CN117181014A - Hydrophilic PVDF ultrafiltration membrane and preparation process thereof - Google Patents
Hydrophilic PVDF ultrafiltration membrane and preparation process thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 100
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 76
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 76
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 12
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 3
- 238000005266 casting Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000614 phase inversion technique Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000003361 porogen Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000001112 coagulating effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 230000004907 flux Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000007790 scraping Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides a hydrophilic PVDF ultrafiltration membrane and a preparation process thereof, and belongs to the technical field of filter membrane materials. The hydrophilic PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 80-90 parts of polyvinylidene fluoride resin powder, 2-8 parts of pore-forming agent, 5-8 parts of active allyl epoxy end-capped polyether, 2-3 parts of 4-methyl catechol and 50-60 parts of solvent. The PVDF is used as a substrate, so that the PVDF has acid-base corrosion resistance, and meanwhile, the PVDF is modified by a special material component proportion, so that the surface hydrophilicity of the PVDF is improved.
Description
Technical Field
The invention relates to the technical field of filter membrane materials, in particular to a hydrophilic PVDF ultrafiltration membrane and a preparation process thereof.
Background
Ultrafiltration membranes are an important membrane separation method in the water treatment process, and are widely applied to the fields of industrial sewage treatment, municipal sewage treatment, food industry, sea water desalination and the like. The development of industry and the deterioration of environment place increasing demands on the development of ultrafiltration membrane technology. The problems of low flux, low porosity, short service life, serious membrane pollution and the like of ultrafiltration membranes make the solution of the membrane surface pollution problem increasingly urgent. Polyvinylidene fluoride (PVDF) as one of the ultrafiltration membrane materials has great potential in the application field of separation membranes due to its excellent heat resistance, mechanical properties, radiation resistance, chemical stability and the like.
However, the surface free energy of the polyvinylidene fluoride is lower, the surface hydrophilicity of the polyvinylidene fluoride membrane is poorer, and the polyvinylidene fluoride is easy to pollute when being used as a water treatment membrane, so that the flux of the PVDF water treatment membrane is reduced, the separation effect is reduced, the cleaning difficulty is increased, and the service life of the membrane is reduced.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides the PVDF ultrafiltration membrane which has acid and alkali corrosion resistance, and meanwhile, the surface hydrophilicity of the PVDF ultrafiltration membrane is improved by modifying the PVDF ultrafiltration membrane through a special material component ratio.
The method comprises the following steps:
the hydrophilic PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 80-90 parts of polyvinylidene fluoride resin powder, 2-8 parts of pore-forming agent, 5-8 parts of active allyl epoxy end-capped polyether, 2-3 parts of 4-methyl catechol and 50-60 parts of solvent.
In carrying out the above embodiment, it is preferable that the polyvinylidene fluoride resin powder has an average molecular weight of 350000 to 400000.
In carrying out the above embodiment, preferably, the porogen is selected from at least one of polyvinylpyrrolidone and polyethylene glycol.
In carrying out the above embodiments, preferably, the solvent is selected from one or more of dimethylacetamide, dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone.
On the other hand, the invention also provides a preparation process of the hydrophilic PVDF ultrafiltration membrane, which comprises the following steps:
step 1, adding 4-methylcatechol 2 and active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring for reaction to obtain a casting solution;
and 3, standing and defoaming the casting solution obtained in the step 2, coating the casting solution subjected to defoaming on a film forming plate by using a scraper, forming, obtaining an ultrafiltration membrane on the film forming plate by using a submerged precipitation phase inversion method, and then taking the ultrafiltration membrane off the film forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
In carrying out the above examples, it is preferable that the dissolution in step 1 is carried out under stirring at a temperature of 40 to 50 ℃.
In carrying out the above examples, it is preferable that the reaction is carried out in step 2 with stirring at a temperature of 50℃to 95℃for 18 to 36 hours.
In the above embodiment, the temperature of the static deaeration in the step 3 is preferably 75 to 85 ℃ and the time is preferably 12 to 24 hours.
In carrying out the above examples, it is preferable that the film sheet is scraped off on a film scraper with a 200 μm doctor blade at a speed of (1.0 to 2.0) m/min in step 3.
In carrying out the above embodiment, it is preferable that deionized water is used as a coagulation bath in the immersion precipitation phase inversion method in step 3, and the coagulation bath temperature is 20 to 30 ℃.
Compared with the prior art, the invention has the beneficial characteristics that:
1. according to the PVDF ultrafiltration membrane disclosed by the invention, 4-methylcatechol and active allyl epoxy-terminated polyether are added into raw material components, and as the 4-methylcatechol contains catechol active functional groups, secondary reaction can be carried out on the 4-methylcatechol and the epoxy-terminated polyether with the active allyl epoxy groups to form long-chain molecules with strong hydrophilicity, so that the inside of a hole of the ultrafiltration membrane and a selective layer have sufficient hydrophilic functional group side chains, and the ultrafiltration membrane has long-term stability after functionalization modification.
2. The PVDF ultrafiltration membrane has the advantages of simple modification process and low cost; the self attribute of the base film remains unchanged; the permeability and selectivity of the membrane can be simultaneously improved, and the diversity of surface engineering can be improved.
3. The PVDF ultrafiltration membrane provided by the invention adopts PVDF as a membrane substrate, and has excellent acid and alkali corrosion resistance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
To facilitate the practice of the invention, the reagents used in the examples and comparative examples will now be described:
polyvinylidene fluoride resin powder, akema France, average molecular weight 400000;
pore-forming agent, polyvinylpyrrolidone k90, shandong hundred chemical industry;
the active allyl epoxy-terminated polyether is SF-11B/91B, and is manufactured by Sophida chemical industry, suzhou;
4-methylcatechol, nantong Runfeng petrochemical industry;
solvent N-methyl pyrrolidone, jinan Ming Wei chemical industry.
Example 1
The hydrophilic PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 80 parts of polyvinylidene fluoride resin powder, 8 parts of a pore-forming agent, 8 parts of active allyl epoxy-terminated polyether, 3 parts of 4-methyl catechol and 60 parts of a solvent.
The preparation process comprises the following steps:
step 1, adding 4-methylcatechol 2 and active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring at the temperature of 40 ℃ to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring and reacting for 36 hours at the temperature of 50 ℃ to obtain a casting solution;
step 3, standing and defoaming the casting film liquid obtained in the step 2, wherein the temperature of standing and defoaming is 75 ℃ and the time is 24 hours; then coating the bubble-removed casting solution on a film forming plate by using a 200 μm scraper at a speed of 1.0m/min on a film scraping machine for forming; an ultrafiltration membrane is obtained on a membrane forming plate by using an immersion precipitation phase inversion method, deionized water is used as a coagulating bath, and the temperature of the coagulating bath is 20 ℃; and then the ultrafiltration membrane is taken down from the membrane forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
Example 2
The hydrophilic PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 90 parts of polyvinylidene fluoride resin powder, 2 parts of a pore-forming agent, 8 parts of active allyl epoxy-terminated polyether, 3 parts of 4-methyl catechol and 60 parts of a solvent.
The preparation process comprises the following steps:
step 1, adding 4-methylcatechol 2 and active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring at the temperature of 40 ℃ to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring and reacting for 36 hours at the temperature of 50 ℃ to obtain a casting solution;
step 3, standing and defoaming the casting film liquid obtained in the step 2, wherein the temperature of standing and defoaming is 75 ℃ and the time is 24 hours; then coating the bubble-removed casting solution on a film forming plate by using a 200 μm scraper at a speed of 1.0m/min on a film scraping machine for forming; an ultrafiltration membrane is obtained on a membrane forming plate by using an immersion precipitation phase inversion method, deionized water is used as a coagulating bath, and the temperature of the coagulating bath is 20 ℃; and then the ultrafiltration membrane is taken down from the membrane forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
Example 3
The hydrophilic PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 90 parts of polyvinylidene fluoride resin powder, 8 parts of a pore-forming agent, 5 parts of active allyl epoxy-terminated polyether, 3 parts of 4-methyl catechol and 60 parts of a solvent.
The preparation process comprises the following steps:
step 1, adding 4-methylcatechol 2 and active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring at the temperature of 40 ℃ to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring and reacting for 18 hours at the temperature of 50 ℃ to obtain a casting solution;
step 3, standing and defoaming the casting film liquid obtained in the step 2, wherein the temperature of standing and defoaming is 75 ℃ and the time is 12 hours; then coating the bubble-removed casting solution on a film forming plate by using a 200 μm scraper at a speed of 1.0m/min on a film scraping machine for forming; an ultrafiltration membrane is obtained on a membrane forming plate by using an immersion precipitation phase inversion method, deionized water is used as a coagulating bath, and the temperature of the coagulating bath is 20 ℃; and then the ultrafiltration membrane is taken down from the membrane forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
Example 4
The hydrophilic PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 90 parts of polyvinylidene fluoride resin powder, 8 parts of a pore-forming agent, 8 parts of active allyl epoxy-terminated polyether, 2 parts of 4-methyl catechol and 60 parts of a solvent.
The preparation process comprises the following steps:
step 1, adding 4-methylcatechol 2 and active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring at 50 ℃ to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring and reacting for 18 hours at the temperature of 95 ℃ to obtain a casting solution;
step 3, standing and defoaming the casting film liquid obtained in the step 2, wherein the temperature of standing and defoaming is 85 ℃ and the time is 12 hours; then coating the bubble-removed casting solution on a film forming plate by using a 200 μm scraper at a speed of 2.0m/min on a film scraping machine for forming; an ultrafiltration membrane is obtained on a membrane forming plate by using an immersion precipitation phase inversion method, deionized water is used as a coagulating bath, and the temperature of the coagulating bath is 30 ℃; and then the ultrafiltration membrane is taken down from the membrane forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
Example 5
The hydrophilic PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 90 parts of polyvinylidene fluoride resin powder, 8 parts of a pore-forming agent, 8 parts of active allyl epoxy-terminated polyether, 3 parts of 4-methyl catechol and 50 parts of a solvent.
The preparation process comprises the following steps:
step 1, adding 4-methylcatechol 2 and active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring at 50 ℃ to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring and reacting for 18 hours at the temperature of 95 ℃ to obtain a casting solution;
step 3, standing and defoaming the casting film liquid obtained in the step 2, wherein the temperature of standing and defoaming is 85 ℃ and the time is 12 hours; then coating the bubble-removed casting solution on a film forming plate by using a 200 μm scraper at a speed of 2.0m/min on a film scraping machine for forming; an ultrafiltration membrane is obtained on a membrane forming plate by using an immersion precipitation phase inversion method, deionized water is used as a coagulating bath, and the temperature of the coagulating bath is 30 ℃; and then the ultrafiltration membrane is taken down from the membrane forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
1. The PVDF ultrafiltration membranes obtained in examples 1 to 5 were subjected to permeation testing:
the water flux is that the ultrafiltration membrane is pre-pressed for 20min under 0.15MPa by pure water. The test solution was then passed through an ultrafiltration membrane at a pressure of 0.10MPa, and the amount of water permeated (V) was recorded at constant time intervals. Then, the ultrafiltration membrane flux (J) is calculated using formula (1):
J＝V/(A×t)
wherein A is the ultrafiltration membrane area (square meter), V is the permeate volume (L), and t is the time (h).
Retention Rate after pure water flux was measured in a stable state, BSA solution (0.1 g/L) was forced through an ultrafiltration membrane under the same pressure and retention rate R at the time of operation was recorded
R＝(Cp-Cf)/Cp×100％
Where Cp and Cf are the concentration (mg/L) of the original BSA after permeation, respectively.
The test results are shown in Table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Flux of water J | 193.7 | 192.8 | 193.5 | 193.1 | 193.0 |
| Retention rate R | 96.1 | 98.7 | 96.9 | 97.4 | 97.1 |
The experimental data show that the PVDF ultrafiltration membrane has the characteristics of high flux and high rejection rate.
2. The PVDF ultrafiltration membranes obtained in examples 1 to 5 were subjected to an anti-corrosion performance test as specified in GB/T13922.1, and the test results are shown in Table 2:
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Acid and alkali corrosion resistance | By passing through | By passing through | By passing through | By passing through | By passing through |
The experimental results show that the PVDF ultrafiltration membrane provided by the invention has excellent acid and alkali corrosion resistance.
3. The invention also designs a comparative example to verify the hydrophilicity.
Comparative example 1
The PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 80 parts of polyvinylidene fluoride resin powder, 8 parts of pore-forming agent, 3 parts of 4-methyl catechol and 60 parts of solvent.
The preparation process comprises the following steps:
step 1, adding 4-methylcatechol into a solvent according to a proportion, and uniformly stirring at the temperature of 40 ℃ to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring and reacting for 36 hours at the temperature of 50 ℃ to obtain a casting solution;
step 3, standing and defoaming the casting film liquid obtained in the step 2, wherein the temperature of standing and defoaming is 75 ℃ and the time is 24 hours; then coating the bubble-removed casting solution on a film forming plate by using a 200 μm scraper at a speed of 1.0m/min on a film scraping machine for forming; an ultrafiltration membrane is obtained on a membrane forming plate by using an immersion precipitation phase inversion method, deionized water is used as a coagulating bath, and the temperature of the coagulating bath is 20 ℃; and then the ultrafiltration membrane is taken down from the membrane forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
Comparative example 2
The PVDF ultrafiltration membrane comprises the following raw materials in parts by weight: 80 parts of polyvinylidene fluoride resin powder, 8 parts of pore-forming agent, 8 parts of active allyl epoxy-terminated polyether and 60 parts of solvent.
The preparation process comprises the following steps:
step 1, adding active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring at the temperature of 40 ℃ to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring and reacting for 36 hours at the temperature of 50 ℃ to obtain a casting solution;
step 3, standing and defoaming the casting film liquid obtained in the step 2, wherein the temperature of standing and defoaming is 75 ℃ and the time is 24 hours; then coating the bubble-removed casting solution on a film forming plate by using a 200 μm scraper at a speed of 1.0m/min on a film scraping machine for forming; an ultrafiltration membrane is obtained on a membrane forming plate by using an immersion precipitation phase inversion method, deionized water is used as a coagulating bath, and the temperature of the coagulating bath is 20 ℃; and then the ultrafiltration membrane is taken down from the membrane forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
The ultrafiltration membranes of example 1 and comparative examples 1 and 2 were subjected to a water drop angle test, respectively, and the test results are shown in table 3:
TABLE 3 Table 3
| Example 1 | Comparative example 1 | Comparative example 2 | |
| Drop corner | 61° | 77° | 75° |
From the above experimental data, it is clear that the component of example 1 of the present invention is different from that of comparative examples 1 and 2 in that it contains both 4-methylcatechol and active allylepoxy-terminated polyether, so that it has hydrophilicity.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The hydrophilic PVDF ultrafiltration membrane is characterized by comprising the following raw materials in parts by weight: 80-90 parts of polyvinylidene fluoride resin powder, 2-8 parts of pore-forming agent, 5-8 parts of active allyl epoxy end-capped polyether, 2-3 parts of 4-methyl catechol and 50-60 parts of solvent.
2. The hydrophilic PVDF ultrafiltration membrane of claim 1, wherein the polyvinylidene fluoride resin powder has an average molecular mass of 350000-400000.
3. The hydrophilic PVDF ultrafiltration membrane of claim 1, wherein the porogen is selected from at least one of polyvinylpyrrolidone and polyethylene glycol.
4. The hydrophilic PVDF ultrafiltration membrane of claim 1, wherein the solvent is selected from one or more of dimethylacetamide, dimethylformamide, dimethylsulfoxide, or N-methylpyrrolidone.
5. A process for preparing a hydrophilic PVDF ultrafiltration membrane according to any of claims 1 to 4, comprising the steps of:
step 1, adding 4-methylcatechol 2 and active allyl epoxy-terminated polyether into a solvent according to a proportion, and uniformly stirring to obtain a mixed solution;
step 2, adding polyvinylidene fluoride resin powder and a pore-forming agent into the mixed solution in the step 1, and stirring for reaction to obtain a casting solution;
and 3, standing and defoaming the casting solution obtained in the step 2, coating the casting solution subjected to defoaming on a film forming plate by using a scraper, forming, obtaining an ultrafiltration membrane on the film forming plate by using a submerged precipitation phase inversion method, and then taking the ultrafiltration membrane off the film forming plate to obtain the hydrophilic PVDF ultrafiltration membrane.
6. The process for preparing a hydrophilic PVDF ultrafiltration membrane according to claim 5, wherein the stirring and dissolving are carried out at a temperature of 40-50deg.C in step 1.
7. The process for preparing a hydrophilic PVDF ultrafiltration membrane according to claim 5, wherein in step 2, the reaction is carried out under stirring at a temperature of 50℃to 95℃for 18 to 36 hours.
8. The process for preparing a hydrophilic PVDF ultrafiltration membrane according to claim 5, wherein the temperature of the static deaeration in step 3 is 75-85 ℃ and the time is 12-24 hours.
9. The process for preparing a hydrophilic PVDF ultrafiltration membrane according to claim 5, wherein in step 3, the membrane is scraped off with a 200 μm scraper at a speed of (1.0-2.0) m/min on a doctor blade machine.
10. The process for preparing a hydrophilic PVDF ultrafiltration membrane according to claim 5, wherein deionized water is used as a coagulation bath in the immersion precipitation phase inversion method in step 3, and the coagulation bath temperature is 20-30 ℃.
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