WO2015196753A1 - 一种聚醚酰亚胺复合纳滤膜及制备方法 - Google Patents

一种聚醚酰亚胺复合纳滤膜及制备方法 Download PDF

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WO2015196753A1
WO2015196753A1 PCT/CN2014/093765 CN2014093765W WO2015196753A1 WO 2015196753 A1 WO2015196753 A1 WO 2015196753A1 CN 2014093765 W CN2014093765 W CN 2014093765W WO 2015196753 A1 WO2015196753 A1 WO 2015196753A1
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polyetherimide
nanofiltration membrane
mass fraction
composite nanofiltration
solution
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李韡
张金利
海玉琰
江乾
周阿洋
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B01D71/643—Polyether-imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides

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  • the invention relates to a polyetherimide composite nanofiltration membrane and a preparation method thereof.
  • Nanofiltration is a pressure-driven membrane separation process. It is a new membrane separation technology developed between reverse osmosis and ultrafiltration in recent years. Its molecular weight cut-off is generally in the range of 200-1000. Nanofiltration is widely used in seawater desalination, ultrapure water manufacturing, food industry, pharmaceutical industry and environmental protection because of its low operating pressure, no chemical reaction, no heating, and low energy consumption.
  • Nanofiltration membranes are mostly composite membranes composed of surface separation layers and support layers, and interfacial polymerization has become the most mature and most commonly used method for preparing composite nanofiltration membranes.
  • the polymerization is carried out at the interface of the two-phase solution and belongs to the irreversible polymerization of the heterogeneous system, and the reaction requires the monomer to have high reactivity.
  • the acid chloride monomer is dissolved in an organic solvent such as cyclohexane or n-hexane, and a monomer such as a diamine is dissolved in the aqueous phase solution, and the two solutions are subjected to a polycondensation reaction on the surface of the porous support layer, and the polymerization obtained by the reaction is carried out.
  • the substance is insoluble in the solvent and adheres to the surface of the support layer to form a dense active separation layer.
  • the commonly used acid chloride monomer for interfacial polymerization is trimesoyl chloride, but its price is relatively expensive.
  • pyromellitic chloride as a reactive monomer.
  • the polyamine is obtained by reacting with a diamine on the surface of the base film, and then a polyimide film composite film is obtained by imidization treatment.
  • Yaw-Terng Chern et al. used an interfacial polymerization reaction of pyromellitic acid chloride and m-phenylenediamine on a polysulfone support membrane, and then thermally imidized to obtain a polyimide film composite membrane for gas separation. It shows good separation performance for carbon dioxide, oxygen and the like.
  • the filter membrane is a support layer, and a polyimide composite membrane is prepared by interfacial polymerization and subsequent chemical imidization of m-phenylenediamine and pyromellitic chloride as aqueous phases and organic phase functional monomers, respectively.
  • the rejection rates of blue 6B (molecular weight 825.97), acid red 4B (molecular weight 502.44), and basic brilliant blue 6B (molecular weight 506.13) were 96.9%, 91.2%, and 72.6%, respectively, and the flux was 8.9 L/(m2, respectively).
  • h 9.1 L/(m2 ⁇ h), 9.2 L/(m2 ⁇ h).
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a polyetherimide composite nanofiltration membrane.
  • a second object of the present invention is to provide a process for preparing a polyetherimide composite nanofiltration membrane.
  • a preparation method of a polyetherimide composite nanofiltration membrane comprises the following steps:
  • the volume ratio of the aqueous solution to the aqueous solution of EDC ⁇ HCl is 1:1; the EDC ⁇ HCl is an abbreviation for 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, the NHS is Abbreviation for N-hydroxysuccinimide.
  • the additive is preferably polyethylene glycol 200, polyethylene glycol 400 or polyvinylpyrrolidone.
  • the organic solvent is preferably N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.
  • the material of the nonwoven fabric is preferably polypropylene, polyester or polyacrylonitrile.
  • the mass fraction of the polyetherimide in the step (1) is preferably 25%.
  • the mass fraction of the additive in the step (1) is preferably 2%.
  • the standing time in the air in the step (1) is preferably from 1 to 10 seconds.
  • the polyetherimide composite nanofiltration membrane prepared by the above method.
  • the method of the present invention uses pyromellitic acid chloride in the interfacial polymerization step of the polyetherimide-based film to reduce the cost.
  • the invention has low energy consumption and low pollution by modifying the surface of the membrane.
  • the polyetherimide composite nanofiltration membrane prepared by the process of the present invention has a high rejection (90% or more) for some low molecular weight (150-200) compounds. And the performance is stable and the service life is long.
  • Figure 1 is a cross-sectional structure of a polyetherimide composite nanofiltration membrane prepared by the method of the present invention
  • FIG. 2 is a surface structure of a polyetherimide composite nanofiltration membrane prepared by the method of the present invention.
  • the substance used in the membrane separation performance experiment was glucose.
  • the experimental conditions were: 25 ° C, and the glucose concentration was 10 g / L.
  • EDC ⁇ HCl in each example is an abbreviation for 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride
  • NHS is an abbreviation for N-hydroxysuccinimide
  • a preparation method of a polyetherimide composite nanofiltration membrane comprises the following steps:
  • the polyetherimide having a molecular weight of 35,000 and the polyethylene glycol 200 are dissolved in N,N-dimethylacetamide to make the polyetherimide mass fraction 15%, and the quality of the polyethylene glycol 200
  • the fraction was 6%, stirred at 80 ° C for 3 hours, and allowed to defoam for 24 hours to form a casting solution, and scraped 12 g of the casting solution on a smooth surface of a 20 cm ⁇ 30 cm polyester nonwoven fabric. , put into deionized water, soak for 60min, take out and dry to obtain base film 1, the side of the non-woven fabric is called A side;
  • the flux of the obtained membrane was 28.1 L h -1 m -2 , and the glucose concentration of 10 g/L was filtered, the rejection was 90.6%, and the operating pressure was 1 MPa.
  • the experiment proves that the n-hexane solution of 1,2,4,5-pyromellitic acid chloride of the present embodiment is replaced by a cyclohexane solution of 1,2,4,5-pyrenetetracarboxylic acid chloride, and the same as the present embodiment.
  • a polyetherimide composite nanofiltration membrane having an effect similar to that of the present embodiment can be obtained.
  • a preparation method of a polyetherimide composite nanofiltration membrane comprises the following steps:
  • the flux of the obtained membrane was 15.5 L h -1 m -2 , and the glucose concentration of 10 g/L was filtered, the rejection was 98.7%, and the operating pressure was 1 MPa.
  • a preparation method of a polyetherimide composite nanofiltration membrane comprises the following steps:
  • the flux of the obtained membrane was 27.8 L h -1 m -2 , and the glucose concentration of 10 g/L was filtered, the rejection was 91.2%, and the operating pressure was 1 MPa.
  • the polyetherimide composite nanofiltration membrane having an effect similar to that of the present embodiment can be obtained by placing it in the air for 1 second instead of the step (1) of the present embodiment for 10 seconds in the air.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

一种聚醚酰亚胺复合纳滤膜及其制备方法，该方法包括如下步骤：（1）将聚醚酰亚胺和添加剂溶于有机溶剂中，搅拌，静置脱泡，制成铸膜液，在无纺布的光滑面上刮该铸膜液，在空气中放置，在去离子水中浸泡，得到第一基膜，将无纺布刮铸膜液的一面称A面；（2）将第一基膜的A面浸泡在间苯二胺水溶液中，取出晾干，再将A面浸泡在1，2，4，5-均苯四甲酰氯的正己烷溶液中，取出晾干，得到第二基膜；（3）将第二基膜的A面浸泡在EDC•HCl水溶液中，再向EDC•HCl水溶液中加入NHS，再加入乙二胺水溶液，静置反应，用去离子水洗涤，得到聚醚酰亚胺复合纳滤膜。该方法具有成本低、能耗低，污染小的优点；该产品具有高截留率、性能稳定，使用寿命长的优点。

Description

一种聚醚酰亚胺复合纳滤膜及制备方法 技术领域
本发明涉及一种聚醚酰亚胺复合纳滤膜及制备方法。
背景技术
纳滤是一种以压力为驱动的膜分离过程，它是近年发展起来的介于反渗透和超滤之间的一种新型膜分离技术，其截留分子量一般在200-1000范围内。纳滤因操作压力低，分离过程无化学反应、无需加热，能耗低等优势，被越来越广泛地应用于海水淡化、超纯水制造、食品工业、制药工业和环境保护等诸多领域。
纳滤膜大多是复合膜，由表面分离层和支撑层组成，而界面聚合法已经成为制备复合纳滤膜最成熟也是最常用的方法。聚合反应在两相溶液的界面上进行，属于非均相体系的不可逆聚合，反应要求单体具有很高的反应活性。一般将酰氯单体溶解于环己烷、正已烷等有机溶剂中，将二元胺等单体溶解于水相溶液中，两种溶液在多孔支撑层的表面发生缩聚反应，反应得到的聚合物不溶于溶剂，黏附于支撑层表面就形成致密的活性分离层。
界面聚合常用的酰氯单体是均苯三甲酰氯，但其价格较昂贵；而价格相对低廉的均苯四甲酰氯作为反应单体的报道较少，已有的报道中大多利用均苯四甲酰氯和二胺在基膜表面反应先得到聚酰胺酸，再通过亚胺化处理得到聚酰亚胺薄膜复合膜。
现有的研究报道大都使用热亚胺化或化学亚胺化的方法对界面聚合后的复合膜进行处理，这两种处理方式需要使用具有高耐热性和高耐溶剂性的基膜，成本较高。同时由于热亚胺化的处理方式需使用高温持续対膜进行加热，增加了能耗，且容易导致膜表面受热不均匀，影响膜的性能；化学亚胺化所用的试剂如苯、乙酸酐、丙酮等不易回收，对环境破坏性较强，且得到的分离膜的截留分子量较大(500-800)，限制了膜的使用。
Yaw-Terng Chern等用均苯四甲酰氯和间苯二胺在聚砜支撑膜上发生界面聚合反应，再经热亚胺化得到了用于气体分离的聚酰亚胺薄膜复合膜，该膜对二氧化碳、氧气等表现出了良好的分离性能。[Yaw-Terng Chern,Leo-Wang Chen.Preparation of Composite Membranes via Interfacial Polyfunctional Condensation for Gas Separation Applications.Journal of Applied Polymer Science,1992,44:1087-1093.]杨振生等以丙烯酰胺接枝的聚丙烯超滤膜为支撑层，以间苯二胺、均苯四甲酰氯分别为水相、有机相功能单体通过界面聚合及后续化学亚胺化制备了聚酰亚胺复合膜，该膜对酸性艳蓝6B(分子量为825.97)、酸性红4B(分子量为502.44)、碱性艳蓝6B(分子量为506.13)的截留率分别达96.9％、91.2％、72.6％，通量分别为8.9L/(m2·h)、9.1L/(m2·h)、9.2L/(m2·h)。[杨振生,张磊,张广厚,李春利.界面聚合法PI/PP耐溶剂复合纳滤膜的制备与表征.化工学报,2012,63(8):2635-2641.]SungPyo Hong等以聚砜超滤膜为支撑层，用间苯二胺和均苯四甲酰氯在其表面发生界面聚合反应，再经热亚胺化处理制备了聚酰亚胺复合膜，所得膜在1.5MPa下，对NaCl截留率达96.7％，通量为23.6L/(m2·h)。[SungPyo Hong,In-Chul Kim,Taemoon Tak,Young-Nam Kwon.Interfacially synthesized chlorine-resistant polyimide thin film composite(TFC)reverse osmosis(RO)membranes.Desalination,2013,309: 18-26.]
针对目前纳滤膜制备过程中采用的亚胺化方法产生的高能耗、环境污染以及截留率低(特别是分子量在150-200的化合物)等问题，迫切需要采用新的方法制备出性能优良的复合纳滤膜。
发明内容
本发明的目的是克服现有技术的不足，提供一种聚醚酰亚胺复合纳滤膜。
本发明的第二个目的是提供一种聚醚酰亚胺复合纳滤膜的制备方法。
本发明的技术方案概述如下：
一种聚醚酰亚胺复合纳滤膜的制备方法，包括如下步骤：
(1)将分子量为35000-55000的聚醚酰亚胺和添加剂溶于有机溶剂中，使所述聚醚酰亚胺的质量分数为15％-27％，添加剂的质量分数为1％-6％，在40-80℃，搅拌3-8小时，静置脱泡8-24小时，制成铸膜液，按比例在20cm×30cm无纺布的光滑面上刮12-20g的铸膜液，在空气中放置0-60秒，放入去离子水中，浸泡5-60min，取出晾干后得到基膜1，将无纺布刮铸膜液的一面称A面；
(2)将基膜1的A面浸泡在质量分数为0.5％-4％的间苯二胺水溶液中30-120秒，取出晾干，再将所述A面浸泡在质量分数为0.02％-0.2％的1,2,4,5-均苯四甲酰氯的正己烷溶液中或1,2,4,5-均苯四甲酰氯的环己烷溶液中30-120秒，取出晾干，得到基膜2；
(3)将基膜2的A面浸泡在质量分数为4％-8％的EDC·HCl水溶液中10-20min后，再向EDC·HCl水溶液中加入NHS使质量分数为2％-4％，晃动使NHS溶解，再加入质量分数为2％-8％的乙二胺水溶液，静置反应4-16h，用去离子水洗涤，得到聚醚酰亚胺复合纳滤膜，所述乙二胺水溶液与EDC·HCl水溶液的体积比为1:1；所述EDC·HCl是1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐的缩写，所述NHS是N-羟基琥珀酰亚胺的缩写。
添加剂优选为聚乙二醇200、聚乙二醇400或聚乙烯吡咯烷酮。
有机溶剂优选为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺或N-甲基吡咯烷酮。
无纺布的材质优选为聚丙烯、聚酯或聚丙烯腈。
步骤(1)所述聚醚酰亚胺的质量分数优选为25％。
步骤(1)所述添加剂的质量分数优选为2％。
步骤(1)所述在空气中放置时间优选为1-10秒。
上述方法制备的聚醚酰亚胺复合纳滤膜。
本发明的优点在于：
1.本发明的方法在聚醚酰亚胺基膜的界面聚合步骤中选用均苯四甲酰氯，使成本降低。
2.本发明通过对膜表面进行改性处理，能耗低，污染小。
3.本发明的方法制备的聚醚酰亚胺复合纳滤膜对一些低分子量(150-200)化合物具有较高截留率(90％以上)。并且性能稳定，使用寿命较长。
4.工艺简单，反应条件温和，反应时间短。
附图说明
图1为本发明的方法制备的聚醚酰亚胺复合纳滤膜的断面结构；
图2为本发明的方法制备的聚醚酰亚胺复合纳滤膜的表面结构。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，本发明的实施例是为了使本领域的技术人员能够更好地理解本发明，但并不对本发明作任何限制。
膜分离性能实验中所用的物质为葡萄糖，实验的测试条件为：25℃，葡萄糖浓度均为10g/L。
各实施例中的EDC·HCl是1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐的缩写，NHS是N-羟基琥珀酰亚胺的缩写。
实施例1
一种聚醚酰亚胺复合纳滤膜的制备方法，包括如下步骤：
(1)将分子量为35000的聚醚酰亚胺和聚乙二醇200溶于N，N-二甲基乙酰胺使聚醚酰亚胺的质量分数为15％，聚乙二醇200的质量分数为6％，在80℃，搅拌3小时，静置脱泡24小时，制成铸膜液，按比例在20cm×30cm材质为聚酯的无纺布的光滑面上刮12g的铸膜液，放入去离子水中，浸泡60min，取出晾干后得到基膜1，将无纺布刮铸膜液的一面称A面；
(2)将基膜1的A面浸泡在质量分数为0.5％间苯二胺的水溶液中30秒，取出晾干，再将A面浸泡在质量分数为0.02％的1,2,4,5-均苯四甲酰氯的正己烷溶液中30秒，取出晾干，得到基膜2；
(3)将基膜2的A面浸泡在质量分数为4％的EDC·HCl水溶液中10min后，再向EDC·HCl水溶液中加入NHS使质量分数为2％，晃动使NHS溶解，再加入质量分数为2％的乙二胺水溶液，静置反应16h，用去离子水洗涤，得到聚醚酰亚胺复合纳滤膜，乙二胺水溶液与EDC·HCl水溶液的体积比为1:1。
所得膜的通量为28.1L h-1m-2，过滤浓度为10g/L的葡萄糖溶液，截留率为90.6％，操作压力为1MPa。
实验证明，用1,2,4,5-均苯四甲酰氯的环己烷溶液替代本实施例的1,2,4,5-均苯四甲酰氯的正己烷溶液，其它同本实施例，可以得到效果与本实施例相似的聚醚酰亚胺复合纳滤膜。
实施例2
一种聚醚酰亚胺复合纳滤膜的制备方法，包括如下步骤：
(1)将分子量为48000的聚醚酰亚胺和聚乙二醇400溶于N，N-二甲基甲酰胺中，使聚醚酰亚胺的质量分数为27％，聚乙二醇400的质量分数为1％，在40℃，搅拌8小时，静置脱泡8小时，制成铸膜液，按比例在20cm×30cm材质为聚丙烯的无纺布的光滑面上刮16g的铸膜液，在空气中放置60秒，放入去离子水中，浸泡5min，取出晾干后得到基膜1，将无纺布刮铸膜液的一面称A面；
(2)将基膜1的A面浸泡在质量分数为4％间苯二胺的水溶液中60秒，取出晾干，再将A面浸泡在质量分数为0.2％的1,2,4,5-均苯四甲酰氯的环己烷溶液中60秒，取出晾干，得 到基膜2；
(3)将基膜2的A面浸泡在质量分数为8％的EDC·HCl水溶液中15min后，再向EDC·HCl水溶液中加入NHS使质量分数为4％，晃动使NHS溶解，再加入质量分数为8％的乙二胺水溶液，静置反应4h，用去离子水洗涤，得到聚醚酰亚胺复合纳滤膜，所述乙二胺水溶液与EDC·HCl水溶液的体积比为1:1。
所得膜的通量为15.5L h-1m-2，过滤浓度为10g/L的葡萄糖溶液，截留率为98.7％，操作压力为1MPa。
实施例3
一种聚醚酰亚胺复合纳滤膜的制备方法，包括如下步骤：
(1)将分子量为55000的聚醚酰亚胺和聚乙烯吡咯烷酮溶于N-甲基吡咯烷酮中，使聚醚酰亚胺的质量分数为25％，聚乙烯吡咯烷酮的质量分数为2％，在60℃，搅拌5小时，静置脱泡12小时，制成铸膜液，按比例在20cm×30cm材质为聚丙烯腈的无纺布的光滑面上刮20g的铸膜液，在空气中放置10秒，放入去离子水中，浸泡30min，取出晾干后得到基膜1，将无纺布刮铸膜液的一面称A面；
(2)将基膜1的A面浸泡在质量分数为2％间苯二胺的水溶液中120秒，取出晾干，再将所述A面浸泡在质量分数为0.1％的1,2,4,5-均苯四甲酰氯的正己烷溶液中120秒，取出晾干，得到基膜2；
(3)将基膜2的A面浸泡在质量分数为6％的EDC·HCl水溶液中20min后，再向EDC·HCl水溶液中加入NHS使质量分数为3％，晃动使NHS溶解，再加入质量分数为6％的乙二胺水溶液，静置反应8h，用去离子水洗涤，得到聚醚酰亚胺复合纳滤膜，所述乙二胺水溶液与EDC·HCl水溶液的体积比为1:1。
所得膜的通量为27.8L h-1m-2，过滤浓度为10g/L的葡萄糖溶液，截留率为91.2％，操作压力为1MPa。
实验证明，用在空气中放置1秒替代本实施例步骤(1)在空气中放置10秒，其它同本实施例，可以得到效果与本实施例相似的聚醚酰亚胺复合纳滤膜。

Claims (8)

  1. 一种聚醚酰亚胺复合纳滤膜的制备方法，其特征包括如下步骤：
    (1)将分子量为35000-55000的聚醚酰亚胺和添加剂溶于有机溶剂中，使所述聚醚酰亚胺的质量分数为15％-27％，添加剂的质量分数为1％-6％，在40-80℃，搅拌3-8小时，静置脱泡8-24小时，制成铸膜液，按比例在20cm×30cm无纺布的光滑面上刮12-20g的铸膜液，在空气中放置0-60秒，放入去离子水中，浸泡5-60min，取出晾干后得到基膜1，将无纺布刮铸膜液的一面称A面；
    (2)将基膜1的A面浸泡在质量分数为0.5％-4％的间苯二胺水溶液中30-120秒，取出晾干，再将所述A面浸泡在质量分数为0.02％-0.2％的1,2,4,5-均苯四甲酰氯的正己烷溶液中或1,2,4,5-均苯四甲酰氯的环己烷溶液中30-120秒，取出晾干，得到基膜2；
    (3)将基膜2的A面浸泡在质量分数为4％-8％的EDC·HCl水溶液中10-20min后，再向EDC·HCl水溶液中加入NHS使质量分数为2％-4％，晃动使NHS溶解，再加入质量分数为2％-8％的乙二胺水溶液，静置反应4-16h，用去离子水洗涤，得到聚醚酰亚胺复合纳滤膜，所述乙二胺水溶液与EDC·HCl水溶液的体积比为1:1；所述EDC·HCl是1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐的缩写，所述NHS是N-羟基琥珀酰亚胺的缩写。
  2. 根据权利要求1所述的聚醚酰亚胺复合纳滤膜的制备方法，其特征是所述添加剂为聚乙二醇200、聚乙二醇400或聚乙烯吡咯烷酮。
  3. 根据权利要求1所述的聚醚酰亚胺复合纳滤膜的制备方法，其特征是所述有机溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺或N-甲基吡咯烷酮。
  4. 根据权利要求1所述的聚醚酰亚胺复合纳滤膜的制备方法，其特征是所述无纺布的材质为聚丙烯、聚酯或聚丙烯腈。
  5. 根据权利要求1、2或3所述的聚醚酰亚胺复合纳滤膜的制备方法，其特征是所述步骤(1)所述聚醚酰亚胺的质量分数为25％。
  6. 根据权利要求1、2或3所述的聚醚酰亚胺复合纳滤膜的制备方法，其特征是所述步骤(1)所述添加剂的质量分数为2％。
  7. 根据权利要求1、2或3所述的聚醚酰亚胺复合纳滤膜的制备方法，其特征是所述步骤(1)所述在空气中放置时间为1-10秒。
  8. 权利要求1-7之一的方法制备的聚醚酰亚胺复合纳滤膜。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115364687A (zh) * 2022-08-18 2022-11-22 天津工业大学 高性能纳滤膜及其制备方法和用途
CN115920634A (zh) * 2022-10-26 2023-04-07 浙江工业大学 一种自具微孔聚合物纳滤膜的制备方法
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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106890571A (zh) * 2017-03-06 2017-06-27 江苏凯米膜科技股份有限公司 一种有机管式纳滤膜的制备方法
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CN112642305A (zh) * 2021-01-12 2021-04-13 天津工业大学 一种耐酸复合纳滤膜及其制备方法
CN115368158B (zh) * 2021-05-21 2023-07-07 三达膜科技（厦门）有限公司 一种超薄氧化钛陶瓷纳滤膜的制备方法
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EP4683731A2 (en) * 2023-03-21 2026-01-28 Captura Corp. Direct removal of carbon dioxide from oceanwater based on a composite membrane

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277344A (en) * 1979-02-22 1981-07-07 Filmtec Corporation Interfacially synthesized reverse osmosis membrane
CN101460237A (zh) * 2006-05-12 2009-06-17 陶氏环球技术公司 改性膜
CN103212312A (zh) * 2013-04-28 2013-07-24 中国科学院化学研究所 一种非对称耐氧化渗透膜及其制备方法
CN103260733A (zh) * 2010-12-28 2013-08-21 东丽株式会社 复合半透膜
CN103272498A (zh) * 2013-05-14 2013-09-04 天津大学 表面接枝改性的芳香聚酰胺复合反渗透膜及制备方法
CN103648625A (zh) * 2012-05-31 2014-03-19 Lg化学株式会社 包含碳二亚胺化合物的高渗透通量的反渗透膜及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6162358A (en) * 1998-06-05 2000-12-19 Nl Chemicals Technologies, Inc. High flux reverse osmosis membrane
US20060249446A1 (en) * 2005-05-04 2006-11-09 Gary Yeager Solvent-resistant composite membrane composition
US8580341B2 (en) * 2009-05-22 2013-11-12 General Electric Company Method of making composite membrane
GB201012083D0 (en) * 2010-07-19 2010-09-01 Imp Innovations Ltd Thin film composite membranes for separation
CN102641667A (zh) * 2012-05-03 2012-08-22 天津大学 聚酰胺复合纳滤膜的制备方法
CN102794116B (zh) * 2012-06-06 2014-10-29 复旦大学 介孔二氧化硅球-聚合物纳米复合纳滤膜及其制备方法
CN103768964A (zh) * 2014-03-04 2014-05-07 哈尔滨工业大学 一种二胺交联改性添加聚乙二醇的聚酰亚胺纳滤膜的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277344A (en) * 1979-02-22 1981-07-07 Filmtec Corporation Interfacially synthesized reverse osmosis membrane
CN101460237A (zh) * 2006-05-12 2009-06-17 陶氏环球技术公司 改性膜
CN103260733A (zh) * 2010-12-28 2013-08-21 东丽株式会社 复合半透膜
CN103648625A (zh) * 2012-05-31 2014-03-19 Lg化学株式会社 包含碳二亚胺化合物的高渗透通量的反渗透膜及其制备方法
CN103212312A (zh) * 2013-04-28 2013-07-24 中国科学院化学研究所 一种非对称耐氧化渗透膜及其制备方法
CN103272498A (zh) * 2013-05-14 2013-09-04 天津大学 表面接枝改性的芳香聚酰胺复合反渗透膜及制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115364687A (zh) * 2022-08-18 2022-11-22 天津工业大学 高性能纳滤膜及其制备方法和用途
CN115920634A (zh) * 2022-10-26 2023-04-07 浙江工业大学 一种自具微孔聚合物纳滤膜的制备方法
CN117654271A (zh) * 2023-12-05 2024-03-08 中山大学 一种氨基酸调控聚酰胺纳滤膜的制备方法和应用
CN119656865A (zh) * 2025-02-20 2025-03-21 安徽鑫纪源科技有限公司 一种碳酸锂溶液纳滤浓缩用高通量纳滤膜及其制备方法

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