Preparation method of polyphenylene sulfide fabric diaphragm, polyphenylene sulfide fabric diaphragm and application

Abstract

The invention provides a preparation method of a polyphenylene sulfide fabric diaphragm, the polyphenylene sulfide fabric diaphragm and application, and particularly relates to the technical field of diaphragm materials. The preparation method comprises the following steps: A, carrying out sulfonation treatment on polyphenylene sulfide yarns, and then carrying out first dipping and first induced phase separation on the sulfonated polyphenylene sulfide yarns in an organic solvent of a polysulfone polymer to obtain yarns containing a polysulfone polymer layer; and B, weaving the yarns containing the polysulfone polymer layer to obtain a fabric, and carrying out second dipping, second induced phase separation, cleaning and drying on the fabric to obtain the polyphenylene sulfide fabric diaphragm. The polyphenylene sulfide yarns are subjected to sulfonation treatment, hydrophilic functional groups are introduced, and the hydrophilicity of the fibers and the binding force of the fibers and the coating are enhanced. The yarn is then immersed in a polysulfone polymer solution to form a polysulfone polymer coating. After the fabric is prepared, phase separation is induced again to form a reticular polysulfone polymer structure, so that the aperture of the polyphenylene sulfide fabric diaphragm is reduced, and the air tightness is improved.

Description

Technical Field

[0001] The invention relates to the technical field of diaphragm materials, and in particular to a preparation method of a polyphenylene sulfide fabric diaphragm, a polyphenylene sulfide fabric diaphragm and applications thereof. Background Art

[0002] The diaphragm plays a vital role in the alkaline water electrolyzer. It is located between the anode and the cathode. Its main function is to prevent the oxygen produced at the anode from mixing with the hydrogen produced at the cathode, thereby ensuring the purity of the gas and improving current efficiency and overall safety.

[0003] As a high-performance fiber material, PPS (polyphenylene sulfide) has excellent thermal stability, chemical stability, dimensional stability, and a large specific surface area, which makes it an ideal material for manufacturing diaphragms for alkaline water electrolysis and hydrogen production. However, PPS fabric diaphragms still face some challenges in practical applications:

[0004] 1. Hydrophilic modification requirements: PPS itself is hydrophobic, which is inconsistent with the hydrophilicity requirements of the water electrolyzer for materials. In order to improve this property, PPS needs to be hydrophilic modified. At present, plasma treatment, concentrated sulfuric acid treatment and other methods are widely used to improve the hydrophilicity of PPS. These treatment methods can introduce hydrophilic functional groups on the surface of the fabric, thereby improving the hydrophilicity of the diaphragm. However, during the electrolysis process, especially in an environment with strong bubble precipitation, the hydrophilicity of the fabric may gradually decrease over time, which may lead to a gradual increase in energy consumption.

[0005] 2. Pore size and air tightness issues: The pore size of the fabric prepared by PPS fiber is large, resulting in poor air tightness. The key function of the diaphragm is to strictly isolate the hydrogen and oxygen produced by the cathode and anode, while allowing OH - Ions move freely within the electrolyzer. If the diaphragm is not airtight enough, hydrogen and oxygen may permeate each other, causing safety issues. To improve the airtightness of the diaphragm, a common method is to increase the thickness of the fabric. However, this practice will increase the surface resistance of the diaphragm, thereby increasing energy consumption.

[0006] Although PPS materials have many advantages in manufacturing diaphragms, in order to improve their performance and safety in alkaline water electrolyzers, problems such as hydrophilic modification and airtightness improvement still need to be solved.

[0007] In view of this, the present invention is proposed. Summary of the invention

[0008] One of the purposes of the present invention is to provide a method for preparing a polyphenylene sulfide fabric diaphragm, aiming to solve at least one of the above-mentioned technical problems in the prior art.

[0009] A second object of the present invention is to provide a polyphenylene sulfide fabric diaphragm.

[0010] A third object of the present invention is to provide an application of a polyphenylene sulfide fabric diaphragm.

[0011] In order to solve the above-mentioned technical problems, the present invention particularly adopts the following technical solutions:

[0012] A first aspect of the present invention provides a method for preparing a polyphenylene sulfide fabric diaphragm, comprising the following steps:

[0013] A. sulfonating the polyphenylene sulfide yarn, and then first immersing the sulfonated polyphenylene sulfide yarn in an organic solvent of a polysulfone polymer, and first inducing phase separation to obtain a yarn containing a polysulfone polymer layer;

[0014] B. Weaving the yarn containing the polysulfone polymer layer to obtain a fabric, performing a second impregnation, a second induced phase separation, and washing and drying on the fabric to obtain a polyphenylene sulfide fabric diaphragm.

[0015] Furthermore, the sulfonation treatment is performed using a sulfonating agent.

[0016] Preferably, the sulfonating agent comprises concentrated sulfuric acid.

[0017] Preferably, the mass concentration of the concentrated sulfuric acid is 90-98%.

[0018] Preferably, the sulfonation treatment is carried out at a temperature of 70 to 90° C. and for a time of 5 to 40 minutes.

[0019] Furthermore, the mass concentration of the organic solution of the polysulfone polymer is ≤40%, preferably 10-40%.

[0020] Preferably, the polysulfone polymer includes at least one of polysulfone, sulfonated polysulfone, polyphenylsulfone, sulfonated polyphenylsulfone, sulfonated polyethersulfone and polyethersulfone.

[0021] Preferably, the organic solvent of the polysulfone polymer includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile and dimethyl sulfoxide.

[0022] Preferably, the temperature of the first impregnation is 60-80° C., and the time is 5-30 min.

[0023] Furthermore, the first induced phase separation and the second induced phase separation are each independently induced phase separation using a non-solvent.

[0024] Preferably, the non-solvent is a solvent that cannot dissolve the polysulfone polymer.

[0025] Preferably, the non-solvent comprises water.

[0026] Furthermore, the non-solvent induced phase separation process includes: placing the impregnated yarn or fabric into a pure water bath to obtain the yarn or fabric after phase separation.

[0027] Furthermore, the second impregnation reagent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide.

[0028] Preferably, the second immersion is carried out at a temperature of 40 to 60° C. and for a time of 5 to 30 minutes.

[0029] Preferably, the temperature of the water bath is 70-90° C., and the time is 1-5 min.

[0030] Furthermore, the warp yarn density of the fabric is 25 to 80 yarns per inch, and the weft yarn density is 15 to 50 yarns per inch.

[0031] Preferably, the fabric comprises a plain woven fabric.

[0032] Furthermore, the manufacturing process of the polyphenylene sulfide yarn is as follows:

[0033] The polyphenylene sulfide yarn is obtained by spinning the polyphenylene sulfide fiber through a cotton spinning process of cotton cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting.

[0034] Preferably, the length of the polyphenylene sulfide fiber is 30 to 60 mm.

[0035] Preferably, the polyphenylene sulfide fiber has a fineness of 0.5 to 3.0 dtex.

[0036] The second aspect of the present invention provides a polyphenylene sulfide fabric diaphragm, which is prepared by the preparation method described in the first aspect.

[0037] The third aspect of the present invention provides the use of the polyphenylene sulfide fabric diaphragm in an alkaline water electrolyzer.

[0038] Compared with the prior art, the present invention has at least the following beneficial effects:

[0039] The preparation method provided by the present invention firstly sulfonates the polyphenylene sulfide yarn, and introduces functional groups such as sulfoxide (-SO-) and sulfone (-SO2-) with strong polarity on the fiber surface, which not only enhances the hydrophilicity of the polyphenylene sulfide fiber, but also enhances the binding force between the fiber and the subsequent coating due to its strong polarity. Then, the polyphenylene sulfide yarn after sulfonation is immersed in an organic solution of a polysulfone polymer. As an amorphous polymer, the sulfone and sulfoxide groups contained in the main chain of the polysulfone polymer give the polyphenylene sulfide better hydrophilicity and good acid and alkali resistance. After being immersed in the polysulfone polymer solution, a layer of polysulfone polymer coating is formed on the fiber surface by non-solvent induced phase separation technology. Subsequently, the yarn coated with the polysulfone polymer coating is made into a fabric. In order to further optimize the air tightness of the diaphragm, the fabric was immersed in a solvent and non-solvent induced phase separation was performed again, so that the polysulfone polymer coating formed a network structure inside and on the surface of the fabric, thereby making the pore size of the fabric diaphragm smaller and significantly improving its air tightness.

[0040] The polyphenylene sulfide fabric diaphragm provided by the present invention has achieved two major technical breakthroughs: high air tightness and super hydrophilicity. The average pore size of the diaphragm is controlled at a fine scale of less than 5μm. This property is crucial to prevent the mutual penetration of hydrogen and oxygen, thereby ensuring the safety of the electrolysis process. The surface resistance of the diaphragm is less than 0.15Ω / cm 2 , has a rapid hydrophilic response, significantly reduces the internal resistance of the application site and improves efficiency.

[0041] The application of the polyphenylene sulfide fabric diaphragm provided by the present invention, in view of the surface structure and chemical stability of the polyphenylene sulfide fabric diaphragm, enables it to maintain stable hydrophilic properties in alkaline water electrolysis, reduce energy consumption, and extend service life. The combination of these technical effects not only improves the economic efficiency of water electrolysis hydrogen production, but also provides a reliable guarantee for the long-term stable operation of the electrolyzer. DETAILED DESCRIPTION

[0042] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution in the embodiment of the present invention will be clearly and completely described below in combination with the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, but not all of the embodiments. The components of the embodiment of the present invention can be arranged and designed in various different configurations.

[0043] A first aspect of the present invention provides a method for preparing a polyphenylene sulfide fabric diaphragm, comprising the following steps:

[0044] A. sulfonating the polyphenylene sulfide yarn, and then first immersing the sulfonated polyphenylene sulfide yarn in an organic solvent of a polysulfone polymer, and first inducing phase separation to obtain a yarn containing a polysulfone polymer layer;

[0045] B. Weaving the yarn containing the polysulfone polymer layer to obtain a fabric, performing a second impregnation, a second induced phase separation, and washing and drying on the fabric to obtain a polyphenylene sulfide fabric diaphragm.

[0046] The preparation method provided by the present invention firstly sulfonates the polyphenylene sulfide yarn, and introduces functional groups such as sulfoxide (-SO-) and sulfone (-SO2-) with strong polarity on the fiber surface, which not only enhances the hydrophilicity of the polyphenylene sulfide fiber, but also enhances the binding force between the fiber and the subsequent coating due to its strong polarity. Then, the polyphenylene sulfide yarn after sulfonation is immersed in an organic solution of a polysulfone polymer. As an amorphous polymer, the sulfone and sulfoxide groups contained in the main chain of the polysulfone polymer give the polyphenylene sulfide better hydrophilicity and good acid and alkali resistance. After being immersed in the polysulfone polymer solution, a layer of polysulfone polymer coating is formed on the fiber surface by non-solvent induced phase separation technology. Subsequently, the yarn coated with the polysulfone polymer coating is made into a fabric. In order to further optimize the air tightness of the diaphragm, the fabric was immersed in a solvent and non-solvent induced phase separation was performed again, so that the polysulfone polymer coating formed a network structure inside and on the surface of the fabric, thereby making the pore size of the fabric diaphragm smaller and significantly improving its air tightness.

[0047] The present invention directly carries out sulfonation treatment on the yarn, and can achieve a more uniform modification effect before the fiber is woven into a fabric, because the singleness of the yarn structure allows the sulfonating agent to act more evenly on each fiber, thereby ensuring the consistency of the modification effect. This uniform modification not only improves the efficiency of the treatment, because the treatment area of ​​the yarn is small, so that the chemical reagent can penetrate faster, but also reduces the production cost, reduces the usage amount and treatment time of the sulfonating agent. In addition, before the sulfonated yarn is woven into a fabric, its modification effect has been fixed, which provides convenience for controlling product quality in subsequent weaving and coating processes, and ensures the consistency and reliability of the final product.

[0048] After the polyphenylene sulfide yarn is immersed in an organic solution of a polysulfone polymer, a polysulfone polymer layer is formed on the fiber surface by non-solvent induced phase separation. Non-solvent induced phase separation is achieved by introducing a non-solvent that does not dissolve the polysulfone polymer but causes the polysulfone polymer to precipitate from the solution to form a uniform coating on the fiber surface, thereby improving the hydrophilicity and chemical resistance of the fiber.

[0049] Furthermore, the sulfonation treatment is performed using a sulfonating agent.

[0050] Preferably, the sulfonating agent comprises concentrated sulfuric acid.

[0051] Preferably, the mass concentration of the concentrated sulfuric acid is 90-98%.

[0052] Typically but not limiting, the mass concentration of concentrated sulfuric acid can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97% or 98%, or any value within the range of 90% to 98%.

[0053] Preferably, the sulfonation treatment is carried out at a temperature of 70 to 90° C. and for a time of 5 to 40 minutes.

[0054] Typically, but not limiting, the temperature of the sulfonation treatment may be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 90°C, and the time may be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min,

[0055] 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min,

[0056] 35min, 36min, 37min, 38min, 39min or 40min, that is, the temperature and time can take any value in the range of 70℃~90℃ and 5min~40min.

[0057] Furthermore, the mass concentration of the organic solution of the polysulfone polymer is ≤40%, preferably 10-40%.

[0058] Typically but not limiting, the mass concentration of the organic solution of the polysulfone polymer can be 10%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%, that is, the concentration can take any value within the range of 10% to 40%.

[0059] The polysulfone polymer includes at least one of polysulfone, sulfonated polysulfone, polyphenylsulfone, sulfonated polyphenylsulfone, sulfonated polyethersulfone and polyethersulfone.

[0060] Preferably, the organic solvent of the polysulfone polymer includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile and dimethyl sulfoxide.

[0061] Preferably, the temperature of the first impregnation is 60-80° C., and the time is 5-30 min.

[0062] Typically but not limiting, the temperature of the first impregnation can be 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C or 80°C, and the time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min or 30 min, that is, the temperature and time can take any value in the range of 60°C to 80°C and 5 min to 30 min.

[0063] Furthermore, the first induced phase separation and the second induced phase separation are each independently induced phase separation using a non-solvent.

[0064] Preferably, the non-solvent is a solvent that cannot dissolve the polysulfone polymer.

[0065] Preferably, the non-solvent comprises water.

[0066] Furthermore, the non-solvent induced phase separation process includes: placing the impregnated yarn or fabric into a pure water bath to obtain the yarn or fabric after phase separation.

[0067] Furthermore, the second impregnation reagent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide.

[0068] Preferably, the second immersion is carried out at a temperature of 40 to 60° C. and for a time of 5 to 30 minutes.

[0069] Typically but not limiting, the temperature of the second impregnation can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, and the time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min or 30 min, that is, the temperature and time can take any value in the range of 40°C to 60°C and 5 min to 30 min.

[0070] Preferably, the temperature of the water bath is 70-90° C., and the time is 1-5 min.

[0071] Typically but not limiting, the temperature of the water bath can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C or 90°C, and the time can be 1 min, 2 min, 3 min, 4 min or 5 min, that is, the temperature and time can take any value in the range of 70°C to 90°C and 1 min to 5 min.

[0072] Furthermore, the warp yarn density of the fabric is 25 to 80 yarns per inch, and the weft yarn density is 15 to 50 yarns per inch.

[0073] Typically, but not limiting, the fabric may have a warp density of 25, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110 The warp yarn density can be 7, 78, 79 or 80 roots per inch, and the weft yarn density can be 15, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 roots per inch, that is, the warp yarn density and the weft yarn density can take any value in the range of 25 to 80 roots per inch and 15 to 50 roots per inch.

[0074] Preferably, the fabric comprises a plain woven fabric.

[0075] Furthermore, the manufacturing process of the polyphenylene sulfide yarn is as follows:

[0076] The polyphenylene sulfide yarn is obtained by spinning the polyphenylene sulfide fiber through a cotton spinning process of cotton cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting.

[0077] Preferably, the length of the polyphenylene sulfide fiber is 30 to 60 mm.

[0078] Typically but not limiting, the length of the polyphenylene sulfide fiber can be 30mm, 31mm, 32mm, 33mm, 34mm, 35mm, 36mm, 37mm, 38mm, 39mm, 40mm, 41mm, 42mm, 43mm, 44mm, 45mm, 46mm, 47mm, 48mm, 49mm, 50mm, 51mm, 52mm, 53mm, 54mm, 55mm, 56mm, 57mm, 58mm, 59mm or 60mm, and the length can take any value within the range of 30mm to 60mm.

[0079] Preferably, the polyphenylene sulfide fiber has a fineness of 0.5 to 3.0 dtex.

[0080] Typically but not restrictively, the fineness of the polyphenylene sulfide fiber can be 0.5 dtex, 0.8 dtex, 1.0 dtex, 1.5 dtex, 1.6 dtex, 1.7 dtex, 1.8 dtex, 1.9 dtex, 2.0 dtex, 2.1 dtex, 2.2 dtex, 2.3 dtex, 2.4 dtex, 2.5 dtex or 3.0 dtex, that is, the fineness can take any value in the range of 0.5 to 3.0 dtex.

[0081] The second aspect of the present invention provides a polyphenylene sulfide fabric diaphragm, which is prepared by the preparation method described in the first aspect.

[0082] The polyphenylene sulfide fabric diaphragm provided by the present invention has achieved two major technical breakthroughs: high air tightness and super hydrophilicity. The average pore size of the diaphragm is controlled at a fine scale of less than 5μm. This property is crucial to prevent the mutual penetration of hydrogen and oxygen, thereby ensuring the safety of the electrolysis process. The surface resistance of the diaphragm is less than 0.15Ω / cm 2 , has a rapid hydrophilic response, significantly reduces the internal resistance of the application site and improves efficiency.

[0083] The third aspect of the present invention provides the use of the polyphenylene sulfide fabric diaphragm in an alkaline water electrolyzer.

[0084] The application of the polyphenylene sulfide fabric diaphragm provided by the present invention, in view of the surface structure and chemical stability of the polyphenylene sulfide fabric diaphragm, enables it to maintain stable hydrophilic properties in alkaline water electrolysis, reduce energy consumption, and extend service life. The combination of these technical effects not only improves the economic efficiency of water electrolysis hydrogen production, but also provides a reliable guarantee for the long-term stable operation of the electrolyzer.

[0085] In the following, some embodiments of the present invention are described in detail in conjunction with the examples. In the absence of conflict, the following examples and features in the examples can be combined with each other. The raw materials in the following examples and comparative examples are purchased from the market unless otherwise specified.

[0086] Example 1

[0087] This embodiment provides a polyphenylene sulfide fabric diaphragm, and the preparation process is as follows:

[0088] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 1.56 dtex are spun through a cotton spinning process of cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0089] (2) The polyphenylene sulfide yarn was sulfonated in 95% concentrated sulfuric acid at a temperature of 80° C. for 10 min. After the sulfonation treatment, the yarn was washed and dried.

[0090] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone solution (concentration of 20 wt %, solvent of NMP) at a temperature of 70° C. for 15 min.

[0091] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C pure water for 2 minutes.

[0092] (5) After the water bath is finished, the polyphenylene sulfide yarn is washed and dried to obtain a yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven by a rapier loom to obtain a plain woven fabric with a warp density of 40 yarns / inch and a weft density of 28 yarns / inch.

[0093] (6) The fabric was immersed in 50°C NMP for 15 min, then placed in a water bath at 80°C pure water for 2 min, and finally washed and dried to obtain a polyphenylene sulfide fabric membrane.

[0094] Example 2

[0095] This embodiment provides a polyphenylene sulfide fabric diaphragm, and the preparation process is as follows:

[0096] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 2.22 dtex are spun through a cotton spinning process of cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0097] (2) The polyphenylene sulfide yarn was sulfonated in 90% concentrated sulfuric acid at a temperature of 80° C. for 20 min. After the sulfonation treatment, the yarn was washed and dried.

[0098] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (with a concentration of 30 wt % and a solvent of dimethyl sulfoxide) at a temperature of 60° C. for 20 min.

[0099] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C pure water for 5 minutes.

[0100] (5) After the water bath is finished, the polyphenylene sulfide yarn is washed and dried to obtain a yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven by a rapier loom to obtain a plain woven fabric with a warp density of 36 yarns / inch and a weft density of 25 yarns / inch.

[0101] (6) The fabric was immersed in dimethyl sulfoxide at 60°C for 30 minutes, then placed in a water bath at 80°C for 5 minutes, and finally washed and dried to obtain a polyphenylene sulfide fabric membrane.

[0102] Example 3

[0103] This embodiment provides a polyphenylene sulfide fabric diaphragm, and the preparation process is as follows:

[0104] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 0.89 dtex were spun through a cotton spinning process of cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0105] (2) The polyphenylene sulfide yarn was sulfonated in 95% concentrated sulfuric acid at a temperature of 80° C. for 5 min. After the sulfonation treatment, the yarn was washed and dried.

[0106] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (concentration of 10 wt %, solvent of NMP) at a temperature of 80° C. for 5 min.

[0107] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C pure water for 2 minutes.

[0108] (5) After the water bath is finished, the polyphenylene sulfide yarn is washed and dried to obtain a yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven by a rapier loom to obtain a plain woven fabric with a warp density of 78 yarns / inch and a weft density of 45 yarns / inch.

[0109] (6) The fabric was immersed in NMP at 40°C for 5 min, then placed in a water bath at 80°C for 2 min, and finally washed and dried to obtain a polyphenylene sulfide fabric membrane.

[0110] Comparative Example 1

[0111] This comparative example provides a polyphenylene sulfide fabric diaphragm, and the preparation process is as follows:

[0112] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 1.56 dtex are spun through a cotton spinning process of cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0113] (2) The polyphenylene sulfide yarn is woven by a rapier loom to obtain a plain woven fabric with a warp density of 40 yarns / inch and a weft density of 28 yarns / inch, which is used as the polyphenylene sulfide fabric separator.

[0114] Comparative Example 2

[0115] This comparative example provides a polyphenylene sulfide fabric diaphragm, and the preparation process is as follows:

[0116] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 1.56 dtex are spun through a cotton spinning process of cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0117] (2) The polyphenylene sulfide yarn is sulfonated in 95% concentrated sulfuric acid at a temperature of 80°C for 10 min. After the sulfonation treatment, the yarn is washed and dried, and then woven using a rapier loom to obtain a plain woven fabric with a warp density of 40 yarns / inch and a weft density of 28 yarns / inch, which is used as the polyphenylene sulfide fabric membrane.

[0118] Comparative Example 3

[0119] This comparative example provides a polyphenylene sulfide fabric diaphragm, and the preparation process is as follows:

[0120] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 0.89 dtex were spun through a cotton spinning process of cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0121] (2) The polyphenylene sulfide yarn was sulfonated in 95% concentrated sulfuric acid at a temperature of 80° C. for 5 min. After the sulfonation treatment, the yarn was washed and dried.

[0122] (3) The sulfonated polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (concentration of 10 wt %, solvent of NMP) at a temperature of 80° C. for 5 min.

[0123] (4) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C pure water for 2 minutes.

[0124] (5) After the water bath is finished, the polyphenylene sulfide yarn is washed and dried to obtain a yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven by a rapier loom to obtain a plain woven fabric with a warp density of 78 yarns / inch and a weft density of 45 yarns / inch.

[0125] Comparative Example 4

[0126] This comparative example provides a polyphenylene sulfide fabric diaphragm, and the preparation process is as follows:

[0127] (1) Polyphenylene sulfide fibers with a length of 51 mm and a fineness of 2.22 dtex are spun through a cotton spinning process of cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain polyphenylene sulfide yarn.

[0128] (2) The polyphenylene sulfide yarn was immersed in a polysulfone polymer solution (concentration of 30 wt %, solvent of dimethyl sulfoxide) at a temperature of 60° C. for 20 min.

[0129] (3) The impregnated polyphenylene sulfide yarn is placed in a water bath at 80°C pure water for 5 minutes.

[0130] (4) After the water bath is finished, the polyphenylene sulfide yarn is washed and dried to obtain a yarn with a polysulfone polymer layer. The yarn with the polysulfone polymer layer is woven by a rapier loom to obtain a plain woven fabric with a warp density of 36 yarns / inch and a weft density of 25 yarns / inch.

[0131] (5) The fabric was immersed in dimethyl sulfoxide at 60°C for 30 minutes, then placed in a water bath at 80°C for 5 minutes, and finally washed and dried to obtain a polyphenylene sulfide fabric membrane.

[0132] Test Case

[0133] The polyphenylene sulfide fabric diaphragms obtained in the examples and comparative examples were subjected to the following tests:

[0134] (1) Thickness: The thickness of the fabric was measured according to JIS L1096-2010 “Test methods for woven and knitted fabrics”.

[0135] (2) Weight: The weight of the fabric is measured according to GB / T 4669-2008 “Textiles - Determination of mass per unit length and mass per unit area”.

[0136] (3) Average pore size: According to ASTM F316-03 "Standard test method for determining pore size characteristics of membrane filters by bubble point and pore mean flow method", the average pore size of the fabric is measured using a capillary flow porometer.

[0137] (4) Air tightness: The air tightness of the fabric diaphragm is tested according to the Chinese building materials industry standard JC / T 211-2009 "Diaphragm Asbestos Cloth".

[0138] (5) Surface resistance: The surface resistance of the fabric diaphragm was tested with reference to SJ / T 10171-2016 "General Test Method for Basic Properties of Alkaline Battery Diaphragms". Before the test, the prepared fabric diaphragm was soaked in a 30wt% KOH aqueous solution for 24h. The test solution was a 30wt% KOH aqueous solution at 23℃±2℃. The resistance was tested with an AC low impedance meter. The surface resistance Rs of the composite diaphragm was calculated as follows:

[0139] R s =(R1-R0)×A

[0140] Among them, R1 is the solution resistance when the membrane is added, and R0 is the blank solution resistance.

[0141] (6) Diaphragm alkali resistance stability test: Take a fabric diaphragm of the same size, put it into a 30wt% KOH aqueous solution at 90°C, stir it at 300rpm for 30 days, take it out and wash it with water and dry it. Test the air tightness of the fabric diaphragm before and after the hot alkali treatment according to relevant standards, and calculate the air tightness change rate by the following formula.

[0142]

[0143] The results are shown in Table 1 below.

[0144] Table 1

[0145]

[0146] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a polyphenylene sulfide fabric diaphragm, characterized in that: The following steps are involved: A. sulfonating the polyphenylene sulfide yarn, and then first immersing the sulfonated polyphenylene sulfide yarn in an organic solvent of a polysulfone polymer, and first inducing phase separation to obtain a yarn containing a polysulfone polymer layer; B. Weaving the yarn containing the polysulfone polymer layer to obtain a fabric, performing a second impregnation, a second induced phase separation, and washing and drying on the fabric to obtain a polyphenylene sulfide fabric diaphragm.

2. The preparation method according to claim 1, characterized in that: Using a sulfonating agent to carry out the sulfonation treatment; The sulfonating agent includes concentrated sulfuric acid; The mass concentration of the concentrated sulfuric acid is 90-98%; The temperature of the sulfonation treatment is 70-90° C. and the time is 5-40 minutes.

3. The preparation method according to claim 1, characterized in that: The mass concentration of the organic solution of the polysulfone polymer is ≤40%; The polysulfone polymer includes at least one of polysulfone, sulfonated polysulfone, polyphenylsulfone, sulfonated polyphenylsulfone, sulfonated polyethersulfone and polyethersulfone; The organic solvent of the polysulfone polymer includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile and dimethyl sulfoxide; The temperature of the first immersion is 60-80° C., and the time is 5-30 minutes.

4. The preparation method according to claim 1, characterized in that: The first induced phase separation and the second induced phase separation are each independently induced phase separation using a non-solvent; The non-solvent is a solvent that cannot dissolve the polysulfone polymer; The non-solvent includes water.

5. The preparation method according to claim 4, characterized in that: The process of non-solvent induced phase separation comprises: placing the impregnated yarn or fabric into a pure water bath to obtain the yarn or fabric after phase separation.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The second impregnation reagent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone, acetonitrile, and dimethyl sulfoxide; The second dipping temperature is 40-60°C and the time is 5-30 minutes; The temperature of the water bath is 70-90° C., and the time is 1-5 minutes.

7. The preparation method according to any one of claims 1 to 5, characterized in that: The fabric has a warp density of 25 to 80 yarns per inch and a weft density of 15 to 50 yarns per inch; The fabric comprises a plain woven fabric.

8. The preparation method according to any one of claims 1 to 5, characterized in that: The manufacturing process of the polyphenylene sulfide yarn is as follows: The polyphenylene sulfide fiber is spun through a cotton spinning process of cotton cleaning-combing-drawing-roving-spinning-winding-doubling-twisting-heat setting to obtain the polyphenylene sulfide yarn; The polyphenylene sulfide fiber has a length of 30 to 60 mm and a fineness of 0.5 to 3.0 dtex.

9. A polyphenylene sulfide fabric diaphragm, characterized in that: The preparation is obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the polyphenylene sulfide fabric diaphragm according to claim 9 in an alkaline water electrolyzer.

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