CN102872730B - Method for preparing polyvinylidene fluoride alloy film - Google Patents
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- CN102872730B CN102872730B CN201210362623.4A CN201210362623A CN102872730B CN 102872730 B CN102872730 B CN 102872730B CN 201210362623 A CN201210362623 A CN 201210362623A CN 102872730 B CN102872730 B CN 102872730B
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 62
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 62
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000005266 casting Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000004090 dissolution Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 230000004224 protection Effects 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 29
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000010865 sewage Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000003670 easy-to-clean Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910000601 superalloy Inorganic materials 0.000 abstract description 2
- 239000003085 diluting agent Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000005191 phase separation Methods 0.000 description 11
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 238000002145 thermally induced phase separation Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 4
- 238000000614 phase inversion technique Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种制备聚偏氟乙烯合金膜的方法，包括以下步骤：1）将聚偏氟乙烯、亲水性高分子和己内酰胺混合均匀；2）将混合后的聚偏氟乙烯、亲水性高分子和己内酰胺在氮气保护下加热升温到溶解温度，并在该温度下保持0.5～2h；3）待聚偏氟乙烯、亲水性高分子和己内酰胺完全溶解后，在溶解温度下搅拌0.5～1.5h，静置，得到铸膜液，将铸膜液在溶解温度下保存；4）将上述铸膜液制作成膜，放置在空气中自然冷却，直到完全固化；5）最后，通过萃取剂萃取出己内酰胺，即得到聚偏氟乙烯合金膜。该方法工艺简单、无污染、成本较低，制得的聚偏氟乙烯合金膜具有优良的化学稳定性、机械强度高，耐污染，易清洗，为污水处理、水资源再利用领域的MBR工艺提供高性能的合金膜产品，在工业、医疗、污水处理等领域应用广泛。
The invention relates to a method for preparing a polyvinylidene fluoride alloy film, comprising the following steps: 1) uniformly mixing polyvinylidene fluoride, a hydrophilic polymer and caprolactam; 2) mixing the mixed polyvinylidene fluoride, hydrophilic Heat the polymer and caprolactam under the protection of nitrogen to the dissolution temperature, and keep at this temperature for 0.5~2h; 3) After the polyvinylidene fluoride, hydrophilic polymer and caprolactam are completely dissolved, stir at the dissolution temperature for 0.5 ~1.5h, let it stand still to obtain the casting solution, and store the casting solution at the dissolution temperature; 4) Make the above casting solution into a film, and place it in the air to cool naturally until it is completely solidified; 5) Finally, through extraction The caprolactam is extracted with the solvent to obtain the polyvinylidene fluoride alloy film. The method has simple process, no pollution, and low cost. The polyvinylidene fluoride alloy film obtained has excellent chemical stability, high mechanical strength, pollution resistance, and is easy to clean. It is an MBR process in the field of sewage treatment and water resource reuse. Provide high-performance alloy membrane products, which are widely used in industrial, medical, sewage treatment and other fields.
Description
技术领域 technical field
本发明专利属于高分子材料制造领域，具体来说，涉及一种制备聚偏氟乙烯合金膜的方法，属于热致相分离法。 The patent of the present invention belongs to the field of polymer material manufacturing, and specifically relates to a method for preparing a polyvinylidene fluoride alloy film, which belongs to a thermally induced phase separation method.
背景技术 Background technique
聚偏氟乙烯（PVDF）具有突出的耐溶剂性、耐酸碱性、耐紫外线及耐候性，是一种优异的膜材料。近年来，聚偏氟乙烯合金膜在污水净化处理和生化制药行业得到了很好的应用。 Polyvinylidene fluoride (PVDF) has outstanding solvent resistance, acid and alkali resistance, ultraviolet resistance and weather resistance, and is an excellent membrane material. In recent years, polyvinylidene fluoride alloy membranes have been well applied in sewage purification treatment and biochemical pharmaceutical industries.
聚偏氟乙烯合金膜是一种聚合物多孔膜。聚合物多孔膜的制备有多种方法，主要有相转化法、拉伸法、烧结法和辐照法等，其中相转化法又包括热致相分离法、非溶剂致相分离法等。相转化法是最常见的方法之一，是通过控制聚合物溶液的液—液相分离来转化成膜的方法，根据相分离方式的不同，又可分为热诱导沉淀相分离法、溶液蒸发沉淀相分离法、气相沉淀相分离法和浸入沉淀相分离法。 Polyvinylidene fluoride alloy membrane is a kind of polymer porous membrane. There are many methods for the preparation of polymer porous membranes, mainly including phase inversion method, stretching method, sintering method and irradiation method, among which phase inversion method includes thermal induced phase separation method, non-solvent induced phase separation method and so on. The phase inversion method is one of the most common methods. It is a method of converting the polymer solution into a film by controlling the liquid-liquid phase separation. According to the different phase separation methods, it can be divided into thermally induced precipitation phase separation method, solution evaporation Precipitation phase separation method, gas phase precipitation phase separation method and immersion precipitation phase separation method.
热致相分离法(TIPS) 在近年来的膜分离技术中逐渐得到人们的重视。热致相分离法(TIPS)是20世纪80年代由Castro提出的一种由温度改变导致相分离来制备多孔膜（如微滤膜、超滤膜）的方法。使用高沸点、低分子量的单一或混合稀释剂在高温下与高聚物形成均相溶液，降温时均相溶液发生固-液或液-液相分离，而后脱除稀释剂，从而得到具有一定结构的高聚物微孔膜。与其它制膜方法比较，合适的稀释剂可使热致相分离法制得的膜具有强度好、孔隙率高、孔径易于调控等优势，因此受到人们的关注并得到较为系统的研究。目前采用的稀释剂多为非水溶性潜溶剂，不溶于水，所以成膜后还必须用别的萃取剂把它们萃取出来，工艺复杂，且对环境不友好。此外，由于PVDF的疏水性，单纯的PVDF膜在应用时易被水中的有机物污染，且不易清洗。 Thermally induced phase separation (TIPS) has gradually gained people's attention in membrane separation technology in recent years. Thermally induced phase separation (TIPS) is a method proposed by Castro in the 1980s to prepare porous membranes (such as microfiltration membranes, ultrafiltration membranes) by causing phase separation due to temperature changes. Use a single or mixed diluent with high boiling point and low molecular weight to form a homogeneous solution with the polymer at high temperature. When the temperature is lowered, the homogeneous solution undergoes solid-liquid or liquid-liquid phase separation, and then removes the diluent to obtain a certain Structured polymer microporous membrane. Compared with other membrane-making methods, a suitable diluent can make the membrane prepared by thermally induced phase separation have advantages such as good strength, high porosity, and easy control of pore size, so it has attracted people's attention and been systematically studied. Most of the diluents currently used are non-water-soluble latent solvents and are insoluble in water. Therefore, other extractants must be used to extract them after the film is formed. The process is complicated and it is not friendly to the environment. In addition, due to the hydrophobicity of PVDF, simple PVDF membranes are easily polluted by organic matter in water during application, and are not easy to clean.
发明内容 Contents of the invention
本发明所要解决的技术问题是，针对现有技术的不足，提供一种工艺简单、无污染、成本较低的制备聚偏氟乙烯合金膜的方法。 The technical problem to be solved by the present invention is to provide a method for preparing polyvinylidene fluoride alloy film with simple process, no pollution and low cost in view of the deficiencies in the prior art.
本发明解决上述技术问题所采用的技术方案为：一种制备聚偏氟乙烯合金膜的方法，包括以下步骤： The technical scheme adopted by the present invention to solve the above-mentioned technical problems is: a method for preparing a polyvinylidene fluoride alloy film, comprising the following steps:
1）将聚偏氟乙烯、亲水性高分子和己内酰胺混合均匀，其中，聚偏氟乙烯的重量百分含量为15～25%，亲水性高分子的重量百分含量为1～4%，己内酰胺的重量百分含量为70～85%； 1) Mix polyvinylidene fluoride, hydrophilic polymer and caprolactam evenly, wherein the weight percentage of polyvinylidene fluoride is 15-25%, and the weight percentage of hydrophilic polymer is 1-4% , the weight percentage of caprolactam is 70～85%;
2）将混合后的聚偏氟乙烯、亲水性高分子和己内酰胺在氮气保护下加热升温到溶解温度，并在该温度下保持0.5～2h； 2) Heat the mixed polyvinylidene fluoride, hydrophilic polymer and caprolactam under the protection of nitrogen to the dissolution temperature, and keep at this temperature for 0.5 to 2 hours;
3）待聚偏氟乙烯、亲水性高分子和己内酰胺完全溶解后，在溶解温度下搅拌0.5～1.5h，静置，得到铸膜液，将铸膜液在溶解温度下保存； 3) After the polyvinylidene fluoride, hydrophilic polymer and caprolactam are completely dissolved, stir at the dissolution temperature for 0.5 to 1.5 hours, and let stand to obtain the casting solution, which is stored at the dissolution temperature;
4）将上述铸膜液制作成膜，放置在空气中自然冷却，直到完全固化； 4) Make the above casting liquid into a film, and place it in the air to cool naturally until it is completely solidified;
5）最后，通过萃取剂萃取出己内酰胺，即得到聚偏氟乙烯合金膜。 5) Finally, the caprolactam is extracted by the extractant to obtain the polyvinylidene fluoride alloy film.
优选地，所述的亲水性高分子为聚氧化乙烯（PEO）、聚乙烯醇（PVA）、聚乙烯吡咯烷酮（PVP）中的一种或几种。 Preferably, the hydrophilic polymer is one or more of polyethylene oxide (PEO), polyvinyl alcohol (PVA), and polyvinylpyrrolidone (PVP).
优选地，在步骤2）和步骤3）中，所述的溶解温度的温度范围为140～170℃。 Preferably, in step 2) and step 3), the temperature range of the dissolution temperature is 140-170°C.
优选地，在步骤5）中，所述的萃取剂为水或乙醇。 Preferably, in step 5), the extractant is water or ethanol.
优选地，在步骤5）中，所述的聚偏氟乙烯合金膜的厚度为20～200µm。 Preferably, in step 5), the thickness of the polyvinylidene fluoride alloy film is 20-200 μm.
优选地，所述的聚偏氟乙烯合金膜的厚度为100～140µm。 Preferably, the thickness of the polyvinylidene fluoride alloy film is 100-140 µm.
与现有技术相比，本发明的优点在于：（1）本发明利用了“高温溶解，低温分相”的原理，以己内酰胺作为稀释剂，以亲水性高分子聚氧化乙烯（PEO）、聚乙烯醇（PVA）或聚乙烯吡咯烷酮（PVP）中的一种或几种作为添加剂，将聚偏氟乙烯、亲水性高分子与己内酰胺混合均匀后在高温下混合溶解并搅拌成均匀的铸膜液，再将铸膜液制作成膜，放置在空气中自然冷却至完全固化，使铸膜液体系发生液-液或固-液分离，聚合物体系固化后形成PVDF与稀释剂的双连续结构，此后，将膜上的己内酰胺萃取掉，己内酰胺所在位置形成孔状，而余下的聚合物骨架则被保留下来；（2）本发明在原料中添加了亲水性高分子，改善膜的亲水性，使聚偏氟乙烯合金膜保持永久亲水的性能，与未添加亲水性高分子的传统聚偏氟乙烯合金膜相比，耐污染，易清洗，且清洗后，膜的水通量、截留率等性能恢复较好，对性能的影响不大；（3）本发明方法所制得的聚偏氟乙烯合金膜为双连续网络结构而非通常的球状结构，与球状结构相比较，双连续网络结构的膜的机械强度更好；（4）所采用的稀释剂己内酰胺是水溶性的，用水或乙醇萃取己内酰胺，可避免采用酮、酯类等作为萃取剂，从而降低了聚偏氟乙烯合金膜的生产成本且对环境也无污染，绿色环保；且水溶性的己内酰胺室温下为固体，易于回收利用；（5）本发明的制膜方法工艺简单、无污染、成本较低，制备的聚偏氟乙烯合金膜具有优良的化学稳定性、机械强度高，能为污水处理、水资源再利用领域的MBR（注：MBR，即Membrane Bio-Reactor，又称膜生物反应器）工艺提供高性能的合金膜产品，在工业、医疗、污水处理等领域应用广泛。 Compared with the prior art, the advantages of the present invention are: (1) The present invention utilizes the principle of "dissolving at high temperature and phase separation at low temperature", uses caprolactam as diluent, and uses hydrophilic polymer polyethylene oxide (PEO), One or more of polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) is used as an additive, polyvinylidene fluoride, hydrophilic polymer and caprolactam are mixed uniformly, then mixed and dissolved at high temperature and stirred to form a uniform casting The film liquid, and then make the film casting liquid into a film, and place it in the air to cool naturally until it is completely solidified, so that the liquid-liquid or solid-liquid separation of the film casting liquid system occurs, and the polymer system is solidified to form a double continuous film of PVDF and diluent. After that, the caprolactam on the membrane is extracted, and the position of the caprolactam forms a hole shape, while the remaining polymer skeleton is retained; (2) The present invention adds a hydrophilic polymer to the raw material to improve the hydrophilicity of the membrane. Water-based, which keeps the polyvinylidene fluoride alloy membrane permanently hydrophilic. Compared with the traditional polyvinylidene fluoride alloy membrane without adding hydrophilic polymers, it is resistant to pollution and easy to clean. After cleaning, the water flow of the membrane (3) The polyvinylidene fluoride alloy membrane prepared by the method of the present invention has a bicontinuous network structure rather than the usual spherical structure, and compared with the spherical structure , the mechanical strength of the film with bicontinuous network structure is better; (4) The diluent caprolactam used is water-soluble, and the extraction of caprolactam with water or ethanol can avoid the use of ketones, esters, etc. The production cost of vinyl fluoride alloy film is also non-polluting to the environment, which is green and environmentally friendly; and the water-soluble caprolactam is solid at room temperature, which is easy to recycle; (5) The film-making method of the present invention is simple in process, pollution-free, and low in cost. The prepared polyvinylidene fluoride alloy membrane has excellent chemical stability and high mechanical strength, and can be used in the MBR (Note: MBR, Membrane Bio-Reactor, also known as membrane bioreactor) process in the field of sewage treatment and water resource reuse. Provide high-performance alloy membrane products, which are widely used in industrial, medical, sewage treatment and other fields.
附图说明 Description of drawings
图1是本发明实施例1制备的聚偏氟乙烯合金膜的形貌结构的SEM图。 FIG. 1 is an SEM image of the morphology and structure of the polyvinylidene fluoride alloy film prepared in Example 1 of the present invention.
具体实施方式 Detailed ways
以下结合附图实施例对本发明作进一步详细描述。 The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.
实施例1：准确称量己内酰胺185g、聚偏氟乙烯60g、聚乙烯吡咯烷酮2.5g，将以上三种原料搅拌均匀后倒入500mL带塞广口瓶中，在缓慢通氮气保护条件下，采用油浴加热，所用油浴温度为140℃，加热使原料完全溶解，并在140℃下保持45分钟，然后用电动搅拌器搅拌溶液30分钟，之后在油浴中静置脱泡，得到铸膜液，然后将铸膜液在140℃下保温保存。将所得到的铸膜液倒入模板中刮制成膜，放置在空气中自然冷却，直到完全固化，然后放入水中将稀释剂己内酰胺溶解出来，即得到聚偏氟乙烯合金膜，该聚偏氟乙烯合金膜的厚度为125µm。 Example 1: Accurately weigh 185g of caprolactam, 60g of polyvinylidene fluoride, and 2.5g of polyvinylpyrrolidone. Stir the above three raw materials evenly and pour them into a 500mL jar with a stopper. Under the condition of slow nitrogen protection, use oil Bath heating, the temperature of the oil bath used is 140 ° C, heating to completely dissolve the raw materials, and keeping at 140 ° C for 45 minutes, then stirring the solution with an electric stirrer for 30 minutes, and then standing in the oil bath for defoaming to obtain the casting solution , and then keep the casting solution at 140°C for preservation. Pour the obtained film-casting solution into a template and scrape it into a film, place it in the air to cool naturally until it is completely solidified, and then put it into water to dissolve the diluent caprolactam to obtain a polyvinylidene fluoride alloy film. The thickness of the vinyl fluoride alloy film is 125µm.
本发明实施例1制备的聚偏氟乙烯合金膜的形貌结构的SEM图见图1，从图1可见，所制得的聚偏氟乙烯合金膜为双连续网络结构，而非通常的球状结构。 The SEM image of the morphology and structure of the polyvinylidene fluoride alloy film prepared in Example 1 of the present invention is shown in Figure 1, as can be seen from Figure 1, the prepared polyvinylidene fluoride alloy film is a double continuous network structure, rather than the usual spherical shape structure.
本实施例1制得的聚偏氟乙烯合金膜在25℃时的纯水通量为84.0L/（m2∙h），接触角为57.6o，而未添加亲水性高分子聚乙烯吡咯烷酮的纯PVDF膜的接触角为78o。 The pure water flux of the polyvinylidene fluoride alloy membrane prepared in Example 1 was 84.0L/(m 2 ∙h) at 25°C, and the contact angle was 57.6 o without adding the hydrophilic polymer polyvinylpyrrolidone The pure PVDF membrane has a contact angle of 78o .
实施例2：准确称量己内酰胺182.5g、聚偏氟乙烯62.5g、聚乙烯吡咯烷酮5.1g，将以上三种原料搅拌均匀后倒入500mL带塞广口瓶中，在缓慢通氮气保护条件下，采用油浴加热，所用油浴温度为150℃，加热使原料完全溶解，并在150℃下保持1h，然后用电动搅拌器搅拌溶液30分钟，之后在油浴中静置脱泡，得到铸膜液，然后将铸膜液在150℃下保温保存。将所得到的铸膜液倒入模板中刮制成膜，放置在空气中自然冷却，直到完全固化，然后放入水中将稀释剂己内酰胺溶解出来，即得到聚偏氟乙烯合金膜，该聚偏氟乙烯合金膜的厚度为120µm。 Example 2: Accurately weigh 182.5g of caprolactam, 62.5g of polyvinylidene fluoride, and 5.1g of polyvinylpyrrolidone. Stir the above three raw materials evenly and pour them into a 500mL jar with a stopper. Under the condition of slow nitrogen protection, Heating in an oil bath, the temperature of the oil bath used is 150°C, heating to completely dissolve the raw materials, and keeping at 150°C for 1 hour, then stirring the solution with an electric stirrer for 30 minutes, and then standing in the oil bath for defoaming to obtain a cast film solution, and then the casting solution was kept at 150°C. Pour the obtained film-casting solution into a template and scrape it into a film, place it in the air to cool naturally until it is completely solidified, and then put it into water to dissolve the diluent caprolactam to obtain a polyvinylidene fluoride alloy film. The thickness of the vinyl fluoride alloy film is 120 µm.
本实施例2制得的聚偏氟乙烯合金膜在25℃时的纯水通量为89.0L/（m2∙h），接触角为54.0o。 The pure water flux of the polyvinylidene fluoride alloy membrane prepared in Example 2 was 89.0L/(m 2 ∙h) at 25°C, and the contact angle was 54.0o .
实施例3：准确称量己内酰胺177.5g、聚偏氟乙烯62.5g、聚乙烯吡咯烷酮10g，将以上三种原料搅拌均匀后倒入500mL带塞广口瓶中，在缓慢通氮气保护条件下，采用油浴加热，所用油浴温度为160℃，加热使原料完全溶解，并在160℃下保持1.5h，然后用电动搅拌器搅拌溶液45分钟，之后在油浴中静置脱泡，得到铸膜液，然后将铸膜液在160℃下保温保存。将所得到的铸膜液倒入模板中刮制成膜，放置在空气中自然冷却，直到完全固化，然后放入水中将稀释剂己内酰胺溶解出来，即得到聚偏氟乙烯合金膜，该聚偏氟乙烯合金膜的厚度为115µm。 Example 3: Accurately weigh 177.5g of caprolactam, 62.5g of polyvinylidene fluoride, and 10g of polyvinylpyrrolidone, stir the above three raw materials evenly, pour them into a 500mL jar with a stopper, and use Heating in an oil bath, the temperature of the oil bath used is 160 ° C, heating to completely dissolve the raw materials, and keeping at 160 ° C for 1.5 hours, then stirring the solution with an electric stirrer for 45 minutes, and then standing in the oil bath for defoaming to obtain a cast film solution, and then the casting solution was kept at 160°C. Pour the obtained film-casting solution into a template and scrape it into a film, place it in the air to cool naturally until it is completely solidified, and then put it into water to dissolve the diluent caprolactam to obtain a polyvinylidene fluoride alloy film. The thickness of the vinyl fluoride alloy film is 115 µm.
本实施例3制得的聚偏氟乙烯合金膜在25℃时的纯水通量为109.5L/（m2∙h），接触角为50.4o。 The pure water flux of the polyvinylidene fluoride alloy membrane prepared in Example 3 was 109.5L/(m 2 ∙h) at 25°C, and the contact angle was 50.4o .
实施例4：准确称量己内酰胺108g、聚偏氟乙烯32g、聚乙烯醇4g，将以上三种原料搅拌均匀后倒入250mL带塞广口瓶中，在缓慢通氮气保护条件下，采用油浴加热，所用油浴温度为160℃，加热使原料完全溶解，并在160℃下保持1h，然后用电动搅拌器搅拌溶液1h，之后在油浴中静置脱泡，得到铸膜液，然后将铸膜液在160℃下保温保存。将所得到的铸膜液倒入模板中刮制成膜，放置在空气中自然冷却，直到完全固化，然后放入水中将稀释剂己内酰胺溶解出来，即得到聚偏氟乙烯合金膜，该聚偏氟乙烯合金膜的厚度为110µm。 Example 4: Accurately weigh 108g of caprolactam, 32g of polyvinylidene fluoride, and 4g of polyvinyl alcohol, stir the above three raw materials evenly, pour them into a 250mL jar with a stopper, and use an oil bath under the condition of slow nitrogen protection. Heating, the temperature of the oil bath used is 160 ° C, heating to completely dissolve the raw materials, and keeping at 160 ° C for 1 h, then stirring the solution with an electric stirrer for 1 h, and then standing in the oil bath for defoaming to obtain the casting solution, and then The casting solution was kept warm at 160°C. Pour the obtained film-casting solution into a template and scrape it into a film, place it in the air to cool naturally until it is completely solidified, and then put it into water to dissolve the diluent caprolactam to obtain a polyvinylidene fluoride alloy film. The thickness of the vinyl fluoride alloy film was 110 µm.
本实施例4制得的聚偏氟乙烯合金膜在25℃时的纯水通量为214.1 L/(m2∙h)。 The pure water flux of the polyvinylidene fluoride alloy membrane prepared in Example 4 was 214.1 L/(m 2 ∙h) at 25°C.
实施例5：准确称量己内酰胺178g、聚偏氟乙烯62g、聚乙烯吡咯烷酮10g，将以上三种原料搅拌均匀后倒入500mL带塞广口瓶中，在缓慢通氮气保护条件下，采用油浴加热，所用油浴温度为150℃，加热使原料完全溶解，并在150℃下保持0.5h，然后用电动搅拌器搅拌溶液30分钟，之后在油浴中静置脱泡，得到铸膜液，然后将铸膜液在150℃下保温保存。将所得到的铸膜液倒入模板中刮制成膜，放置在空气中自然冷却，直到完全固化，然后放入水中将稀释剂己内酰胺溶解出来，即得到聚偏氟乙烯合金膜，该聚偏氟乙烯合金膜的厚度为110µm。 Example 5: Accurately weigh 178g of caprolactam, 62g of polyvinylidene fluoride, and 10g of polyvinylpyrrolidone, stir the above three raw materials evenly, pour them into a 500mL jar with a stopper, and use an oil bath under the condition of slow nitrogen protection. Heating, the temperature of the oil bath used is 150°C, heating to completely dissolve the raw materials, and keeping at 150°C for 0.5h, then stirring the solution with an electric stirrer for 30 minutes, and then standing in the oil bath for defoaming to obtain the casting solution. Then the casting solution was kept at 150°C for heat preservation. Pour the obtained film-casting solution into a template and scrape it into a film, place it in the air to cool naturally until it is completely solidified, and then put it into water to dissolve the diluent caprolactam to obtain a polyvinylidene fluoride alloy film. The thickness of the vinyl fluoride alloy film was 110 µm.
本实施例5制得的聚偏氟乙烯合金膜在25℃时的纯水通量为109.4L/（m2∙h）。 The pure water flux of the polyvinylidene fluoride alloy membrane prepared in Example 5 was 109.4 L/(m 2 ∙h) at 25°C.
实施例6：准确称量己内酰胺164g、聚偏氟乙烯30g、聚氧化乙烯6g，将以上三种原料搅拌均匀后倒入500mL带塞广口瓶中，在缓慢通氮气保护条件下，采用油浴加热，所用油浴温度为150℃，加热使原料完全溶解，并在150℃下保持0.5h，然后用电动搅拌器搅拌溶液40分钟，之后在油浴中静置脱泡，得到铸膜液，然后将铸膜液在150℃下保温保存。将所得到的铸膜液倒入模板中刮制成膜，放置在空气中自然冷却，直到完全固化，然后放入水中将稀释剂己内酰胺溶解出来，即得到聚偏氟乙烯合金膜，该聚偏氟乙烯合金膜的厚度为100µm。 Example 6: Accurately weigh 164g of caprolactam, 30g of polyvinylidene fluoride, and 6g of polyethylene oxide, stir the above three raw materials evenly, pour them into a 500mL jar with a stopper, and use an oil bath under the condition of slow nitrogen protection. Heating, the temperature of the oil bath used is 150°C, heating to completely dissolve the raw materials, and keeping at 150°C for 0.5h, then stirring the solution with an electric stirrer for 40 minutes, and then standing in the oil bath for defoaming to obtain the casting solution. Then the casting solution was kept at 150°C for heat preservation. Pour the obtained film-casting solution into a template and scrape it into a film, place it in the air to cool naturally until it is completely solidified, and then put it into water to dissolve the diluent caprolactam to obtain a polyvinylidene fluoride alloy film. The thickness of the vinyl fluoride alloy film was 100 µm.
本实施例6制得的聚偏氟乙烯合金膜在25℃时的纯水通量为728.5L/（m2∙h）。 The pure water flux of the polyvinylidene fluoride alloy membrane prepared in Example 6 was 728.5 L/(m 2 ∙h) at 25°C.
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| CN101342468A (en) * | 2008-08-22 | 2009-01-14 | 清华大学 | A kind of preparation method of β crystal phase polyvinylidene fluoride hollow fiber porous membrane |
| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | A kind of method for preparing polyvinylidene fluoride porous film |
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| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | A kind of method for preparing polyvinylidene fluoride porous film |
| CN101269302A (en) * | 2008-05-06 | 2008-09-24 | 南京奥特高科技有限公司 | Non-crystallization permanent hydrophilic PVDF membrane material and preparation method thereof |
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