技术领域technical field
本发明是关于一种基于光固化3D打印技术的季铵盐型阴离子交换膜，属于阴离子交换膜领域。The invention relates to a quaternary ammonium salt type anion exchange membrane based on photocuring 3D printing technology, belonging to the field of anion exchange membranes.
背景技术Background technique
基于离子交换膜的膜分离技术具有低能耗、低污染、高效率等显著的优势，已经在环境保护、功能蛋白分离、新能源的开发与利用等诸多领域得到越来越广泛的研究与运用。然而，目前阴离子交换膜主要由溶液浇铸法制备，其存在毒性大、生产周期长、易交联等一系列缺点，阻碍了阴离子交换膜的商业化进程。Membrane separation technology based on ion exchange membrane has significant advantages such as low energy consumption, low pollution, and high efficiency. It has been widely researched and applied in many fields such as environmental protection, functional protein separation, and new energy development and utilization. However, at present, anion exchange membranes are mainly prepared by solution casting, which has a series of disadvantages such as high toxicity, long production cycle, and easy cross-linking, which hinder the commercialization of anion exchange membranes.
光固化3D打印技术是在特定波长和路径的紫外光照射下，光敏引发剂因发生光解反应生成活性自由基，从而引发液态的低聚物/单体按程序发生交联聚合而获得三维立体产物的成型技术。它具有高效节能、成型精度高和速度快等优点。以光固化3D打印技术制备离子交换膜，有望克服溶液浇铸法的缺点，促进离子交换膜的规模化生产。Photocuring 3D printing technology is under the irradiation of ultraviolet light with a specific wavelength and path, the photoinitiator generates active free radicals due to photolysis reaction, thereby triggering the cross-linking and polymerization of liquid oligomers/monomers to obtain three-dimensional Product molding technology. It has the advantages of high efficiency and energy saving, high forming precision and fast speed. The preparation of ion exchange membranes by photocuring 3D printing technology is expected to overcome the shortcomings of the solution casting method and promote the large-scale production of ion exchange membranes.
离子传导率和离子选择性是离子交换膜的两个核心性能，与离子交换膜的化学组成和结构之间有紧密的联系。合理的配制光敏树脂的组成，使所得离子交换膜具有较低的吸水率（<50 wt%）、较高的离子传导率和选择性、较高的机械强度等性能，是利用光固化3D打印技术制备阴离子交换膜的重要前提。Ion conductivity and ion selectivity are the two core properties of ion exchange membranes, which are closely related to the chemical composition and structure of ion exchange membranes. Reasonable preparation of the composition of the photosensitive resin, so that the obtained ion exchange membrane has low water absorption (<50 wt%), high ion conductivity and selectivity, high mechanical strength and other properties, is the use of light-cured 3D printing An important prerequisite for the preparation of anion exchange membranes.
发明内容Contents of the invention
本发明为克服现有技术的不足，提供了一种基于光固化3D打印技术的季铵盐型阴离子交换膜，其制备方法简单，成型速度快，所得产物吸水率低，离子传导率高、机械性能和热稳定性好、耐溶剂性好，在阴离子交换膜领域有广阔的应用前景。In order to overcome the deficiencies of the prior art, the present invention provides a quaternary ammonium salt-type anion exchange membrane based on light-curing 3D printing technology. It has good performance and thermal stability, good solvent resistance, and has broad application prospects in the field of anion exchange membranes.
为实现上述目的，本发明采用如下技术方案予以实现：To achieve the above object, the present invention adopts the following technical solutions to achieve:
基于光固化3D打印技术的季铵盐型阴离子交换膜，由一定比例的4-乙烯基苄氯、双酚A型环氧丙烯酸酯和甲基丙烯酸异辛酯为原料，在光敏引发剂的存在下，经光固化3D打印机打印成膜，然后泡在三甲胺水溶液中反应2天而得。The quaternary ammonium salt type anion exchange membrane based on photocuring 3D printing technology is made of a certain proportion of 4-vinylbenzyl chloride, bisphenol A epoxy acrylate and isooctyl methacrylate as raw materials. , printed into a film by a photocuring 3D printer, and then soaked in an aqueous solution of trimethylamine to react for 2 days.
其中，4-乙烯基苄氯、双酚A型环氧丙烯酸酯、甲基丙烯酸异辛酯、光敏引发剂的投料质量比为10~30：50~30：35：5；光敏引发剂为苯基双(2,4,6-三甲基苯甲酰基)氧化膦；光固化3D打印机的灯源波长为402nm，基层固化时间为15~30s，基层打印层数为6~20层；三甲胺水溶液中三甲胺的质量分数为10~40%，三甲胺与所浸泡膜中4-乙烯基苄氯的摩尔比为5~100：1。Among them, the mass ratio of 4-vinylbenzyl chloride, bisphenol A epoxy acrylate, isooctyl methacrylate, and photoinitiator is 10~30:50~30:35:5; the photoinitiator is benzene Bis(2,4,6-trimethylbenzoyl)phosphine oxide; the light source wavelength of the light-curing 3D printer is 402nm, the curing time of the base layer is 15~30s, and the number of printing layers of the base layer is 6~20 layers; trimethylamine The mass fraction of trimethylamine in the aqueous solution is 10-40%, and the molar ratio of trimethylamine to 4-vinylbenzyl chloride in the immersed membrane is 5-100:1.
本发明所得基于光固化3D打印技术的季铵盐型阴离子交换膜与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the quaternary ammonium salt type anion exchange membrane based on photocuring 3D printing technology obtained by the present invention has the following beneficial effects:
（1）生产周期短，成本低。传统溶液浇铸法制备阴离子交换膜的时间一般为几十个小时，而利用光固化3D打印技术，几分钟就可生产出所需膜产品。(1) The production cycle is short and the cost is low. The traditional solution casting method generally takes tens of hours to prepare anion exchange membranes, while using photo-curing 3D printing technology, the required membrane products can be produced in a few minutes.
（2）生产精度高。传统溶液浇铸法制备阴离子交换膜很难精确控制成膜厚度，而光固化3D打印机的精度可达到0.01mm，可有效控制膜的厚度要求。(2) High production precision. It is difficult to accurately control the thickness of anion exchange membranes prepared by traditional solution casting methods, but the precision of photo-curing 3D printers can reach 0.01mm, which can effectively control the thickness requirements of the membranes.
（3）所得产物的吸水率低、离子传导率高、机械性能好、热稳定性好、耐溶剂性好。(3) The obtained product has low water absorption, high ion conductivity, good mechanical properties, good thermal stability, and good solvent resistance.
（4）所得产物的离子交换容量可以通过4-乙烯基苄氯的投料量来轻易控制。(4) The ion exchange capacity of the obtained product can be easily controlled by the feeding amount of 4-vinylbenzyl chloride.
附图说明Description of drawings
图1是本发明实施例中基于光固化3D打印技术的季铵盐型阴离子交换膜的扫描电镜图。Figure 1 is a scanning electron microscope image of a quaternary ammonium salt-type anion exchange membrane based on photocuring 3D printing technology in an embodiment of the present invention.
图2是本发明实施例中基于光固化3D打印技术的季铵盐型阴离子交换膜的红外光谱图。Fig. 2 is an infrared spectrogram of the quaternary ammonium salt type anion exchange membrane based on photocuring 3D printing technology in the embodiment of the present invention.
图3是本发明实施例中基于光固化3D打印技术的季铵盐型阴离子交换膜的热重曲线图。Fig. 3 is a thermogravimetric graph of a quaternary ammonium salt-type anion exchange membrane based on photocuring 3D printing technology in an embodiment of the present invention.
具体实施方式Detailed ways
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明。In order to make the content of the present invention easier to understand, the technical solution of the present invention will be further described below in conjunction with specific embodiments.
实施例1：光敏树脂的调配Embodiment 1: the deployment of photosensitive resin
按表1所示比例称取4-乙烯基苄氯、双酚A型环氧丙烯酸酯、甲基丙烯酸异辛酯和苯基双(2,4,6-三甲基苯甲酰基)氧化膦，在烧杯中搅拌15分钟，进行超声处理1分钟，制得PAEK-10、PAEK-20和PAEK-30三种光敏树脂。Weigh 4-vinylbenzyl chloride, bisphenol A type epoxy acrylate, isooctyl methacrylate and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide according to the ratio shown in Table 1 , stirred in a beaker for 15 minutes, and ultrasonically treated for 1 minute to prepare three photosensitive resins of PAEK-10, PAEK-20 and PAEK-30.
表1 光敏树脂的调配Table 1 Preparation of photosensitive resin
实施例2：薄膜的光固化3D打印Example 2: Photocuring 3D printing of thin films
用MOONRAY高精度光固化3D打印机对所配制的一系列光敏树脂分别进行打印。光固化3D打印机的灯源波长为402nm，调节基层固化时间为30s，基层打印层数为8层，分组打印出50 mm × 10 mm × 0.2 mm的薄膜。Use MOONRAY high-precision light-curing 3D printer to print a series of photosensitive resins prepared separately. The light source wavelength of the light-curing 3D printer is 402nm, the curing time of the base layer is adjusted to 30s, the number of printing layers of the base layer is 8 layers, and a film of 50 mm × 10 mm × 0.2 mm is printed in groups.
实施例3：基于光固化3D打印技术的季铵盐型阴离子交换膜的制备Example 3: Preparation of quaternary ammonium salt-type anion exchange membrane based on photocuring 3D printing technology
将实施例2中的薄膜用乙醇和去离子水分别清洗3次，然后浸泡在20wt%的三甲胺水溶液中反应两天，接着取出薄膜，在80℃条件下真空烘干24小时。PAEK-10、PAEK-20和PAEK-30分别反应成QPAEK-10、QPAEK-20和QPAEK-30。经表征，QPAEK-10、QPAEK-20和QPAEK-30不溶于任何溶剂，其相关性能数据如表2所示。The film in Example 2 was washed three times with ethanol and deionized water respectively, and then soaked in 20 wt% trimethylamine aqueous solution to react for two days, then the film was taken out and dried in vacuum at 80°C for 24 hours. PAEK-10, PAEK-20 and PAEK-30 are reacted into QPAEK-10, QPAEK-20 and QPAEK-30 respectively. After characterization, QPAEK-10, QPAEK-20 and QPAEK-30 are insoluble in any solvent, and their relevant performance data are shown in Table 2.
表2 基于光固化3D打印技术的季铵盐型阴离子交换膜的性能数据Table 2 Performance data of quaternary ammonium salt anion exchange membrane based on photocuring 3D printing technology
| Application Number | Priority Date | Filing Date | Title |
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| CN201810570687.0ACN108786482A (en) | 2018-06-05 | 2018-06-05 | A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810570687.0ACN108786482A (en) | 2018-06-05 | 2018-06-05 | A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique |
| Publication Number | Publication Date |
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| CN108786482Atrue CN108786482A (en) | 2018-11-13 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201810570687.0APendingCN108786482A (en) | 2018-06-05 | 2018-06-05 | A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique |
| Country | Link |
|---|---|
| CN (1) | CN108786482A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113021877A (en)* | 2021-03-16 | 2021-06-25 | 杭州电子科技大学 | Preparation method of 3D printing patterned ion exchange membrane |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028849B2 (en)* | 1979-03-27 | 1985-07-06 | 株式会社トクヤマ | Manufacturing method of composite ion exchange membrane |
| CN1634865A (en)* | 2004-11-04 | 2005-07-06 | 中山大学 | Photosensitive quaternary ammonium salt and its preparation method and use |
| CN1649944A (en)* | 2002-03-05 | 2005-08-03 | 佩密斯股份有限公司 | Proton conducting electrolyte membrane for use in high temperatures and the use thereof in fuel cells |
| CN101850218A (en)* | 2010-02-09 | 2010-10-06 | 厦门大学 | A kind of preparation method of quaternary ammonium salt polymer anion exchange membrane |
| CN102099405A (en)* | 2008-07-18 | 2011-06-15 | 富士胶片制造欧洲有限公司 | Process for preparing membranes |
| CN104817835A (en)* | 2015-04-29 | 2015-08-05 | 中国科学院福建物质结构研究所 | Photosensitive resin composition and application thereof in three-dimensional printing |
| CN105643931A (en)* | 2015-08-27 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Method for preparing organic separating membrane through three-dimensional molding technology |
| CN106243290A (en)* | 2016-05-11 | 2016-12-21 | 杭州乐新材料科技有限公司 | A kind of rubber-type photocuring 3D printed material and preparation method thereof |
| CN106345324A (en)* | 2016-08-31 | 2017-01-25 | 山东天维膜技术有限公司 | Method for preparing hybridized ion exchange membrane |
| CN106696258A (en)* | 2016-11-21 | 2017-05-24 | 浙江大学 | Fast 3D printing method |
| CN107207878A (en)* | 2015-01-16 | 2017-09-26 | 富士胶片制造欧洲有限公司 | Curable compositions and film |
| CN107522827A (en)* | 2017-09-20 | 2017-12-29 | 杨军 | A kind of photocuring 3D printing photosensitive resin and its preparation method and application |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028849B2 (en)* | 1979-03-27 | 1985-07-06 | 株式会社トクヤマ | Manufacturing method of composite ion exchange membrane |
| CN1649944A (en)* | 2002-03-05 | 2005-08-03 | 佩密斯股份有限公司 | Proton conducting electrolyte membrane for use in high temperatures and the use thereof in fuel cells |
| CN1634865A (en)* | 2004-11-04 | 2005-07-06 | 中山大学 | Photosensitive quaternary ammonium salt and its preparation method and use |
| CN1281577C (en)* | 2004-11-04 | 2006-10-25 | 中山大学 | Photosensitive quaternary ammonium salt and its preparation method and use |
| CN102099405A (en)* | 2008-07-18 | 2011-06-15 | 富士胶片制造欧洲有限公司 | Process for preparing membranes |
| CN101850218A (en)* | 2010-02-09 | 2010-10-06 | 厦门大学 | A kind of preparation method of quaternary ammonium salt polymer anion exchange membrane |
| CN107207878A (en)* | 2015-01-16 | 2017-09-26 | 富士胶片制造欧洲有限公司 | Curable compositions and film |
| CN104817835A (en)* | 2015-04-29 | 2015-08-05 | 中国科学院福建物质结构研究所 | Photosensitive resin composition and application thereof in three-dimensional printing |
| CN105643931A (en)* | 2015-08-27 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Method for preparing organic separating membrane through three-dimensional molding technology |
| CN106243290A (en)* | 2016-05-11 | 2016-12-21 | 杭州乐新材料科技有限公司 | A kind of rubber-type photocuring 3D printed material and preparation method thereof |
| CN106345324A (en)* | 2016-08-31 | 2017-01-25 | 山东天维膜技术有限公司 | Method for preparing hybridized ion exchange membrane |
| CN106696258A (en)* | 2016-11-21 | 2017-05-24 | 浙江大学 | Fast 3D printing method |
| CN107522827A (en)* | 2017-09-20 | 2017-12-29 | 杨军 | A kind of photocuring 3D printing photosensitive resin and its preparation method and application |
| Title |
|---|
| JIHO SEO ET AL.: "3D Printing of Micropatterned Anion Exchange Membranes", 《ACS APPLIED MATERIALS & INTERFACES》* |
| 张学敏等: "《涂料与涂装技术》", 31 January 2006, 化学工业出版社* |
| 莫健华等: "《液态树脂光固化3D打印技术》", 30 September 2016, 西安电子科技大学出版社* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113021877A (en)* | 2021-03-16 | 2021-06-25 | 杭州电子科技大学 | Preparation method of 3D printing patterned ion exchange membrane |
| CN113021877B (en)* | 2021-03-16 | 2022-09-02 | 杭州电子科技大学 | Preparation method of 3D printing patterned ion exchange membrane |
| Publication | Publication Date | Title |
|---|---|---|
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