An antioxidant ion exchange membrane and a preparation method thereof

Abstract

The invention is applicable to the technical field of ion exchange membranes, and provides an antioxidant ion exchange membrane and a preparation method thereof. The antioxidant ion exchange membrane comprises a modified microporous membrane and an ion exchange resin, wherein the modified microporous membrane comprises a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, wherein the coating comprises the following raw materials: modified agarose, modified polyethylene glycol, modified nano cerium dioxide, nano titanium dioxide, and water. The antioxidant ion exchange membrane provided by the invention is prepared by making a modified microporous membrane, wherein the modified microporous membrane comprises a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, wherein the coating is added with modified agarose, modified polyethylene glycol, and modified nano cerium dioxide, and the three have a synergistic effect, and can improve the antioxidant performance of the ion exchange membrane on the one hand, and can improve the mechanical performance of the ion exchange membrane on the other hand.

Description

Technical Field

[0001] The invention belongs to the technical field of ion exchange membranes, and in particular relates to an anti-oxidation ion exchange membrane and a preparation method thereof. Background Art

[0002] Ion exchange membrane is a functional membrane that allows ions to pass selectively. It is used in fuel cells, SPE water electrolysis hydrogen production technology and liquid flow batteries, because ion exchange membrane has the dual functions of transferring ions and dispersing anode and cathode gases.

[0003] The performance and stability of the ion exchange membrane directly determine the performance and stability of the entire fuel cell. During the electrochemical reaction of the membrane electrode, oxygen will produce a large number of hydroxyl radicals under the catalytic action of the catalyst, causing the ion exchange membrane to degrade and affecting the service life of the ion exchange membrane. Therefore, it is very important to improve the antioxidant performance of the ion exchange membrane. Summary of the invention

[0004] The present invention provides an anti-oxidation ion exchange membrane, aiming to solve the above problems.

[0005] The present invention is achieved in this way: an antioxidant ion exchange membrane comprises a modified microporous membrane and an ion exchange resin, wherein the modified microporous membrane comprises a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, wherein the coating comprises the following raw materials in parts by weight: 20-30 parts of modified agarose, 15-25 parts of modified polyethylene glycol, 3-7 parts of modified nano cerium dioxide, 1-2 parts of nano titanium dioxide, and 80-100 parts of water.

[0006] Preferably, the coating comprises the following raw materials in parts by weight: 22-27 parts of modified agarose, 18-22 parts of modified polyethylene glycol, 4-6 parts of modified nano-cerium dioxide, 1.2-1.7 parts of nano-titanium dioxide, and 85-95 parts of water.

[0007] Preferably, the coating comprises the following raw materials in parts by weight: 25 parts of modified agarose, 20 parts of modified polyethylene glycol, 5 parts of modified nano-cerium dioxide, 1.5 parts of nano-titanium dioxide, and 90 parts of water.

[0008] Preferably, the preparation method of the modified agarose is as follows: agarose and isopropanol solution are fully stirred to obtain a suspension, the molecular weight of agarose is 630.5471, and it is sourced from Qingdao Zeshuo Biotechnology Co., Ltd., the mass volume ratio of agarose to isopropanol solution is 1g:13-15mL, NaOH solution is added to the above suspension, the concentration of the NaOH solution is 10-12M and the addition amount is 150-250mL / L, ethylenediaminetetraacetic acid is added at 150-200g / L while stirring to react, the temperature is raised to 45-65°C and maintained for 1-1.5h, the reaction system is placed in an ultrasonic cleaner and water is used as an oscillation medium, the ultrasonic output power is 50-80W, and then 30-50 g / L of nano activated carbon fiber is added, reacted for 20-30 minutes, and finally precipitated by alcohol precipitation method, filtered, washed and dried to obtain modified agarose; carboxyl groups and amino groups are grafted onto agarose to react, forming a cross-linked tight network structure, increasing the intermolecular force, improving the stability and mechanical properties, and adding nano activated carbon fiber to play a bridging role, and having the advantages of large specific surface area and strong adsorption capacity, thereby improving the exchange adsorption performance of agarose; adding modified agarose has an antioxidant effect on the one hand, and on the other hand, as a structural skeleton, has high mechanical properties, and has a pore system composed of uniform and dense micropores and large meshes, has a large capacity, and has rapid exchange adsorption performance.

[0009] Preferably, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol is mixed with succinic anhydride, and N, N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin are added, wherein the mass ratio of the polyethylene glycol to succinic anhydride, N, N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin is 1:1-2:4-6:2-3:2-5, the temperature is raised to 60-80°C and stirred for 2-3h, and then extracted with cyclohexane to obtain a dispersion, and the dispersion is mixed with thionyl chloride at a mass ratio of 10 :1-3 mixed, stirred for reaction, and then distilled under reduced pressure to obtain modified polyethylene glycol; wherein the polyethylene glycol has a molecular weight of 2000 and is sourced from Wuhan Yixingda Chemical Co., Ltd. By grafting amino groups on the ends of the polyethylene glycol, the reactivity of the polyethylene glycol is enhanced, and it is compounded with other components to react with each other to form a macromolecular network structure, thereby improving the stability and mechanical properties of the microporous membrane. By adding cyclodextrin, the hydrophilic ether bonds and hydroxyl groups in the polyethylene glycol molecular chain produce hydrogen bonds with the hydroxyl groups on the hydrophilic edges of the cyclodextrin to form a more stable system.

[0010] Preferably, the preparation method of the modified nano cerium dioxide is as follows: 6-10 parts of nano cerium dioxide are taken by weight, dispersed in a 75-85% ethanol solution with a weight of 10-15 times the weight of the nano cerium dioxide, then 5-13 parts of acetic acid are added, stirred for 30-50 minutes, filtered and washed with deionized water for 3 times to obtain a product, the product is added to deionized water with a weight of 60-80 times the weight of the nano cerium dioxide, ultrasonically treated for 20-30 minutes, 0.5-1 parts of sodium dodecylbenzene sulfonate are added, the pH is adjusted to 3-11, and the product is reacted in a water bath at 55-65°C for 1-2 hours and then filtered, the filter cake is taken out and dried in an oven at 120°C for 2-3 hours, and the modified nano cerium dioxide is obtained by grinding; the surface of the nano cerium dioxide is modified by acetic acid and sodium dodecylbenzene sulfonate in turn to improve its adsorption and dispersibility, and the antioxidant performance is better.

[0011] Preferably, the preparation method of the modified microporous membrane is as follows: weigh each raw material according to the ratio; stir modified agarose, modified polyethylene glycol, modified nano-cerium dioxide, nano-titanium dioxide, and water at a speed of 2000-3000r / min for 30-50min to obtain a mixed dispersion; dip-coat the polytetrafluoroethylene fiber membrane with the mixed dispersion, and then dry it at 40-50°C, repeat the above dip-coating and drying operations 2-5 times; place the membrane in an environment of 80-100°C for heat treatment to obtain a modified microporous membrane.

[0012] Preferably, the polytetrafluoroethylene fiber membrane is pretreated before use, and the pretreatment method is: put the polytetrafluoroethylene fiber membrane into a culture vessel and inject bacterial cellulose fermentation liquid, wrap it, and culture it at 25-28°C for 3-5 days, rinse the cultured polytetrafluoroethylene fiber membrane with deionized water, remove the residual culture liquid, soak it with deionized water until it is colorless, and finally dry it at 40-50°C for use. During the fermentation process, bacterial cellulose grows into the polytetrafluoroethylene fiber membrane to form an interlaced interpenetrating network with it. On the one hand, the mechanical properties of the polytetrafluoroethylene fiber membrane are improved. On the other hand, the bacterial cellulose has a large storage space and good adsorption performance, adsorbs more coating raw materials, and is tightly connected to the coating, thereby improving the performance of the microporous membrane.

[0013] Preferably, the preparation method of the bacterial cellulose fermentation liquid is as follows: inoculating Acetobacter xylinum into the culture liquid, the temperature is 25-28°C, the stirring speed is 200-220r / min, and the culture time is 20-30h to obtain seed liquid; the seed liquid with a volume of 6-10% of the culture liquid is added to the culture liquid, mixed and set aside to obtain bacterial cellulose fermentation liquid.

[0014] The present invention also provides a method for preparing the above-mentioned antioxidant ion exchange membrane, comprising the following steps:

[0015] dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion;

[0016] The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

[0017] Compared with the prior art, the embodiments of the present application have the following beneficial effects:

[0018] The antioxidant ion exchange membrane provided by the present invention is prepared by a modified microporous membrane, wherein the modified microporous membrane comprises a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, wherein the coating is added with modified agarose, modified polyethylene glycol and modified nano-cerium dioxide, and the three have a synergistic effect, which can improve the antioxidant performance of the ion exchange membrane on the one hand, and can improve the mechanical properties of the ion exchange membrane on the other hand. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a flow chart for preparing a modified microporous membrane in an antioxidant ion exchange membrane provided by the present invention;

[0020] Figure 2 The present invention provides a flow chart for preparing an antioxidant ion exchange membrane. DETAILED DESCRIPTION

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by technicians in the technical field of this application; the terms used in the specification of the application herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned drawings are intended to cover non-exclusive inclusions. The terms "first", "second", etc. in the specification and claims of this application or the above-mentioned drawings are used to distinguish different objects, not to describe a specific order.

[0022] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0023] Example 1

[0024] The embodiment of the present invention provides an antioxidant ion exchange membrane, such as Figure 1-Figure 2As shown, it includes a modified microporous membrane and an ion exchange resin, the modified microporous membrane includes a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, the coating includes the following raw materials in parts by weight: 20 parts of modified agarose, 15 parts of modified polyethylene glycol, 3 parts of modified nano cerium dioxide, 1 part of nano titanium dioxide, and 80 parts of water. The preparation method of the modified microporous membrane is as follows: weigh each raw material according to the ratio; stir the modified agarose, modified polyethylene glycol, modified nano cerium dioxide, nano titanium dioxide, and water at a speed of 2000r / min for 30min to obtain a mixed dispersion; dip the polytetrafluoroethylene fiber membrane in the mixed dispersion, and then dry it at 40°C, repeat the above dip coating and drying operations 3 times; place the membrane in an environment of 80°C for heat treatment to obtain a modified microporous membrane;

[0025] The method for preparing the above-mentioned antioxidant ion exchange membrane comprises the following steps:

[0026] dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion;

[0027] The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

[0028] The preparation method of the modified agarose is as follows: agarose and isopropanol solution are fully stirred to obtain a suspension, the molecular weight of agarose is 630.5471, and it is sourced from Qingdao Zeshuo Biotechnology Co., Ltd. The mass volume ratio of the agarose to the isopropanol solution is 1g:13mL, and NaOH solution is added to the above suspension, the concentration of the NaOH solution is 10M and the addition amount is 150mL / L, and ethylenediaminetetraacetic acid is added at 150g / L while stirring to react, and the temperature is raised to 45°C and maintained for 1.5h. The reaction system is placed in an ultrasonic cleaner and water is used as an oscillation medium. The ultrasonic output power is 50W, and then 30g / L of nano-activated carbon fiber is added, and the reaction is reacted for 20min. Finally, it is precipitated by alcohol precipitation, filtered, washed, and dried to obtain modified agarose.

[0029] Specifically, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol is mixed with succinic anhydride, and N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin are added, wherein the mass ratio of the polyethylene glycol to succinic anhydride, N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin is 1:1:4:2:2, the temperature is raised to 60°C and stirred for 2 hours, and then extracted with cyclohexane to obtain a dispersion, the dispersion is mixed with thionyl chloride at a mass ratio of 10:1, stirred for reaction, and then distilled under reduced pressure to obtain the modified polyethylene glycol.

[0030] In this embodiment, the preparation method of the modified nano-cerium dioxide is as follows: 6 parts of nano-cerium dioxide are taken by weight and dispersed in a 75% ethanol solution 10 times its mass, then 5 parts of acetic acid are added, stirred for 30 minutes, filtered and washed with deionized water 3 times to obtain a product, the product is added to deionized water 60 times its mass, ultrasonically treated for 20 minutes, 0.5 parts of sodium dodecylbenzene sulfonate are added, the pH is adjusted to 3, and reacted in a water bath at 55°C for 1 hour and then filtered, the filter cake is taken out and dried in an oven at 120°C for 2 hours, and ground to obtain modified nano-cerium dioxide.

[0031] Example 2

[0032] The embodiment of the present invention provides an antioxidant ion exchange membrane, such as Figure 1-Figure 2 As shown, it includes a modified microporous membrane and an ion exchange resin, the modified microporous membrane includes a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, the coating includes the following raw materials in parts by weight: 22 parts of modified agarose, 18 parts of modified polyethylene glycol, 4 parts of modified nano cerium dioxide, 1.2 parts of nano titanium dioxide, and 85 parts of water. The preparation method of the modified microporous membrane is as follows: weigh each raw material according to the ratio; stir the modified agarose, modified polyethylene glycol, modified nano cerium dioxide, nano titanium dioxide, and water at a speed of 2000r / min for 30min to obtain a mixed dispersion; dip the polytetrafluoroethylene fiber membrane in the mixed dispersion, and then dry it at 40°C, repeat the above dip coating and drying operations 3 times; place the membrane in an environment of 80°C for heat treatment to obtain a modified microporous membrane;

[0033] The method for preparing the above-mentioned antioxidant ion exchange membrane comprises the following steps:

[0034] dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion;

[0035] The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

[0036] The preparation method of the modified agarose is as follows: agarose and isopropanol solution are fully stirred to obtain a suspension, the molecular weight of agarose is 630.5471, and it is sourced from Qingdao Zeshuo Biotechnology Co., Ltd. The mass volume ratio of the agarose to the isopropanol solution is 1g:13mL, and NaOH solution is added to the above suspension, the concentration of the NaOH solution is 10M and the addition amount is 150mL / L, and ethylenediaminetetraacetic acid is added at 150g / L while stirring to react, and the temperature is raised to 45°C and maintained for 1.5h. The reaction system is placed in an ultrasonic cleaner and water is used as an oscillation medium. The ultrasonic output power is 50W, and then 30g / L of nano-activated carbon fiber is added, and the reaction is reacted for 20min. Finally, it is precipitated by alcohol precipitation, filtered, washed, and dried to obtain modified agarose.

[0037] Specifically, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol is mixed with succinic anhydride, and N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin are added, wherein the mass ratio of the polyethylene glycol to succinic anhydride, N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin is 1:1:4:2:2, the temperature is raised to 60°C and stirred for 2 hours, and then extracted with cyclohexane to obtain a dispersion, the dispersion is mixed with thionyl chloride at a mass ratio of 10:1, stirred for reaction, and then distilled under reduced pressure to obtain the modified polyethylene glycol.

[0038] In this embodiment, the preparation method of the modified nano-cerium dioxide is as follows: 6 parts of nano-cerium dioxide are taken by weight and dispersed in a 75% ethanol solution 10 times its mass, then 5 parts of acetic acid are added, stirred for 30 minutes, filtered and washed with deionized water 3 times to obtain a product, the product is added to deionized water 60 times its mass, ultrasonically treated for 20 minutes, 0.5 parts of sodium dodecylbenzene sulfonate are added, the pH is adjusted to 3, and reacted in a water bath at 55°C for 1 hour and then filtered, the filter cake is taken out and dried in an oven at 120°C for 2 hours, and ground to obtain modified nano-cerium dioxide.

[0039] Example 3

[0040] The embodiment of the present invention provides an antioxidant ion exchange membrane, such as Figure 1-Figure 2 As shown, it includes a modified microporous membrane and an ion exchange resin, the modified microporous membrane includes a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, the coating includes the following raw materials in parts by weight: 25 parts of modified agarose, 20 parts of modified polyethylene glycol, 5 parts of modified nano cerium dioxide, 1.5 parts of nano titanium dioxide, and 90 parts of water. The preparation method of the modified microporous membrane is as follows: weigh each raw material according to the ratio; stir the modified agarose, modified polyethylene glycol, modified nano cerium dioxide, nano titanium dioxide, and water at a speed of 2000-3000r / min for 30-50min to obtain a mixed dispersion; dip the polytetrafluoroethylene fiber membrane in the mixed dispersion, and then dry it at 40-50°C, repeat the above dip coating and drying operations 3 times; place the membrane in an environment of 80-100°C for heat treatment to obtain a modified microporous membrane;

[0041] The method for preparing the above-mentioned antioxidant ion exchange membrane comprises the following steps:

[0042] dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion;

[0043] The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

[0044] The preparation method of the modified agarose is as follows: agarose and isopropanol solution are fully stirred to obtain a suspension, the molecular weight of agarose is 630.5471, and it is sourced from Qingdao Zeshuo Biotechnology Co., Ltd. The mass volume ratio of the agarose to the isopropanol solution is 1g:14mL, and NaOH solution is added to the above suspension, the concentration of the NaOH solution is 11M and the addition amount is 200mL / L, and ethylenediaminetetraacetic acid is added at 175g / L while stirring to react, and the temperature is raised to 55°C and maintained for 1.25h. The reaction system is placed in an ultrasonic cleaner and water is used as an oscillation medium. The ultrasonic output power is 65W, and then 40g / L of nano-activated carbon fiber is added, and the reaction is reacted for 25min. Finally, it is precipitated by alcohol precipitation, filtered, washed, and dried to obtain modified agarose.

[0045] Specifically, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol is mixed with succinic anhydride, and N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin are added, wherein the mass ratio of the polyethylene glycol to succinic anhydride, N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin is 1:1.5:5:2.5:3.5, the temperature is raised to 70°C and stirred for 2.5 hours, and then extracted with cyclohexane to obtain a dispersion, and the dispersion is mixed with thionyl chloride at a mass ratio of 10:2, stirred for reaction, and then distilled under reduced pressure to obtain the modified polyethylene glycol.

[0046] In this embodiment, the preparation method of the modified nano-cerium dioxide is as follows: 8 parts of nano-cerium dioxide are taken by weight and dispersed in an 80% ethanol solution with a mass of 12.5 times that of the nano-cerium dioxide, and then 9 parts of acetic acid are added, stirred for 40 minutes, filtered and washed with deionized water for 3 times to obtain a product, the product is added to deionized water with a mass of 70 times that of the nano-cerium dioxide, ultrasonically treated for 25 minutes, 0.5-1 parts of sodium dodecylbenzene sulfonate are added, the pH is adjusted to 7, and the reaction is carried out in a water bath at 60°C for 1.5 hours and then filtered, the filter cake is taken out and dried in an oven at 120°C for 2.5 hours, and the modified nano-cerium dioxide is obtained by grinding.

[0047] Example 4

[0048] The embodiment of the present invention provides an antioxidant ion exchange membrane, such as Figure 1-Figure 2As shown, it includes a modified microporous membrane and an ion exchange resin, the modified microporous membrane includes a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, the coating includes the following raw materials in parts by weight: 27 parts of modified agarose, 22 parts of modified polyethylene glycol, 6 parts of modified nano cerium dioxide, 1.7 parts of nano titanium dioxide, and 95 parts of water. The preparation method of the modified microporous membrane is as follows: weigh each raw material according to the ratio; stir the modified agarose, modified polyethylene glycol, modified nano cerium dioxide, nano titanium dioxide, and water at a speed of 3000r / min for 50min to obtain a mixed dispersion; dip the polytetrafluoroethylene fiber membrane in the mixed dispersion, and then dry it at 50°C, repeat the above dip coating and drying operations 3 times; place the membrane in an environment of 100°C for heat treatment to obtain a modified microporous membrane;

[0049] The method for preparing the above-mentioned antioxidant ion exchange membrane comprises the following steps:

[0050] dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion;

[0051] The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

[0052] The preparation method of the modified agarose is as follows: agarose and isopropanol solution are fully stirred to obtain a suspension, the molecular weight of agarose is 630.5471, and it is sourced from Qingdao Zeshuo Biotechnology Co., Ltd. The mass volume ratio of the agarose to the isopropanol solution is 1g:15mL, and NaOH solution is added to the above suspension, the concentration of the NaOH solution is 12M and the addition amount is 250mL / L, and ethylenediaminetetraacetic acid is added at 200g / L while stirring to react, and the temperature is raised to 65°C and maintained for 1.5h. The reaction system is placed in an ultrasonic cleaner and water is used as an oscillation medium, the ultrasonic output power is 80W, and then 50g / L of nano-activated carbon fiber is added, and the reaction is reacted for 30min, and finally precipitated by alcohol precipitation, filtered, washed, and dried to obtain modified agarose.

[0053] Specifically, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol is mixed with succinic anhydride, and N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin are added, wherein the mass ratio of the polyethylene glycol to succinic anhydride, N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin is 1:2:6:3:5, the temperature is raised to 80°C and stirred for 3 hours, and then extracted with cyclohexane to obtain a dispersion, the dispersion is mixed with thionyl chloride at a mass ratio of 10:3, stirred for reaction, and then distilled under reduced pressure to obtain the modified polyethylene glycol.

[0054] In this embodiment, the preparation method of the modified nano-cerium dioxide is as follows: 10 parts of nano-cerium dioxide are taken by weight and dispersed in an 85% ethanol solution with a weight of 15 times the weight of the nano-cerium dioxide, and then 13 parts of acetic acid are added, stirred for 50 minutes, filtered and washed with deionized water for 3 times to obtain a product, the product is added to deionized water with a weight of 80 times the weight of the nano-cerium dioxide, ultrasonically treated for 30 minutes, 0.1 parts of sodium dodecylbenzene sulfonate are added, the pH is adjusted to 11, and the reaction is carried out in a water bath at 65°C for 2 hours and then filtered, the filter cake is taken out and dried in an oven at 120°C for 3 hours, and the modified nano-cerium dioxide is obtained by grinding.

[0055] Example 5

[0056] The embodiment of the present invention provides an antioxidant ion exchange membrane, such as Figure 1-Figure 2 As shown, it includes a modified microporous membrane and an ion exchange resin, the modified microporous membrane includes a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, the coating includes the following raw materials in parts by weight: 30 parts of modified agarose, 25 parts of modified polyethylene glycol, 7 parts of modified nano cerium dioxide, 2 parts of nano titanium dioxide, and 100 parts of water. The preparation method of the modified microporous membrane is as follows: weigh each raw material according to the ratio; stir the modified agarose, modified polyethylene glycol, modified nano cerium dioxide, nano titanium dioxide, and water at a speed of 3000r / min for 50min to obtain a mixed dispersion; dip the polytetrafluoroethylene fiber membrane in the mixed dispersion, and then dry it at 50°C, repeat the above dip coating and drying operations 3 times; place the membrane in an environment of 100°C for heat treatment to obtain a modified microporous membrane;

[0057] The method for preparing the above-mentioned antioxidant ion exchange membrane comprises the following steps:

[0058] dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion;

[0059] The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

[0060] The preparation method of the modified agarose is as follows: agarose and isopropanol solution are fully stirred to obtain a suspension, the molecular weight of agarose is 630.5471, and it is sourced from Qingdao Zeshuo Biotechnology Co., Ltd. The mass volume ratio of the agarose to the isopropanol solution is 1g:15mL, and NaOH solution is added to the above suspension, the concentration of the NaOH solution is 12M and the addition amount is 250mL / L, and ethylenediaminetetraacetic acid is added at 200g / L while stirring to react, and the temperature is raised to 65°C and maintained for 1.5h. The reaction system is placed in an ultrasonic cleaner and water is used as an oscillation medium, the ultrasonic output power is 80W, and then 50g / L of nano-activated carbon fiber is added, and the reaction is reacted for 30min, and finally precipitated by alcohol precipitation, filtered, washed, and dried to obtain modified agarose.

[0061] Specifically, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol is mixed with succinic anhydride, and N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin are added, wherein the mass ratio of the polyethylene glycol to succinic anhydride, N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin is 1:2:6:3:5, the temperature is raised to 80°C and stirred for 3 hours, and then extracted with cyclohexane to obtain a dispersion, the dispersion is mixed with thionyl chloride at a mass ratio of 10:3, stirred for reaction, and then distilled under reduced pressure to obtain the modified polyethylene glycol.

[0062] In this embodiment, the preparation method of the modified nano-cerium dioxide is as follows: 10 parts of nano-cerium dioxide are taken by weight and dispersed in an 85% ethanol solution with a weight of 15 times the weight of the nano-cerium dioxide, and then 13 parts of acetic acid are added, stirred for 50 minutes, filtered and washed with deionized water for 3 times to obtain a product, the product is added to deionized water with a weight of 80 times the weight of the nano-cerium dioxide, ultrasonically treated for 30 minutes, 0.1 parts of sodium dodecylbenzene sulfonate are added, the pH is adjusted to 11, and the reaction is carried out in a water bath at 65°C for 2 hours and then filtered, the filter cake is taken out and dried in an oven at 120°C for 3 hours, and the modified nano-cerium dioxide is obtained by grinding.

[0063] Example 6

[0064] The embodiment of the present invention provides an antioxidant ion exchange membrane, such as Figure 1-Figure 2 As shown, it includes a modified microporous membrane and an ion exchange resin, the modified microporous membrane includes a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, the coating includes the following raw materials in parts by weight: 25 parts of modified agarose, 20 parts of modified polyethylene glycol, 5 parts of modified nano cerium dioxide, 1.5 parts of nano titanium dioxide, and 90 parts of water. The preparation method of the modified microporous membrane is as follows: weigh each raw material according to the ratio; stir the modified agarose, modified polyethylene glycol, modified nano cerium dioxide, nano titanium dioxide, and water at a speed of 2000-3000r / min for 30-50min to obtain a mixed dispersion; dip the polytetrafluoroethylene fiber membrane in the mixed dispersion, and then dry it at 40-50°C, repeat the above dip coating and drying operations 3 times; place the membrane in an environment of 80-100°C for heat treatment to obtain a modified microporous membrane;

[0065] The method for preparing the above-mentioned antioxidant ion exchange membrane comprises the following steps:

[0066] dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion;

[0067] The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

[0068] The preparation method of the modified agarose is as follows: agarose and isopropanol solution are fully stirred to obtain a suspension, the molecular weight of agarose is 630.5471, and it is sourced from Qingdao Zeshuo Biotechnology Co., Ltd. The mass volume ratio of the agarose to the isopropanol solution is 1g:14mL, and NaOH solution is added to the above suspension, the concentration of the NaOH solution is 11M and the addition amount is 200mL / L, and ethylenediaminetetraacetic acid is added at 175g / L while stirring to react, and the temperature is raised to 55°C and maintained for 1.25h. The reaction system is placed in an ultrasonic cleaner and water is used as an oscillation medium. The ultrasonic output power is 65W, and then 40g / L of nano-activated carbon fiber is added, and the reaction is reacted for 25min. Finally, it is precipitated by alcohol precipitation, filtered, washed, and dried to obtain modified agarose.

[0069] Specifically, the preparation method of the modified polyethylene glycol is as follows: polyethylene glycol is mixed with succinic anhydride, and N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin are added, wherein the mass ratio of the polyethylene glycol to succinic anhydride, N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin is 1:1.5:5:2.5:3.5, the temperature is raised to 70°C and stirred for 2.5 hours, and then extracted with cyclohexane to obtain a dispersion, and the dispersion is mixed with thionyl chloride at a mass ratio of 10:2, stirred for reaction, and then distilled under reduced pressure to obtain the modified polyethylene glycol.

[0070] In this embodiment, the preparation method of the modified nano-cerium dioxide is as follows: 8 parts of nano-cerium dioxide are taken by weight and dispersed in an 80% ethanol solution with a mass of 12.5 times that of the nano-cerium dioxide, and then 9 parts of acetic acid are added, stirred for 40 minutes, filtered and washed with deionized water for 3 times to obtain a product, the product is added to deionized water with a mass of 70 times that of the nano-cerium dioxide, ultrasonically treated for 25 minutes, 0.5-1 parts of sodium dodecylbenzene sulfonate are added, the pH is adjusted to 7, and the reaction is carried out in a water bath at 60°C for 1.5 hours and then filtered, the filter cake is taken out and dried in an oven at 120°C for 2.5 hours, and the modified nano-cerium dioxide is obtained by grinding.

[0071] In this embodiment, the polytetrafluoroethylene fiber membrane is pretreated before use, and the pretreatment method is: the polytetrafluoroethylene fiber membrane is placed in a culture vessel and injected with bacterial cellulose fermentation liquid, wrapped, and cultured at 26°C for 4 days, the cultured polytetrafluoroethylene fiber membrane is rinsed with deionized water, the residual culture liquid is removed, and the polytetrafluoroethylene fiber membrane is soaked in deionized water until it is colorless, and finally dried at 45°C for use.

[0072] Furthermore, the preparation method of the bacterial cellulose fermentation liquid is as follows: inoculating Acetobacter xylinum into the culture liquid, the temperature is 27°C, the stirring speed is 210r / min, and the culture time is 25h to obtain seed liquid; the seed liquid with a volume of 8% of the culture liquid is added to the culture liquid, mixed and set aside, to obtain bacterial cellulose fermentation liquid.

[0073] Comparative Example 1: Compared with Example 3, the modified agarose was replaced with ordinary agarose.

[0074] Comparative Example 2: Compared with Example 3, the modified polyethylene glycol was replaced by ordinary polyethylene glycol.

[0075] Comparative Example 3: Compared with Example 3, the modified nano-cerium dioxide is replaced by ordinary nano-cerium dioxide.

[0076] Comparative Example 4: Compared with Example 3, the modified agarose was replaced by ordinary agarose, the modified polyethylene glycol was replaced by ordinary polyethylene glycol, and the modified nano-cerium dioxide was replaced by ordinary nano-cerium dioxide.

[0077] Comparative Example 5: A commercially available ion exchange membrane.

[0078] experiment

[0079] The ion exchange membranes of Examples 1-6 and Comparative Examples 1-5 were tested for oxidation resistance and mechanical properties. The results are shown in Table 1 below:

[0080]

[0081]

[0082] It can be seen from the above results that the ion exchange membrane prepared by the present invention has good antioxidant properties and mechanical properties, especially by adding modified agarose, modified polyethylene glycol and modified nano-cerium dioxide to the coating of the modified microporous membrane, the three have a synergistic effect; taking antioxidant properties as an example, the difference between Comparative Example 4 and Comparative Examples 1, 2, and 3 is 0.6, 0.9, and 1.1, respectively, that is, the effect values ​​of the modified agarose, modified polyethylene glycol, and modified nano-cerium dioxide alone are 0.6, 0.9, and 1.1, respectively, so 3.3-(0.6+0.9+1.1)=0.6, and 0.6>0.1, which shows that the modified agarose, modified polyethylene glycol, and modified nano-cerium dioxide have a synergistic effect.

[0083] It should be noted that, for the above embodiments, for the sake of simplicity, they are all described as a series of action combinations, but those skilled in the art should know that the present invention is not limited by the described order of actions, because according to the present invention, some steps may be performed in other orders or simultaneously. Secondly, those skilled in the art should also know that the embodiments described in the specification are all preferred embodiments, and the actions and modules involved are not necessarily required by the present invention.

[0084] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on these embodiments, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in this field can still combine, add, delete or make other adjustments to the features in the various embodiments of the present invention according to the circumstances without conflict, without making creative work, so as to obtain different other technical solutions that do not deviate from the concept of the present invention in essence, and these technical solutions also belong to the scope of protection of the present invention.

Claims

1. An antioxidant ion exchange membrane, characterized in that: The invention comprises a modified microporous membrane and an ion exchange resin, wherein the modified microporous membrane comprises a polytetrafluoroethylene fiber membrane and a coating coated on the surface of the polytetrafluoroethylene fiber membrane, wherein the coating comprises the following raw materials in parts by weight: 20-30 parts of modified agarose, 15-25 parts of modified polyethylene glycol, 3-7 parts of modified nano cerium dioxide, 1-2 parts of nano titanium dioxide, and 80-100 parts of water, and the agarose and isopropanol solution are fully stirred to obtain a suspension, a NaOH solution is added to the suspension, ethylenediaminetetraacetic acid is added while stirring to react, and nano activated carbon fibers are added, and after the reaction, the modified agarose is precipitated by an alcohol precipitation method, filtered, washed, and dried to obtain the modified agarose; Mixing polyethylene glycol and succinic anhydride, adding N,N-dimethylformamide, 3-amino-1,2-propylene glycol and β-cyclodextrin, heating and stirring, extracting with cyclohexane to obtain a dispersion, mixing the dispersion with thionyl chloride, stirring for reaction, and distilling under reduced pressure to obtain modified polyethylene glycol; Dispersing nano-cerium dioxide in an ethanol solution, then adding acetic acid, stirring, filtering and washing with deionized water to obtain a product, adding the product into deionized water, ultrasonically treating, adding sodium dodecylbenzene sulfonate, adjusting the pH, reacting in a water bath, and then filtering, taking out the filter cake, drying it, and grinding it to obtain modified nano-cerium dioxide; First, the polytetrafluoroethylene fiber membrane is placed in a culture vessel and injected with bacterial cellulose fermentation liquid, wrapped, and cultured. The polytetrafluoroethylene fiber membrane after culture is rinsed with deionized water, the residual culture liquid is removed, and the membrane is soaked with deionized water until it is colorless, and finally dried for use; By adding modified agarose, modified polyethylene glycol and modified nano-cerium dioxide into the coating of the modified microporous membrane, the three have a synergistic effect on the antioxidant and mechanical properties of the ion exchange membrane.

2. The antioxidant ion exchange membrane according to claim 1, characterized in that: The coating comprises the following raw materials in parts by weight: 22-27 parts of modified agarose, 18-22 parts of modified polyethylene glycol, 4-6 parts of modified nano cerium dioxide, 1.2-1.7 parts of nano titanium dioxide, and 85-95 parts of water.

3. The antioxidant ion exchange membrane according to claim 2, characterized in that: The coating comprises the following raw materials in parts by weight: 25 parts of modified agarose, 20 parts of modified polyethylene glycol, 5 parts of modified nano cerium dioxide, 1.5 parts of nano titanium dioxide, and 90 parts of water.

4. The antioxidant ion exchange membrane according to claim 1, characterized in that: The preparation method of the modified microporous membrane is as follows: weighing various raw materials according to the ratio; stirring modified agarose, modified polyethylene glycol, modified nano-cerium dioxide, nano-titanium dioxide and water at a speed of 2000-3000 r / min for 30-50 minutes to obtain a mixed dispersion; dipping a polytetrafluoroethylene fiber membrane in the mixed dispersion, and then drying it at 40-50° C., repeating the dipping and drying operations 2-5 times; placing the membrane in an environment of 80-100° C. for heat treatment to obtain a modified microporous membrane.

5. The antioxidant ion exchange membrane according to claim 1, characterized in that: The preparation method of the bacterial cellulose fermentation liquid is as follows: inoculating Acetobacter xylinum into a culture liquid, the temperature is 25-28°C, the stirring speed is 200-220r / min, and the culture time is 20-30h to obtain a seed liquid; the seed liquid with a volume of 6-10% of the culture liquid is added to the culture liquid, mixed and reserved, and the bacterial cellulose fermentation liquid is obtained.

6. The method for preparing an antioxidant ion exchange membrane according to any one of claims 1 to 5, characterized in that: The steps include: dispersing the ion exchange resin in a forming solvent to obtain an ion exchange resin dispersion; The ion exchange membrane resin dispersion is coated on the surface of the modified microporous membrane to obtain the desired ion exchange membrane.

Images