CN112760991A - Method for preparing anion exchange membrane in green manner - Google Patents
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- CN112760991A CN112760991A CN202110094425.3A CN202110094425A CN112760991A CN 112760991 A CN112760991 A CN 112760991A CN 202110094425 A CN202110094425 A CN 202110094425A CN 112760991 A CN112760991 A CN 112760991A
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Abstract
The invention belongs to the technical field of membranes, and particularly relates to a method for preparing an anion exchange membrane in a green manner. The method provided by the invention can completely avoid the use of organic solvent in the preparation process of the anion exchange membrane, and is a green membrane preparation method with remarkable environmental benefits. Meanwhile, the invention can realize the one-step preparation of the anion exchange membrane by regulating and controlling the membrane preparation process and optimizing the functional agent, thereby greatly simplifying the membrane preparation process and greatly reducing the membrane preparation cost.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a method for preparing an anion exchange membrane in an environment-friendly manner.
Background
Anion exchange membranes are polymer membranes which are mainly positively charged and can conduct anions through ion exchange, and are widely applied to the fields of water treatment industry, heavy metal recovery, hydrometallurgy, fuel cells and the like.
The Netherlands Journal of Membrane Science (Journal of Membrane Science, 443, 2013, 193-Bu 200) reports a preparation method of an anion exchange Membrane, which comprises the steps of firstly dissolving polyphenyl ether in chlorobenzene to obtain a uniform solution, then dripping liquid bromine for bromination reaction, pouring the solution into methanol for precipitation after the reaction is finished to obtain brominated polyphenyl ether, then dissolving the brominated polyphenyl ether in N-methylpyrrolidone to form a uniform solution, dripping 1-methylbenzimidazole for reaction to obtain a casting solution, and finally coating the casting solution on glass for heating and evaporation to remove the N-methylpyrrolidone to obtain the final anion exchange Membrane. The preparation of anion exchange membranes by this method requires the use of large amounts of toxic organic solvents including chlorobenzene, methanol and N-methylpyrrolidone. The use of the organic solvent not only increases the film preparation cost, but also causes serious environmental pollution due to emission, and particularly, the removal of the N-methylpyrrolidone is carried out by adopting a direct heating evaporation method, so that the energy consumption is extremely high and the pollution is serious.
The Chinese patent with application number 201911199810.3 discloses a preparation method of an anion exchange membrane, which comprises the steps of selecting any one of organic solvents of N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, dissolving polyvinyl chloride with the organic solvent to obtain a membrane casting solution, coating the membrane on reinforced gridding cloth, heating to remove the organic solvent to obtain a base membrane, soaking the base membrane in a mixed solution of 1-vinylimidazole and an initiator for suction soaking, and carrying out high-temperature polymerization to obtain the polyvinyl chloride anion exchange membrane. It must be noted that the preparation of anion exchange membranes by this method also faces the problems of increased cost and environmental pollution due to the use of solvents.
In view of the problem that a large amount of toxic organic solvent is required in the process of producing the anion exchange membrane, the development of a green membrane-forming method without using an organic solvent has been receiving attention.
The Chinese patent with the application number of 201110057825.3 discloses a preparation method of an anion exchange membrane, which comprises the steps of dissolving phenolphthalein polyether ketone in a polymerization monomer mixed solution of chloromethyl styrene and divinylbenzene, adding an initiator to form a casting solution, coating the casting solution on a reinforced fabric, thermally initiating polymerization to form a base membrane, and soaking the base membrane in a trimethylamine aqueous solution for quaternization modification to obtain the anion exchange membrane. Although the method avoids the use of organic solvent in the film preparation process, the obtained anion exchange membrane has poor chemical stability, especially poor alkali resistance, because the inside of the base membrane is lack of effective chemical crosslinking, and cannot meet the actual use requirement. The Chinese patent with the application number of 201210056988.4 reports a preparation method of an anion exchange membrane, which is based on the method disclosed by the Chinese patent with the application number of 201110057825.3, adopts a similar method, and only adds a cross-linking agent in the preparation process of a base membrane to realize chemical cross-linking of the base membrane, thereby preparing the anion exchange membrane with better stability.
The two methods do not need to use organic solvent when preparing the anion exchange membrane, thereby avoiding the economic and environmental problems caused by the use of the organic solvent and being a green membrane preparation process. However, because the prepared base membrane does not contain a positively charged functional group as an anion exchange group, the base membrane must be soaked in a trimethylamine aqueous solution for quaternization modification to realize the positively charged functionalization of the base membrane, and the anion exchange membrane containing the anion exchange group can be finally obtained. In other words, the above method comprises two steps of base membrane preparation and base membrane modification when preparing the anion exchange membrane, and the process is complicated. Meanwhile, the trimethylamine functional agent is flammable and explosive and has a foul hazardous gas, and has a strong stimulation effect on eyes, nose, throat and respiratory tract of a human body, and the treatment and discharge of the soaked trimethylamine solution can cause serious environmental pollution while increasing the cost.
In summary, the preparation of the traditional anion exchange membrane requires the use of a large amount of organic solvent with high toxicity, which causes serious environmental pollution while increasing the cost. The prior art can avoid the use of organic solvent, but still has the problems of complicated process and subsequent discharge of organic reagent. Therefore, the development of a simpler and more convenient and green preparation method of the anion exchange membrane has outstanding practical application value.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing an anion exchange membrane in a green manner, so as to solve the above problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention claims a method for preparing an anion exchange membrane in a green way, which comprises the steps of mixing and stirring phenolphthalein polyether ketone, chloromethyl styrene, divinyl benzene, an initiator and a functional agent to obtain a membrane casting solution, then coating the membrane casting solution on a reinforced fabric, and heating and polymerizing to obtain the anion exchange membrane.
The chemical structural formula of the phenolphthalein polyether ketone is as follows:
。
the chemical structural formula of the chloromethyl styrene is as follows:
。
the chemical structural formula of the divinylbenzene is as follows:
。
the functional agent is a micromolecular compound containing 2 or more than 2 tertiary amine groups, and the chemical structural general formula of the functional agent is as follows:
wherein R is1、R2、R3、R4、R5Each independently selected from alkyl or alkylamine; preferably, the functional agent may be N, N '-tetramethyldiaminomethane, N' -tetramethylethylenediamine, N '-tetramethyl-1, 3-propanediamine, N' -tetramethyl-1, 2-diaminopropane, N '-tetramethyl-1, 4-butanediamine, N' -tetramethyl-2, 2-dimethyl-1, 3-propanediamine, N '' -pentamethyldiethylenetriamine, N '' -pentamethyldipropylenetriamine.
The initiator is selected from azobisisobutyronitrile, dibenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tert-butyl peroxyacetate, cumene hydroperoxide, tert-butyl hydroperoxide or tert-butyl hydroperoxide.
The mass ratio of the phenolphthalein polyether ketone to the chloromethylstyrene to the divinylbenzene to the initiator to the functional agent is 1: 3-9: 0.06-1.8): (0.6-2.7).
The reinforced fabric is polyethylene cloth, polypropylene cloth, polyamide cloth, polyester cloth or nylon cloth.
The coating method is scraping, spraying, dipping, flowing or spin coating.
The heating polymerization temperature is 40-200 ℃, and the time is 1-120 hours.
The invention also claims the anion exchange membrane prepared by the method, which correspondingly consists of a macromolecular copolymer formed by polymerizing macromolecular reinforcing agents of phenolphthalein polyether ketone, monomer chloromethyl styrene and divinylbenzene, a functional agent grafted in the membrane through reaction and a reinforced fabric.
The invention has the following remarkable advantages:
(1) the invention adopts the polymerization monomer to directly dissolve the high polymer and then carries out one-step thermal polymerization to form the membrane, thereby avoiding the use of organic solvent in the membrane preparation process, realizing zero waste discharge, being a green membrane preparation method and having outstanding environmental benefit.
(2) The invention selects the functional agent containing 2 or more than 2 tertiary amine groups to carry out sufficient crosslinking and quaternization treatment on the prepared anion-exchange membrane, and can graft anion-exchange groups in the membrane while avoiding micro-phase separation in the membrane, thereby realizing the one-step preparation of the anion-exchange membrane. The method not only can effectively improve the chemical stability of the membrane, but also can completely avoid economic consumption and environmental pollution caused by the use of the trimethylamine aqueous solution for quaternization modification, thereby effectively improving economic and environmental benefits.
In conclusion, the preparation method of the anion exchange membrane disclosed by the invention can effectively overcome the defects in the prior art, and can effectively regulate and control the physicochemical properties of the prepared anion exchange membrane by controlling each condition of the membrane preparation process, including the addition proportion of each component and the time and temperature of reaction, so that the anion exchange membrane with optimal properties is selected, and is beneficial to large-scale application of the anion exchange membrane.
Detailed Description
The technical solution of the present invention is described in detail and completely by using the following embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The chemical reagents used in the examples of the present invention are all commercially available.
Comparative example
Taking the disclosure of the chinese patent with application number 201210056988.4 (example 12) as a reference, the specific preparation method is as follows: dissolving 1g of phenolphthalein polyether ketone and 0.02g of dibenzoyl peroxide in a mixed solution of 2g of p-chloromethyl styrene and 0.02g of divinylbenzene, adding 0.01g of ethylenediamine, uniformly stirring, uniformly coating the obtained casting solution on polyethylene cloth, and thermally initiating in-situ polymerization at 70 ℃ for 4 hours to obtain a base film; and finally, soaking the base membrane in a trimethylamine aqueous solution with the mass fraction of 33% for quaternization reaction for 48 hours, washing with deionized water, and naturally drying in the air at room temperature to obtain the anion exchange membrane.
The prepared anion exchange membrane was tested for chemical stability: soaking an anion exchange membrane in 2mol/L NaOH aqueous solution at 25 ℃, testing the ion exchange capacity of the anion exchange membrane before and after soaking in alkali liquor, and calculating the ratio of the ion exchange capacity of the anion exchange membrane before and after soaking. The experimental result shows that after the prepared anion exchange membrane is soaked in 2mol/L NaOH aqueous solution at the temperature of 25 ℃ for 7 days, the ion exchange capacity is 35 percent of that before soaking.
Ion Exchange Capacity (IEC), water content (WU), hydroxyl (OH) to the membrane-) The conductivity was tested. Water content and ion exchange content tests show that the water content of the ion exchange membrane prepared by the comparative example is 36.1%, the anion exchange capacity is 1.24mmol/g, and the hydroxide conductivity is 0.023S/cm. Meanwhile, the tensile strength of the film was tested, and the tensile strength of the film was 46 MPa.
Example 1
Dissolving 1g of phenolphthalein polyether ketone and 0.06g of dibenzoyl peroxide in a mixed solution of 3g of chloromethylstyrene and 0.06g of divinylbenzene, adding 0.6g N, N, N ', N' -tetramethyldiaminomethane, uniformly stirring, uniformly spraying the obtained casting film liquid on polypropylene cloth, and thermally initiating in-situ polymerization at 80 ℃ for 24 hours to obtain the anion exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 97% of that before soaking. The anion exchange content was 1.28mmol/g, the water content was 35.7%, and the hydroxide conductivity was 0.025S/cm. Meanwhile, the tensile strength of the film was 61 MPa.
Compared with the anion exchange membrane prepared by the comparative example, the anion exchange membrane prepared by the embodiment has similar ion exchange capacity, water content and hydroxyl conductivity, but the chemical stability of the anion exchange membrane prepared by the embodiment is greatly improved. Specifically, after being soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, the ion exchange capacity of the anion exchange membrane prepared in the embodiment is 97% of that of the anion exchange membrane prepared in the embodiment without soaking, which proves that the alkali resistance of the anion exchange membrane prepared in the comparative example 1 is obviously improved (only 35% under the same condition).
Example 2
Dissolving 1g of phenolphthalein polyether ketone and 1.8g of azobisisobutyronitrile into a mixed solution of 9g of chloromethylstyrene and 1.8g of divinylbenzene, adding 2.7g N, N, N ', N' -tetramethylethylenediamine, uniformly stirring, scraping the obtained casting solution on polyethylene cloth, and thermally initiating in-situ polymerization at 80 ℃ for 120 hours to obtain the anion exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 99% of that before soaking. The anion exchange content is 1.15mmol/g, the water content is 30.9 percent, and the hydroxide conductivity is 0.020S/cm. Meanwhile, the tensile strength of the film was 57 MPa. The results show that the anion exchange membrane prepared by the embodiment has higher ion exchange content, proper water content, excellent conductivity, mechanical property and chemical stability, and meets the requirements of conditions applied to fuel cells.
Example 3
Dissolving 1g of phenolphthalein polyether ketone and 0.24g of acetyl peroxide in a mixed solution of 4g of chloromethylstyrene and 0.24g of divinylbenzene, adding 1.2g N, N, N ', N' -tetramethyl-1, 3-propanediamine, uniformly stirring, soaking the obtained casting solution on polyamide fabric, taking out, and carrying out thermal initiation in-situ polymerization at 180 ℃ for 1 hour to obtain the anion-exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 97% of that before soaking. The anion exchange content was 2.57 mmol/g, the water content was 61.4%, and the hydroxide conductivity was 0.044S/cm. Meanwhile, the tensile strength of the film was 55 MPa.
Example 4
Dissolving 1g of phenolphthalein polyether ketone and 0.24g of lauroyl peroxide in a mixed solution of 4g of chloromethylstyrene and 0.24g of divinylbenzene, adding 1.2g N, N, N ', N' -tetramethyl-1, 2-diaminopropane, uniformly stirring, uniformly coating the obtained casting solution on polyester fabric, and thermally initiating in-situ polymerization at 40 ℃ for 120 hours to obtain the anion exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 98% of that before soaking. The anion exchange content was 2.41mmol/g, the water content was 59.1%, and the hydroxide conductivity was 0.039S/cm. Meanwhile, the tensile strength of the film was 56 MPa.
Example 5
Dissolving 1g of phenolphthalein polyether ketone and 0.24g of tert-butyl peroxyacetate in a mixed solution of 4g of chloromethylstyrene and 0.24g of divinylbenzene, adding 1.2g N, N, N ', N' -tetramethyl-1, 4-butanediamine, uniformly stirring, uniformly coating the obtained casting solution on nylon cloth in a rotating manner, and thermally initiating in-situ polymerization for 12 hours at 80 ℃ to obtain the anion exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 98% of that before soaking. The anion exchange content was 2.24mmol/g, the water content was 58.4%, and the hydroxide conductivity was 0.038S/cm. Meanwhile, the tensile strength of the film was 54 MPa.
Example 6
Dissolving 1g of phenolphthalein polyether ketone and 0.24g of cumene hydroperoxide in a mixed solution of 4g of chloromethylstyrene and 0.24g of divinylbenzene, adding 1.2g N, N, N ', N' -tetramethyl-2, 2-dimethyl-1, 3-propanediamine, uniformly stirring, uniformly coating the obtained casting solution on nylon cloth in a rotating manner, and thermally initiating in-situ polymerization for 12 hours at 80 ℃ to obtain the anion exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 98% of that before soaking. The anion exchange content was 2.18mmol/g, the water content was 55.2%, and the hydroxide conductivity was 0.035S/cm. Meanwhile, the tensile strength of the film was 57 MPa.
Example 7
Dissolving 1g of phenolphthalein polyether ketone and 0.24g of tert-butyl hydroperoxide in a mixed solution of 4g of chloromethylstyrene and 0.24g of divinylbenzene, adding 1.2g N, N, N ', N ' ', N ' ' -pentamethyl divinyl triamine, uniformly stirring, uniformly coating the obtained casting solution on nylon cloth in a rotating manner, and thermally initiating in-situ polymerization for 12 hours at 80 ℃ to obtain the anion exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 99% of that before soaking. The anion exchange content was 2.42mmol/g, the water content was 59.3%, and the hydroxide conductivity was 0.040S/cm. Meanwhile, the tensile strength of the film was 56 MPa.
Example 8
Dissolving 1g of phenolphthalein polyether ketone and 0.24g of tert-butyl hydroperoxide in a mixed solution of 4g of chloromethylstyrene and 0.24g of divinylbenzene, adding 1.2g N, N, N ', N ' ', N ' ' -pentamethyl dipropylenetriamine, uniformly stirring, uniformly coating the obtained casting solution on nylon cloth in a rotating manner, and thermally initiating in-situ polymerization for 12 hours at 80 ℃ to obtain the anion exchange membrane.
The anion exchange membrane prepared in the embodiment is soaked in 2mol/L NaOH aqueous solution at 25 ℃ for 7 days, and the ion exchange capacity of the membrane is 99% of that before soaking. The anion exchange content was 2.27mmol/g, the water content was 59.9%, and the hydroxide conductivity was 0.039S/cm. Meanwhile, the tensile strength of the film was 53 MPa.
The results of the above examples show that by using the preparation method of the present invention, the properties of the prepared anion exchange membrane can be effectively controlled by controlling various conditions in the membrane preparation process, including the components of the membrane casting solution, the reaction temperature and the reaction time, so as to meet different application requirements, and the anion exchange membrane with the optimal performance is selected from the membrane.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A method for preparing an anion exchange membrane in a green way is characterized in that phenolphthalein polyether ketone, chloromethyl styrene, divinylbenzene, an initiator and a functional agent are mixed and stirred to obtain a membrane casting solution, then the membrane casting solution is coated on a reinforced fabric, and the anion exchange membrane is obtained by heating and polymerizing;
the functional agent is a micromolecular compound containing 2 or more than 2 tertiary amine groups, and the chemical structural general formula of the functional agent is as follows:
wherein R is1、R2、R3、R4、R5Each independently selected from alkyl or alkylamine.
2. The method for preparing an anion-exchange membrane by greening according to claim 1, wherein the initiator is azobisisobutyronitrile, dibenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tert-butyl peroxyacetate, cumene hydroperoxide, tert-butyl hydroperoxide or tert-butyl hydroperoxide.
3. The method for preparing the anion exchange membrane in the green manner according to claim 1, wherein the mass ratio of the phenolphthalein polyether ketone, the chloromethyl styrene, the divinylbenzene, the initiator and the functional agent is 1: 3-9: 0.06-1.8): (0.6-2.7).
4. The method for preparing an anion-exchange membrane by greening according to claim 1, wherein the reinforced fabric is polyethylene fabric, polypropylene fabric, polyamide fabric, polyester fabric or nylon fabric.
5. The greening method for preparing an anion-exchange membrane according to claim 1, wherein the method for coating the membrane is scraping, spraying, dipping, flowing or spin coating.
6. The method for preparing the anion-exchange membrane in a greening manner according to claim 1, wherein the heating polymerization temperature is 40-200 ℃ and the time is 1-120 hours.
7. An anion exchange membrane prepared by the method of any of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155337A (en) * | 2022-06-29 | 2022-10-11 | 福州大学 | Preparation method of three-dimensional porous cross-linked anion exchange membrane |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS568048B2 (en) * | 1972-12-28 | 1981-02-21 | ||
| CN102580572A (en) * | 2012-03-06 | 2012-07-18 | 中国科学技术大学 | Anion-exchange membrane and preparation method thereof |
| CN103159974A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparation method of crosslinking type polymer anion exchange membrane |
| CN105642136A (en) * | 2014-11-18 | 2016-06-08 | 北京化工大学 | A copolymer quaternization crosslinking type anion-exchange membrane containing soft and hard segments and a preparing method thereof |
| CN108348864A (en) * | 2015-11-05 | 2018-07-31 | 莫纳什大学 | Asymmetric porous ion exchange membrane and its manufacturing method |
| CN109265715A (en) * | 2018-09-06 | 2019-01-25 | 大连理工大学 | A kind of polystyrene thermoplastic elastomer/polystyrene composite membrane and preparation method |
| CN110896150A (en) * | 2018-09-12 | 2020-03-20 | 中国科学院大连化学物理研究所 | Method for preparing anion exchange membrane by polymerizing ionic liquid monomer |
-
2021
- 2021-01-25 CN CN202110094425.3A patent/CN112760991B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS568048B2 (en) * | 1972-12-28 | 1981-02-21 | ||
| CN103159974A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparation method of crosslinking type polymer anion exchange membrane |
| CN102580572A (en) * | 2012-03-06 | 2012-07-18 | 中国科学技术大学 | Anion-exchange membrane and preparation method thereof |
| CN105642136A (en) * | 2014-11-18 | 2016-06-08 | 北京化工大学 | A copolymer quaternization crosslinking type anion-exchange membrane containing soft and hard segments and a preparing method thereof |
| CN108348864A (en) * | 2015-11-05 | 2018-07-31 | 莫纳什大学 | Asymmetric porous ion exchange membrane and its manufacturing method |
| CN109265715A (en) * | 2018-09-06 | 2019-01-25 | 大连理工大学 | A kind of polystyrene thermoplastic elastomer/polystyrene composite membrane and preparation method |
| CN110896150A (en) * | 2018-09-12 | 2020-03-20 | 中国科学院大连化学物理研究所 | Method for preparing anion exchange membrane by polymerizing ionic liquid monomer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155337A (en) * | 2022-06-29 | 2022-10-11 | 福州大学 | Preparation method of three-dimensional porous cross-linked anion exchange membrane |
| CN115155337B (en) * | 2022-06-29 | 2023-10-27 | 福州大学 | Preparation method of three-dimensional porous cross-linked anion exchange membrane |
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