obtains the casting solution of 17wt%；Appropriate casting solution is taken on a glass, is 150 μm of scraper with intermembrane space is scraped
It is immersed in 15 DEG C of deionization water-baths after hand coatings, film forming is fully cured from glass plate after Automatic-falling, by base after casting solution
Film collection saves in deionized water.
The performance test of gained basement membrane is as follows: water contact angle is 77.0 °, pure water flux 413LMH, and flux recovery rate is
57.6%。
It takes 36.1g polyethyleneimine to be dissolved in 375g deionized water and obtains the modifier solution of 8.76wt%, it will at 70 DEG C
The chloromethyl polyether-ketone basement membrane for saving 2d in deionized water impregnates 5h in the solution and is modified, and it is anti-to obtain chloromethyl polyether-ketone
Ultrafiltration membrane is polluted, is saved in deionized water.
The performance test of the modified chloromethyl polyether-ketone antipollution ultrafiltration membrane of gained is as follows: water contact angle is 51.3 °, pure
Water flux is 321LMH, and flux recovery rate is 91.5%.
It takes 38.6g propane sultone to be dissolved in 382g ethyl alcohol and obtains the modifier solution of 9.05wt%, will gone at 40 DEG C
The chloromethyl polyether-ketone Modified Membrane that 2d is saved in ionized water is impregnated 6h in the solution and is modified, and final chloromethyl polyethers is obtained
Ketone antipollution ultrafiltration membrane saves in deionized water.
The performance test of gained chloromethyl polyether-ketone antipollution ultrafiltration membrane is as follows: water contact angle is 37.2 °, and pure water flux is
308LMH, flux recovery rate are 99.7%.Test result shows that ultrafiltration membrane prepared in the present embodiment has good anti-pollution
Metachromia energy.
It should be noted that the foregoing is merely presently preferred embodiments of the present invention, embodiment of the present invention is illustrative
, without being restrictive, all other embodiments sides obtained according to the technique and scheme of the present invention by those skilled in the art
Formula also belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane, it is characterised in that:
(1) in organic solvent by chloromethyl polyether-ketone and pore-foaming agent dissolution, stirring obtains flat plate ultrafiltration after standing and defoaming
Film casting solution；
(2) by the casting solution on matrix film, chloromethyl polyether-ketone plate base is prepared in coagulating bath using phase inversion
Film；
(3) the plate basement membrane is subjected to hydrophilic modifying with the big molecular modification agent with hydrophilic radical, obtains modified chlorine
Methyl polyether-ketone antipollution ultrafiltration membrane；Modified chloromethyl polyether-ketone antipollution ultrafiltration membrane is stored in deionized water；
(4) Modified Membrane is subjected to second step hydrophilic modifying, introduces amphoteric ion group, obtains final chloromethyl polyethers
Ketone antipollution ultrafiltration membrane；Modified chloromethyl polyether-ketone antipollution ultrafiltration membrane is stored in deionized water.
2. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as described in claim 1, it is characterised in that: described
Chloromethyl polyether-ketone is the chloromethyl substituent of polyether-ketone in step (1), and structure is, wherein x=10-70%；The step (1)
Middle pore-foaming agent is polyethylene glycol or polyvinylpyrrolidone.
3. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as described in claim 1, it is characterised in that: described
Organic solvent is N-Methyl pyrrolidone or N,N-dimethylformamide in step (1).
4. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as described in claim 1, it is characterised in that: described
The chloromethyl polyether-ketone mass concentration of casting solution is 10-20wt% in step (1), and pore-foaming agent mass concentration is 2-10wt%.
5. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as described in claim 1, it is characterised in that: described
Mixing time is 4-10h in step (1), and the standing and defoaming time is 12-24h.
6. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as described in claim 1, it is characterised in that: described
Matrix is glass plate, the phase inversion in step (2) specifically: is taken casting solution on a glass in right amount, using manual
It is immersed in deionization water-bath after knifing cutter painting film, film forming Automatic-falling from glass plate is fully cured to casting solution and obtains chloromethyl
Polyether-ketone plate basement membrane, wherein deionized water bath temperature is 10-25 DEG C, and gained wet-film thickness is 50-100 μm；The plate base
Film is stored in deionized water.
7. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as described in claim 1, it is characterised in that: described
Hydrophilic modifying in step (3), (4) method particularly includes: chloromethyl polyether-ketone plate basement membrane is immersed in modifier solution, is controlled
Temperature and time makes modified molecules carry out graft reaction in membrane surface, obtains chloromethyl polyether-ketone antipollution ultrafiltration membrane.
8. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as claimed in claim 7, it is characterised in that: described
Modifying agent is polyethyleneimine, structural formula in step (3) are as follows:；
For the modifier solution using water, ethyl alcohol or methanol as solvent, modifying agent mass concentration is 3-10wt%；Graft reaction temperature
It is 20-70 DEG C；The reaction time is 1-5h；The modified chloromethyl polyether-ketone antipollution ultrafiltration membrane structure are as follows:,
Wherein x=10-70%.
9. a kind of preparation method of chloromethyl polyether-ketone antipollution ultrafiltration membrane as claimed in claim 7, it is characterised in that: described
Modifying agent is propane sultone, structural formula in step (4) are as follows:；
For the modifier solution using ethyl alcohol as solvent, modifying agent mass concentration is 3-10wt%；Graft reaction temperature is 20-70 DEG C；
The reaction time is 1-6h；The final chloromethyl polyether-ketone antipollution ultrafiltration membrane structure are as follows:,
Wherein x=10-70%.
10. a kind of chloromethyl polyether-ketone antipollution ultrafiltration membrane prepared such as any one of claim 1 ~ 9 the method.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115155337A (en) * | 2022-06-29 | 2022-10-11 | 福州大学 | Preparation method of three-dimensional porous cross-linked anion exchange membrane |
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| CN106215701A (en) * | 2016-07-29 | 2016-12-14 | 林小城 | A kind of crosslinking hollow fiber anion-exchange membrane and preparation method thereof |
| CN107029555A (en) * | 2017-04-19 | 2017-08-11 | 大连理工大学 | A kind of solvent resistant NF membrane and preparation method thereof |
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| CN104190265A (en) * | 2014-08-31 | 2014-12-10 | 浙江大学 | Low-pressure high-flux chlorine-containing polymer nanofiltration membrane with stable separation layer and preparation method thereof |
| CN106215701A (en) * | 2016-07-29 | 2016-12-14 | 林小城 | A kind of crosslinking hollow fiber anion-exchange membrane and preparation method thereof |
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