Polyarylene sulfide sulfone-polyphenylene sulfide fabric type composite diaphragm as well as preparation method and application thereof

Abstract

The invention provides a polyarylene sulfide sulfone-polyphenylene sulfide fabric type composite diaphragm as well as a preparation method and application thereof. The preparation method comprises the following steps: dissolving dehydrated sodium sulfide, NaOH and a catalyst in an organic solvent to obtain a to-be-reacted solution; putting the polyphenylene sulfide fabric into the reaction solution to be soaked; 4, 4-dichlorodiphenyl sulfone is added into the to-be-reacted liquid where the polyphenylene sulfide fabric is soaked for a reaction; and S3, pouring the solution after reaction in the step S3 and the polyphenylene sulfide fabric soaked in the solution into deionized water for ultrasonic washing to prepare the polyarylene sulfide sulfone-polyphenylene sulfide fabric type composite diaphragm. The PASS grows and is stacked on the surface of the PPS fabric, so that the hydrophobicity of the PPS diaphragm is converted into hydrophilicity, and the hydrophilicity of the diaphragm is effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of polymer membrane materials, and in particular relates to a polyarylene sulfide sulfone-polyphenylene sulfide fabric-type composite separator and a preparation method and application thereof. Background Art

[0002] Polyphenylene sulfide (PPS) is a high-performance new thermoplastic resin, known as the world's sixth largest engineering plastic. It has excellent heat resistance, radiation resistance, acid and alkali corrosion resistance and electrical properties, and also has excellent mechanical strength. It is suitable for various industrial scenarios requiring high temperature, chemical stability and electrical properties, and is widely used in the fields of automobiles, electronics and electrical appliances, aerospace, etc.

[0003] Hydrogen energy, as an efficient and clean secondary energy, has received wide attention. Alkaline water electrolysis for hydrogen production is currently the most cost-effective hydrogen production technology. The separator is one of the key core materials of the water electrolysis equipment. The polyphenylene sulfide fabric separator is widely used in the industry due to its excellent chemical stability and good mechanical properties. However, the hydrophobicity of PPS will make the surface of the prepared PPS porous separator hydrophobic, which will cause ions to be difficult to transport and diffuse in the separator during water electrolysis, thus affecting the efficiency and speed of the electrolysis reaction and limiting the water electrolysis efficiency. Summary of the Invention

[0004] In view of this, the present invention aims to overcome the defects in the prior art and proposes a polyarylene sulfide sulfone-polyphenylene sulfide fabric-type composite separator and a preparation method and application thereof. By the similarity of the structures of polyphenylene sulfide (PPS) and polyarylene sulfide sulfone (PASS), the polyarylene sulfide sulfone molecules are stacked and grown on the surface of the PPS fabric, and finally a hydrophilic PASS-PPS fabric-type composite separator is prepared.

[0005] To achieve the above object, the technical solution of the present invention is realized as follows:

[0006] As the first aspect of the present invention, a preparation method of a polyarylene sulfide sulfone-polyphenylene sulfide fabric-type composite separator is provided, including the following steps:

[0007] S1: Dissolve dehydrated sodium sulfide, NaOH and a catalyst in an organic solvent to obtain a reaction solution to be reacted;

[0008] S2: Immerse the polyphenylene sulfide fabric in the reaction solution to be reacted;

[0009] S3: Add 4,4-dichlorodiphenyl sulfone to the reaction solution to be reacted in which the polyphenylene sulfide fabric is immersed for a two-stage temperature-raising reaction;

[0010] S4: Pour the solution after the reaction in step S3 together with the polyphenylene sulfide fabric immersed therein into deionized water for ultrasonic washing to obtain a polyarylene sulfide sulfone-polyphenylene sulfide fabric-type composite separator.

[0011] In some embodiments of the present invention, in step S2, the soaking temperature is 125-180°C, and the soaking time is 25-60 min. The present invention utilizes the similarity of the molecular structures of PPS and PASS. First, the PPS fibers are softened at a high temperature, so that the synthesized PASS molecules in the subsequent reaction can firmly coat on the PPS fibers, and a stable composite separator (PASS does not easily detach from the fabric surface under alkaline conditions) is prepared.

[0012] In some embodiments of the present invention, step S3 includes a two-stage temperature-rising reaction. The temperature of the first-stage temperature-rising reaction is 125-145°C, and the time is 4-6 h. The temperature of the second-stage temperature-rising reaction is 155-185°C, and the time is 1-3 h. In the first step of the present invention, a low-temperature reaction is carried out first, aiming to control the production of short PASS molecular chains. These short-chain PASS can grow better on PPS; then, in the second step of raising the temperature, the short-chain PASS growing on the surface of PPS can continue to grow again, further improving the stability of the composite membrane. If a one-step temperature-rising reaction at 185°C is directly adopted, the synthesized PASS molecular chains will be very long, resulting in the aggregation of PASS molecular chains in the solution and not easily growing onto the PPS fibers.

[0013] In some embodiments of the present invention, the grammage of the polyphenylene sulfide fabric separator is 350 g / m 2 ~500 g / m 2 .

[0014] In some embodiments of the present invention, the organic solvent in step S1 is any one or a mixture of two or more of N-methylpyrrolidone, dimethyl sulfoxide, hexamethylphosphoric triamide, N,N'-dimethylacetamide, and N,N'-dimethylformamide.

[0015] In some embodiments of the present invention, the catalyst in step S1 is any one or a mixture of two or more of LiOH, Na5PO4, C7H5O2Na, Na2CO3, NaNO3, ZnCl2, NaOAc, C6H5SO3Na, and C7H5O2Li.

[0016] In some embodiments of the present invention, the concentration of Na2S in the reaction solution to be reacted in step S1 is 0.75 mol / L - 3 mol / L.

[0017] In some embodiments of the present invention, the concentration of NaOH in the reaction solution to be reacted in step S1 is 0.05 mol / L - 0.2 mol / L.

[0018] In some embodiments of the present invention, the concentration of the catalyst in the reaction solution to be reacted in step S1 is 0.15 mol / L to 0.6 mol / L.

[0019] In some embodiments of the present invention, the concentration of 4,4-dichlorodiphenyl sulfone in step S3 is 0.75 mol / L to 3 mol / L.

[0020] In some embodiments of the present invention, the dehydrated sodium sulfide in step S1 is obtained by drying and dehydrating Na2S·9H2O, and the drying and dehydrating parameters are: the vacuum degree <0.1 MPa, the temperature is carried out at 105°C to 125°C, and it lasts for 2 to 6 h.

[0021] As a second aspect of the present invention, there is provided a polyarylene sulfide sulfone-polyphenylene sulfide fabric-type composite separator prepared by the above preparation method.

[0022] As a third aspect of the present invention, there is provided an application of the above polyarylene sulfide sulfone-polyphenylene sulfide fabric-type composite separator in the electrolysis of water to produce hydrogen.

[0023] The mechanism of the polyarylene sulfide sulfone-polyphenylene sulfide fabric-type composite separator of the present invention is to utilize the similarity of the molecular structures of PPS and PASS. First, soften the PPS fibers at a high temperature, so that the PASS molecules synthesized in the subsequent reaction can firmly coat the PPS fibers, and a stable composite separator (PASS does not easily detach from the fabric surface when working in an alkaline environment) is prepared.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] (1) Based on the excellent physical and chemical properties of the PPS fabric separator, the present invention does not damage the fabric structure of the separator itself, and a PPS separator with high hydrophilicity is prepared.

[0026] (2) By growing and stacking PASS on the surface of the PPS fabric, the present invention realizes the transformation of the hydrophobicity of the PPS separator into hydrophilicity, effectively improves the hydrophilicity of the composite separator. After modification, the water contact angle of the membrane changes from 157° to 49°, and the water droplets are absorbed within 3 s to 5 s after contacting the separator, and relatively high hydrophilic performance can be achieved;

[0027] (3) The preparation method of the present invention significantly reduces the surface resistance of the separator and reduces the energy consumption during the electrolysis process;

[0028] (4) By stacking PASS on the fabric surface, the present invention effectively regulates the porosity and improves the airtightness of the composite separator;

[0029] (5) The separator of the present invention has good ion conduction ability, realizing the application possibility of the PPS separator in the electrolysis of water. Brief Description of the Drawings

[0030] Figure 1 Optical micrograph of the poly(arylene sulfide sulfone)-polyphenylene sulfide fabric composite separator prepared in Example 1;

[0031] Figure 2 Contact angle measurement diagram of the PPS fabric separator used in Example 1;

[0032] Figure 3 1 s contact angle measurement diagram of the poly(arylene sulfide sulfone)-polyphenylene sulfide fabric composite separator prepared in Example 1;

[0033] Figure 4 2 s contact angle measurement diagram of the poly(arylene sulfide sulfone)-polyphenylene sulfide fabric composite separator prepared in Example 1;

[0034] Figure 5 The water droplet has been completely absorbed at 3 s for the poly(arylene sulfide sulfone)-polyphenylene sulfide fabric composite separator prepared in Example 1;

[0035] Figure 6 Scanning electron micrograph of the PPS fabric separator used in Example 1;

[0036] Figure 7 Scanning electron micrograph of the poly(arylene sulfide sulfone)-polyphenylene sulfide fabric composite separator prepared in Example 1. Detailed Description of the Preferred Embodiments

[0037] Embodiments of the present invention will be described in detail below. The following described embodiments are exemplary and are only used to explain the present invention and should not be construed as a limitation of the present invention.

[0038] In this document, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs.

[0039] In this document, when a value is described as a range, it should be understood that such disclosure includes the disclosure of all possible sub-ranges within that range, as well as specific numerical values falling within that range, regardless of whether specific numerical values or specific sub-ranges are explicitly indicated.

[0040] In this document, when referring to "a plurality of", etc., unless otherwise specified, it means greater than 2 or equal to 2 in quantity. For example, "one or more" means one or greater than or equal to two.

[0041] In this document, when referring to "preferred", "more preferred", etc., they are only used to describe embodiments or examples with better effects and should be understood that they do not constitute a limitation on the protection scope of the present invention.

[0042] In this text, terms such as "further" are used for descriptive purposes, indicating differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0043] In this text, the term "and / or" describes the associated relationship of an object, indicating that three relationships can exist. For example, A and / or B means: A or B, or the three relationships of A and B.

[0044] In this text, the terms "comprising", "including", "having", "containing", etc. are all open-ended terms, meaning including but not limited to.

[0045] Unless otherwise specified, all technical and scientific terms used in this text have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described in this text can also be used in the implementation or testing of the present invention.

[0046] The present invention will be described in detail below in conjunction with embodiments.

[0047] In the embodiments of the present invention, the grammage of the PPS fabric diaphragm used is 350 - 500 g / m 2 。

[0048] Example 1

[0049] (1) Sodium sulfide nonahydrate Na2S·9H2O was dried under a vacuum of <0.1 MPa and at 115 °C for 4 h to obtain dehydrated sodium sulfide;

[0050] (2) The dehydrated sodium sulfide, sodium hydroxide, and lithium hydroxide were dissolved in 100 ml of N-methylpyrrolidone (NMP) to form a reaction solution to be reacted. The concentration of sodium sulfide in the reaction solution to be reacted was 1.5 mol / L, the concentration of sodium hydroxide was 0.1 mol / L, and the concentration of lithium hydroxide was 0.3 mol / L. The PPS fabric diaphragm was immersed in the reaction solution to be reacted at a temperature of 145 °C for 25 min.

[0051] (3) 4,4-Dichlorodiphenyl sulfone (DCDPS) was added to the reaction solution to be reacted in which the PPS fabric was immersed. The concentration of DCDPS was 1.5 mol / L, the temperature was 145 °C, and after reacting for 5 h, the temperature was raised to 185 °C and the reaction continued for 2 h; the reacted solution together with the fabric immersed therein was introduced into deionized water for ultrasonic washing to obtain a polyarylene sulfone - polyphenylene sulfide fabric composite diaphragm.

[0052] Figure 1 is the optical micrograph of the hydrophilic diaphragm of polyphenylene sulfide fiber fabric prepared in this example;

[0053] Figure 2Contact angle measurement diagram of the PPS fabric diaphragm used in this embodiment; Figure 3 1s contact angle measurement diagram of the polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm prepared in this embodiment;

[0054] Figure 4 2s contact angle measurement diagram of the polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm prepared in this embodiment; Figure 5 The water droplet has been completely absorbed at 3s for the polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm prepared in this embodiment; Figure 6 Scanning electron micrograph of the PPS fabric diaphragm used in this embodiment; Figure 7 Scanning electron micrograph of the polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm prepared in this embodiment.

[0055] Example 2

[0056] (1) Sodium sulfide nonahydrate Na2S·9H2O was dried at a vacuum of <0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide;

[0057] (2) The dehydrated sodium sulfide, sodium hydroxide, and pentasodium phosphate were dissolved in 100 ml of dimethyl sulfoxide to form a reaction solution. The concentration of sodium sulfide in the reaction solution was 3 mol / L, the concentration of sodium hydroxide was 0.1 mol / L, and the concentration of lithium hydroxide was 0.3 mol / L. The PPS fabric diaphragm was immersed in the reaction solution at a temperature of 145 °C for 25 min.

[0058] (3) 4,4-Dichlorodiphenyl sulfone (DCDPS) was added to the reaction solution in which the PPS fabric diaphragm was immersed. The concentration of DCDPS was 1.5 mol / L, the temperature was 145 °C, and after reacting for 5 h, the temperature was raised to 185 °C and the reaction continued for 2 h; the reaction solution together with the fabric immersed therein was introduced into deionized water and ultrasonically washed to obtain a polyarylene sulfone sulfone / polyphenylene sulfide fabric composite diaphragm.

[0059] Example 3

[0060] (1) Sodium sulfide nonahydrate Na2S·9H2O was dried at a vacuum of <0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide;

[0061] (2) The dehydrated sodium sulfide, sodium hydroxide, and C7H5O2Na were dissolved in 100 ml of hexamethylphosphoramide to form a reaction solution. The concentration of sodium sulfide in the reaction solution was 0.75 mol / L, the concentration of sodium hydroxide was 0.1 mol / L, and the concentration of lithium hydroxide was 0.3 mol / L. The PPS fabric diaphragm was immersed in the reaction solution at a temperature of 145 °C for 25 min.

[0062] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is soaked. The concentration of DCDPS is 1.5 mol / L, the temperature is 145 °C, and after reacting for 5 h, the temperature is raised to 185 °C and the reaction continues for 2 h. After ultrasonic washing the reacted solution together with the fabric soaked therein in deionized water, a polyarylene sulfone - polyphenylene sulfide fabric - type composite diaphragm is prepared.

[0063] Example 4

[0064] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum of <0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0065] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and Na2CO3 in 200 ml of N,N'-dimethylacetamide to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 0.75 mol / L, the concentration of sodium hydroxide is 0.05 mol / L, and the concentration of lithium hydroxide is 0.15 mol / L. Soak the PPS fabric in the reaction solution at a temperature of 145 °C for 25 min.

[0066] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is soaked. The concentration of DCDPS is 0.75 mol / L, the temperature is 145 °C, and after reacting for 5 h, the temperature is raised to 185 °C and the reaction continues for 2 h. After ultrasonic washing the reacted solution together with the PPS fabric diaphragm soaked therein in deionized water, a polyarylene sulfone - polyphenylene sulfide fabric - type composite diaphragm is prepared.

[0067] Example 5

[0068] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum of <0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0069] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and NaNO3 in 50 ml of N,N’-dimethylformamide to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 3 mol / L, the concentration of sodium hydroxide is 0.2 mol / L, and the concentration of lithium hydroxide is 0.6 mol / L. Soak the PPS fabric diaphragm in the reaction solution at a temperature of 145 °C for 25 min.

[0070] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is immersed. The concentration of DCDPS is 3 mol / L, the temperature is 145 °C, and after reacting for 5 h, the temperature is raised to 185 °C and the reaction continues for 2 h. After the reaction solution and the fabric immersed therein are introduced into deionized water and ultrasonically washed, a polyarylene sulfone - polyphenylene sulfide fabric - type composite diaphragm is prepared.

[0071] Example 6

[0072] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0073] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and ZnCl2 in 100 ml of N - methylpyrrolidone (NMP) to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 1.5 mol / L, the concentration of sodium hydroxide is 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L. Immerse the PPS fabric diaphragm in the reaction solution at a temperature of 145 °C for 25 min.

[0074] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is immersed. The concentration of DCDPS is 0.77 mol / L, the temperature is 145 °C, and after reacting for 5 h, the temperature is raised to 185 °C and the reaction continues for 2 h. After the reaction solution and the fabric immersed therein are introduced into deionized water and ultrasonically washed, a polyarylene sulfone - polyphenylene sulfide fabric - type composite diaphragm is prepared.

[0075] Example 7

[0076] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0077] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and NaOAc in 100 ml of N - methylpyrrolidone (NMP) to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 2.5 mol / L, the concentration of sodium hydroxide is 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L. Immerse the PPS fabric diaphragm in the reaction solution at a temperature of 145 °C for 25 min.

[0078] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is immersed. The concentration of DCDPS is 3 mol / L, the temperature is 145 °C, and after reacting for 5 h, the temperature is raised to 185 °C and the reaction continues for 2 h. After the reaction solution and the fabric immersed therein are introduced into deionized water and ultrasonically washed, a polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm is prepared.

[0079] Example 8

[0080] (1) Dry sodium sulfide Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0081] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and C6H5SO3Na in 100 ml of N-methylpyrrolidone (NMP) to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 2.5 mol / L, the concentration of sodium hydroxide is 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L. Immerse the PPS fabric diaphragm in the reaction solution at a temperature of 145 °C for 25 min.

[0082] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is immersed. The concentration of DCDPS is 1.5 mol / L, the temperature is 125 °C, and after reacting for 5 h, the temperature is raised to 155 °C and the reaction continues for 2 h. After the reaction solution and the fabric immersed therein are introduced into deionized water and ultrasonically washed, a polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm is prepared.

[0083] Example 9

[0084] (1) Dry sodium sulfide Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 105 °C for 6 h to obtain dehydrated sodium sulfide.

[0085] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and C7H5O2Li in 100 ml of N-methylpyrrolidone (NMP) to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 2.5 mol / L, the concentration of sodium hydroxide is  = 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L. Immerse the PPS fabric in the reaction solution at a temperature of 145 °C for 25 min.

[0086] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is immersed. The concentration of DCDPS is 1.5 mol / L, the temperature is 145 °C, and after reacting for 4 h, the temperature is raised to 185 °C and the reaction continues for 2 h. After the reaction solution and the fabric immersed therein are introduced into deionized water and ultrasonically washed, a polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm is prepared.

[0087] Example 10

[0088] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 125 °C for 2 h to obtain Na2S.

[0089] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and lithium hydroxide in 100 ml of N-methylpyrrolidone (NMP) to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 2.5 mol / L, the concentration of sodium hydroxide is 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L. Immerse the PPS fabric diaphragm in the reaction solution, with a temperature of 145 °C and a time of 25 min.

[0090] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution in which the PPS fabric diaphragm is immersed. The concentration of DCDPS is 1.5 mol / L, the temperature is 145 °C, and after reacting for 5 h, the temperature is raised to 185 °C and the reaction continues for 1 h. After the reaction solution and the fabric immersed therein are introduced into deionized water and ultrasonically washed, a polyarylene sulfone sulfone-polyphenylene sulfide fabric composite diaphragm is prepared.

[0091] Comparative Example 1

[0092] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0093] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and lithium hydroxide in 100 ml of N-methylpyrrolidone (NMP) to form a reaction solution. The concentration of sodium sulfide in the reaction solution is 1.5 mol / L, the concentration of sodium hydroxide is 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L.

[0094] (3) Add 4,4-dichlorodiphenyl sulfone (DCDPS) to the reaction solution. The concentration of DCDPS is 1.5 mol / L, the temperature is 145 °C, and after reacting for 5 h, the temperature is raised to 185 °C and the reaction continues for 2 h. Pour the reaction solution into deionized water to precipitate polyarylene sulfone sulfone solid, and after ultrasonic washing, polyarylene sulfone sulfone (PASS) is prepared.

[0095] (4) Dissolve 20 g of PASS in 100 ml of N-methylpyrrolidone, immerse the PPS fabric in it, with the temperature at 185 °C and the time for 1 h; take out the fabric and ultrasonically wash it in deionized water to obtain the separator.

[0096] Comparative Example 2

[0097] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0098] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and lithium hydroxide in 100 ml of N-methylpyrrolidone (NMP) to form a reaction solution to be reacted. The concentration of sodium sulfide in the reaction solution to be reacted is 1.5 mol / L, the concentration of sodium hydroxide is 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L.

[0099] (3) Add 4,4'-dichlorodiphenyl sulfone (DCDPS) to the reaction solution to be reacted. The concentration of DCDPS is 1.5 mol / L, the temperature is 145 °C, react for 5 h, then raise the temperature to 185 °C and continue to react for 2 h.

[0100] (4) Immerse the PPS fabric in the solution after the reaction ends, with the temperature at 145 °C and the time for 1 h; take out the fabric and ultrasonically wash it in deionized water to obtain the separator.

[0101] Comparative Example 3

[0102] (1) Dry sodium sulfide nonahydrate Na2S·9H2O under the conditions of a vacuum degree < 0.1 MPa and 115 °C for 4 h to obtain dehydrated sodium sulfide.

[0103] (2) Dissolve the dehydrated sodium sulfide, sodium hydroxide, and lithium hydroxide in 100 ml of N-methylpyrrolidone (NMP) to form a reaction solution to be reacted. The concentration of sodium sulfide in the reaction solution to be reacted is 1.5 mol / L, the concentration of sodium hydroxide is 0.1 mol / L, and the concentration of lithium hydroxide is 0.3 mol / L. Immerse the PPS fabric separator in the reaction solution to be reacted, with the temperature at 145 °C and the time for 25 min.

[0104] (3) Add 4,4'-dichlorodiphenyl sulfone (DCDPS) to the reaction solution to be reacted that is soaking the PPS fabric. The concentration of DCDPS is 1.5 mol / L, raise the temperature to 185 °C and react for 2 h; introduce the reacted solution together with the fabric soaked in it into deionized water for ultrasonic washing to obtain a polyarylene sulfone sulfone-polyphenylene sulfide fabric-type composite separator.

[0105] The hydrophilicity and basic performance of water electrolysis of the polyarylene sulfide sulfone-polyphenylene sulfide fabric composite membranes prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were tested.

[0106] 1. Hydrophilicity test method: The hydrophilicity of the membrane was determined by the contact angle measurement method, and measured using a full-automatic contact angle measuring instrument (KRUSS DSA30S, Germany).

[0107] 2. Air tightness test method: The air tightness of the membrane was measured by the bubble point method. The membrane was cut into a circle with a diameter of 2 cm, fully wetted in deionized water, and tested using a Porolux 1000 gas-liquid interface pore size tester from Prometec NV, Belgium. The pressure was set to 0-1 bar.

[0108] 3. Porosity test method: The porosity of the membrane was measured by the weighing method. A 5 cm×5 cm sample was cut from the membrane, and the dry weight was recorded. Then the sample was fully wetted in deionized water, and the mass after wetting was recorded. The calculation formula for the porosity M is as follows:

[0109]

[0110] In the above formula: M is the porosity, %; m1 is the weight of the membrane in the wet state, g; m 2 is the weight of the membrane in the dry state, g; H is the thickness of the sample, cm; A is the area of the sample, cm 2 ; ρ is the density of deionized water, g / cm 3 .

[0111] 4. Surface resistance test method: The surface resistance test was carried out using a surface resistance test platform built in the laboratory, and the test method was electrochemical impedance spectroscopy. The membrane sample was cut into a circle with a diameter of 2 cm, clamped in the middle of the mold, and 10 mL of KOH alkaline solution (30 °C, concentration 30 wt%) was injected on both sides. An impedance measurement was performed using a Donghua DH7002A electrochemical analyzer. The calculation formula is as follows:

[0112] AR = A × R d

[0113] R d = R c - R e ;

[0114] In the above formula: AR is the membrane resistance, Ω·cm 2 ; A is the effective area of the membrane, cm 2 ; Rd is the membrane resistance, Ω; Rc is the total internal resistance of the electrolytic cell, Ω; Re is the electrolyte resistance, Ω.

[0115] 5. Method for testing alkali loss: The alkali loss is tested by the weighing method. A 5 cm×5 cm sample is cut from the diaphragm, and the dry weight is recorded. The sample is soaked in 30 wt% KOH alkali solution at 80 °C for 48 h; the sample is taken out, washed, dried and weighed, and the weight of the sample after treatment is recorded. Among them, alkali loss = (mass of the sample before alkali treatment - mass of the sample after alkali treatment) / mass of the sample before alkali treatment × 100%.

[0116] The test results of airtightness, surface resistance, porosity, contact angle, and alkali loss of the polyarylene sulfone - polyphenylene sulfide fabric - type composite diaphragms prepared in Examples 1 to 10 and Comparative Examples 1 to 3, as well as the unmodified diaphragm, are shown in Table 1.

[0117] Table 1 Test Results

[0118]

[0119] It can be seen from the data results in the above table that first preparing PASS solid, then preparing PASS solution, soaking PPS fabric in PASS solution, coating PASS on the surface of PPS fabric (Comparative Example 1), putting PPS fabric immediately after the synthesis reaction of PASS ends (Comparative Example 2), and one - step temperature rise (Comparative Example 3) will lead to a decrease in the amount of PASS grown on the surface of PPS, and further lead to a decrease in airtightness, an increase in surface resistance, an increase in porosity, a decrease in hydrophilic performance, and an increase in alkali loss.

[0120] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a polyarylene sulfide sulfone-polyphenylene sulfide fabric composite separator, characterized in that: It includes the following steps: S1: Dissolve dehydrated sodium sulfide, NaOH, and a catalyst in an organic solvent to obtain a reaction solution to be reacted; S2: Immerse polyphenylene sulfide fabric in the reaction solution to be reacted; S3: Add 4,4'-dichlorodiphenyl sulfone to the reaction solution to be reacted in which the polyphenylene sulfide fabric is immersed and conduct a two-stage temperature-raising reaction; S4: Pour the solution after the reaction in step S3 together with the polyphenylene sulfide fabric immersed therein into deionized water for ultrasonic washing to obtain a polyarylene sulfone-polyphenylene sulfide fabric type composite separator.

2. The preparation method according to claim 1, characterized in that: The temperature of the reaction solution to be reacted in step S2 is 125°C to 180°C, and the immersion time is 25 min to 60 min.

3. The preparation method according to claim 1, characterized in that: The two-stage temperature-raising reaction in step S3 includes that the temperature of the first-stage temperature-raising reaction is 125°C to 145°C, and the reaction time is 4 h to 6 h; the temperature of the second-stage temperature-raising reaction is 155°C to 185°C, and the reaction time is 1 to 3 h.

4. The preparation method according to claim 1, characterized in that: The organic solvent in step S1 is any one or a mixture of two or more of N-methylpyrrolidone, dimethyl sulfoxide, hexamethylphosphoric triamide, N,N'-dimethylacetamide, and N,N'-dimethylformamide; and / or The catalyst in step S1 is any one or a mixture of two or more of LiOH, Na5PO4, C7H5O2Na, Na2CO3, NaNO3, ZnCl2, NaOAc, C6H5SO3Na, and C7H5O2Li.

5. The preparation method according to claim 1, characterized in that: The concentration of Na2S in step S1 is 0.75 mol / L to 3 mol / L; the concentration of NaOH is 0.05 mol / L to 0.2 mol / L; the concentration of the catalyst is 0.15 mol / L to 0.6 mol / L.

6. The preparation method according to claim 1, characterized in that: The concentration of 4,4'-dichlorodiphenyl sulfone in step S3 is 0.75 mol / L to 3 mol / L.

7. The preparation method according to claim 1, wherein: The dehydrated sodium sulfide in step S1 is obtained by drying and dehydrating Na2S·9H2O, and the drying and dehydrating parameters are: the vacuum degree < 0.1 MPa, carried out at a temperature of 105°C to 125°C for 2 to 6 h.

8. The preparation method according to claim 1, characterized in that: The grammage of the polyphenylene sulfide fabric diaphragm is 350 g / m 2 ~500 g / m 2 .

9. A polyarylene sulfone-polyphenylene sulfide fabric type composite separator prepared by the preparation method according to any one of claims 1-8.

10. Application of the polyarylene sulfone-polyphenylene sulfide fabric type composite separator according to claim 9 in hydrogen production by electrolyzing water.

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