技术领域technical field
本发明涉及一种改性膜的制备方法。The invention relates to a preparation method of a modified membrane.
背景技术Background technique
在水处理领域，膜分离技术作为一种新型的水处理技术，由于其工艺设备简单，对水源条件适应性强，处理过程中选择性好、无相变且节约能耗，处理完成后无二次污染等特点，膜分离技术被视为替代传统水处理工艺的理想选择。膜分离系统运行过程中污染物质通过吸附或沉积附着在膜表面或膜孔内部，造成膜污染问题。污染物的累积造成污垢层的形成，膜的传质阻力增大使得膜过水能力减弱，从而降低膜的产水效率；同时污垢对膜结构的破坏缩短了膜的使用寿命，极大地阻碍了膜分离技术的运用。因此膜污染的控制对分离膜的应用推广尤为关键。In the field of water treatment, membrane separation technology is a new type of water treatment technology. Due to its simple process equipment, strong adaptability to water source conditions, good selectivity, no phase change and energy saving during the treatment process, there is no difference after treatment. Due to secondary pollution and other characteristics, membrane separation technology is regarded as an ideal choice to replace traditional water treatment processes. During the operation of the membrane separation system, pollutants attach to the surface of the membrane or inside the pores of the membrane through adsorption or deposition, causing membrane fouling. The accumulation of pollutants causes the formation of a fouling layer, and the increase of the mass transfer resistance of the membrane weakens the water passing capacity of the membrane, thereby reducing the water production efficiency of the membrane; at the same time, the damage to the membrane structure by the fouling shortens the service life of the membrane, which greatly hinders the The application of membrane separation technology. Therefore, the control of membrane fouling is particularly critical for the application and promotion of separation membranes.
由于水体中大部分污染物为疏水性物质，亲水膜表面改性通常作为缓解膜污染的手段。但水体中存在的两亲性物质与亲水性物质，如腐殖酸，也会污染膜。因此构建一种亲疏水膜表面层可以在抵抗疏水物质对膜的污染，并缓解亲水物质造成的膜污染。Since most pollutants in water are hydrophobic substances, surface modification of hydrophilic membranes is usually used as a means to alleviate membrane fouling. However, amphiphilic substances and hydrophilic substances in the water, such as humic acid, will also pollute the membrane. Therefore, constructing a hydrophilic and hydrophobic membrane surface layer can resist the fouling of the membrane by hydrophobic substances and alleviate the membrane fouling caused by hydrophilic substances.
目前亲疏水膜表面的构建途径有两种。其一是先合成由亲水链段与疏水链段构成的高分子聚合物，而后将高分子聚合物涂覆在膜表面。这种方式制得的亲疏水层通常厚度较大；同时由于疏水链段的存在，高分子聚合物在聚合液中分散得并不均匀。第二种方式是通过化学气相沉积，将亲水单体与疏水单体转变为气态混匀，而后引发两者聚合。这种方式对操作环境与设备的要求高，成本较高。At present, there are two ways to construct the hydrophilic and hydrophobic membrane surface. One is to first synthesize a high molecular polymer composed of a hydrophilic segment and a hydrophobic segment, and then coat the high molecular polymer on the membrane surface. The hydrophilic-hydrophobic layer prepared in this way is usually thicker; at the same time, due to the presence of hydrophobic segments, the high molecular polymer is not uniformly dispersed in the polymerization solution. The second way is to change the hydrophilic monomer and the hydrophobic monomer into a gaseous state and mix them through chemical vapor deposition, and then initiate the polymerization of the two. This method has high requirements on the operating environment and equipment, and the cost is relatively high.
发明内容Contents of the invention
本发明的目的是要解决现有亲疏水物质对膜造成的严重污染、膜改性过程中对操作环境要求高以及对膜的过水能力削减严重的问题，而提供一种亲疏水相间超薄水凝胶改性膜的制备方法。The purpose of the present invention is to solve the serious pollution of the membrane caused by the existing hydrophilic and hydrophobic substances, the high requirements for the operating environment in the membrane modification process, and the serious reduction of the membrane's water passing ability, and to provide a hydrophilic and hydrophobic interphase ultra-thin Preparation method of hydrogel modified membrane.
本发明通过界面引发的自由基聚合反应在膜表面构建一层亲疏水相间超薄水凝胶改性层，缓解亲疏水物质对膜造成的严重污染、膜改性过程中对操作环境要求高以及对膜的过水能力削减严重的问题。The invention builds a layer of ultra-thin hydrogel modification layer between hydrophilic and hydrophobic phases on the surface of the membrane through the free radical polymerization reaction initiated by the interface, so as to alleviate the severe pollution of the membrane caused by the hydrophilic and hydrophobic substances, and the high requirements on the operating environment during the membrane modification process. There is a serious problem of reducing the water passing ability of the membrane.
一种亲疏水相间超薄水凝胶改性膜的制备方法，是按以下步骤完成的：A method for preparing an ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases is completed according to the following steps:
一、制备水相聚合液和有机相聚合液：1. Preparation of aqueous phase polymerization liquid and organic phase polymerization liquid:
向去离子水中加入亲水聚合物单体和交联剂，磁力搅拌，得到水相聚合液；向有机溶剂中加入疏水聚合物单体和光引发剂，搅拌，得有机相聚合液；adding a hydrophilic polymer monomer and a cross-linking agent to deionized water, and stirring magnetically to obtain an aqueous phase polymerization liquid; adding a hydrophobic polymer monomer and a photoinitiator to an organic solvent, and stirring to obtain an organic phase polymerization liquid;
步骤一中所述的亲水聚合物单体为[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺丙基)氢氧化铵、2-甲基丙烯酰氧乙基磷酰胆碱、羧基甜菜碱甲基丙烯酸酯和羧基甜菜碱丙烯酰胺中的任意一种或其中几种以任意比的组合；The hydrophilic polymer monomer described in step one is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 2-methacryloyloxyethyl Any one of phosphorylcholine, carboxybetaine methacrylate and carboxybetaine acrylamide or a combination of several of them in any ratio;
步骤一中所述的疏水聚合物单体为甲基丙烯酸六氟丁酯、丙烯酸六氟异丙酯、丙烯酸六氟丁酯和甲基丙烯酸六氟异丙酯中的任意一种或其中几种以任意比的组合；The hydrophobic polymer monomer described in step 1 is any one or several of hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluorobutyl acrylate and hexafluoroisopropyl methacrylate combination in any ratio;
二、制备改性膜：2. Preparation of modified membrane:
对膜片进行清洗，将清洗干净的膜片固定在玻璃板上，将去离子水倒在膜表面，待膜片被润湿后将表面的水倒掉并吹干膜表面；再将水相聚合液倒在膜表面，待膜片被润湿后将表面水相聚合液倒掉并去除表面残留液滴；最后将有机相聚合液倒在膜表面并置于紫外灯下反应，得到亲疏水相间超薄水凝胶改性膜；Clean the membrane, fix the cleaned membrane on a glass plate, pour deionized water on the surface of the membrane, pour off the water on the surface after the membrane is wet and dry the surface of the membrane; then pour the water phase The polymer solution is poured on the surface of the membrane, and after the membrane is wet, the surface water phase polymer solution is poured off and the residual droplets on the surface are removed; finally, the organic phase polymer solution is poured on the membrane surface and reacted under ultraviolet light to obtain a hydrophilic and hydrophobic Interphase ultrathin hydrogel modified membrane;
步骤二中所述的润湿为：液体倒在膜表面后静置等待液体接触5min～7min，液体通过毛细作用进入膜孔；The wetting described in step 2 is: pour the liquid on the surface of the membrane and wait for the liquid to contact for 5 minutes to 7 minutes, and the liquid enters the membrane pores through capillary action;
步骤二中所述的膜片为聚砜膜、聚醚砜膜、聚氯乙烯膜和聚偏氟乙烯膜中的任意一种；The diaphragm described in step 2 is any one of polysulfone membrane, polyethersulfone membrane, polyvinyl chloride membrane and polyvinylidene fluoride membrane;
三、清洗膜：3. Cleaning membrane:
使用去离子水对亲疏水相间超薄水凝胶改性膜清洗3次～5次，保存在去离子水中。The ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases is washed 3 to 5 times with deionized water, and stored in deionized water.
本发明的优点：Advantages of the present invention:
一、本发明制备膜时对基膜的材质要求低，适用的膜改性范围大；1. The present invention has low requirements on the material of the base film when preparing the film, and the applicable film modification range is large;
二、本发明制备膜的过程中对基膜的结构无破坏，且形成的凝胶层不存在缺陷；2. The structure of the basement membrane is not damaged in the process of preparing the membrane in the present invention, and the formed gel layer has no defects;
三、本发明制备的改性膜的凝胶层厚度为纳米级，超薄的凝胶层缓解了改性对膜过水能力的削减；3. The thickness of the gel layer of the modified membrane prepared by the present invention is nano-scale, and the ultra-thin gel layer alleviates the reduction of the water-passing ability of the membrane by modification;
四、本发明制备改性膜的工艺设备简单，操作简便，工艺周期短，对操作环境要求低；Four, the present invention prepares the process equipment of modified membrane simple, easy and simple to operate, process cycle is short, low to operating environment requirement;
五、本发明制备的亲疏水相间水凝胶改性膜具有良好的抗污染性能，经过2小时污染物过滤后，亲疏水相间水凝胶改性膜的通量较亲水水凝胶改性膜提升可达25％；经简单冲洗之后，亲疏水相间水凝胶改性膜的通量较亲水水凝胶改性膜提升可达15％。Five, the hydrophilic-hydrophobic interphase hydrogel modified membrane prepared by the present invention has good anti-pollution performance. After 2 hours of pollutant filtration, the flux of the hydrophilic-hydrophobic interphase hydrogel modified membrane is higher than that of the hydrophilic hydrogel modified membrane. The membrane can be improved by 25%; after simple washing, the flux of the hydrophilic-hydrophobic interphase hydrogel modified membrane can be increased by 15% compared with the hydrophilic hydrogel-modified membrane.
本发明可获得一种亲疏水相间超薄水凝胶改性膜。The invention can obtain an ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases.
附图说明Description of drawings
图1为实施例一制备的亲疏水相间超薄水凝胶改性膜的扫描电镜截面图；Fig. 1 is the scanning electron microscope sectional view of the ultra-thin hydrogel modified film between hydrophilic and hydrophobic phases prepared in Example 1;
图2为实施例二制备的亲疏水相间超薄水凝胶改性膜的扫描电镜截面图；Fig. 2 is the scanning electron microscope sectional view of the ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases prepared in Example 2;
图3为实施例三制备的亲水超薄水凝胶改性膜的扫描电镜截面图；Fig. 3 is the scanning electron microscope sectional view of the hydrophilic ultra-thin hydrogel modified membrane prepared in embodiment three;
图4为污染-清洗循环测试过程中膜通量的变化趋势。Figure 4 shows the change trend of membrane flux during the pollution-cleaning cycle test.
具体实施方式Detailed ways
具体实施方式一：本实施方式一种亲疏水相间超薄水凝胶改性膜的制备方法，是按以下步骤完成的：Specific Embodiment 1: In this embodiment, a method for preparing an ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases is completed according to the following steps:
一、制备水相聚合液和有机相聚合液：1. Preparation of aqueous phase polymerization liquid and organic phase polymerization liquid:
向去离子水中加入亲水聚合物单体和交联剂，磁力搅拌，得到水相聚合液；向有机溶剂中加入疏水聚合物单体和光引发剂，搅拌，得有机相聚合液；adding a hydrophilic polymer monomer and a cross-linking agent to deionized water, and stirring magnetically to obtain an aqueous phase polymerization liquid; adding a hydrophobic polymer monomer and a photoinitiator to an organic solvent, and stirring to obtain an organic phase polymerization liquid;
步骤一中所述的亲水聚合物单体为[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺丙基)氢氧化铵、2-甲基丙烯酰氧乙基磷酰胆碱、羧基甜菜碱甲基丙烯酸酯和羧基甜菜碱丙烯酰胺中的任意一种或其中几种以任意比的组合；The hydrophilic polymer monomer described in step one is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 2-methacryloyloxyethyl Any one of phosphorylcholine, carboxybetaine methacrylate and carboxybetaine acrylamide or a combination of several of them in any ratio;
步骤一中所述的疏水聚合物单体为甲基丙烯酸六氟丁酯、丙烯酸六氟异丙酯、丙烯酸六氟丁酯和甲基丙烯酸六氟异丙酯中的任意一种或其中几种以任意比的组合；The hydrophobic polymer monomer described in step 1 is any one or several of hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluorobutyl acrylate and hexafluoroisopropyl methacrylate combination in any ratio;
二、制备改性膜：2. Preparation of modified membrane:
对膜片进行清洗，将清洗干净的膜片固定在玻璃板上，将去离子水倒在膜表面，待膜片被润湿后将表面的水倒掉并吹干膜表面；再将水相聚合液倒在膜表面，待膜片被润湿后将表面水相聚合液倒掉并去除表面残留液滴；最后将有机相聚合液倒在膜表面并置于紫外灯下反应，得到亲疏水相间超薄水凝胶改性膜；Clean the membrane, fix the cleaned membrane on a glass plate, pour deionized water on the surface of the membrane, pour off the water on the surface after the membrane is wet and dry the surface of the membrane; then pour the water phase The polymer solution is poured on the surface of the membrane, and after the membrane is wet, the surface water phase polymer solution is poured off and the residual droplets on the surface are removed; finally, the organic phase polymer solution is poured on the membrane surface and reacted under ultraviolet light to obtain a hydrophilic and hydrophobic Interphase ultrathin hydrogel modified membrane;
步骤二中所述的润湿为：液体倒在膜表面后静置等待液体接触5min～7min，液体通过毛细作用进入膜孔；The wetting described in step 2 is: pour the liquid on the surface of the membrane and wait for the liquid to contact for 5 minutes to 7 minutes, and the liquid enters the membrane pores through capillary action;
步骤二中所述的膜片为聚砜膜、聚醚砜膜、聚氯乙烯膜和聚偏氟乙烯膜中的任意一种；The diaphragm described in step 2 is any one of polysulfone membrane, polyethersulfone membrane, polyvinyl chloride membrane and polyvinylidene fluoride membrane;
三、清洗膜：3. Cleaning membrane:
使用去离子水对亲疏水相间超薄水凝胶改性膜清洗3次～5次，保存在去离子水中。The ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases is washed 3 to 5 times with deionized water, and stored in deionized water.
具体实施方式二：本实施方式与具体实施方式一不同点是：步骤一中所述的交联剂为聚乙二醇二丙烯酸酯、N,N-亚甲基双(丙烯酰胺)和N,N-二甲基丙烯酰胱氨酸中的任意一种或其中几种以任意比的组合。其它步骤与具体实施方式一相同。Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the crosslinking agent described in step 1 is polyethylene glycol diacrylate, N, N-methylene bis(acrylamide) and N, Any one of N-dimethylacryloylcystine or a combination of several of them in any ratio. Other steps are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二之一不同点是：步骤一中所述的光引发剂为1-羟基环己基苯基甲酮、2-羟基-2-甲基-1-苯基丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮和二苯基乙酮中的任意一种。其它步骤与具体实施方式一或二相同。Specific embodiment three: the difference between this embodiment and specific embodiment one or two is: the photoinitiator described in step one is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxyl-2-methyl- Any one of 1-phenylacetone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone and diphenylethanone. Other steps are the same as those in Embodiment 1 or 2.
具体实施方式四：本实施方式与具体实施方式一至三之一不同点是：步骤一中所述的有机溶剂为Isopar-G、苯、二甲苯、正己烷和环己烷中的任意一种或其中几种以任意比的组合。其它步骤与具体实施方式一至三相同。Specific embodiment four: the difference between this embodiment and specific embodiment one to three is: the organic solvent described in step one is any one of Isopar-G, benzene, xylene, normal hexane and hexanaphthene or Several of them can be combined in any ratio. Other steps are the same as those in Embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同点是：步骤一中所述的水相聚合液中亲水聚合物单体的质量分数为1％～10％，交联剂的质量分数为0.001％～1％。其它步骤与具体实施方式一至四相同。Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that: the mass fraction of the hydrophilic polymer monomer in the aqueous phase polymerization liquid described in step 1 is 1% to 10%, and the crosslinking agent The mass fraction is 0.001% to 1%. Other steps are the same as those in Embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同点是：步骤一中所述的有机相聚合液中疏水聚合物单体的质量分数为1％～10％；光引发剂的浓度为0.01g/mL。其它步骤与具体实施方式一至五相同。Specific embodiment six: the difference between this embodiment and one of specific embodiments one to five is: the mass fraction of the hydrophobic polymer monomer in the organic phase polymerization liquid described in step 1 is 1% to 10%; The concentration is 0.01g/mL. Other steps are the same as those in Embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同点是：步骤一中所述的磁力搅拌的搅拌速度为300r/min～500r/min，磁力搅拌的时间为5h～7h。其它步骤与具体实施方式一至六相同。Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that: the stirring speed of the magnetic stirring described in step 1 is 300r/min-500r/min, and the time of magnetic stirring is 5h-7h. Other steps are the same as those in Embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同点是：步骤二中对膜片进行清洗的工艺为：将膜片浸泡在异丙醇中5h～7h，再使用去离子水清洗3次～5次，再保存在去离子水中。其它步骤与具体实施方式一至七相同。Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that the process of cleaning the membrane in step 2 is: soak the membrane in isopropanol for 5h to 7h, and then use deionized water Wash 3 to 5 times, and then store in deionized water. Other steps are the same as those in Embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同点是：步骤二中所述固定为：使用1厘米厚镂空聚四氟乙烯板将膜片沿四周通过长尾夹夹在玻璃板上，膜与板之间添加镂空橡胶垫以避免聚合液漏失；中间镂空区域为膜改性区域，板厚可用于容纳水相聚合液与有机相聚合液；步骤二中所述去除表面残留液滴为：利用气枪喷出氮气轻轻吹脱表面残留液滴，仅在膜表面留存吸附的超薄液层。其它步骤与具体实施方式一至八相同。Embodiment 9: The difference between this embodiment and Embodiments 1 to 8 is that the fixation described in step 2 is as follows: use a 1 cm thick hollow polytetrafluoroethylene plate to clamp the diaphragm on the glass through long tail clips along the four sides. On the board, a hollow rubber pad is added between the film and the plate to avoid the leakage of the polymerization solution; the hollow area in the middle is the membrane modification area, and the thickness of the plate can be used to accommodate the aqueous phase polymerization liquid and the organic phase polymerization liquid; remove the surface residue as described in step 2 The droplet is: use an air gun to spray nitrogen to gently blow off the residual liquid droplets on the surface, leaving only the adsorbed ultra-thin liquid layer on the surface of the membrane. Other steps are the same as those in Embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同点是：步骤二中所述的紫外灯下反应为在稳定运行10min的紫外光照下引发有机相中的光引发剂产生自由基，自由基在有机相和水相界面处引发亲水聚合物单体、疏水聚合物单体与交联剂进行聚合反应生成水凝胶层；紫外灯下反应的时间为5min～60min；所述的紫外灯的功率为10W～40W。其它步骤与具体实施方式一至九相同。Embodiment ten: the difference between this embodiment and embodiment one to nine is: the reaction under the ultraviolet light described in the step 2 is to cause the photoinitiator in the organic phase to generate free radicals under the ultraviolet light of stable operation 10min , the free radical initiates the polymerization reaction of the hydrophilic polymer monomer, the hydrophobic polymer monomer and the cross-linking agent at the interface between the organic phase and the aqueous phase to form a hydrogel layer; the reaction time under an ultraviolet light is 5min to 60min; the described The power of the ultraviolet lamp is 10W ~ 40W. Other steps are the same as those in Embodiments 1 to 9.
采用以下实施例验证本发明的有益效果：Adopt the following examples to verify the beneficial effects of the present invention:
实施例1：一种亲疏水相间超薄水凝胶改性膜的制备方法，是按以下步骤完成的：Embodiment 1: A kind of preparation method of ultra-thin hydrogel modified film between hydrophilic and hydrophobic phases is completed according to the following steps:
一、制备水相聚合液和有机相聚合液：1. Preparation of aqueous phase polymerization liquid and organic phase polymerization liquid:
向去离子水中加入亲水聚合物单体和交联剂，在300r/min下磁力搅拌1h，得到水相聚合液；向有机溶剂中加入疏水聚合物单体和光引发剂，在搅拌速度为300r/min下搅拌5h，得有机相聚合液；Add hydrophilic polymer monomer and cross-linking agent to deionized water, stir magnetically at 300r/min for 1h to obtain aqueous phase polymerization liquid; add hydrophobic polymer monomer and photoinitiator to organic solvent, and stir at 300r/min Stirring 5h under /min, obtains the organic phase polymerization liquid;
步骤一中所述的亲水聚合物单体为[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺丙基)氢氧化铵；The hydrophilic polymer monomer described in step 1 is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide;
步骤一中所述的交联剂为聚乙二醇二丙烯酸酯；The cross-linking agent described in step 1 is polyethylene glycol diacrylate;
步骤一中所述的疏水聚合物单体为甲基丙烯酸六氟丁酯；The hydrophobic polymer monomer described in step 1 is hexafluorobutyl methacrylate;
步骤一中所述的光引发剂为1-羟基环己基苯基甲酮；The photoinitiator described in step 1 is 1-hydroxycyclohexyl phenyl ketone;
步骤一中所述的有机溶剂为Isopar-G；The organic solvent described in step 1 is Isopar-G;
步骤一中所述的水相聚合液中亲水聚合物单体的质量分数为2.5％，交联剂的质量分数为0.1％；The mass fraction of the hydrophilic polymer monomer in the aqueous phase polymerization solution described in step 1 is 2.5%, and the mass fraction of the crosslinking agent is 0.1%;
步骤一中所述的有机相聚合液中疏水聚合物单体的质量分数为2.5％；光引发剂的浓度为0.01g/mL；The mass fraction of the hydrophobic polymer monomer in the organic phase polymerization solution described in step 1 is 2.5%; the concentration of the photoinitiator is 0.01g/mL;
二、制备改性膜：2. Preparation of modified membrane:
对膜片进行清洗，将清洗干净的膜片固定在玻璃板上，将去离子水倒在膜表面，待膜片被润湿后将表面的水倒掉并吹干膜表面；再将水相聚合液倒在膜表面，待膜片被润湿后将表面水相聚合液倒掉并去除表面残留液滴；最后将有机相聚合液倒在膜表面并置于紫外灯下反应，得到亲疏水相间超薄水凝胶改性膜；Clean the membrane, fix the cleaned membrane on a glass plate, pour deionized water on the surface of the membrane, pour off the water on the surface after the membrane is wet and dry the surface of the membrane; then pour the water phase The polymer solution is poured on the surface of the membrane, and after the membrane is wet, the surface water phase polymer solution is poured off and the residual droplets on the surface are removed; finally, the organic phase polymer solution is poured on the membrane surface and reacted under ultraviolet light to obtain a hydrophilic and hydrophobic Interphase ultrathin hydrogel modified membrane;
步骤二中所述的润湿为：液体倒在膜表面后静置等待液体接触5min，液体通过毛细作用进入膜孔；The wetting described in step 2 is: pour the liquid on the surface of the membrane and wait for the liquid to contact for 5 minutes, and the liquid enters the membrane pores through capillary action;
步骤二中所述的膜片为聚砜膜；The diaphragm described in step 2 is a polysulfone membrane;
步骤二中对膜片进行清洗的工艺为：将膜片浸泡在异丙醇中6h，再使用去离子水清洗3次，再保存在去离子水中；The process of cleaning the diaphragm in step 2 is: soak the diaphragm in isopropanol for 6 hours, then wash it with deionized water for 3 times, and then store it in deionized water;
步骤二中所述固定为：使用1厘米厚镂空聚四氟乙烯板将膜片沿四周通过长尾夹夹在玻璃板上，膜与板之间添加镂空橡胶垫以避免聚合液漏失；中间镂空区域为膜改性区域，板厚可用于容纳水相聚合液与有机相聚合液；步骤二中所述去除表面残留液滴为：利用气枪喷出氮气轻轻吹脱表面残留液滴，仅在膜表面留存吸附的超薄液层；The fixation described in step 2 is: use a 1 cm thick hollow PTFE plate to clamp the diaphragm on the glass plate through long tail clips along the four sides, and add a hollow rubber pad between the film and the plate to avoid leakage of the polymer solution; hollow out the middle The area is the membrane modification area, and the thickness of the plate can be used to accommodate the aqueous phase polymerization liquid and the organic phase polymerization liquid; the removal of residual liquid droplets on the surface in step 2 is: use an air gun to blow off the residual liquid droplets on the surface gently. Adsorbed ultra-thin liquid layer remains on the surface of the membrane;
步骤二中所述的紫外灯下反应为在稳定运行10min的紫外光照下引发有机相中的光引发剂产生自由基，自由基在有机相和水相界面处引发亲水聚合物单体、疏水聚合物单体与交联剂进行聚合反应生成水凝胶层；紫外灯下反应的时间为5min；所述的紫外灯的功率为36W；The reaction under the ultraviolet light described in step 2 is to cause the photoinitiator in the organic phase to generate free radicals under the ultraviolet light of stable operation 10min, and the free radicals initiate the hydrophilic polymer monomer, hydrophobic The polymer monomer and the crosslinking agent are polymerized to generate a hydrogel layer; the reaction time under the ultraviolet lamp is 5min; the power of the ultraviolet lamp is 36W;
三、清洗膜：3. Cleaning membrane:
使用去离子水对亲疏水相间超薄水凝胶改性膜清洗3次，保存在去离子水中。The ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases was washed 3 times with deionized water, and stored in deionized water.
实施例2：本实施例与实施例1的不同点是：步骤一中所述的水相聚合液中交联剂的质量分数为1％。其它步骤及参数与实施例1均相同。Embodiment 2: The difference between this embodiment and Embodiment 1 is that the mass fraction of the crosslinking agent in the aqueous phase polymerization solution described in step 1 is 1%. Other steps and parameters are all the same as in Example 1.
实施例3：本实施例与实施例1的不同点是：步骤一中所述的水相聚合液中亲水聚合物单体的质量分数为5％，交联剂的质量分数为0.01％；步骤一中所述的有机相聚合液中疏水聚合物单体的质量分数为0％；实施例3得到了亲水超薄水凝胶改性膜。其它步骤及参数与实施例1均相同。Embodiment 3: The difference between this embodiment and Embodiment 1 is: the mass fraction of the hydrophilic polymer monomer in the aqueous phase polymerization liquid described in step 1 is 5%, and the mass fraction of the crosslinking agent is 0.01%; The mass fraction of the hydrophobic polymer monomer in the organic phase polymerization liquid described in step 1 was 0%; in Example 3, a hydrophilic ultrathin hydrogel modified membrane was obtained. Other steps and parameters are all the same as in Example 1.
图1为实施例一制备的亲疏水相间超薄水凝胶改性膜的扫描电镜截面图；Fig. 1 is the scanning electron microscope sectional view of the ultra-thin hydrogel modified film between hydrophilic and hydrophobic phases prepared in Example 1;
从图1可知：纳米级厚度的亲疏水相间水凝胶层连续的涂覆在聚砜膜表面，其厚度约为175nm，且水凝胶层与膜表面无明显分界线，两者紧密的结合保证了凝胶膜的稳定性。It can be seen from Figure 1 that the hydrophilic-hydrophobic interphase hydrogel layer with a nanometer thickness is continuously coated on the surface of the polysulfone membrane, and its thickness is about 175nm, and there is no obvious dividing line between the hydrogel layer and the membrane surface, and the two are closely combined The stability of the gel film is guaranteed.
图2为实施例二制备的亲疏水相间超薄水凝胶改性膜的扫描电镜截面图；Fig. 2 is the scanning electron microscope sectional view of the ultra-thin hydrogel modified membrane between hydrophilic and hydrophobic phases prepared in Example 2;
从图2可知：纳米级厚度的亲疏水相间水凝胶层连续的涂覆在聚砜膜表面，其厚度约为180nm，增大了交联剂含量后，水凝胶层的厚度略有增大；水凝胶层与膜表面同样无明显分界线，两者紧密的结合保证了凝胶膜的稳定性。It can be seen from Figure 2 that the hydrophilic-hydrophobic interphase hydrogel layer with a nanoscale thickness is continuously coated on the surface of the polysulfone membrane, and its thickness is about 180nm. After increasing the content of the cross-linking agent, the thickness of the hydrogel layer increases slightly. Large; there is no obvious boundary between the hydrogel layer and the membrane surface, and the tight combination of the two ensures the stability of the gel membrane.
图3为实施例三制备的亲水超薄水凝胶改性膜的扫描电镜截面图；Fig. 3 is the scanning electron microscope sectional view of the hydrophilic ultra-thin hydrogel modified membrane prepared in embodiment three;
从图3可知：纳米级厚度的亲水水凝胶层连续的涂覆在聚砜膜表面，其厚度约为140nm，去除有机相中的疏水性单体后，水凝胶层的厚度减小；水凝胶层与膜表面同样无明显分界线，两者紧密的结合保证了凝胶膜的稳定性。It can be seen from Figure 3 that the hydrophilic hydrogel layer with a nanoscale thickness is continuously coated on the surface of the polysulfone membrane, and its thickness is about 140nm. After removing the hydrophobic monomer in the organic phase, the thickness of the hydrogel layer decreases. ; The hydrogel layer and the membrane surface also have no obvious boundary, and the tight combination of the two ensures the stability of the gel membrane.
使用美国MILLIPORE公司生产的Millipore 8200型超滤杯为核心构建的膜过滤装置对膜的抗污染性能进行评价。以腐殖酸溶液为膜污染测试液，采用污染-清洗循环测试通过膜通量的变化趋势表征膜抗污染性能及其稳定性，如图2所示；The anti-fouling performance of the membrane was evaluated by using the membrane filtration device constructed with the Millipore 8200 ultrafiltration cup produced by the American MILLIPORE company as the core. Using humic acid solution as the membrane fouling test solution, the fouling-cleaning cycle test is used to characterize the anti-fouling performance and stability of the membrane through the change trend of the membrane flux, as shown in Figure 2;
图4为污染-清洗循环测试过程中膜通量的变化趋势；Fig. 4 is the variation trend of membrane flux in the pollution-cleaning cycle test process;
由图4可知，经2h的腐殖酸溶液过滤污染后，商品聚砜超滤膜的通量由8.6L m-2h-1下降到1.9L m-2h-1，亲水超薄水凝胶改性聚砜膜的通量由7.4L m-2h-1下降到2.3L m-2h-1，实施例一亲疏水相间超薄水凝胶改性聚砜膜的通量由7.6L m-2h-1下降到2.6L m-2h-1，实施例二亲疏水相间超薄水凝胶改性聚砜膜的通量由7.0L m-2h-1下降到3.0L m-2h-1；通过去离子水简单冲洗之后，商品聚砜超滤膜、亲水超薄水凝胶改性聚砜膜、实施例一亲疏水相间超薄水凝胶改性聚砜膜和实施例二亲疏水相间超薄水凝胶改性聚砜膜的通量分别为4.7L m-2h-1、6.0L m-2h-1、6.9L m-2h-1和6.5L m-2h-1；亲疏水相间水凝胶改性膜的膜通量最大，与所购买的商品聚砜超滤膜及亲水改性膜相比，其抗污染性能得到显著提升。通过重复腐殖酸溶液过滤及污染膜清洗流程，亲疏水相间水凝胶改性膜的通量始终维持三者最高水平，其抗污染的稳定性得到验证。It can be seen from Figure 4 that after 2 hours of humic acid solution filtration pollution, the flux of the commercial polysulfone ultrafiltration membrane dropped from 8.6L m-2 h-1 to 1.9L m-2 h-1 , and the hydrophilic ultra-thin water The flux of the gel-modified polysulfone membrane decreased from 7.4L m-2 h-1 to 2.3L m-2 h-1 , and the flux of the ultrathin hydrogel-modified polysulfone membrane between hydrophilic and hydrophobic phases in Example 1 was given by From 7.6L m-2 h-1 to 2.6L m-2 h-1 , the flux of the ultrathin hydrogel modified polysulfone membrane between hydrophilic and hydrophobic phases in Example 2 dropped from 7.0L m-2 h-1 to 3.0 L m-2 h-1 ; after simple washing with deionized water, commercial polysulfone ultrafiltration membrane, hydrophilic ultrathin hydrogel modified polysulfone membrane, embodiment 1 hydrophilic and hydrophobic interphase ultrathin hydrogel modified polysulfone The fluxes of the sulfone membrane and the polysulfone membrane modified by the ultra-thin hydrogel between the two hydrophilic and hydrophobic phases of the example are 4.7L m-2 h-1 , 6.0L m-2 h-1 , and 6.9L m-2 h-1 , respectively and 6.5L m-2 h-1 ; the membrane flux of the hydrophilic-hydrophobic interphase hydrogel modified membrane is the largest, and its anti-fouling performance is significantly improved compared with the purchased commercial polysulfone ultrafiltration membrane and hydrophilic modified membrane. promote. Through repeated humic acid solution filtration and fouled membrane cleaning processes, the flux of the hydrogel modified membrane between hydrophilic and hydrophobic phases always maintained the highest level among the three, and its anti-pollution stability was verified.
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