技术领域technical field
本发明涉及一种用于分离领域的分离膜材的制备方法，具体涉及一种疏水膜材的制备方法。The invention relates to a preparation method of a separation membrane material used in the separation field, in particular to a preparation method of a hydrophobic membrane material.
技术背景technical background
疏水性是聚四氟乙烯(PTFE)材料的重要性质，是聚四氟乙烯多孔膜被应用于膜材料的主要性能。聚四氟乙烯材料虽然具有低表面能，但是，光滑聚四氟乙烯平面的水接触角在98到112°之间，疏水性能并不佳。Hydrophobicity is an important property of polytetrafluoroethylene (PTFE) materials, and it is the main performance of PTFE porous membranes applied to membrane materials. Although polytetrafluoroethylene material has low surface energy, the water contact angle of smooth polytetrafluoroethylene plane is between 98° and 112°, and the hydrophobic performance is not good.
目前聚四氟乙烯多孔膜制备多采用双向拉伸方法。这种方法要想得到较高孔隙率的薄膜时，需要对薄膜进行大比例拉伸，无法对表面结构进行控制，且膜厚仅在十几微米以下，使用中需要支撑材料，而支撑材料本身往往在耐热性或化学稳定性或疏水性能上有一定局限，因而限制了这种双向拉伸膜的应用。同时高比例拉伸往往难以控制膜的形状，因此主要以平板膜为主。中国专利CN1775847A、CN102007242A、CN101543734B、CN102151494A等专利都基于以上双向拉伸工艺进行聚四氟乙烯多孔膜制备。At present, the biaxial stretching method is mostly used in the preparation of polytetrafluoroethylene porous membranes. When this method wants to obtain a film with a higher porosity, the film needs to be stretched at a large scale, the surface structure cannot be controlled, and the film thickness is only less than a dozen microns. Supporting materials are needed in use, and the supporting materials themselves are often There are certain limitations in heat resistance or chemical stability or hydrophobic properties, thus limiting the application of this biaxially stretched film. At the same time, high-ratio stretching is often difficult to control the shape of the film, so it is mainly flat film. Chinese patents such as CN1775847A, CN102007242A, CN101543734B, and CN102151494A are all based on the above biaxial stretching process for the preparation of polytetrafluoroethylene porous membranes.
载体法是制备聚四氟乙烯纤维的重要方法，CN101994161A和CN102282301A等专利采用静电纺丝技术对聚四氟乙烯超细纤维的制备进行了报道。这些报道中都涉及高温烧结除去成纤载体的步骤，但是这些烧结过程仅关注成纤模板的去除。具体地说：CN101994161A的目的是制备一种聚四氟乙烯超细纤维，其制备方法是采用聚乙烯醇作载体，通过静电纺丝方法纺织出聚四氟乙烯纤维前体，后处理方法为将聚四氟乙烯纤维前体在100～120℃下干燥5～15分钟，再于280～350℃下烧结30～90分钟；烧结的目的是为了使聚乙烯醇分解而去除。而CN102282301A的主要是提供一种聚四氟乙烯垫的改进方法，其目的是为了改进电纺的工艺参数(纺丝液粘度)来获得直径均匀的聚四氟乙烯纤维垫前体，再于400℃下烧结得到聚四氟乙烯纤维垫，载体(成纤聚合物)的灰分小于5％。CN101994161A和CN102282301A等专利采用静电纺丝技术对聚四氟乙烯超细纤维(垫)，仅考虑了如何得到聚四氟乙烯超细纤维(垫)，可以说只得到常规聚四氟乙烯超细纤维(垫)。The carrier method is an important method for preparing polytetrafluoroethylene fibers. Patents such as CN101994161A and CN102282301A report the preparation of polytetrafluoroethylene ultrafine fibers by using electrospinning technology. These reports all involve high-temperature sintering to remove the fiber-forming support, but these sintering processes only focus on the removal of the fiber-forming template. Specifically: the purpose of CN101994161A is to prepare a kind of polytetrafluoroethylene superfine fiber, and its preparation method is to adopt polyvinyl alcohol as carrier, weaves the polytetrafluoroethylene fiber precursor by electrospinning method, and post-processing method is to The polytetrafluoroethylene fiber precursor is dried at 100-120°C for 5-15 minutes, and then sintered at 280-350°C for 30-90 minutes; the purpose of sintering is to decompose and remove polyvinyl alcohol. And what CN102282301A mainly is to provide a kind of improved method of polytetrafluoroethylene mat, its purpose is to obtain the polytetrafluoroethylene fiber mat precursor with uniform diameter in order to improve the process parameter (spinning liquid viscosity) of electrospinning, then in 400 The polytetrafluoroethylene fiber mat is obtained by sintering at ℃, and the ash content of the carrier (fiber-forming polymer) is less than 5%. Patents such as CN101994161A and CN102282301A adopt electrospinning technology to polytetrafluoroethylene superfine fiber (mat), only consider how to obtain polytetrafluoroethylene superfine fiber (mat), it can be said that only conventional polytetrafluoroethylene superfine fiber is obtained (pad).
发明内容Contents of the invention
本发明的目的在于提供一种聚四氟乙烯膜的制备方法，通过控制含成纤载体的聚四氟乙烯前驱膜的后处理烧结条件，通过程序控温的方法精密控制烧结条件以得到纤维形态保持完好并具有串珠状结构的超细纤维网状膜，这种纳米尺度的特殊结构与超细纤维一道形成具有多级粗糙结构的疏水表面。因而具有超疏水性能。The purpose of the present invention is to provide a preparation method of polytetrafluoroethylene film, by controlling the post-treatment sintering conditions of the polytetrafluoroethylene precursor film containing the fiber-forming carrier, the sintering conditions are precisely controlled by the method of program temperature control to obtain the fiber shape The microfiber network membrane remains intact and has a beaded structure. This special nanoscale structure forms a hydrophobic surface with a multi-level rough structure together with the microfibers. Therefore, it has superhydrophobic properties.
本发明的目的由以下技术措施实现：The object of the present invention is achieved by the following technical measures:
一种聚四氟乙烯膜的制备方法，包括纺丝液配液、制纤、烧结，其特征在于：成纤载体与溶剂配制成溶液后加入聚四氟乙烯乳液，成纤载体为聚乙烯醇，溶剂为水；所述烧结采用程序控温分段连续烧结，在流动气氛下，在90℃～120℃保温30～120min，以3～10℃/min的速率从90℃～120℃升温到260℃～300℃，在260℃～300℃保温30～120min；以2～8℃/min的速率从260℃～300℃升温到370℃～390℃，在370℃～390℃保温5～120min。通过控制含成纤载体的聚四氟乙烯前驱膜的后处理烧结条件，在应力作用下，在载体保护作用下，聚四氟乙烯颗粒开始重新取向排列，随后在恰当时机载体分解，聚四氟乙烯颗粒进一步取向重排，形成串珠状的超细纤维网状结构。采用所述的程序控制条件进行制备方可制得具有特殊结构的超疏水聚四氟乙烯纤维膜。若不在本发明的程序控制条件下，如CN101994161A所述于280-350℃下烧结30-90分钟，则无法获得具有多级粗糙度的、水接触角150°以上的超疏水聚四氟乙烯纤维膜，且膜没有柔性。另外若不采用程序控制(如CN102282301A于400℃下烧结得到聚四氟乙烯纤维垫，载体(成纤聚合物)的灰分小于5％。)则无法保持纤维的原有形态，致使纤维塌陷成扁平状。A method for preparing a polytetrafluoroethylene film, including dosing of spinning solution, fiber making, and sintering, characterized in that: the fiber-forming carrier and solvent are formulated into a solution and then polytetrafluoroethylene emulsion is added, and the fiber-forming carrier is polyvinyl alcohol , the solvent is water; the sintering adopts the step-by-step continuous sintering with programmed temperature control. 260℃～300℃, heat preservation at 260℃～300℃ for 30～120min; heat up from 260℃～300℃ to 370℃～390℃ at a rate of 2～8℃/min, heat preservation at 370℃～390℃ for 5～120min . By controlling the post-treatment sintering conditions of the PTFE precursor film containing the fiber-forming carrier, under the action of stress and under the protection of the carrier, the PTFE particles begin to re-orientate, and then the carrier decomposes at the right time, and the PTFE The ethylene particles are further oriented and rearranged to form a beaded microfiber network structure. The superhydrophobic polytetrafluoroethylene fiber membrane with special structure can be prepared by adopting the above-mentioned program control conditions for preparation. If it is not under the program control conditions of the present invention, as described in CN101994161A, it is sintered at 280-350 ° C for 30-90 minutes, then it is impossible to obtain superhydrophobic polytetrafluoroethylene fibers with multi-level roughness and a water contact angle of more than 150° membrane, and the membrane is not flexible. In addition, if program control is not adopted (such as CN102282301A is sintered at 400° C. to obtain a polytetrafluoroethylene fiber mat, the ash content of the carrier (fiber-forming polymer) is less than 5%.) then the original shape of the fiber cannot be maintained, causing the fiber to collapse into a flat shape.
优选地，上述烧结采用程序控温分段连续烧结，在流动气氛下，以2～15℃/min从室温升温至90℃～120℃，在90℃～120℃保温50～100min，以5～8℃/min的速率从100℃～120℃升温到280℃～300℃，在280℃～300℃保温60～120min；以4～7℃/min的速率从280℃～300℃升温到380℃～390℃，在380℃～390℃保温30～80min。Preferably, the above-mentioned sintering adopts segmental continuous sintering with programmed temperature control. Under a flowing atmosphere, the temperature is raised from room temperature to 90°C-120°C at a rate of 2-15°C/min, kept at 90°C-120°C for 50-100min, and at a rate of 5-15°C. Heating at a rate of 8°C/min from 100°C to 120°C to 280°C to 300°C, holding at 280°C to 300°C for 60 to 120 minutes; heating at a rate of 4 to 7°C/min from 280°C to 300°C to 380°C ～390℃, keep warm at 380℃～390℃ for 30～80min.
上述聚四氟乙烯膜的制备方法，制纤后烧结前包括预成型步骤，所述预成型是将聚四氟乙烯前驱膜缠绕在支撑模上，通过缠绕层数控制聚四氟乙烯膜厚度及平均孔径大小。纤维的缠绕叠加有利于烧结过程的应力取向。The preparation method of the above-mentioned polytetrafluoroethylene film includes a preforming step before sintering after fiber making, and the preforming is to wind the polytetrafluoroethylene precursor film on the support mold, and control the thickness and thickness of the polytetrafluoroethylene film by the number of winding layers. average pore size. The intertwined superposition of fibers is beneficial to the stress orientation during the sintering process.
聚乙烯醇水溶液的质量浓度为0.5％～30％，聚乙烯醇与聚四氟乙烯干重比为1∶1～50。The mass concentration of the polyvinyl alcohol aqueous solution is 0.5%-30%, and the dry weight ratio of polyvinyl alcohol to polytetrafluoroethylene is 1:1-50.
具体地，一种聚四氟乙烯膜的制备方法，包括以下步骤：Specifically, a kind of preparation method of polytetrafluoroethylene film, comprises the following steps:
(1)纺丝液配制；将聚乙烯醇溶于水配成浓度为0.5％～30％质量浓度的均匀溶液，然后搅拌加入聚四氟乙烯乳液，得到均匀的混合液；聚乙烯醇与聚四氟乙烯干重比在1∶1～50；(1) Spinning solution preparation; dissolving polyvinyl alcohol in water to make a uniform solution with a concentration of 0.5% to 30% mass concentration, then stirring and adding polytetrafluoroethylene emulsion to obtain a uniform mixed solution; polyvinyl alcohol and polyvinyl alcohol The dry weight ratio of tetrafluoroethylene is 1:1~50;
(2)制纤；采用纺丝或拉伸的方法对(1)中配制的纺丝液进行纺丝制备纤维得到聚四氟乙烯前驱膜；(2) fiber making; the spinning solution prepared in (1) is spun to prepare fibers by spinning or stretching to obtain a polytetrafluoroethylene precursor film;
(3)预成型：按照预期的使用规格，将(2)中所得到的得到聚四氟乙烯前驱膜缠绕在相应形状的支撑模上，形成平板式、管式、中空纤维式或卷式等不同形状和规格的膜，通过缠绕层数控制膜厚；(3) Preforming: According to the expected use specifications, the PTFE precursor film obtained in (2) is wound on a support mold of a corresponding shape to form a flat, tubular, hollow fiber or roll type, etc. For films of different shapes and specifications, the thickness of the film is controlled by the number of winding layers;
(4)烧结；将(3)中得到的预成型聚四氟乙烯前驱膜连同支撑模放入高温炉中在连续通入气氛的条件下进行烧结；烧结采用程序控温分段连续烧结，在惰性流动气氛下，在90℃～120℃保温30～120min，以3～10℃/min的速率从90℃～120℃升温到260℃～300℃，在260℃～300℃保温30～120min；以2～8℃/min的速率从260℃～300℃升温到370℃～390℃，在370℃～390℃保温5～120min。(4) sintering; the preformed polytetrafluoroethylene precursor film obtained in (3) is put into a high-temperature furnace together with the support mold and sintered under the condition of continuously feeding the atmosphere; Under an inert flowing atmosphere, keep warm at 90°C-120°C for 30-120min, raise the temperature from 90°C-120°C to 260°C-300°C at a rate of 3-10°C/min, and keep warm at 260°C-300°C for 30-120min; Raise the temperature from 260°C to 300°C to 370°C to 390°C at a rate of 2 to 8°C/min, and keep at 370°C to 390°C for 5 to 120 minutes.
上述流动气氛为氮气、空气或惰性气体至少一种。The above-mentioned flow atmosphere is at least one of nitrogen, air or inert gas.
有益效果Beneficial effect
1.本发明制得了结构独特的聚四氟乙烯膜，具有由串珠状纤维丝纵横交错形成的孔隙三维连通结构，是一道形成具有多级粗糙结构的疏水表面，串珠状纤维丝是指聚四氟乙烯颗粒之间相互点和/或面黏结形成的纤维丝；孔隙呈曲径孔，最大孔径为1.0μm，最小孔径为0.01μm，平均孔径为0.1μm～0.5μm；纤维丝为纳米纤维，平均直径为500±50nm。1. The present invention has made the polytetrafluoroethylene film of unique structure, has the pore three-dimensional interconnected structure that is formed by the criss-cross pattern of beaded fiber silk, is to form the hydrophobic surface with multi-level rough structure together, and beaded fiber silk refers to polytetrafluoroethylene Fiber filaments formed by point and/or surface bonding between vinyl fluoride particles; the pores are labyrinth pores, with a maximum pore diameter of 1.0 μm, a minimum pore diameter of 0.01 μm, and an average pore diameter of 0.1 μm to 0.5 μm; the fiber filaments are nanofibers, The average diameter is 500±50nm.
2.本发明极好的解决了在聚四氟乙烯前驱膜烧结中纤维易塌陷的问题，并且得到了具有串珠状超细纤维网状膜，纤维之间由无序堆叠变为相互粘连，纤维形态均一、表面完好，强度和韧性也有较大提高，并能够承受一定真空压力(可在0.7kPa真空度下仍可稳定操作)。2. The present invention perfectly solves the problem that the fibers are easy to collapse in the sintering of the polytetrafluoroethylene precursor film, and obtains a beaded ultrafine fiber mesh film, and the fibers change from disordered stacking to mutual adhesion, and the fibers The shape is uniform, the surface is intact, the strength and toughness are also greatly improved, and it can withstand a certain vacuum pressure (it can still operate stably under a vacuum of 0.7kPa).
3.本发明所制得的聚四氟乙烯多孔膜，具有特殊超疏水性结构，得到的PTFE纤维表面形成大量粗糙表面，表面水接触角≥150°，孔隙率高达80％以上。3. The polytetrafluoroethylene porous membrane obtained by the present invention has a special superhydrophobic structure, and a large number of rough surfaces are formed on the surface of the obtained PTFE fiber, the surface water contact angle is more than or equal to 150°, and the porosity is as high as more than 80%.
4、本发明所制得的聚四氟乙烯多孔膜无需支撑，厚度可控，应用于膜蒸馏过程，通量≥26L/m2·h，截留率在99％以上。4. The polytetrafluoroethylene porous membrane prepared by the present invention does not need support, and its thickness is controllable. It is applied to the membrane distillation process, with a flux ≥ 26L/m2 ·h and a rejection rate of over 99%.
5、本发明提出了烧结前的缠绕工艺进行预成型，对最终产品膜的形状和厚度能够进行控制，在保证高孔隙率(80％以上)的同时，提供了膜所需的厚度和强度。对比于为得到高孔隙率而高比例拉伸的双向拉伸工艺，本发明方法所得到的聚四氟乙烯膜无需支撑，形式多样，厚度可控。5. The present invention proposes preforming by winding process before sintering, which can control the shape and thickness of the final product membrane, and provide the required thickness and strength of the membrane while ensuring high porosity (above 80%). Compared with the biaxial stretching process of high-ratio stretching to obtain high porosity, the polytetrafluoroethylene membrane obtained by the method of the invention does not need support, has various forms, and has controllable thickness.
6、本发明提供的聚四氟乙烯超疏水膜制备方法，采用烧结条件控制步骤，使载体在恰当时机分解，而聚四氟乙烯颗粒熔融取向重排，得到了具有串珠状超细纤维网状膜，这种纳米尺度的特殊结构与超细纤维一道形成具有多级粗糙结构的疏水表面。因而具有超疏水性能。6. The preparation method of the polytetrafluoroethylene superhydrophobic membrane provided by the present invention adopts the sintering condition control step, so that the carrier is decomposed at the right time, and the polytetrafluoroethylene particles are melted and oriented to rearrange, and a network with beaded ultrafine fibers is obtained. Membranes, this nanoscale special structure together with microfibers form a hydrophobic surface with a multi-level rough structure. Therefore, it has superhydrophobic properties.
7、本发明避免了双向拉伸中润滑剂等的使用，不存在润滑剂的除去问题，工艺简单，无需挤出，压膜等复杂流程，污染小。7. The present invention avoids the use of lubricants in biaxial stretching, does not have the problem of removing lubricants, has a simple process, does not require complex processes such as extrusion and film pressing, and has little pollution.
附图说明Description of drawings
图1是本发明所述制备方法制得的聚四氟乙烯膜的扫描电镜图；从附图中可以观察到：本发明的聚四氟乙烯膜具有由串珠状纤维丝纵横交错形成的孔隙三维连通结构，孔隙呈曲径孔，孔隙分布均匀连通，纳米纤维形态均一完好。Fig. 1 is the scanning electron micrograph of the polytetrafluoroethylene film that preparation method of the present invention makes; Can observe from accompanying drawing: the polytetrafluoroethylene film of the present invention has the pore three-dimensional that is formed by the criss-cross pattern of beaded filaments Connected structure, the pores are labyrinth pores, the pores are evenly distributed and connected, and the shape of nanofibers is uniform and intact.
具体实施方式detailed description
下面通过实施例对本发明进行具体的描述，有必要在此指出的是本实施例只能用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。The present invention is specifically described below through the examples, it is necessary to point out that the present examples can only be used to further illustrate the present invention, can not be interpreted as the limitation of protection scope of the present invention, those skilled in the art can according to above-mentioned The contents of the present invention make some non-essential improvements and adjustments.
实施例1Example 1
将固含量60％的聚四氟乙烯乳液滴加到质量分数为15％的聚乙烯醇水溶液中搅拌均匀，配成纺丝液。然后采用静电纺丝方法制成聚四氟乙烯前驱膜。缠绕到直径5cm圆筒支撑模上，缠绕5层，并送到管式炉中通氮气，烧结过程程序控温，以10℃/min从室温升温至110℃，110℃保温90min，以7℃/min升温速度从110℃升温至290℃,290℃保温100min，从290℃升温到380℃，升温速度为6℃/min，保温60min。冷却后取出后抽出圆筒支撑模，得到厚度为156μm的圆筒状聚四氟乙烯膜，剪开可得到平板式多孔膜片。该膜疏水接触角173°，孔隙率88％，平均孔径0.4μm，拉伸强度495psi，伸长率370％，用于膜蒸馏操作时，通量40L/m2·h，截留率99.7％。The polytetrafluoroethylene emulsion with a solid content of 60% is added dropwise to a polyvinyl alcohol aqueous solution with a mass fraction of 15%, and stirred evenly to form a spinning solution. Then the polytetrafluoroethylene precursor film was fabricated by electrospinning method. Winding on a cylindrical support mold with a diameter of 5cm, winding 5 layers, and sending it to a tube furnace with nitrogen gas, the temperature of the sintering process is controlled by a program, and the temperature is raised from room temperature to 110°C at 10°C/min, kept at 110°C for 90min, and at 7°C /min The heating rate is from 110°C to 290°C, and the temperature is kept at 290°C for 100 minutes, and the temperature is raised from 290°C to 380°C. After cooling, take it out and pull out the cylindrical support mold to obtain a cylindrical polytetrafluoroethylene membrane with a thickness of 156 μm, which can be cut to obtain a flat porous membrane. The membrane has a hydrophobic contact angle of 173°, a porosity of 88%, an average pore diameter of 0.4 μm, a tensile strength of 495 psi, and an elongation of 370%. When used in membrane distillation operations, the flux is 40L/m2 ·h and the rejection rate is 99.7%.
实施例2Example 2
将固含量60％的聚四氟乙烯乳液滴加到质量分数为8％的聚乙烯醇水溶液中搅拌均匀，配成纺丝液。然后采用静电纺丝方法制成聚四氟乙烯前驱膜。缠绕到直径5cm圆筒支撑模上，缠绕5层，并送到管式炉中通氮气，烧结过程程序控温，以2℃/min从室温升温至90℃，90℃保温120min，以10℃/min升温速度从90℃升温至260℃,260℃保温120min，从260℃升温到375℃，升温速度为8℃/min，保温115min。冷却后取出后抽出圆筒支撑模，得到厚度为165um的圆筒状聚四氟乙烯膜，剪开可得到平板式多孔膜片。该膜疏水接触角158°，孔隙率82％，平均孔径0.45μm，拉伸强度445psi，伸长率310％，用于膜蒸馏操作时，通量26L/m2·h，截留率99.3％。The polytetrafluoroethylene emulsion with a solid content of 60% is added dropwise to an aqueous solution of polyvinyl alcohol with a mass fraction of 8%, and stirred evenly to form a spinning solution. Then the polytetrafluoroethylene precursor film was fabricated by electrospinning method. Winding on a cylindrical support mold with a diameter of 5cm, winding 5 layers, and sending it to a tube furnace with nitrogen gas. The temperature of the sintering process is controlled by a program. /min The heating rate is raised from 90°C to 260°C, kept at 260°C for 120 minutes, and raised from 260°C to 375°C, with a heating rate of 8°C/min and kept at 115 minutes. After cooling, take it out and pull out the cylindrical support mold to obtain a cylindrical polytetrafluoroethylene membrane with a thickness of 165um, which can be cut to obtain a flat porous membrane. The membrane has a hydrophobic contact angle of 158°, a porosity of 82%, an average pore diameter of 0.45 μm, a tensile strength of 445 psi, and an elongation of 310%. When used in membrane distillation operations, the flux is 26 L/m2 ·h and the rejection rate is 99.3%.
实施例3Example 3
将固含量60％的聚四氟乙烯乳液滴加到质量分数为6％的聚乙烯醇水溶液中搅拌均匀，配成纺丝液。然后采用静电纺丝方法制成聚四氟乙烯前驱膜。缠绕到直径5cm圆筒支撑模上，缠绕5层，并送到管式炉中通氮气，烧结过程程序控温，以5℃/min从室温升温至100℃，100℃保温110min，以10℃/min升温速度从100℃升温至275℃,275℃保温110min，从275℃升温到380℃，升温速度为3℃/min，保温90min。冷却后取出后抽出圆筒支撑模，得到厚度为168um的圆筒状聚四氟乙烯膜，剪开可得到平板式多孔膜片。该膜疏水接触角165°，孔隙率81％，平均孔径0.20μm，拉伸强度460psi，伸长率320％，用于膜蒸馏操作时，通量29L/m2·h，截留率99.5％。The polytetrafluoroethylene emulsion with a solid content of 60% is added dropwise to a polyvinyl alcohol aqueous solution with a mass fraction of 6%, and stirred evenly to form a spinning solution. Then the polytetrafluoroethylene precursor film was fabricated by electrospinning method. Winding on a cylindrical support mold with a diameter of 5cm, winding 5 layers, and sending it to a tube furnace with nitrogen gas. The temperature of the sintering process is controlled by a program. /min The heating rate is raised from 100°C to 275°C, the temperature is kept at 275°C for 110 minutes, the temperature is raised from 275°C to 380°C, the heating rate is 3°C/min, and the temperature is kept for 90 minutes. After cooling, take it out and pull out the cylindrical support mold to obtain a cylindrical polytetrafluoroethylene membrane with a thickness of 168um, which can be cut to obtain a flat porous membrane. The membrane has a hydrophobic contact angle of 165°, a porosity of 81%, an average pore diameter of 0.20 μm, a tensile strength of 460 psi, and an elongation of 320%. When used in membrane distillation operations, the flux is 29L/m2 ·h and the rejection rate is 99.5%.
实施例4Example 4
将固含量60％的聚四氟乙烯乳液滴加到质量分数为5％的聚乙烯醇水溶液中搅拌均匀，配成纺丝液。然后采用静电纺丝方法制成聚四氟乙烯前驱膜。缠绕到直径5cm圆筒支撑模上，缠绕6层，并送到管式炉中通空气，烧结过程程序控温，以8℃/min从室温升温至100℃，100℃保温100min，以8℃/min升温速度从100℃升温至280℃，280℃保温120min，从280℃升温到385℃，升温速度为4℃/min，保温80min。冷却后取出后抽出圆筒支撑模，得到厚度为215um的的圆筒状聚四氟乙烯膜，剪开可得到平板式多孔膜片。该膜疏水接触角168°，孔隙率85％，平均孔径0.40μm，拉伸强度475psi，伸长率325％，用于膜蒸馏操作时，通量31L/m2·h，截留率99.3％。The polytetrafluoroethylene emulsion with a solid content of 60% is added dropwise to a polyvinyl alcohol aqueous solution with a mass fraction of 5%, and stirred evenly to prepare a spinning solution. Then the polytetrafluoroethylene precursor film was fabricated by electrospinning method. Wound onto a cylindrical support mold with a diameter of 5 cm, wound 6 layers, and sent to a tube furnace for ventilation. The temperature of the sintering process was controlled by a program. /min The heating rate is raised from 100°C to 280°C, kept at 280°C for 120 minutes, raised from 280°C to 385°C, the heating rate is 4°C/min, and kept at 80 minutes. After cooling, take it out and pull out the cylindrical support mold to obtain a cylindrical polytetrafluoroethylene membrane with a thickness of 215um, which can be cut to obtain a flat porous membrane. The membrane has a hydrophobic contact angle of 168°, a porosity of 85%, an average pore diameter of 0.40 μm, a tensile strength of 475 psi, and an elongation of 325%. When used in membrane distillation operations, the flux is 31L/m2 ·h and the rejection rate is 99.3%.
实施例5Example 5
将固含量60％的聚四氟乙烯乳液滴加到质量分数为10％的聚乙烯醇水溶液中搅拌均匀，配成纺丝液。然后采用静电纺丝方法制成聚四氟乙烯前驱膜。缠绕到直径0.5cm圆筒支撑模上，缠绕5层，并送到马弗炉中通氮气，烧结过程程序控温，以15℃/min从室温升温至120℃，120℃保温30min，以3℃/min升温速度从120℃升温至295℃，295℃保温120min，从295℃升温到390℃，升温速度为2℃/min，保温10min。冷却后取出后抽出圆筒支撑模，得到厚度为165um的管式膜。该膜疏水接触角170°，孔隙率84％，平均孔径0.5μm，拉伸强度436psi，伸长率355％，用于管式膜膜蒸馏操作时，通量35L/m2·h，截留率99.6％。The polytetrafluoroethylene emulsion with a solid content of 60% is added dropwise to a polyvinyl alcohol aqueous solution with a mass fraction of 10%, and stirred evenly to prepare a spinning solution. Then the polytetrafluoroethylene precursor film was fabricated by electrospinning method. Wound onto a cylindrical support mold with a diameter of 0.5 cm, wound 5 layers, and sent to the muffle furnace to pass nitrogen gas. The temperature of the sintering process was controlled by a program, and the temperature was raised from room temperature to 120 °C at 15 °C/min, and kept at 120 °C for 30 minutes. °C/min heating rate from 120 °C to 295 °C, 120 min at 295 °C, heating from 295 °C to 390 °C at a heating rate of 2 °C/min, and holding time for 10 min. After cooling, take out the cylindrical support mold and obtain a tubular membrane with a thickness of 165um. The membrane has a hydrophobic contact angle of 170°, a porosity of 84%, an average pore diameter of 0.5 μm, a tensile strength of 436 psi, and an elongation of 355%. When used in tubular membrane distillation operations, the flux is 35L/m2 ·h, and the rejection rate is 99.6%.
实施例6Example 6
将固含量60％的聚四氟乙烯乳液滴加到质量分数为6％的聚乙烯醇水溶液中搅拌均匀，配成纺丝液。然后采用静电纺丝方法制成聚四氟乙烯前驱膜。缠绕到直径0.5cm圆筒支撑模上，缠绕5层，并送到管式炉中通氩气，烧结过程程序控温，以12℃/min从室温升温至115℃，115℃保温50min，以5℃/min升温速度从115℃升温至300℃，300℃保温60min，从300℃升温到390℃，升温速度为6℃/min，保温30min。冷却后取出后抽出圆筒支撑模，得到厚度为168um的管式膜。该膜疏水接触角172°，孔隙率87％，平均孔径0.35μm，拉伸强度475psi，伸长率355％，用于管式膜膜蒸馏操作时，通量37L/m2·h，截留率99.6％。The polytetrafluoroethylene emulsion with a solid content of 60% is added dropwise to a polyvinyl alcohol aqueous solution with a mass fraction of 6%, and stirred evenly to form a spinning solution. Then the polytetrafluoroethylene precursor film was fabricated by electrospinning method. Wound onto a cylindrical support mold with a diameter of 0.5 cm, wound 5 layers, and sent to a tube furnace with argon gas. The temperature of the sintering process was controlled by a program. 5°C/min heating rate from 115°C to 300°C, heat preservation at 300°C for 60 minutes, heating from 300°C to 390°C, heating rate 6°C/min, heat preservation for 30 minutes. After cooling, take out the cylindrical support mold and obtain a tubular membrane with a thickness of 168um. The membrane has a hydrophobic contact angle of 172°, a porosity of 87%, an average pore diameter of 0.35 μm, a tensile strength of 475 psi, and an elongation of 355%. When used in tubular membrane distillation operations, the flux is 37L/m2 ·h, and the rejection rate is 99.6%.
实施例7Example 7
将固含量60％的聚四氟乙烯乳液滴加到质量分数为3％的聚乙烯醇水溶液中搅拌均匀，配成纺丝液。然后采用静电纺丝方法制成聚四氟乙烯前驱膜。缠绕到直径0.1cm圆筒支撑模上，缠绕6层，并送到管式炉中通空气，烧结过程程序控温，以9℃/min从室温升温至110℃，110℃保温80min，以6℃/min升温速度从110℃升温至285℃，285℃保温70min，从285℃升温到380℃，升温速度为5℃/min，保温60min。冷却后取出后抽出圆筒支撑模，得到厚度为209um的中空纤维膜。该膜疏水接触角174°，孔隙率86％，平均孔径0.4μm，拉伸强度490psi，伸长率365％，用于中空纤维膜膜蒸馏操作时，通量42L/m2·h，截留率99.7％。The polytetrafluoroethylene emulsion with a solid content of 60% is added dropwise to a polyvinyl alcohol aqueous solution with a mass fraction of 3%, and stirred evenly to form a spinning solution. Then the polytetrafluoroethylene precursor film was fabricated by electrospinning method. Wound onto a cylindrical support mold with a diameter of 0.1 cm, wound 6 layers, and sent to a tube furnace for ventilation. The temperature of the sintering process was controlled by a program. °C/min heating rate from 110 °C to 285 °C, 70 min at 285 °C, heating from 285 °C to 380 °C at a heating rate of 5 °C/min, and holding time for 60 min. After cooling, take out the cylindrical support mold to obtain a hollow fiber membrane with a thickness of 209um. The membrane has a hydrophobic contact angle of 174°, a porosity of 86%, an average pore diameter of 0.4 μm, a tensile strength of 490 psi, and an elongation of 365%. When used for hollow fiber membrane distillation operations, the flux is 42L/m2 ·h, and the rejection rate is 99.7%.
| Application Number | Priority Date | Filing Date | Title |
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| CN201410163139.8ACN104998558B (en) | 2014-04-22 | 2014-04-22 | A kind of preparation method of superhydrophobic polytetrafluoroethylene film |
| CN201710777909.1ACN107837691B (en) | 2014-04-22 | 2014-04-22 | Preparation method of super-hydrophobic polytetrafluoroethylene membrane |
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| CN201410163139.8ACN104998558B (en) | 2014-04-22 | 2014-04-22 | A kind of preparation method of superhydrophobic polytetrafluoroethylene film |
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| CN201710777909.1ADivisionCN107837691B (en) | 2014-04-22 | 2014-04-22 | Preparation method of super-hydrophobic polytetrafluoroethylene membrane |
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| CN104998558A CN104998558A (en) | 2015-10-28 |
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| CN201410163139.8AExpired - Fee RelatedCN104998558B (en) | 2014-04-22 | 2014-04-22 | A kind of preparation method of superhydrophobic polytetrafluoroethylene film |
| CN201710777909.1AExpired - Fee RelatedCN107837691B (en) | 2014-04-22 | 2014-04-22 | Preparation method of super-hydrophobic polytetrafluoroethylene membrane |
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| CN201710777909.1AExpired - Fee RelatedCN107837691B (en) | 2014-04-22 | 2014-04-22 | Preparation method of super-hydrophobic polytetrafluoroethylene membrane |
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