CN116607172B - Preparation method of special resin for alkaline water electrolyzer diaphragm, product and application thereof - Google Patents
Preparation method of special resin for alkaline water electrolyzer diaphragm, product and application thereof Download PDFInfo
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- CN116607172B CN116607172B CN202310558929.5A CN202310558929A CN116607172B CN 116607172 B CN116607172 B CN 116607172B CN 202310558929 A CN202310558929 A CN 202310558929A CN 116607172 B CN116607172 B CN 116607172B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a preparation method of a special resin for an alkaline water electrolytic cell diaphragm, which comprises the steps of firstly, putting N-methyl pyrrolidone and sodium sulfide aqueous solution into a polymerization kettle, heating and then carrying out a dehydration procedure, secondly, adding N-methyl pyrrolidone and p-dichlorobenzene into the polymerization kettle, continuously heating and polymerizing, and finally carrying out a post-treatment procedure, wherein nano zirconia is also added in the preparation method, and can be added with the sodium sulfide aqueous solution in the first step or with the p-dichlorobenzene in the second step. According to the preparation method disclosed by the invention, the nano zirconia is added in the preparation process of the resin, so that the nano zirconia is uniformly dispersed, the hydrophilic modification effect of the polyphenylene sulfide is improved, and further, the preparation method is further characterized in that a third monomer with a special substituent group is added in the polymerization stage while the nano zirconia is added, and the aim of remarkably improving the hydrophilicity of the polyphenylene sulfide is achieved by utilizing the cooperation of the nano zirconia and the third monomer.
Description
Technical Field
The invention relates to the technical field of diaphragms, in particular to a preparation method of a special resin for an alkaline water electrolysis cell diaphragm, a product and application thereof.
Background
The hydrogen energy is widely paid attention to worldwide as an efficient and clean secondary energy, and the large-scale and low-cost production of H 2 is one of important links for developing and utilizing H 2 energy. The hydrogen production by water electrolysis has the advantages of relatively simple operation, relatively mature technology, high purity of the prepared H 2 and no pollution in the hydrogen production process, and is an important means for realizing the large-scale production of H 2. Currently, domestic alkaline water electrolysis is dominant in the water electrolysis industry.
Typically, an alkaline electrolyzer is charged with electrolyte (typically 20-30 wt% aqueous potassium hydroxide), water is decomposed under the action of direct current, H 2 is generated at the cathode, O 2 is generated at the anode, and H 2、O2 generated at the diaphragm is strictly isolated while allowing free movement of ions in the circuitry within the electrolyzer. The quality of the diaphragm is directly related to the purity and electricity consumption of H 2、O2, so that the diaphragm becomes a thermoelectric for people to study. The requirements for the separator include:
1) Can be wetted by electrolyte, so that ions in the solution can smoothly pass through;
2) The air tightness is good, and the safe operation of the electrolytic tank and the purity of the outlet gas are not affected;
3) Has enough mechanical strength;
4) The electrolyte is not corroded by alkali liquor, so that the chemical stability is strong;
5) Low price and is suitable for industrial use.
For a long time, the main raw material of the alkaline electrolytic cell diaphragm is asbestos, the asbestos diaphragm has good hydrophilic performance and easy passage of ions, but the asbestos diaphragm has the defects of serious swelling in a specific operating environment, especially under high current load, due to the swelling property and chemical instability, the service life is shortened, and the temperature of electrolyte can only be controlled below 90 ℃ due to the limitation of the asbestos material, when the temperature of the electrolyte exceeds 90 ℃, the corrosion of the asbestos diaphragm is aggravated, so that the electrolyte is polluted, and the service life is influenced. In view of the above, the development of a novel diaphragm material capable of replacing an asbestos diaphragm has become an important topic in the industry.
Polyphenylene Sulfide (PPS) materials have the advantage of being chemically stable, and resistant to severe water electrolysis conditions of high temperatures and strong alkali, thereby becoming a popular choice for replacing asbestos diaphragms. However, PPS is highly hydrophobic and requires treatment such as grafting, oxidation, sulfonation, and plasma to form a hydrophilic surface.
According to the high-temperature-resistant alkaline water electrolysis cell diaphragm and the preparation method thereof disclosed in Chinese patent document with the application publication number of CN101372752A, a polyphenylene sulfide diaphragm is prepared by a needle punching non-woven fabric technology, and then the PPS non-woven fabric is subjected to sulfonation treatment and neutralization by sequentially using 90-98% concentrated sulfuric acid and 30% potassium hydroxide solution so as to improve the hydrophilicity of the non-woven fabric. Although the water absorption rate of the product prepared by adopting the technical scheme is up to more than 310%, the production process is extremely not environment-friendly, not only is strong corrosive raw materials such as strong acid, strong alkali and the like adopted, but also has great production danger, needs to consume a large amount of water resources in the cleaning process of post-treatment, has longer cleaning time, and is complex in process operation and not suitable for industrial production. And meanwhile, fiber embrittlement exists after sulfonation treatment, so that the service life of the diaphragm is shortened.
In addition, for example, in chinese patent document CN 104746202A, a membrane fabric for a water electrolysis cell and a method for producing the same are disclosed, wherein polyphenylene sulfide fibers are spun by a cotton spinning process of blowing-carding-drawing-roving-spinning-winding-doubling-twisting-heat setting, the obtained polyphenylene sulfide yarns are woven by a loom to obtain a high-density woven fabric, and finally hydrophilic groups are generated on the surface of the woven fabric by plasma treatment and hydrophilic processing. However, the plasma treatment adopted in the technical scheme can only generate hydrophilic groups on the surface of the fiber in nanometer level depth, and meanwhile, the change of the surface property has a certain effectiveness, and the obtained hydrophilic groups gradually decrease along with the extension of time, so that the loss of hydrophilicity is caused, and the degree of hydrophilic wettability of the material is limited in improvement. Moreover, the process equipment investment is high, and the method is not suitable for large-scale industrial production.
Then, as disclosed in Chinese patent document with application publication number CN 113862821A, a polyphenylene sulfate fiber fabric type alkaline water electrolysis diaphragm and a preparation method thereof are disclosed, wherein zirconia inorganic nano particles and polyphenylene sulfide resin are mixed and granulated, zirconia modified polyphenylene sulfide fibers are obtained through melt spinning, and then the fibers are spun and woven into cloth, and then through a water needling process, the polyphenylene sulfide fiber fabric type alkaline water electrolysis diaphragm is obtained. In the technical scheme, only the nano zirconia and the polyphenylene sulfide are simply blended and modified, and the problem of agglomeration of the nano material is known, so that the method is difficult to disperse the zirconia in nano scale, and the hydrophilic modification effect of the zirconia on the polyphenylene sulfide is further affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a preparation method of resin special for an alkaline water electrolysis cell diaphragm, which is characterized in that nano zirconia is added in the preparation process of the resin, so that the nano zirconia is uniformly dispersed, the hydrophilic modification effect of polyphenylene sulfide is improved, and further, a third monomer with a special substituent group is added in the polymerization stage while the nano zirconia is added, and the aim of obviously improving the hydrophilicity of the polyphenylene sulfide is achieved by utilizing the cooperation of the nano zirconia and the third monomer.
The specific technical scheme is as follows:
the preparation method of the resin special for the alkaline water electrolysis cell diaphragm comprises the following steps:
Step one, putting N-methyl pyrrolidone and sodium sulfide aqueous solution into a polymerization kettle, and carrying out dehydration procedure after heating;
adding N-methyl pyrrolidone and p-dichlorobenzene into a polymerization kettle, continuously heating for polymerization, and finally obtaining the resin special for the alkaline water electrolytic cell diaphragm through a post-treatment procedure;
The preparation method is also added with nano zirconia, wherein the nano zirconia can be added together with sodium sulfide aqueous solution in the first step, or can be added together with paradichlorobenzene in the second step.
According to the preparation method disclosed by the invention, the nano zirconia is added in the polymerization stage of the PPS resin, so that the nano zirconia is uniformly dispersed, and the hydrophilic modification effect on the polyphenylene sulfide is improved. Experiments show that compared with the method without adding nano zirconia or the method that nano zirconia is added in a blending mode after the preparation of PPS resin is completed, the effect of hydrophilic modification on polyphenylene sulfide is inferior to that of the invention. Experiments also find that the addition of nano zirconia can obviously reduce the average grain diameter of the prepared PPS resin, improve the crystallization temperature of the PPS resin, ensure that the crystallization temperature is higher, and are easier to process and form in the spinning process, thereby being convenient for processing.
Preferably, a third monomer is further added in the second step of the preparation method disclosed by the invention;
the third monomer is selected from monosubstituted paradichlorobenzene, and the substituent is selected from one or more of sulfonic acid group, hydroxyl group, carboxylic acid group, aldehyde group and phosphate group;
Experiments show that the addition of the third monomer can further reduce the average particle size of the prepared PPS resin and improve the crystallization temperature of the PPS resin, and the hydrophilia of the finally prepared PPS-based alkaline water electrolytic cell diaphragm can be obviously improved through the synergistic addition of the third monomer and the nano zirconia.
Preferably, the molar ratio of the added nano zirconia to the sodium sulfide is 0.05-3.00:100, and the average grain size of the nano zirconia is 1-100 nm.
Further preferably, the molar ratio of the nano zirconia to the sodium sulfide is 0.5-3.0:100, and the average particle size of the nano zirconia is 50-100 nm.
Preferably:
The molar ratio of the third monomer to the sodium sulfide in the first step is 0.01-0.5:1;
The ratio of the sum of the mole numbers of paradichlorobenzene and the third monomer to the mole number of sodium sulfide in the first step is 0.8-1.3.
Further preferably, the substituent in the third monomer is selected from one or more of a sulfonic acid group, a hydroxyl group, a carboxylic acid group, and a phosphoric acid group;
the molar ratio of the third monomer to the sodium sulfide in the first step is 0.05-0.1:1;
The ratio of the sum of the mole numbers of paradichlorobenzene and the third monomer to the mole number of sodium sulfide in the first step is 1.0-1.2.
Still more preferably:
The molar ratio of the nano zirconia to the sodium sulfide is 0.5:100, and the average grain diameter of the nano zirconia is 50nm;
the substituent in the third monomer is selected from sulfonic acid groups and/or hydroxyl groups;
the molar ratio of the third monomer to the sodium sulfide in the first step is 0.1:1;
the ratio of the sum of the moles of p-dichlorobenzene and the moles of the third monomer to the moles of sodium sulfide in step one was 1.1.
With the continuous preference of the raw materials and the technological parameters, the hydrophilicity of the finally prepared PPS-based alkaline water electrolysis cell diaphragm is continuously improved.
In the first step:
the mass concentration of the sodium sulfide aqueous solution is 20-80%, preferably 35% by weight.
The molar ratio of N-methyl pyrrolidone to sodium sulfide is 1.0-5.0:1, preferably 2.0:1.
In the first step, the temperature rising rate is 1-10 ℃ per minute, and the temperature rises to 150-210 ℃ for dehydration;
in the second step, polymerization is carried out after the temperature is raised to 240-280 ℃, the temperature raising rate is 1-20 ℃ per minute, and the polymerization time is 1-8 hours;
The post-treatment includes a washing treatment and a drying treatment.
The washing treatment sequentially comprises acetone washing and pure water washing;
the acetone is washed, the molar ratio of the acetone to the sodium sulfide in the first step is 1-50:1, the washing times are 1-6, and the washing temperature is 10-40 ℃;
the pure water is washed, the molar ratio of the pure water to the sodium sulfide in the first step is 1-100:1, the washing times are 1-10, and the washing temperature is 50-200 ℃;
The temperature of the drying treatment is 80-180 ℃ and the time is 1-12 h.
Preferably:
The nano zirconia is added together with the sodium sulfide aqueous solution in the first step, and experiments show that the nano zirconia is added in the dehydration stage, which is more favorable for reducing the average particle size of the prepared PPS resin and improving the crystallization temperature of the PPS resin, but the effect is different at a lower nano zirconia addition amount and is more remarkable at a higher addition amount.
The invention also discloses the resin special for the alkaline water electrolysis cell diaphragm prepared by the method.
The invention also discloses a preparation method of the alkaline water electrolysis cell diaphragm, which is prepared by taking the resin special for the alkaline water electrolysis cell diaphragm prepared by the method as a raw material and performing a melt spinning process and a needle punching non-woven fabric process.
The alkaline water electrolytic cell membrane prepared by the invention has excellent hydrophilicity, the water absorption rate can reach 285% at the highest, and the wicking height can reach 421mm at the highest.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method disclosed by the invention, the nano zirconia is added in the polymerization stage of the PPS resin, so that the nano zirconia is uniformly dispersed, the hydrophilic modification effect on the polyphenylene sulfide is improved, the average particle size of the prepared PPS resin can be obviously reduced, and the crystallization temperature of the PPS resin is improved.
The invention also discloses a preferable preparation method, wherein a third monomer with a special substituent group is added in the polymerization stage, and the third monomer is cooperated with the addition of nano zirconia, so that the average particle size of the prepared PPS resin is further reduced, the crystallization temperature of the PPS resin is increased, and the hydrophilicity of the finally prepared PPS-based alkaline water electrolytic cell diaphragm is further obviously improved.
Detailed Description
The present invention will be described in further detail with reference to examples and comparative examples, but embodiments of the present invention are not limited thereto.
Example 1
Firstly, adding N-methyl pyrrolidone (NMP), a sodium sulfide aqueous solution (35 wt%) and nano zirconia (D50=50 nm) into a polymerization kettle, wherein the sodium sulfide is 100mol, the NMP is 200mol, the mol ratio of the nano zirconia to the sodium sulfide is 0.5:100, after heating, carrying out a dehydration procedure, wherein the dehydration heating rate is 5 ℃ per minute, the dehydration end point temperature is 180 ℃, and no bubble is generated in an absorption liquid after dehydration is carried out until the dehydration is carried out for 1min at the outlet of an air duct of the dehydration kettle;
Adding NMP, paradichlorobenzene and a third monomer 2-hydroxy-1, 4 dichlorobenzene into a polymerization kettle, wherein the molar ratio of paradichlorobenzene to sodium sulfide added in the first step is 1.05,2-hydroxy-1, 4 dichlorobenzene to sodium sulfide added in the first step is 0.05, the NMP is 300mol, further heating, then carrying out polymerization, the heating rate of the polymerization is 5 ℃ per minute, the heat preservation temperature of the polymerization stage is 240 ℃, and the polymerization duration is 4 hours.
And thirdly, respectively and continuously washing the product obtained in the second step with acetone for 2 times at the washing temperature of 30 ℃ and the molar ratio of the resin to the acetone of 50:1 each time, respectively and continuously washing with pure water for 5 times at the washing temperature of 80 ℃ and the molar ratio of the resin to the pure water of 100:1 each time, and finally drying at 120 ℃ for 6 hours to obtain the resin special for the alkaline water electrolysis cell diaphragm.
Comparative example 1
The preparation process was substantially the same as in example 1, except that nano zirconia was not added in the dehydration process of step one.
Comparative example 2
The preparation process is substantially the same as in example 1, except that:
the nano zirconia is not added in the dehydration procedure of the first step;
The third monomer is not added in the polymerization step of the second step.
Example 2
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-sulfo-1, 4-dichlorobenzene.
Example 3
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-carboxylate-1, 4-dichlorobenzene.
Example 4
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-aldehyde-1, 4-dichlorobenzene.
Example 5
The preparation process was substantially the same as in example 1, except that the third monomer added in the polymerization step of step two was replaced with equimolar 2-phosphate-1, 4-dichlorobenzene.
Example 6
The preparation process was substantially the same as in example 1, except that in the polymerization step of the second step, the molar ratio of p-dichlorobenzene to sodium sulfide added in the first step was 1.0:1, 2-hydroxy-1, 4-dichlorobenzene to sodium sulfide added in the first step was 0.1:1.
Example 7
The preparation process was substantially the same as in example 2, except that the molar ratio of nano zirconia to sodium sulfide added in the dehydration step one was replaced with 0.05:100.
Example 8
The preparation process was substantially the same as in example 2, except that the molar ratio of nano zirconia to sodium sulfide added in the dehydration step one was replaced with 1.5:100.
Example 9
The preparation process was substantially the same as in example 2, except that the molar ratio of nano zirconia to sodium sulfide added in the dehydration step one was replaced with 3.0:100.
Example 10
The preparation process was essentially the same as in example 9, except that the nano zirconia was not added in the dehydration step of step one, but was added simultaneously with the third monomer in step two, the molar ratio of added nano zirconia to sodium sulfide in step one was still 3.0:100.
Example 11
The preparation process was substantially the same as in example 2, except that the average particle size of the nano zirconia added in the dehydration step one was replaced with d50=100 nm, respectively.
Example 12
The preparation process was substantially the same as in example 1, except that the third monomer was not added in the polymerization process of step two.
Example 13
The preparation process is substantially the same as in example 1, except that the nano zirconia is not added in the dehydration step of step one, but is added simultaneously with the third monomer in step two, and the molar ratio of the added nano zirconia to sodium sulfide in step one is still 0.5:100.
The average particle diameter and crystallization temperature data of the resins prepared in each example and comparative example are given in table 1 below.
TABLE 1
| Numbering device | Average particle diameter a/. Mu.m | Crystallization temperature b/°c |
| Example 1 | 430 | 225 |
| Comparative example 1 | 1300 | 198 |
| Comparative example 2 | 1500 | 193 |
| Example 2 | 440 | 225 |
| Example 3 | 445 | 225 |
| Example 4 | 490 | 223 |
| Example 5 | 460 | 224 |
| Example 6 | 405 | 226 |
| Example 7 | 1100 | 204 |
| Example 8 | 550 | 222 |
| Example 9 | 650 | 219 |
| Example 10 | 670 | 218 |
| Example 11 | 560 | 221 |
| Example 12 | 520 | 222 |
| Example 13 | 480 | 224 |
A. the average particle diameter is obtained by sieving
B. the crystallization temperature is obtained by DSC test, specifically, the temperature is raised to 380 ℃ from normal temperature at 5 ℃ per minute, the temperature is kept for 5 minutes, and then the temperature is lowered to normal temperature at a temperature-reducing speed of 5 ℃ per minute.
Performance test:
The resins prepared in each example and each comparative example are respectively melted and blended by a double screw extruder, extruded and granulated, dried for 12 hours under vacuum at 100 ℃, and then prepared into an alkaline water electrolytic cell diaphragm by combining a conventional spinning process with a conventional needle-punched non-woven fabric process, and the specific process flow is as follows:
The spinning process comprises pelleting, drying, spinning, winding, bundling, drafting, heat setting, crimping and cutting. Wherein the spinning temperature is 340 ℃, the circular blowing speed is 0.9m/min, the circular blowing temperature is 25 ℃, and the tension heat setting temperature is 245 ℃.
The needling non-woven fabric process comprises bale opener, coarse opening, cotton mixing bin, fine opening, carding, lapping, needling and cutting. Wherein the main cylinder speed is 600m/min, the needling density is 1000 needles/cm 2, the gram weight is 550g/m 2, and the needling rolling speed is 5m/min.
The alkaline water electrolysis cell diaphragms prepared by the resin raw materials of examples 1 to 13 through the spinning and needling processes are numbered as samples 1 to 13 in sequence, and the alkaline water electrolysis cell diaphragms prepared by the resin raw materials of comparative examples 1 to 2 through the spinning and needling processes are numbered as samples 14 to 15 in sequence.
The resin prepared in comparative example 2 was mechanically blended with nano zirconia (average particle size 50 nm), wherein nano zirconia accounts for 3% of the mass of the resin, melt blended and extruded to pelletize by a twin screw extruder, vacuum dried at 100 ℃ for 12 hours, and then prepared into an alkaline water electrolytic cell membrane, numbered sample 16, by combining the conventional spinning process described above with the conventional needle punched non-woven fabric process.
The resin prepared in comparative example 2 was melt-extruded through a twin screw extruder, pelletized, vacuum-dried at 100 ℃ for 12 hours, and then polyphenylene sulfide fiber was prepared according to the above spinning process and subjected to the following surface treatment:
And (3) sulfonating the polyphenylene sulfide fiber in 540g/L sulfuric acid and 320g/L chromic acid at the temperature of 80 ℃ for 10min, and then sequentially washing the sulfonated polyphenylene sulfide fiber with water at normal temperature, washing with hot water at 50 ℃, reducing and washing, washing with ultrasonic water, and drying to obtain the hydrophilic polyphenylene sulfide fiber.
And then the alkaline water electrolysis cell diaphragm is prepared by adopting the conventional needle punched non-woven fabric process, and the number of the alkaline water electrolysis cell diaphragm is sample 17.
Mechanically blending the resin prepared in comparative example 2 with nano zirconia (average particle size of 50 nm), wherein the nano zirconia accounts for 3% of the mass of the resin, melt blending and extrusion granulating by a twin screw extruder, vacuum drying at 100 ℃ for 12 hours, preparing polyphenylene sulfide fiber according to the spinning process, and carrying out the following surface treatment:
and (3) carrying out sulfonation treatment on the polyphenylene sulfide fiber in 540g/L sulfuric acid and 320g/L chromic acid, wherein the treatment temperature is 80 ℃ and the treatment time is 10min, and then sequentially carrying out normal-temperature water washing, 50 ℃ hot water washing, reduction cleaning, ultrasonic water washing and drying on the polyphenylene sulfide fiber subjected to the sulfonation treatment to obtain the hydrophilic polyphenylene sulfide fiber.
The alkaline water electrolysis cell membrane, sample 18, was then prepared using the conventional needle punched non-woven process described above.
All alkaline water electrolysis cell separators prepared as described above were tested separately and the test data are shown in table 2 below.
TABLE 2
The applicant states that the present invention is illustrated by the above examples as a detailed method of the present invention, but the present invention is not limited to the above detailed method.
Claims (10)
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| CN101134815A (en) * | 2007-10-17 | 2008-03-05 | 东华大学 | Method for preparing anti-ultraviolet polyphenylene sulfide resin by in-situ polymerization |
| CN103012234A (en) * | 2011-09-21 | 2013-04-03 | 中国石油化工股份有限公司 | Purification method of N-methyl pyrrolidone for high polymerization degree polyphenylene sulfide synthesis |
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| JP4765264B2 (en) * | 2003-07-23 | 2011-09-07 | 東レ株式会社 | Process for producing polyphenylene sulfide |
| JP5549851B2 (en) * | 2009-12-24 | 2014-07-16 | 東ソー株式会社 | Process for producing polyphenylene sulfide |
| CN103073720B (en) * | 2011-10-26 | 2016-02-17 | 中国石油化工股份有限公司 | A kind of method of synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin |
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