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CN108404684A - A kind of preparation method of the anti-pollution PVDF seperation film of super hydrophilic modification - Google Patents

A kind of preparation method of the anti-pollution PVDF seperation film of super hydrophilic modification Download PDF

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CN108404684A
CN108404684A CN201810207011.5A CN201810207011A CN108404684A CN 108404684 A CN108404684 A CN 108404684A CN 201810207011 A CN201810207011 A CN 201810207011A CN 108404684 A CN108404684 A CN 108404684A
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separation membrane
pvdf
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CN108404684B (en
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王志伟
文越
张星冉
陈颖青
王巧英
吴志超
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Tongji University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/34Polyvinylidene fluoride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • B01D67/0006Organic membrane manufacture by chemical reactions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2323/00Details relating to membrane preparation
    • B01D2323/30Cross-linking
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/36Hydrophilic membranes

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

本发明涉及一种超亲水改性的抗污染PVDF分离膜的制备方法,利用碱性溶液处理PVDF表面生成双键,通过氨基‑烯加成反应和氨基‑环氧开环反应在PVDF膜表面通过化学键交联超支化聚乙烯亚胺;膜表面的超支化聚乙烯亚胺与环氧丙醇溶液进行氨基‑环氧开环反应制得具有抗污染性能的PVDF膜。改性后的PVDF膜具有大量氨基和羟基等活性基团,使得膜表面的亲水性大大提高。本发明解决PVDF分离膜本身较强的疏水性,防止应用过程中污染物易吸附、沉积在膜表面或膜孔内,提高膜的抗污染能力,延长膜的使用寿命。本发明采用化学方法进行改性,条件温和,操作简便,不需要昂贵的仪器,易于推广,所得产物牢固,具有良好抗污染性能,在水处理领域具有潜在的广泛应用价值。

The invention relates to a preparation method of a super-hydrophilic modified anti-pollution PVDF separation membrane. The surface of PVDF is treated with an alkaline solution to generate double bonds, and the double bonds are formed on the surface of the PVDF membrane through amino-ene addition reaction and amino-epoxy ring-opening reaction. The hyperbranched polyethyleneimine is cross-linked by chemical bonds; the hyperbranched polyethyleneimine on the surface of the membrane undergoes amino-epoxy ring-opening reaction with a glycidol solution to prepare a PVDF membrane with anti-fouling properties. The modified PVDF membrane has a large number of active groups such as amino and hydroxyl groups, which greatly improves the hydrophilicity of the membrane surface. The invention solves the strong hydrophobicity of the PVDF separation membrane itself, prevents pollutants from being easily adsorbed and deposited on the surface of the membrane or in the pores of the membrane during the application process, improves the anti-pollution ability of the membrane, and prolongs the service life of the membrane. The invention adopts a chemical method for modification, has mild conditions, is easy to operate, does not need expensive instruments, is easy to popularize, and the obtained product is firm, has good anti-pollution performance, and has potential wide application value in the field of water treatment.

Description

一种超亲水改性的抗污染PVDF分离膜的制备方法A kind of preparation method of superhydrophilic modified antifouling PVDF separation membrane

技术领域technical field

本发明涉及一种超亲水改性的抗污染PVDF分离膜的制备方法,属于水处理科学与技术领域。The invention relates to a preparation method of a superhydrophilic modified anti-pollution PVDF separation membrane, belonging to the field of water treatment science and technology.

背景技术Background technique

膜分离技术以其精准分离、高效纯化、绿色环保等优势,被广泛应用于膜法污水污水处理领域。聚偏氟乙烯(PVDF)是一种性能优良的膜材料,它具有强度高、耐高温、耐化学腐蚀等特点。但是在PVDF膜分离技术应用过程中,PVDF膜表面能低、有极强的疏水性导致其通量低、易污染,严重限制了其在膜法污水处理领域的应用。因此,对PVDF分离膜进行亲水改性,提升膜的抗污染性能、延长膜使用寿命已经成为膜制备领域的热点。Membrane separation technology is widely used in the field of membrane wastewater treatment due to its advantages of precise separation, efficient purification, and environmental protection. Polyvinylidene fluoride (PVDF) is a membrane material with excellent performance, which has the characteristics of high strength, high temperature resistance, and chemical corrosion resistance. However, in the application process of PVDF membrane separation technology, the low surface energy and strong hydrophobicity of PVDF membrane lead to low flux and easy pollution, which seriously limits its application in the field of membrane wastewater treatment. Therefore, it has become a hot spot in the field of membrane preparation to carry out hydrophilic modification on PVDF separation membranes to improve the anti-pollution performance of the membrane and prolong the service life of the membrane.

目前已有大量关于PVDF分离膜抗污染改性的相关报道。其中,通过在膜面构筑抗污染功能层界面、实现PVDF膜污染控制的表面接枝改性方法,以其改性方法丰富、改性效率高等优势受到PVDF膜制备领域研究人员的广泛关注。例如,发明专利CN107096398A以过硫酸钾为催化剂,使2-丙烯酰胺基-2-甲基丙磺酸(AMPS)与甲基丙烯酸甲酯(MMA)反应生成两亲性共聚物,将PVDF膜进行脱氟化氢处理,再以上述两亲性共聚物为接枝单体,改善PVDF膜亲水性,提高膜的抗污染性能。发明专利CN104043351A采用紫外辐射接枝法、以硫酸高铈为引发剂、以马来酸酐为接枝单体,接枝于PVDF超滤膜表面,达到抗污染的目的。发明专利CN103736407A将PVDF微滤膜脱氟化氢预处理后,以过氧化二苯甲酰为引发剂,以环烷酸钻或蔡酸钻为促进剂,以顺丁烯二酸酐为接枝单体,得到亲水抗污染膜。但以上改性方法多是将双离子型聚合物和聚乙二醇型聚合物等线性高分子改性剂接枝于PVDF膜材料表面,受线性分子链结构影响(位阻效应),亲水基团修饰数量较少,导致改性剂膜面覆盖率低,抗污染效率提升有限;此外,以上改性方法复杂、反应条件苛刻,难以满足商业化生产的需求。At present, there have been a large number of related reports on the anti-fouling modification of PVDF separation membranes. Among them, the surface grafting modification method of constructing an anti-fouling functional layer interface on the membrane surface and realizing PVDF membrane fouling control has attracted extensive attention from researchers in the field of PVDF membrane preparation due to its advantages of rich modification methods and high modification efficiency. For example, the invention patent CN107096398A uses potassium persulfate as a catalyst to react 2-acrylamido-2-methylpropanesulfonic acid (AMPS) with methyl methacrylate (MMA) to form an amphiphilic copolymer, and the PVDF membrane is After dehydrofluorination treatment, the above-mentioned amphiphilic copolymer is used as a graft monomer to improve the hydrophilicity of the PVDF membrane and improve the anti-pollution performance of the membrane. Invention patent CN104043351A adopts the ultraviolet radiation grafting method, uses ceric sulfate as the initiator, and uses maleic anhydride as the grafting monomer to graft on the surface of the PVDF ultrafiltration membrane to achieve the purpose of anti-pollution. Invention patent CN103736407A, after dehydrofluorination pretreatment of PVDF microfiltration membrane, dibenzoyl peroxide is used as initiator, cobalt naphthenate or cobalt naphthenate is used as accelerator, and maleic anhydride is used as grafting monomer. A hydrophilic antifouling film is obtained. However, most of the above modification methods are to graft linear polymer modifiers such as diionic polymers and polyethylene glycol polymers on the surface of PVDF membrane materials, affected by the linear molecular chain structure (steric hindrance effect), hydrophilic The small number of group modifications leads to low membrane surface coverage of the modifier and limited improvement in anti-pollution efficiency; in addition, the above modification methods are complicated and the reaction conditions are harsh, which is difficult to meet the needs of commercial production.

超支化聚乙烯亚胺作为一种高度支化,且支化末端具有大量氨基活性基团的聚合物,在相同接枝浓度下,比其线性类似物有更高的抗污染效率。本发明利用超支化聚乙烯亚胺为载体,将大量的氨基活性基团引入到膜表面,增加膜的亲水性,再通过开环反应在超支化聚乙烯亚胺末端引入带负电的羟基,进一步提升膜表面亲水性的同时提高膜表面的电负性,实现膜表面的超亲水改性,形成具有抗污染效果的PVDF分离膜。本发明操作简单,易于控制,制备得到的抗污染层牢固高效,能够有效地解决膜分离技术使用过程中的膜污染问题,为膜材料在水处理等领域的应用提供技术支持。As a highly branched polymer with a large number of amino active groups at the end of the branch, hyperbranched polyethyleneimine has higher anti-pollution efficiency than its linear analogues at the same grafting concentration. The present invention uses hyperbranched polyethyleneimine as a carrier to introduce a large number of amino active groups into the surface of the membrane to increase the hydrophilicity of the membrane, and then introduces negatively charged hydroxyl groups at the end of the hyperbranched polyethyleneimine through a ring-opening reaction. Further improve the hydrophilicity of the membrane surface and at the same time increase the electronegativity of the membrane surface, realize the superhydrophilic modification of the membrane surface, and form a PVDF separation membrane with anti-pollution effect. The invention is simple in operation and easy to control, and the prepared anti-pollution layer is firm and efficient, can effectively solve the problem of membrane pollution in the process of using the membrane separation technology, and provide technical support for the application of membrane materials in the fields of water treatment and the like.

发明内容Contents of the invention

本发明的目的是解决现有PVDF膜很强的疏水性,提供一种超亲水性改性的抗污染PVDF分离膜的制备方法。The purpose of the invention is to solve the strong hydrophobicity of the existing PVDF membrane, and provide a preparation method of a superhydrophilic modified anti-pollution PVDF separation membrane.

本发明提出的超亲水改性的PVDF分离膜的制备方法,经改性后的分离膜表面能够显著提高膜表面亲水性,降低蛋白质、多糖在膜表面的粘附、沉积,具有显著地抗污染效果。The preparation method of the superhydrophilic modified PVDF separation membrane proposed by the present invention can significantly improve the hydrophilicity of the surface of the separation membrane after modification, reduce the adhesion and deposition of proteins and polysaccharides on the surface of the membrane, and have significant advantages. Anti-pollution effect.

为实现上述目的,本发明提出的一种超亲水改性的抗污染PVDF分离膜的制备方法,所述抗污染膜利用化学键交联超支化聚乙烯亚胺,通过开环作用交联环氧丙醇,进行表面改性制备得到,具体步骤如下:In order to achieve the above object, the present invention proposes a method for preparing a superhydrophilic modified anti-pollution PVDF separation membrane. Propanol is prepared by surface modification, and the specific steps are as follows:

(1)将二元胺加入至pH为11.0的碳酸钠缓冲溶液中;所述二元胺溶液质量浓度为8.0~24.0%;(1) Diamine is added to a sodium carbonate buffer solution with a pH of 11.0; the mass concentration of the diamine solution is 8.0-24.0%;

(2)以PVDF分离膜为基膜,将基膜浸泡到步骤(1)所得的溶液中,在200~300 rpm,20~30oC条件下反应10~12 h,通过氨基-烯加成反应和氨基-环氧开环反应,使其表面形成氨盐化合物层,得到活化后的PVDF分离膜,洗干净后待用;(2) Use the PVDF separation membrane as the base membrane, soak the base membrane into the solution obtained in step (1), react at 200-300 rpm, 20-30 o C for 10-12 h, and undergo amino-ene addition Reaction and amino-epoxy ring-opening reaction to form an ammonium salt compound layer on the surface to obtain an activated PVDF separation membrane, which is cleaned and used;

(3)将步骤(2)得到的PVDF分离膜浸泡于环氧氯丙烷的乙醇溶液中,在氮气保护下,加入催化剂,在100~200 rpm,55~65oC下反应5~7 h,再逐滴加入氢氧化钠溶液,并在100~200rpm,40~50oC下继续反应3~5 h,通过相转移催化法,在PVDF分离膜表面形成环氧类化合物层,用乙醇、去离子水洗干净待用;所述环氧氯丙烷溶液质量浓度为1.0%~3.0%;所述催化剂质量浓度为0.01~0.03;所述的催化剂为氯代季铵盐类催化剂;所述氢氧化钠溶液浓度为0.01~0.03%;(3) Soak the PVDF separation membrane obtained in step (2) in an ethanol solution of epichlorohydrin, add a catalyst under nitrogen protection, and react at 100-200 rpm, 55-65 o C for 5-7 h, Then add sodium hydroxide solution dropwise, and continue to react at 100~200rpm, 40~50 o C for 3~5 h. By phase transfer catalysis, an epoxy compound layer is formed on the surface of the PVDF separation membrane. The ionized water is washed clean and ready for use; the mass concentration of the epichlorohydrin solution is 1.0% to 3.0%; the mass concentration of the catalyst is 0.01 to 0.03; the catalyst is a chlorinated quaternary ammonium salt catalyst; the sodium hydroxide The solution concentration is 0.01~0.03%;

(4)将超支化聚乙烯亚胺乙醇溶液与步骤(3)中所得PVDF分离膜在70~90oC下反应24~36h,使超支化聚乙烯亚胺通过化学键交联到步骤(3)所得PVDF分离膜表面,用乙醇、去离子水洗干净待用;超支化聚乙烯亚胺质量分数为2.5%~7.5%;(4) React the hyperbranched polyethyleneimine ethanol solution with the PVDF separation membrane obtained in step (3) at 70-90 o C for 24-36 hours, so that the hyperbranched polyethyleneimine can be cross-linked to step (3) through chemical bonds The surface of the obtained PVDF separation membrane is washed with ethanol and deionized water for use; the mass fraction of hyperbranched polyethyleneimine is 2.5% to 7.5%;

(5)将步骤(4)得到PVDF分离膜浸没于甲醇溶液中,逐滴加入环氧丙醇,在200~300rpm,20~30oC条件下反应10~12 h,通过氨基-环氧开环反应,使其表面的超支化聚乙烯亚胺层末端氨基被羟基覆盖,形成超亲水的抗污染PVDF分离膜材料;环氧丙醇的质量分数为0.1%~5%;(5) Submerge the PVDF separation membrane obtained in step (4) in methanol solution, add glycidyl alcohol drop by drop, react at 200~300rpm, 20~30 o C for 10~12 h, and decompose through amino-epoxy The ring reaction makes the terminal amino groups of the hyperbranched polyethyleneimine layer on the surface covered by hydroxyl groups to form a super-hydrophilic anti-pollution PVDF separation membrane material; the mass fraction of glycidol is 0.1%~5%;

(6)反应结束后,取出超亲水的抗污染PVDF分离膜材料,用乙醇、去离子水冲洗干净并烘干,得到具有抗污染性能的PVDF分离膜。(6) After the reaction, take out the super-hydrophilic anti-pollution PVDF separation membrane material, rinse it with ethanol and deionized water, and dry it to obtain a PVDF separation membrane with anti-pollution performance.

本发明中,步骤(1)所述二元胺为丙二胺、丁二胺或戊二胺中的一种或几种。In the present invention, the diamine in step (1) is one or more of propylenediamine, butylenediamine or pentamethylenediamine.

本发明中,步骤(3)所述的氯代季铵盐类催化剂为苄基三乙基氯化铵、十六烷基三甲基氯化铵或四丁基氯化铵中任一种。In the present invention, the chlorinated quaternary ammonium salt catalyst described in step (3) is any one of benzyltriethylammonium chloride, cetyltrimethylammonium chloride or tetrabutylammonium chloride.

本发明中,步骤(3)所述的聚合物分离膜浸泡方式为全部浸入溶液中,且所要改性的面朝上。In the present invention, the soaking method of the polymer separation membrane described in step (3) is completely immersed in the solution, and the side to be modified faces upward.

本发明中,步骤(4)所述超支化聚乙烯亚胺的重均分子量为600 g/mol、10,000 g/mol或60,000 g/mol中任一种。In the present invention, the weight average molecular weight of the hyperbranched polyethyleneimine in step (4) is any one of 600 g/mol, 10,000 g/mol or 60,000 g/mol.

本发明的有益效果在于:与现有技术相比,本发明中的膜制备方法创新地采用表面改性将有氨基活性基团的超支化聚合物固定在膜表面,并通过开环作用化学键交联环氧丙醇,从而使膜表面含有大量羟基、氨基等亲水基团,成功进行了超亲水改性,提高了膜的抗污染性能。该方法制备的抗菌抗污染改性聚合物分离膜具有以下优点:The beneficial effect of the present invention is that: compared with the prior art, the film preparation method in the present invention innovatively adopts surface modification to immobilize the hyperbranched polymer with amino active groups on the surface of the film, and chemically bonds through ring opening Diglycol, so that the surface of the membrane contains a large number of hydroxyl groups, amino groups and other hydrophilic groups, successfully carried out super-hydrophilic modification, and improved the anti-pollution performance of the membrane. The antibacterial and anti-pollution modified polymer separation membrane prepared by the method has the following advantages:

(1) 提出了一种在聚合物分离膜表面超支化亲水改性的方法,该方法以超支化聚乙烯亚胺为载体层,通过化学键交联环氧丙醇提高膜表面的抗污染性能,亲水性能稳定持久、抗污染性能显著增加;(1) A method of hyperbranched hydrophilic modification on the surface of the polymer separation membrane is proposed. The method uses hyperbranched polyethyleneimine as the carrier layer, and cross-links glycidol through chemical bonds to improve the anti-fouling performance of the membrane surface. , the hydrophilic property is stable and long-lasting, and the anti-pollution performance is significantly increased;

(2) 经亲水改性的PVDF分离膜表面具有大量羟基基团,对水分子的结合能力比传统线性聚乙二醇衍生物更为强烈,对蛋白质、多糖等污染物具有明显的抗粘附作用,抗污染性能持久;(2) The surface of the hydrophilically modified PVDF separation membrane has a large number of hydroxyl groups, and its binding ability to water molecules is stronger than that of traditional linear polyethylene glycol derivatives, and it has obvious anti-adhesion to proteins, polysaccharides and other pollutants Attachment effect, long-lasting anti-pollution performance;

(3) 所用超支化聚乙烯亚胺价廉易得,表面具有大量活性氨基基团,是进行多种修饰的良好载体;(3) The hyperbranched polyethyleneimine used is cheap and easy to obtain, and has a large number of active amino groups on the surface, which is a good carrier for various modifications;

(4) 制膜条件温和,操作易行,设备低廉,可控性好,容易工业化实施。(4) Membrane forming conditions are mild, operation is easy, equipment is cheap, controllability is good, and industrialization is easy to implement.

附图说明Description of drawings

图1是实施例1所制得膜P0、P-NH2、P-EPI、P-HPEI和P-HPEI-GLY的不同时刻的水接触角变化图。Fig. 1 is a graph of water contact angle changes at different times for the films P0, P-NH 2 , P-EPI, P-HPEI and P-HPEI-GLY prepared in Example 1.

图2是是实施例1所制得膜P0和P-HPEI-GLY的清水通量图。Fig. 2 is the clear water flux diagram of the membrane P0 and P-HPEI-GLY prepared in Example 1.

图3是蛋白质、多糖与实施例1所制得膜P0和P-HPEI-GLY接触3 h后的CLSM图,染色部分是蛋白质/多糖。图(A)是蛋白质与实施例1所得膜P0接触3 h后CLSM图,图(B)是蛋白质与实施例1所得膜P-HPEI-GLY接触3 h后CLSM图,图(C)是多糖与实施例1所得膜P接触3 h后CLSM图,图(D)是多糖与实施例1所得膜P-HPEI-GLY接触3 h后CLSM图。Fig. 3 is a CLSM image of proteins and polysaccharides contacted with the membrane P0 and P-HPEI-GLY prepared in Example 1 for 3 h, and the stained part is protein/polysaccharide. Figure (A) is the CLSM image of the protein contacted with the membrane P0 obtained in Example 1 for 3 h, Figure (B) is the CLSM image of the protein contacted with the membrane P-HPEI-GLY obtained in Example 1 for 3 h, and Figure (C) is the polysaccharide The CLSM diagram after contacting the membrane P obtained in Example 1 for 3 h, and Figure (D) is the CLSM diagram after contacting the polysaccharide with the membrane P-HPEI-GLY obtained in Example 1 for 3 h.

图4是实施例1所制得膜P0和P-HPEI-GLY动态抗蛋白质、多糖污染性能统计。图(A)是以蛋白质为污染物,实施例1所得膜P0和P-HPEI-GLY死端过滤190 min后的FRR、IFR、RFR值对比图,图(B)是以多糖为污染物,实施例1所得膜P0和P-HPEI-GLY死端过滤190 min后的FRR、IFR、RFR值对比图。Fig. 4 is the statistics of the dynamic anti-protein and polysaccharide fouling performance of the membrane P0 and P-HPEI-GLY prepared in Example 1. Figure (A) is a comparison of FRR, IFR, and RFR values of the membrane P0 obtained in Example 1 and P-HPEI-GLY after 190 min of dead-end filtration with protein as the pollutant. Figure (B) is polysaccharide as the pollutant. Comparison chart of FRR, IFR, and RFR values of membranes P0 and P-HPEI-GLY obtained in Example 1 after dead-end filtration for 190 min.

具体实施方式Detailed ways

为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及具体实施方式,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施方式仅用以解释本发明,并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, and are not intended to limit the present invention.

实施例1:Example 1:

将PVDF分离膜在清水中浸泡24 h,去除PVDF分离膜表面的杂质(记为P0)。将经预处理的分离物膜置于在聚四氟乙烯封闭盒内(单面反应盒),配置1 M的1,4-丁二胺溶解到碳酸钠缓冲溶液(调pH=11.0)中, 200 rpm、25oC条件下反应12 h,直至膜上有淡黄色氨盐化合物层出现。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到经第一步改性后的PVDF分离膜(记为P-NH2)。将得到的膜P-NH2正面朝上浸泡于150 mL无水乙醇中,向其中滴加3 mL环氧氯丙烷,对装置进行充氮保护,缓慢加入40 mg苄基三乙基氯化铵,在100 rpm,65oC下反应5 h,再逐滴加入5 mL的0.06 M氢氧化钠溶液,并在100 rpm,40oC下继续反应3h。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到环氧类化合物交联的PVDF分离膜(记为P-EPI)。将得到的膜P-EPI浸泡于30 g/L的超支化聚乙烯亚胺(重均分子量为10,000 g/mol)的乙醇溶液中,在100 rpm,85oC下反应24 h,使超支化聚乙烯亚胺通过化学键交联到PVDF分离膜表面。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到超支化聚乙烯亚胺交联的PVDF分离膜(记为P-HPEI)。将超支化聚乙烯亚胺交联的PVDF分离膜单面浸没于甲醇溶液中,逐滴加入0.5 mL环氧丙醇,在250 rpm,25oC条件下反应10 h,将环氧丙醇通过化学键固定在超支化聚乙烯亚胺表面。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到超亲水的抗污染PVDF分离膜(记为P-HPEI-GLY)。Soak the PVDF separation membrane in clean water for 24 h to remove the impurities on the surface of the PVDF separation membrane (denoted as P0). Place the pretreated isolate membrane in a polytetrafluoroethylene closed box (single-sided reaction box), configure 1 M 1,4-butanediamine and dissolve it in sodium carbonate buffer solution (adjust pH=11.0), React at 200 rpm and 25 o C for 12 h until a light yellow ammonium salt compound layer appears on the membrane. Afterwards, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain the PVDF separation membrane modified in the first step (denoted as P-NH 2 ). Soak the obtained membrane P- NH2 face up in 150 mL of absolute ethanol, add 3 mL of epichlorohydrin dropwise to protect the device with nitrogen, and slowly add 40 mg of benzyltriethylammonium chloride , react at 100 rpm, 65 o C for 5 h, then add 5 mL of 0.06 M sodium hydroxide solution dropwise, and continue to react at 100 rpm, 40 o C for 3 h. After that, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain a PVDF separation membrane cross-linked by epoxy compounds (denoted as P-EPI). Soak the obtained membrane P-EPI in 30 g/L ethanol solution of hyperbranched polyethyleneimine (weight average molecular weight 10,000 g/mol), and react at 100 rpm, 85 o C for 24 h to make hyperbranched Polyethyleneimine is cross-linked to the surface of the PVDF separation membrane through chemical bonds. After that, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain a hyperbranched polyethyleneimine cross-linked PVDF separation membrane (denoted as P-HPEI). Immerse one side of the PVDF separation membrane cross-linked with hyperbranched polyethyleneimine in the methanol solution, add 0.5 mL glycidol dropwise, react at 250 rpm, 25 o C for 10 h, pass the glycidol through Chemical bonds are fixed on the surface of hyperbranched polyethyleneimine. Afterwards, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain a super-hydrophilic antifouling PVDF separation membrane (denoted as P-HPEI-GLY).

实施例2:Example 2:

将PVDF分离膜在清水中浸泡24 h,去除PVDF分离膜表面的杂质(记为P0)。将经预处理的分离物膜置于在聚四氟乙烯封闭盒内(单面反应盒),配置1 M的1,4-戊二胺溶解到碳酸钠缓冲溶液(调pH=11.0)中,置于摇床中,200 rpm、25oC条件下反应12 h,直至膜上有淡黄色氨盐化合物层出现。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到经第一步改性后的PVDF分离膜(记为P-NH2)。将得到的膜P-NH2正面朝上浸泡于150 mL无水乙醇中,向其中滴加3 mL环氧氯丙烷,对装置进行充氮保护,缓慢加入40 mg苄基三乙基氯化铵,在100rpm,65oC下反应5 h,再逐滴加入5 mL的0.06 M氢氧化钠溶液,并在100 rpm,40oC下继续反应3 h。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到环氧类化合物交联的PVDF分离膜(记为P-EPI)。将得到的膜P-EPI浸泡于30 g/L的超支化聚乙烯亚胺(重均分子量为60,000 g/mol)的乙醇溶液中,在100 rpm,85oC下反应24 h,使超支化聚乙烯亚胺通过化学键交联到PVDF分离膜表面。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到超支化聚乙烯亚胺交联的PVDF分离膜(记为P-HPEI)。将超支化聚乙烯亚胺交联的PVDF分离膜单面浸没于甲醇溶液中,逐滴加入0.5 mL环氧丙醇,在250 rpm,25oC条件下反应10 h,将环氧丙醇通过化学键固定在超支化聚乙烯亚胺表面。后用水、乙醇交替清洗24 h,在40oC条件下真空干燥,得到超亲水的抗污染PVDF分离膜(记为P-HPEI-GLY)。Soak the PVDF separation membrane in clean water for 24 h to remove the impurities on the surface of the PVDF separation membrane (denoted as P0). Place the pretreated isolate membrane in a polytetrafluoroethylene closed box (single-sided reaction box), configure 1 M 1,4-pentanediamine and dissolve it in sodium carbonate buffer solution (adjust pH=11.0), Place in a shaker, react at 200 rpm, 25 o C for 12 h, until a light yellow ammonium salt compound layer appears on the membrane. Afterwards, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain the PVDF separation membrane modified in the first step (denoted as P-NH 2 ). Soak the obtained membrane P- NH2 face up in 150 mL of absolute ethanol, add 3 mL of epichlorohydrin dropwise to protect the device with nitrogen, and slowly add 40 mg of benzyltriethylammonium chloride , reacted at 100 rpm, 65 o C for 5 h, then added 5 mL of 0.06 M sodium hydroxide solution dropwise, and continued to react at 100 rpm, 40 o C for 3 h. After that, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain a PVDF separation membrane cross-linked by epoxy compounds (denoted as P-EPI). Soak the obtained membrane P-EPI in 30 g/L ethanol solution of hyperbranched polyethyleneimine (weight-average molecular weight: 60,000 g/mol), and react at 100 rpm, 85 o C for 24 h to make hyperbranched Polyethyleneimine is cross-linked to the surface of the PVDF separation membrane through chemical bonds. After that, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain a hyperbranched polyethyleneimine cross-linked PVDF separation membrane (denoted as P-HPEI). Immerse one side of the PVDF separation membrane cross-linked with hyperbranched polyethyleneimine in the methanol solution, add 0.5 mL glycidol dropwise, react at 250 rpm, 25 o C for 10 h, pass the glycidol through Chemical bonds are fixed on the surface of hyperbranched polyethyleneimine. Afterwards, it was alternately washed with water and ethanol for 24 h, and dried in vacuum at 40 o C to obtain a super-hydrophilic antifouling PVDF separation membrane (denoted as P-HPEI-GLY).

实施例3:Example 3:

接触角测试:采用接触角测试仪测试水在PVDF膜表面的接触角。Contact angle test: Use a contact angle tester to test the contact angle of water on the PVDF membrane surface.

经测试,实施例1所得的膜P0接触角为85-95o,经改性后膜P-HPEI和P-HPEI-GLY接触角比膜P0显著下降至30-40 o,且在15 s内降至0o,证明改性后膜亲水性良好。After testing, the P0 contact angle of the film obtained in Example 1 was 85-95 o , and after modification, the contact angles of the P-HPEI and P-HPEI-GLY films were significantly lower than the film P0 to 30-40 o , and within 15 s decreased to 0 o , which proves that the modified membrane has good hydrophilicity.

实施例4:Example 4:

清水通量测试:分别选取实施例1所制得的膜P0和P-HPEI-GLY在20 kPa条件下死端过滤,进水为去离子水,记录并计算二者清水通量。Clean water flux test: select the membranes P0 and P-HPEI-GLY prepared in Example 1 to perform dead-end filtration under the condition of 20 kPa, and the feed water is deionized water, record and calculate the clean water flux of the two.

经测试,实施例1所得的膜P0清水通量显著小于改性膜P-HPEI-GLY,证明改性膜亲水性良好,与接触角测试一致。After testing, the clear water flux of the membrane P0 obtained in Example 1 is significantly smaller than that of the modified membrane P-HPEI-GLY, which proves that the modified membrane has good hydrophilicity, which is consistent with the contact angle test.

实施例5:Example 5:

静态抗蛋白质/多糖吸附测试:本发明中膜的抗蛋白质/多糖实验使用的是牛血清蛋白的PBS溶液和海藻酸钠水溶液,浓度为50 mg/L。分别选取实施例1中的PVDF原膜P0和抗污染PVDF膜P-HPEI-GLY切割成1 × 1 cm2大小并浸没在5 mL的蛋白质溶液/多糖溶液中,在37oC条件下在暗处震荡3 h,将膜片取出并用PBS溶液/去离子水溶液冲洗2次。将膜片置于载玻片上,并用异硫氰酸荧光素(FITC)/刀豆素A(Con A)对膜片进行染色,并在37oC条件下在暗处培养0.5 h。将染完色的膜片用PBS溶液/去离子水溶液冲洗2次,封片用激光共聚焦扫描显微镜(CLSM)进行观察。Static anti-protein/polysaccharide adsorption test: the anti-protein/polysaccharide test of the membrane in the present invention uses a PBS solution of bovine serum albumin and an aqueous sodium alginate solution with a concentration of 50 mg/L. The original PVDF membrane P0 and the anti-fouling PVDF membrane P-HPEI-GLY in Example 1 were selected and cut into 1 × 1 cm 2 size and immersed in 5 mL of protein solution/polysaccharide solution. After shaking for 3 h, the membrane was taken out and rinsed twice with PBS solution/deionized water solution. The membrane slices were placed on glass slides, stained with fluorescein isothiocyanate (FITC)/concanavalin A (Con A), and incubated in the dark at 37 o C for 0.5 h. The stained membranes were rinsed twice with PBS solution/deionized water solution, and mounted for observation with a confocal laser scanning microscope (CLSM).

通过CLSM分析可以看出,抗污染PVDF膜P-HPEI-GLY上蛋白质和多糖污染物的含量显著少于原膜P0,说明膜P-HPEI-GLY有明显的抗粘附作用。Through CLSM analysis, it can be seen that the content of protein and polysaccharide pollutants on the anti-pollution PVDF membrane P-HPEI-GLY is significantly less than that of the original membrane P0, indicating that the membrane P-HPEI-GLY has obvious anti-adhesion effect.

实施例6:Embodiment 6:

动态抗蛋白质/多糖测试:分别选取实施例1所制得的膜P0和P-HPEI-GLY在20 kPa条件下死端过滤,进水程序为20 min纯水-60 min蛋白质/多糖溶液-30 min纯水进行反冲洗,共进行2次循环。记录二者的通量随时间的衰减情况。用水通量恢复比(FRR)、不可逆水通量下降比(IFR)和相对污染比(RFR)来衡量膜的抗污染性能。三者的计算公式如下:Dynamic anti-protein/polysaccharide test: respectively select the membrane P0 and P-HPEI-GLY prepared in Example 1 to filter at the dead end under the condition of 20 kPa, and the water intake program is 20 min pure water-60 min protein/polysaccharide solution-30 min pure water for backwashing, a total of 2 cycles. Record the decay of the flux of the two with time. The anti-fouling performance of the membrane was measured by the water flux recovery ratio (FRR), irreversible water flux decline ratio (IFR) and relative fouling ratio (RFR). The calculation formulas of the three are as follows:

其中,J r表示膜进行反冲洗后恢复的通量,J 0表示膜初始通量,J p表示膜污染60 min后稳定的水通量。Among them, J r represents the flux recovered after the membrane was backwashed, J 0 represents the initial flux of the membrane, and J p represents the stable water flux after membrane fouling for 60 min.

经测试,膜P-HPEI-GLY经过蛋白质或多糖污染后,其水通量恢复比均显著高于原膜P0,不可逆水通量比和相对污染比显著低于原膜P0,说明改性膜不易被污染,易于清洗,抗污染性能良好。After testing, the water flux recovery ratio of the P-HPEI-GLY membrane was significantly higher than that of the original membrane P0 after being polluted by protein or polysaccharide, and the irreversible water flux ratio and relative pollution ratio were significantly lower than the original membrane P0, indicating that the modified membrane It is not easy to be polluted, easy to clean, and has good anti-pollution performance.

以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.

Claims (5)

1.一种超亲水改性的抗污染PVDF分离膜的制备方法,其特征在于具体步骤如下:1. a preparation method of an anti-pollution PVDF separation membrane of superhydrophilic modification, is characterized in that concrete steps are as follows: (1)将二元胺加入至pH为11.0的碳酸钠缓冲溶液中;所述二元胺溶液质量浓度为8.0~24.0%; (1) Diamine is added to a sodium carbonate buffer solution with a pH of 11.0; the mass concentration of the diamine solution is 8.0-24.0%; (2)以PVDF分离膜为基膜,将基膜浸泡到步骤(1)所得溶液中,在200~300rpm,20~30oC条件下反应10~12 h,通过氨基-烯加成反应和氨基-环氧开环反应,使其表面形成氨盐化合物层,得到活化后的PVDF分离膜,洗干净后待用;(2) Use the PVDF separation membrane as the base membrane, soak the base membrane into the solution obtained in step (1), react at 200~300rpm, 20~30 o C for 10~12 h, through the amino-ene addition reaction and Amino-epoxy ring-opening reaction to form an ammonium salt compound layer on the surface to obtain an activated PVDF separation membrane, which is cleaned and ready for use; (3)将步骤(2)得到PVDF分离膜浸泡于环氧氯丙烷的乙醇溶液中,在氮气保护下,加入催化剂,在100~200rpm,55~65oC下反应5~7 h,再逐滴加入氢氧化钠溶液,并在100~200rpm,40~50oC下继续反应3~5 h,通过相转移催化法,在PVDF分离膜表面形成环氧类化合物层,用乙醇、去离子水洗干净待用;所述环氧氯丙烷溶液质量浓度为1.0%~3.0%;所述催化剂质量浓度为0.01~0.03,所述的催化剂为氯代季铵盐类催化剂;所述氢氧化钠溶液浓度为0.01~0.03%;(3) Soak the PVDF separation membrane obtained in step (2) in the ethanol solution of epichlorohydrin, under the protection of nitrogen, add the catalyst, react at 100~200rpm, 55~65 o C for 5~7 h, and then gradually Add sodium hydroxide solution dropwise, and continue to react at 100~200rpm, 40~50 o C for 3~5 h, and form an epoxy compound layer on the surface of PVDF separation membrane by phase transfer catalysis, wash with ethanol and deionized water Clean and ready for use; the mass concentration of the epichlorohydrin solution is 1.0% to 3.0%; the mass concentration of the catalyst is 0.01 to 0.03, and the catalyst is a chlorinated quaternary ammonium salt catalyst; the concentration of the sodium hydroxide solution is 0.01~0.03%; (4)将超支化聚乙烯亚胺乙醇溶液与步骤(3)所得PVDF分离膜在70~90oC下反应24~36h,使超支化聚乙烯亚胺通过化学键交联到步骤(3)所得PVDF分离膜表面,用乙醇、去离子水洗干净待用;超支化聚乙烯亚胺质量分数为2.5%~7.5%;(4) React the hyperbranched polyethyleneimine ethanol solution with the PVDF separation membrane obtained in step (3) at 70~90 o C for 24~36 hours, so that the hyperbranched polyethyleneimine is cross-linked to the obtained product in step (3) through chemical bonds. Wash the surface of PVDF separation membrane with ethanol and deionized water for use; the mass fraction of hyperbranched polyethyleneimine is 2.5%~7.5%; (5)将步骤(4)得到PVDF分离膜浸没于甲醇溶液中,逐滴加入环氧丙醇,在200~300rpm,20~30oC条件下反应10~12 h,通过氨基-环氧开环反应,使其表面的超支化聚乙烯亚胺层末端氨基被羟基覆盖,形成超亲水的抗污染PVDF分离膜材料;环氧丙醇的质量分数为0.1%~5%;(5) Submerge the PVDF separation membrane obtained in step (4) in methanol solution, add glycidyl alcohol drop by drop, react at 200~300rpm, 20~30 o C for 10~12 h, and decompose through amino-epoxy The ring reaction makes the terminal amino groups of the hyperbranched polyethyleneimine layer on the surface covered by hydroxyl groups to form a super-hydrophilic anti-pollution PVDF separation membrane material; the mass fraction of glycidol is 0.1%~5%; (6)反应结束后,取出超亲水的抗污染PVDF分离膜材料,用乙醇、去离子水冲洗干净并烘干,得到具有抗污染性能的PVDF分离膜。(6) After the reaction, take out the super-hydrophilic anti-pollution PVDF separation membrane material, rinse it with ethanol and deionized water, and dry it to obtain a PVDF separation membrane with anti-pollution performance. 2.根据权利要求1所述的抗污染PVDF分离膜的制备方法,其特征在于,步骤(1)所述二元胺为丙二胺、丁二胺或戊二胺的一种或几种。2. The method for preparing an anti-fouling PVDF separation membrane according to claim 1, wherein the diamine in step (1) is one or more of propylenediamine, butylenediamine or pentamethylenediamine. 3.根据权利要求1所述的抗污染PVDF分离膜的制备方法,其特征在于,步骤(3)所述的氯代季铵盐类催化剂为苄基三乙基氯化铵、十六烷基三甲基氯化铵或四丁基氯化铵中任一种。3. The preparation method of anti-pollution PVDF separation membrane according to claim 1, characterized in that, the chlorinated quaternary ammonium salt catalyst described in step (3) is benzyltriethylammonium chloride, hexadecyl Either of trimethylammonium chloride or tetrabutylammonium chloride. 4.根据权利要求1所述的抗菌抗生物污染聚合物分离膜的制备方法,其特征在于,步骤(3)所述的聚合物分离膜浸泡方式为全部浸入溶液中,且所要改性的面朝上。4. The preparation method of antibacterial and anti-biological pollution polymer separation membrane according to claim 1, characterized in that, the immersion method of the polymer separation membrane described in step (3) is completely immersed in the solution, and the surface to be modified up. 5.根据权利要求1所述的抗污染PVDF分离膜的制备方法,其特征在于,步骤(4)所述超支化聚乙烯亚胺的重均分子量为600 g/mol、10,000 g/mol或60,000 g/mol中任一种。5. The preparation method of the anti-fouling PVDF separation membrane according to claim 1, characterized in that the weight average molecular weight of the hyperbranched polyethyleneimine in step (4) is 600 g/mol, 10,000 g/mol or 60,000 Either of g/mol.
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