CN103736407A - Modifying method for hydrophilia of PVDF (Polyvinylidene Fluoride) micro-filtration membrane - Google Patents
Modifying method for hydrophilia of PVDF (Polyvinylidene Fluoride) micro-filtration membrane Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 338
- 239000012528 membrane Substances 0.000 title claims abstract description 337
- 238000001471 micro-filtration Methods 0.000 title claims abstract description 305
- 238000000034 method Methods 0.000 title claims abstract description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 337
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 113
- 238000005406 washing Methods 0.000 claims abstract description 46
- 238000005796 dehydrofluorination reaction Methods 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 230000004048 modification Effects 0.000 claims abstract description 29
- 238000012986 modification Methods 0.000 claims abstract description 29
- 238000002715 modification method Methods 0.000 claims abstract 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 162
- 239000007864 aqueous solution Substances 0.000 claims description 72
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 66
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 50
- 239000012286 potassium permanganate Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000003999 initiator Substances 0.000 claims description 45
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 28
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 24
- 235000011187 glycerol Nutrition 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 21
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 38
- 238000004519 manufacturing process Methods 0.000 description 23
- 239000000654 additive Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 229920001223 polyethylene glycol Polymers 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 19
- 239000002202 Polyethylene glycol Substances 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 18
- 238000001914 filtration Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
一种PVDF微滤膜亲水改性方法，属于材料技术领域。所述改性方法包括如下步骤：PVDF微滤膜预处理、脱氟化氢、洗涤、自由基化、接枝。本发明改性的PVDF微滤膜亲水效果提高显著，改性后的PVDF微滤膜水通量提高了50%以上；本发明制作的PVDF微滤亲水性膜质量可靠，而采用化学方法进行改性，使得反应均匀，操作简单，工艺稳定，易用于工业化生产；本发明产品中使用的改性材料及药品均为国产工业级产品，价格低廉，适用于大规模工业生产。The invention discloses a hydrophilic modification method of a PVDF microfiltration membrane, which belongs to the technical field of materials. The modification method comprises the following steps: PVDF microfiltration membrane pretreatment, dehydrofluorination, washing, radicalization and grafting. The hydrophilic effect of the modified PVDF microfiltration membrane of the present invention is significantly improved, and the water flux of the modified PVDF microfiltration membrane is increased by more than 50%; the quality of the PVDF microfiltration hydrophilic membrane produced by the present invention is reliable, and the chemical method The modification makes the reaction uniform, the operation is simple, the process is stable, and it is easy to be used in industrial production; the modified materials and medicines used in the product of the present invention are domestic industrial-grade products with low price and are suitable for large-scale industrial production.
Description
技术领域 technical field
本发明属于材料技术领域，涉及一种滤水膜材料聚偏氟聚乙烯（PVDF）亲水改性方法。 The invention belongs to the technical field of materials and relates to a method for hydrophilic modification of polyvinylidene fluoride (PVDF), a water filtration membrane material.
背景技术 Background technique
聚偏氟乙烯（PVDF）材料由于含有较高键能的C-F键，使得较低键能的C-C键被C-F键所包围，故具有优良的化学稳定性、热稳定性、机械稳定性、耐辐射性。它主要作为一种微滤和超滤膜材料广泛的应用于生活污水处理、工业废水处理等各种水处理。但是， PVDF膜表面的C-F键和C-H键又决定了其弱亲水性，使得PVDF与水分子很难产生氢键的作用，可润湿性能差、疏水作用强，水分子较难附着在PVDF膜表面，导致水通量较低，不能满足实际生产中对于水通量的要求。所以PVDF在分离油水体系时，由于其疏水作用强，表面能低，油性污染物易于吸附在膜表面，并造成膜孔的堵塞。随着滤水膜使用时间的增加膜的水通量逐渐下降，最终导致滤水膜无法使用。较强的疏水性作用成为了限制PVDF通量的重要因素，限制了PVDF在实际生产生活中的进一步推广应用。 Polyvinylidene fluoride (PVDF) material has excellent chemical stability, thermal stability, mechanical stability and radiation resistance because it contains C-F bonds with higher bond energy, so that C-C bonds with lower bond energy are surrounded by C-F bonds. sex. It is mainly used as a microfiltration and ultrafiltration membrane material and is widely used in various water treatments such as domestic sewage treatment and industrial wastewater treatment. However, the C-F bond and C-H bond on the surface of the PVDF membrane determine its weak hydrophilicity, making it difficult for PVDF to form hydrogen bonds with water molecules, resulting in poor wettability and strong hydrophobicity, making it difficult for water molecules to attach to PVDF. The surface of the membrane leads to low water flux, which cannot meet the requirements for water flux in actual production. Therefore, when PVDF separates oil-water systems, due to its strong hydrophobic effect and low surface energy, oily pollutants are easily adsorbed on the membrane surface and cause blockage of the membrane pores. As the water filtration membrane is used for a long time, the water flux of the membrane gradually decreases, and finally the water filtration membrane cannot be used. The strong hydrophobic effect has become an important factor limiting the flux of PVDF, which limits the further popularization and application of PVDF in actual production and life.
发明内容 Contents of the invention
本发明的目的是为了克服现有的PVDF滤水膜表面的C-F键和C-H键所导致的弱亲水性，PVDF与水分子难产生氢键的作用导致PVDF可润湿性能差、疏水作用强、水通量较低，而不能满足实际生产中对于水通量的要求的缺陷，提供一种PVDF滤水膜亲水改性的方法，使PVDF亲水性得以改善，水通量得以提高。 The purpose of the present invention is to overcome the weak hydrophilicity caused by the C-F bond and C-H bond on the surface of the existing PVDF water filtration membrane, and the hydrogen bond between PVDF and water molecules is difficult to produce, resulting in poor wettability and strong hydrophobic effect of PVDF 1. The water flux is relatively low, which cannot meet the requirements for water flux in actual production. A method for hydrophilic modification of PVDF water filtration membrane is provided, so that the hydrophilicity of PVDF can be improved and the water flux can be increased.
本发明的目的是通过下述技术方案予以实现的： The purpose of the present invention is achieved through the following technical solutions:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将PVDF微滤膜放置于清水中浸泡12~24h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂、溶剂及其它物质； Soak the PVDF microfiltration membrane in clean water for 12~24 hours to remove the additives, solvents and other substances added in the production process contained in the PVDF microfiltration membrane;
B、脱氟化氢 B. Dehydrofluorination
在温度40~60℃与搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于氢氧化钠和高锰酸钾混合水溶液中处理10~20min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键； Under the conditions of temperature 40~60℃ and stirring, the PVDF microfiltration membrane pretreated in step A was placed in a mixed aqueous solution of sodium hydroxide and potassium permanganate for 10~20min to remove the HF on the surface of the PVDF microfiltration membrane forms a C=C double bond;
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10~20min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾； The PVDF microfiltration membrane after the dehydrofluorination of step B is placed in clear water and washed repeatedly for 10 to 20 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane;
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有引发剂与促进剂的乙醇溶液中，在室温的条件下处理5~10min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基； Add the PVDF microfiltration membrane after washing with clear water in step C to the ethanol solution containing the initiator and the accelerator, and process it for 5 to 10 minutes at room temperature, so that the initiator will wash the PVDF microfiltration membrane in the water. The C=C double bond on the membrane surface initiates the generation of free radicals;
E、接枝 E. Grafting
向步骤D得到的溶液中加入含有顺丁烯二酸酐、浓硫酸和正硅酸乙酯的混合水溶液，然后在温度70~85℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应3~6h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10~30min后浸泡在10~20%甘油水溶液（质量分数）中2~3h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution containing maleic anhydride, concentrated sulfuric acid and ethyl orthosilicate to the solution obtained in step D, and then make the free radicals on the surface of the PVDF microfiltration membrane and Maleic anhydride grafting reaction 3 ~ 6h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane is washed under pure water for 10-30 minutes, soaked in 10-20% glycerin aqueous solution (mass fraction) for 2-3 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface. filter membrane. the
根据本发明的一种优选实施方式，所述氢氧化钠和高锰酸钾混合水溶液中高锰酸钾的浓度当量是0.15~0.2mol/L， According to a preferred embodiment of the present invention, the concentration equivalent of potassium permanganate in the mixed aqueous solution of sodium hydroxide and potassium permanganate is 0.15 ~ 0.2mol/L,
根据本发明的一种优选实施方式，所述氢氧化钠和高锰酸钾混合水溶液中氢氧化钠的浓度当量是1.5~2.5mol/L。 According to a preferred embodiment of the present invention, the concentration equivalent of sodium hydroxide in the mixed aqueous solution of sodium hydroxide and potassium permanganate is 1.5-2.5 mol/L.
根据本发明的一种优选实施方式，所述混合水溶液中含有质量分数分别为20~30%顺丁烯二酸酐、3~5%浓硫酸和3~8%正硅酸乙酯。 According to a preferred embodiment of the present invention, the mixed aqueous solution contains 20-30% maleic anhydride, 3-5% concentrated sulfuric acid and 3-8% ethyl orthosilicate in mass fractions respectively.
根据本发明的一种优选实施方式，所述顺丁烯二酸酐单体在混合水溶液的质量浓度为20~25%。 According to a preferred embodiment of the present invention, the mass concentration of the maleic anhydride monomer in the mixed aqueous solution is 20-25%.
根据本发明的一种优选实施方式，所述脱氟化氢反应的温度为50~55℃。 According to a preferred embodiment of the present invention, the temperature of the dehydrofluorination reaction is 50-55°C.
根据本发明的一种优选实施方式，所述浓硫酸的用量是顺丁烯二酸酐质量的10~20%。 According to a preferred embodiment of the present invention, the amount of the concentrated sulfuric acid is 10-20% of the mass of maleic anhydride.
根据本发明的一种优选实施方式，所述乙醇溶液中含有质量分数为3~4%的引发剂与质量分数为 0.5~0.8%的促进剂。 According to a preferred embodiment of the present invention, the ethanol solution contains a mass fraction of 3-4% initiator and a mass fraction of 0.5-0.8% accelerator.
根据本发明的一种优选实施方式，所述引发剂为过氧化二苯甲酰，促进剂为环烷酸钴或萘酸钴。 According to a preferred embodiment of the present invention, the initiator is dibenzoyl peroxide, and the accelerator is cobalt naphthenate or cobalt naphthenate.
根据本发明的一种优选实施方式，所述接枝反应温度为77~82℃。 According to a preferred embodiment of the present invention, the grafting reaction temperature is 77-82°C.
根据本发明的一种优选实施方式，所述环烷酸钴促进剂的用量是所述顺丁烯二酸酐单体质量的1.0~2.0%。 According to a preferred embodiment of the present invention, the amount of the cobalt naphthenate accelerator is 1.0-2.0% of the mass of the maleic anhydride monomer.
根据本发明的一种优选实施方式，所述正硅酸乙酯的用量是所述顺丁烯二酸酐单体质量的10~30%。 According to a preferred embodiment of the present invention, the amount of tetraethyl orthosilicate is 10-30% of the mass of the maleic anhydride monomer.
根据本发明的一种优选实施方式，所述正硅酸乙酯的用量是所述顺丁烯二酸酐单体质量的20~25%。 According to a preferred embodiment of the present invention, the amount of tetraethyl orthosilicate is 20-25% of the mass of the maleic anhydride monomer.
本发明具有如下有益效果： The present invention has following beneficial effect:
1、本发明改性的PVDF微滤膜亲水效果提高显著，从图2可以看出，改性后的PVDF微滤膜水通量提高了50%以上。 1. The hydrophilic effect of the modified PVDF microfiltration membrane of the present invention is significantly improved. As can be seen from Figure 2, the water flux of the modified PVDF microfiltration membrane has increased by more than 50%.
2、本发明制作的PVDF微滤亲水性膜质量可靠，而采用化学方法进行改性，使得反应均匀，操作简单，工艺稳定，易用于工业化生产。 2. The PVDF microfiltration hydrophilic membrane produced by the present invention is reliable in quality, and is modified by chemical methods, so that the reaction is uniform, the operation is simple, the process is stable, and it is easy to be used in industrial production.
3、本发明产品中使用的改性材料及药品均为国产工业级产品，价格低廉，适用于大规模工业生产。 3. The modified materials and medicines used in the product of the present invention are domestic industrial-grade products with low price and are suitable for large-scale industrial production.
附图说明 Description of drawings
图1为改性后的PVDF微滤膜红外图谱分析； Fig. 1 is the infrared spectrum analysis of PVDF microfiltration membrane after modification;
图2为改性前后水通量值。 Figure 2 shows the water flux values before and after modification.
具体实施方式 Detailed ways
下面结合实施例对本发明的技术方案作进一步的说明，但并不局限如此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。 The technical solution of the present invention will be further described below in conjunction with the examples, but it is not limited to this. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the technical solution of the present invention. in the scope of protection.
实施例1：Example 1:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将PVDF微滤膜放置于清水中浸泡12~24h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂、溶剂及其它物质。 Place the PVDF microfiltration membrane in clean water and soak for 12~24 hours to remove the additives, solvents and other substances added during the production process contained in the PVDF microfiltration membrane.
本发明使用的PVDF微滤膜是市场上销售的成品，如由北京碧水源公司所生产的PVDF微滤膜。本发明使用的PVDF微滤膜产品通常具有以下性能特点：有较高的强度；水通量达到一定值；可以用于污水处理。 The PVDF microfiltration membrane used in the present invention is a finished product sold on the market, such as the PVDF microfiltration membrane produced by Beijing Origin Water Company. The PVDF microfiltration membrane product used in the present invention usually has the following performance characteristics: high strength; water flux reaches a certain value; and can be used for sewage treatment.
在这个步骤中，所要除去的添加剂通常是氯化锂、二氧化硅等。所要除去的溶剂通常是N，N二甲基甲酰胺等。所要除去的其它物质通常是聚乙二醇等。 In this step, the additives to be removed are usually lithium chloride, silica, etc. The solvent to be removed is usually N,N dimethylformamide and the like. Other substances to be removed are usually polyethylene glycols and the like.
B、脱氟化氢 B. Dehydrofluorination
在温度为40~60℃与搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于氢氧化钠和高锰酸钾混合水溶液中处理10~20min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 40~60℃ and stirring, the PVDF microfiltration membrane pretreated in step A is placed in the mixed aqueous solution of sodium hydroxide and potassium permanganate for 10~20min to remove the pretreatment in step A. After the HF on the surface of the PVDF microfiltration membrane, a C=C double bond is formed.
在本步骤中，使用的氢氧化钠和高锰酸钾混合水溶液中高锰酸钾的浓度当量是0.15~0.2mol/L，氢氧化钠的浓度当量是1.5~2.5mol/L。氢氧化钠的量应该严格控制在一定范围，若氢氧化钠量过少，则形成的双键含量较少，不利于下一步的改性；氢氧化钠含量过多，则PVDF中双键含量较多，会使膜的强度大大降低。 In this step, the concentration equivalent of potassium permanganate in the mixed aqueous solution of sodium hydroxide and potassium permanganate used is 0.15~0.2mol/L, and the concentration equivalent of sodium hydroxide is 1.5~2.5mol/L. The amount of sodium hydroxide should be strictly controlled within a certain range. If the amount of sodium hydroxide is too small, the amount of double bonds formed will be less, which is not conducive to the next step of modification; if the amount of sodium hydroxide is too high, the amount of double bonds in PVDF will More, the strength of the film will be greatly reduced.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10~20min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B is placed in clear water and washed repeatedly for 10-20 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
根据本发明，所述脱氟化氢后的PVDF微滤膜表面上的氢氧化钠未被除干净，则会对PVDF微滤膜后续处理步骤产生不利的影响。若氢氧化钠未完全除去，则会与下一步参加反应的物质进行反应，影响反应进行。 According to the present invention, if the sodium hydroxide on the surface of the dehydrofluorinated PVDF microfiltration membrane is not completely removed, it will adversely affect the subsequent processing steps of the PVDF microfiltration membrane. If the sodium hydroxide is not completely removed, it will react with the substances that will participate in the reaction in the next step, affecting the progress of the reaction.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到质量分数为3~4%过氧化二苯甲酰引发剂与质量分数为 0.5~0.8%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5~10min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution that mass fraction is 3 ~ 4% dibenzoyl peroxide initiator and mass fraction is 0.5 ~ 0.8% cobalt naphthenate accelerator, at room temperature Treated under the conditions of 5 ~ 10min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20~30%顺丁烯二酸酐、3~5%浓硫酸和3%~8%正硅酸乙酯的混合水溶液，然后在温度70~85℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10~30min后浸泡在质量分数为10~20%的甘油水溶液中2~3h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mass fraction of 20~30% maleic anhydride, 3~5% concentrated sulfuric acid and 3%~8% tetraethyl orthosilicate in the solution obtained in step D, and then add the mixed aqueous solution at a temperature of 70~85°C Under the conditions, the free radicals on the surface of the PVDF microfiltration membrane were grafted with maleic anhydride for 4 hours. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane is washed under pure water for 10 to 30 minutes, then soaked in an aqueous glycerin solution with a mass fraction of 10 to 20% for 2 to 3 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface. filter membrane.
如图1所示，在800cm-1和1080cm-1处可以看到两个峰证明有硅氧键。 As shown in Figure 1, two peaks can be seen at 800cm -1 and 1080cm -1 , proving that there are silicon-oxygen bonds.
在此步骤中，混合水溶液中的各物质浓度对于接枝亲水改性反应非常重要，若正硅酸乙酯浓度低于3%时，则形成的接枝链较短，亲水改性效果差；若正硅酸乙酯浓度高于8%时，则形成的接枝链段过长，导致PVDF滤水膜微滤孔被链段堵塞；因此，正硅酸乙酯的浓度为3~8%是合适的。 In this step, the concentration of each substance in the mixed aqueous solution is very important for the grafting hydrophilic modification reaction. If the concentration of tetraethyl orthosilicate is lower than 3%, the graft chain formed is shorter and the hydrophilic modification effect Poor; if the concentration of tetraethyl orthosilicate is higher than 8%, the grafted segment formed is too long, causing the microfiltration pores of PVDF water filtration membrane to be blocked by the segment; therefore, the concentration of tetraethyl orthosilicate is 3~ 8% is suitable.
实施例2：Example 2:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡12h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 12 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为60℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.15 mol/L氢氧化钠和1.5mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 60°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.15 mol/L sodium hydroxide and 1.5 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例3： Example 3:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为60℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.15 mol/L氢氧化钠和1.5mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 60°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.15 mol/L sodium hydroxide and 1.5 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例4：Example 4:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡24h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 24 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为60℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.15 mol/L氢氧化钠和1.5mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 60°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.15 mol/L sodium hydroxide and 1.5 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
采用本说明书描述的方法检测了该实施例制备的具有亲水层的PVDF微滤膜含有亲水性基团、水通量增大，同时检测了该实施例使用PVDF微滤膜的亲水性增强、水通量增大。上述实施例清楚地表明此实施例可成功，且在A步浸泡12~24h都有较好效果。 The PVDF microfiltration membrane with a hydrophilic layer prepared in this specification is used to detect that the PVDF microfiltration membrane with a hydrophilic layer contains hydrophilic groups and the water flux increases, and the hydrophilicity of the PVDF microfiltration membrane used in this embodiment is detected at the same time. Enhanced, increased water flux. Above-mentioned embodiment clearly shows that this embodiment can be successful, and all have better effect in A step soaking 12～24h.
实施例5：Example 5:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.15 mol/L氢氧化钠和1.5mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.15 mol/L sodium hydroxide and 1.5 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% ethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, then soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例6：Embodiment 6:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为50℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.15 mol/L氢氧化钠和1.5mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 50°C and stirring at 50 rpm, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.15 mol/L sodium hydroxide and 1.5 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
采用本说明书描述的方法检测了该实施例制备的具有亲水层的PVDF微滤膜含有亲水性基团、水通量增大，同时检测了该实施例使用PVDF微滤膜的亲水性增强、水通量增大。上述实施例清楚地表明此实施例可成功，且在B步55℃反应效率较高。 The PVDF microfiltration membrane with a hydrophilic layer prepared in this specification is used to detect that the PVDF microfiltration membrane with a hydrophilic layer contains hydrophilic groups and the water flux increases, and the hydrophilicity of the PVDF microfiltration membrane used in this embodiment is detected at the same time. Enhanced, increased water flux. The above examples clearly show that this example can be successful, and the reaction efficiency is higher in step B at 55°C.
实施例7：Embodiment 7:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和1.5mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 1.5 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例8：Embodiment 8:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理20min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 20min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例9： Embodiment 9:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤15min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clean water and washed repeatedly for 15 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例10：Example 10:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤20min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 20 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为3%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 3% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
采用本说明书描述的方法检测了该实施例制备的具有亲水层的PVDF微滤膜含有亲水性基团、水通量增大，同时检测了该实施例使用PVDF微滤膜的亲水性增强、水通量增大。上述实施例清楚地表明 The PVDF microfiltration membrane with a hydrophilic layer prepared in this specification is used to detect that the PVDF microfiltration membrane with a hydrophilic layer contains hydrophilic groups and the water flux increases, and the hydrophilicity of the PVDF microfiltration membrane used in this embodiment is detected at the same time. Enhanced, increased water flux. The above examples clearly show that
在步骤C中随着洗涤时间的增加，改性膜样虽效果有部分提升，但考虑工业制备水洗10min即可。 In step C, as the washing time increases, although the effect of the modified membrane sample is partially improved, it is enough to consider washing for 10 minutes for industrial preparation.
实施例11：Example 11:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例12：Example 12:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.8%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理5min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 Adding the PVDF microfiltration membrane after step C clear water washing to the ethanol solution containing 4% dibenzoyl peroxide initiator and 0.8% cobalt naphthenate accelerator containing mass fraction, at room temperature Treat for 5 minutes, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例13：Example 13:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理40min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 40min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 3% tetraethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例14：Example 14:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理40min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 40min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、5%浓硫酸和3%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 5% concentrated sulfuric acid and 3% ethyl orthosilicate to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例15：Example 15:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理40min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 40min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和6%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 6% ethyl orthosilicate in mass fraction to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例16：Example 16:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理40min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 40min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和8%正硅酸乙酯的混合水溶液，然后在温度80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 8% ethyl orthosilicate in mass fraction to the solution obtained in step D, and then microfilter the PVDF at a temperature of 80°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, then soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例17：Example 17:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理40min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 40min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和6%正硅酸乙酯的混合水溶液，然后在温度70℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 6% ethyl orthosilicate in mass fraction to the solution obtained in step D, and then microfilter the PVDF at a temperature of 70°C The free radicals on the membrane surface were grafted with maleic anhydride for 4h. One deck hydrophilic layer can be obtained on the surface of the PVDF microfiltration membrane after the reaction finishes. The PVDF microfiltration membrane was washed under pure water for 10 minutes, then soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例18：Example 18:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理40min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 40min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和6%正硅酸乙酯的混合水溶液，然后在温度70℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应5h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤10min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mixed aqueous solution of 20% maleic anhydride, 3% concentrated sulfuric acid and 6% ethyl orthosilicate in mass fraction to the solution obtained in step D, and then microfilter the PVDF at a temperature of 70°C The free radicals on the surface of the membrane were grafted with maleic anhydride for 5 h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 10 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
实施例19：Example 19:
聚偏氟乙烯微滤膜亲水改性的实施步骤如下： The implementation steps of hydrophilic modification of polyvinylidene fluoride microfiltration membrane are as follows:
A、PVDF微滤膜预处理 A. PVDF microfiltration membrane pretreatment
将北京碧水源公司所生产的PVDF微滤膜放置于清水中浸泡18h，以除去PVDF微滤膜中所含的生产过程中添加的添加剂氯化锂、二氧化硅，N，N二甲基甲酰胺溶剂及聚乙二醇等。 Soak the PVDF microfiltration membrane produced by Beijing Origin Water Co., Ltd. in clean water for 18 hours to remove the additives added in the production process contained in the PVDF microfiltration membrane, lithium chloride, silicon dioxide, N, N dimethylformamide Solvents and polyethylene glycol, etc.
B、脱氟化氢 B. Dehydrofluorination
在温度为55℃与50转/分搅拌的条件下，将在步骤A预处理后的PVDF微滤膜置于含有0.2 mol/L氢氧化钠和2.0mol/L高锰酸钾混合水溶液中处理10min，以除去在步骤A预处理后的PVDF微滤膜表面上的HF，形成C=C双键。 Under the condition that the temperature is 55°C and 50 rpm stirring, the PVDF microfiltration membrane pretreated in step A is placed in a mixed aqueous solution containing 0.2 mol/L sodium hydroxide and 2.0 mol/L potassium permanganate 10min, to remove the HF on the PVDF microfiltration membrane surface after step A pretreatment, form C=C double bond.
C、洗涤 C. washing
将步骤B脱氟化氢后的PVDF微滤膜置于清水中进行反复洗涤10min，以除去残留在所述脱氟化氢的PVDF微滤膜表面上的氢氧化钠和高锰酸钾。 The PVDF microfiltration membrane after dehydrofluorination in step B was placed in clear water and washed repeatedly for 10 minutes to remove sodium hydroxide and potassium permanganate remaining on the surface of the dehydrofluorinated PVDF microfiltration membrane.
D、自由基化 D. free radicalization
把在步骤C清水洗涤后的PVDF微滤膜加到含有质量分数为4%过氧化二苯甲酰引发剂与质量分数为 0.6%环烷酸钴促进剂的乙醇溶液中，在室温的条件下处理40min，以使所述引发剂将在所述水洗涤PVDF微滤膜表面上的C=C双键引发生成自由基。 The PVDF microfiltration membrane after step C clear water washing is added to the ethanol solution containing the mass fraction of 4% dibenzoyl peroxide initiator and the mass fraction of 0.6% cobalt naphthenate accelerator, at room temperature Treat for 40min, so that the initiator will initiate the C=C double bond on the surface of the water-washed PVDF microfiltration membrane to generate free radicals.
E、接枝 E. Grafting
向步骤D得到的溶液中加入质量分数为20%顺丁烯二酸酐、3%浓硫酸和6%正硅酸乙酯的混合水溶液，然后在温度:80℃的条件下，使所述PVDF微滤膜表面上的自由基与顺丁烯二酸酐进行接枝反应4h。反应结束所述的PVDF微滤膜表面可得一层亲水层。所述PVDF微滤膜放在纯水下洗涤15min后浸泡在质量分数为20%的甘油水溶液中2h，最后在室温下晾干即可得到表面有亲水层的PVDF微滤膜。 Add a mass fraction of 20% maleic anhydride, 3% concentrated sulfuric acid and 6% tetraethyl orthosilicate in the solution obtained in step D, and then make the PVDF slightly The free radicals on the membrane surface were grafted with maleic anhydride for 4h. After the reaction finishes, the surface of the PVDF microfiltration membrane can obtain a layer of hydrophilic layer. The PVDF microfiltration membrane was washed under pure water for 15 minutes, soaked in 20% glycerol aqueous solution for 2 hours, and finally dried at room temperature to obtain a PVDF microfiltration membrane with a hydrophilic layer on the surface.
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| CN106621842A (en) * | 2017-01-16 | 2017-05-10 | 南京大学 | Preparation method, regeneration method and application of chelating microfiltration membrane |
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| CN108514818A (en) * | 2018-05-02 | 2018-09-11 | 熊振 | A kind of hydrophilic PVDF film and preparation method thereof |
| CN108927007A (en) * | 2018-07-25 | 2018-12-04 | 哈尔滨工业大学（威海） | The modified PVDF filter membrane of method of modifying, gained of PVDF filter membrane and its application |
| CN111100300A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polymerizable polyether organic silicon, composition, preparation method and application thereof |
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