Zirconium aromatic acid-zirconium phosphate / polyarylene sulfide hydrophilic compound and preparation method thereof

Abstract

The invention belongs to the technical field of polymer synthesis, and particularly relates to an aromatic acid zirconium-zirconium phosphate / polyarylene sulfide hydrophilic compound and a preparation method thereof. The invention provides a preparation method of an aromatic acid zirconium-zirconium phosphate / polyarylene sulfide hydrophilic compound, which comprises the following steps: preparing an aromatic acid zirconium compound from a polyfunctional group active aromatic acid compound and a soluble zirconium salt through a chemical synthesis method, and synthesizing zirconium phosphate; then, active polyarylene sulfide is prepared from the sulfide and a polymeric monomer through a polymerization reaction; finally, the aromatic acid zirconium compound, zirconium phosphate and active polyarylene sulfide are subjected to in-situ compounding or blending extrusion, and the aromatic acid zirconium-zirconium phosphate / polyarylene sulfide hydrophilic compound is obtained. A polar hydrophilic group is added to a side chain of a polyphenylene sulfide molecule and fused with a high-polarity hydrophilic zirconium compound with multiple molecular structures, so that the high-polarity hydrophilic polyarylene sulfide material with high strength and high stability is formed.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis technology, specifically relating to an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex and its preparation method. Background Technology

[0002] Polyaryl sulfide (PPS) possesses excellent properties such as high temperature resistance, chemical corrosion resistance, electrical properties, radiation resistance, flame retardancy, high mechanical strength, and dimensional stability. It is widely used in coatings, plastics, structural materials, adhesives, fibers, and films in the automotive, aerospace, petrochemical, light industrial machinery, electronics, food, and engineering technology industries. Global production of PPS has exceeded 300,000 tons. The structure of PPS is... The absence of other functional groups on the benzene ring contributes to its excellent properties, including high rigidity, high strength, corrosion resistance, and high temperature resistance. However, this structure also results in very weak polarity and poor hydrophilicity. Long-term use and testing show that polyphenylene sulfide (PPS) has a hydrophilic angle around 100° and high hydrophobicity, meaning it cannot be wetted by water. This limits its use in polar environments. For example, as a membrane in alkaline water electrolysis for hydrogen production, it needs high hydrophilicity to allow hydrogen ions to pass through smoothly, while also exhibiting low resistance. Pure PPS is insufficient for this application. To meet these requirements, zirconium oxide or similar coatings are applied to the PPS surface to increase its polarity. However, the adhesion between the coating and the PPS matrix is ​​weak, and it may detach under stress, potentially peeling off over time. Similarly, fuel cell membranes require ion and proton exchange to provide good ion passage for the electrolyte while maintaining low resistivity. Pure PPS also struggles to meet these requirements.

[0003] To date, commercially available lithium-ion battery separator materials still primarily utilize polyethylene and polypropylene microporous membranes. Although recent research has explored the use of other materials to prepare lithium-ion battery separators, such as using polyvinylidene fluoride (PVDF) as the bulk polymer via phase inversion and investigating cellulose composite membranes as lithium-ion battery separator materials, the performance of the separator directly impacts the battery's internal resistance, discharge capacity, cycle life, and safety. Therefore, lithium-ion battery manufacturing demands extremely high consistency in separator materials, requiring not only specific thickness, surface density, and mechanical properties, but also high uniformity in the size and distribution of micropores. Proton exchange membranes remain predominantly perfluorosulfonic acid (PFSA) membranes. PFSA PSA is a solid polymer electrolyte with advantages such as good chemical and thermal stability, voltage reduction, high conductivity, and high mechanical strength, allowing it to be used under harsh conditions including strong acids, strong alkalis, strong oxidants, and high temperatures. Due to its inherent properties, perfluorosulfonic acid proton exchange membranes (PTMs) are not only used as a key component of proton exchange membrane fuel cells (PEMFCs), but also widely applied in chlor-alkali industries, water electrolysis for hydrogen production, electrochemical synthesis, and gas sensors. However, PFM membrane materials have high requirements for temperature and water content (proton conductivity deteriorates significantly at medium to high temperatures). When used in direct methanol fuel cells, the high methanol permeability makes the manufacturing process difficult. As a core technology material in the current hydrogen energy industry, the manufacturing process of PFMs is complex and has long been monopolized by international giants such as DuPont, Gore, and Asahi Glass. As of 2022, China's dependence on foreign imports for PFMs reached as high as 99%. DuPont was the first company in the world to develop and sell PFMs, having developed high-performance perfluorosulfonic acid PFMs, namely the Nafion series, as early as 1962. To date, Nafion membranes are the most widely used in the world. Summary of the Invention

[0004] To address the aforementioned deficiencies, this invention provides an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic composite and its preparation method. By adding polar hydrophilic groups to the side chains of polyphenylene sulfide molecules and fusing highly polar hydrophilic zirconium compounds with various molecular structures, a high-strength, highly stable, highly polar hydrophilic polyarylene sulfide material is formed. A highly hydrophilic film is then prepared by casting and hot-press etching.

[0005] The technical solution of this invention:

[0006] The first technical problem to be solved by the present invention is to provide a method for preparing an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex. The preparation method is as follows: aromatic zirconium acid compounds are prepared by chemical synthesis using multifunctional active aromatic acid compounds and soluble zirconium salts, and zirconium phosphate is synthesized; then, active polyarylene sulfides are prepared by polymerization reaction using sulfides and polymeric monomers; finally, the aromatic zirconium acid compounds and zirconium phosphate are compounded or co-extruded with the active polyarylene sulfides in situ to obtain the aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex.

[0007] The multifunctional active aromatic acid compound is a benzenepolycarboxylic acid containing at least three polar functional groups or a salicylic acid containing at least three polar functional groups; the polymerization monomer is a p-dihalobenzene and a monomer containing a polar hydrophilic side group, wherein the monomer containing a polar hydrophilic side group is a carboxylbenzene compound, a sulfonic acid benzene compound, or a hydroxybenzene compound.

[0008] Furthermore, the phenylpolycarboxylic acid containing at least three polar functional groups is 1,2,4-phenyltricarboxylic acid, 1,2,3-phenyltricarboxylic acid, 1,3,5-phenyltricarboxylic acid, 2-hydroxyterephthalic acid, 4-hydroxyphthalic acid, 3-hydroxyphthalic anhydride, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2,5-dihydroxyterephthalic acid, 2-aminoterephthalic acid, 4-aminophthalic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 4-aminoisophthalic acid, pyromellitic dianhydride, 4-hydroxy-1,8-naphthalic anhydride, 3-hydroxy-1,8-naphthalic anhydride, 3-amino-4-hydroxy-1,8-naphthalic anhydride, or 4-amino-3-sulfo-1,8-naphthalic anhydride.

[0009] Furthermore, the salicylic acid containing at least three polar functional groups is 5-aminosalicylic acid, 4-aminosalicylic acid, 3-aminosalicylic acid, 3,5-diaminosalicylic acid, 3,6-diaminosalicylic acid, 2,5-diaminoterephthalic acid, p-hydroxysalicylic acid, m-hydroxysalicylic acid, o-hydroxysalicylic acid, or 5-sulfosalicylic acid.

[0010] Preferably, the multifunctional active aromatic acid compound is 1,2,4-benzenetricarboxylic acid, pyromellitic dianhydride, or 4-hydroxyphthalic acid.

[0011] Furthermore, the soluble zirconium salt is zirconium acetate, zirconium nitrate, or zirconium oxychloride.

[0012] Furthermore, the sulfide is sodium sulfide, sodium hydrosulfide, or hydrogen sulfide.

[0013] Furthermore, the monomer containing polar hydrophilic side groups is , or X is F, Cl, B or I, and R is H, hydroxyl, carboxyl or sulfonic acid group.

[0014] Furthermore, the monomer containing polar hydrophilic side groups is , , , , , , , or X is F, Cl, B or I.

[0015] Furthermore, the monomer containing the polar hydrophilic side group is 2,5-dichlorohydroquinone or 2,5-dichloroterephthalic acid.

[0016] Furthermore, the p-dihalobenzene is p-dichlorobenzene.

[0017] Furthermore, the aromatic zirconium acid compound is: a benzopolyacid containing an active functional group. Salicylic acid containing active functional groups Zirconium polybenzoate chain compounds Or polyzirconium salicylate chain compounds Where Z is NH2, OH, COOH or SHO3, and n is the total number of moles of aromatic zirconium acid compounds and zirconium phosphate involved in the reaction.

[0018] Furthermore, the polyphenol containing the active functional group is... or The salicylic acid containing the active functional group is... or .

[0019] Furthermore, the active polyarylene sulfide is an active carboxyl polyarylene sulfide, an active sulfonic acid polyarylene sulfide, or an active hydroxy polyarylene sulfide.

[0020] Furthermore, during the preparation of the complex, the active polyarylene sulfide and the aromatic zirconium acid compound have a corresponding relationship: when the free active functional group of the aromatic zirconium acid compound is hydroxyl or amino, the polar group of the active polyarylene sulfide is carboxyl; when the free active functional group of the aromatic zirconium acid compound is carboxyl or sulfonic acid, the polar group of the active polyarylene sulfide is hydroxyl; when the aromatic zirconium acid compound is a poly(zirconium benzoate) chain compound or a poly(zirconium salicylate) chain compound, the polar group of the active polyarylene sulfide is carboxyl or hydroxyl.

[0021] Furthermore, a method for preparing an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex, the preparation method comprising the following steps:

[0022] S1. Dissolve soluble zirconium salt in deionized water, then add it to a deionized aqueous solution of a multifunctional active aromatic acid compound and guanidine carbonate, stir to dissolve, filter, wash, add water and stir evenly, then transfer to an autoclave and perform hydrothermal pressure treatment to obtain aromatic zirconium compounds.

[0023] S2. Dissolve the soluble organic zirconium salt in deionized water, then add it to a deionized aqueous solution of phosphoric acid and guanidine carbonate, stir to dissolve, filter, wash, add water, stir evenly, transfer to an autoclave, and perform hydrothermal pressure treatment to obtain zirconium phosphate.

[0024] S3. Place the sulfide in a polar aprotic solvent, dehydrate and cool it down, then add p-dihalobenzene and monomers containing polar hydrophilic side groups, polymerize, cool and filter, wash and dry to obtain active polyarylene sulfide.

[0025] S4. Add the aromatic zirconium acid compound and zirconium phosphate to a polar aprotic solvent for dehydration, then add them to an active polyarylene sulfide for in-situ composite formation. After cooling, filter, wash, and dry to obtain an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex.

[0026] Alternatively, aromatic zirconium compounds and zirconium phosphate are dried, then a coupling agent is added, followed by co-extrusion with active polyarylene sulfide, followed by cooling and drying to obtain an aromatic zirconium-zirconium phosphate / polyarylene sulfide hydrophilic complex.

[0027] Furthermore, in step S1, the molar ratio of the multifunctional active aromatic acid compound to the soluble zirconium salt is 0.9-2.1:1, and the molar ratio of guanidine carbonate to the soluble zirconium salt is 2.1-2.5:1.

[0028] Furthermore, when the synthesized aromatic zirconium acid compound is a benzoic acid containing an active functional group or a salicylic acid containing an active functional group, the molar ratio of the multifunctional active aromatic acid compound to the soluble zirconium salt is 1.9-2.1:1; when the synthesized aromatic zirconium acid compound is a poly(zirconium polybenzoate) chain compound or a poly(zirconium polysalicylate) chain compound, the molar ratio of the multifunctional active aromatic acid compound to the soluble zirconium salt is 0.9-1.1:1.

[0029] Furthermore, in step S1, during the hydrothermal pressurization treatment, nitrogen is used to replace the air, and the water is hydrothermally treated at 0.4-0.5 MPa and 120-150 ℃ for 3-8 h, and then cooled to room temperature.

[0030] Furthermore, in step S2, the soluble organic zirconium salt is zirconium acetate.

[0031] Furthermore, in step S2, the molar ratio of phosphoric acid to soluble organic zirconium salt is 0.9-1.1:1.

[0032] Furthermore, in step S2, the molar ratio of guanidine carbonate to soluble organic zirconium salt is 0.9-1.1:1.

[0033] Furthermore, in step S2, during the hydrothermal pressurization treatment, nitrogen is used to replace the air, and the water is hydrothermally treated at 0.4-0.5 MPa and 120-150 ℃ for 3-8 h, and then cooled to room temperature.

[0034] Furthermore, in step S3, the sulfide is sodium sulfide, sodium hydrosulfide, or hydrogen sulfide.

[0035] Furthermore, in step S3, the sulfide contains less than 15 ppm of iron and less than 20 ppm of heavy metal ions.

[0036] Further, in step S3, the polar aprotic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone (MI) lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.

[0037] Furthermore, in step S3, the molar ratio of the p-dihalobenzene and the monomer containing the polar hydrophilic side group is 80-97.5:20-2.5.

[0038] Furthermore, in step S3, the total molar ratio of p-dihalobenzene and monomers containing polar hydrophilic side groups to the molar ratio of sulfides is 0.95-1.05:1.

[0039] Furthermore, in step S3, the total molar amount of the dihalobenzene and the monomer containing the polar hydrophilic side group is: the volume of the polar aprotic solvent = 1 mol : 0.3-1 L.

[0040] Furthermore, in step S3, the polymerization reaction is carried out at 180-280 °C for 3-16 h, and after the polymerization is stopped, the temperature is cooled to below 150 °C.

[0041] Furthermore, in step S4, during in-situ recombination, the mass ratio of the aromatic zirconium acid compound to zirconium phosphate is 10-20:10-20.

[0042] Furthermore, in step S4, the total mass of the aromatic zirconium acid compound and zirconium phosphate is equal to the volume of the polar aprotic solvent, which is 100 g to 500-1000 mL.

[0043] Furthermore, in step S4, the total mass of the aromatic zirconium acid compound and zirconium phosphate is equal to the molar mass of the active polyarylene sulfide in the ratio of 5-30 g to 1 mol.

[0044] Further, in step S4, the polar aprotic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone (MI) lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.

[0045] Furthermore, in step S4, during the blending extrusion, the extrusion temperature is 280-356 ℃, the screw speed is 100-300 rpm, and the plasticizing time is 1-5 min.

[0046] Furthermore, in step S4, the mass ratio of the aromatic zirconium acid compound to zirconium phosphate is 10-20:10-20.

[0047] Furthermore, in step S4, the total mass of the aromatic zirconium acid compound and zirconium phosphate is 5-30:70-95 for the mass of the active polyarylene sulfide.

[0048] Furthermore, in step S4, the amount of coupling agent used is 1-6 wt% of the total mass of the aromatic zirconium acid compound and zirconium phosphate.

[0049] Furthermore, in step S4, the coupling agent is KH550, KH560, or KH570.

[0050] The second technical problem to be solved by the present invention is to provide an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex, which is prepared by the above-mentioned preparation method of the aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex.

[0051] Further, the aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic composite obtained by blending and extrusion is cut into granules with a diameter of 2-3 mm and a length of 3-5 mm, and vacuum dried for 6-12 h to obtain masterbatch; then the masterbatch is melt-spun at 280-330 ℃ with a spinning diameter of 5-20 μm, and the continuous fibers obtained by spinning are wound to form a uniform network structure, and sprayed with bis(amino) silicone oil for shaping to obtain polyphenylene sulfide composite nonwoven fabric with a thickness of 100-500 μm.

[0052] The present invention has the following beneficial effects:

[0053] The aromatic zirconium-zirconium phosphate / polyarylene sulfide hydrophilic composite of the present invention is prepared by in-situ compounding or co-extrusion of aromatic zirconium compounds and zirconium phosphate with active polyarylene sulfide. By adding polar hydrophilic groups to the side chains of polyphenylene sulfide molecules and fusing highly polar hydrophilic zirconium compounds with various molecular structures, a high-strength, high-stability highly polar hydrophilic polyarylene sulfide material is formed and used to prepare highly hydrophilic films. Detailed Implementation

[0054] This invention provides a method for preparing an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex, the preparation method comprising the following steps:

[0055] S1. Dissolve soluble zirconium salt in deionized water, then add it to a deionized aqueous solution of a multifunctional active aromatic acid compound and guanidine carbonate, stir to dissolve, filter, wash, add water and stir evenly, then transfer to an autoclave and perform hydrothermal pressure treatment to obtain aromatic zirconium compounds.

[0056] S2. Dissolve the soluble organic zirconium salt in deionized water, then add it to a deionized aqueous solution of phosphoric acid and guanidine carbonate, stir to dissolve, filter, wash, add water, stir evenly, transfer to an autoclave, and perform hydrothermal pressure treatment to obtain zirconium phosphate.

[0057] S3. Place the sulfide in a polar aprotic solvent, dehydrate and cool it down, then add p-dihalobenzene and monomers containing polar hydrophilic side groups, polymerize, cool and filter, wash and dry to obtain active polyarylene sulfide.

[0058] S4. Add the aromatic zirconium acid compound and zirconium phosphate to a polar aprotic solvent for dehydration, then add them to an active polyarylene sulfide for in-situ composite formation. After cooling, filter, wash, and dry to obtain an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex.

[0059] Alternatively, aromatic zirconium compounds and zirconium phosphate are dried, then a coupling agent is added, followed by co-extrusion with active polyarylene sulfide, followed by cooling and drying to obtain an aromatic zirconium-zirconium phosphate / polyarylene sulfide hydrophilic complex.

[0060] The multifunctional active aromatic acid compound is a benzenepolycarboxylic acid containing at least three polar functional groups or a salicylic acid containing at least three polar functional groups; the polymerization monomer is a p-dihalobenzene and a monomer containing a polar hydrophilic side group, wherein the monomer containing a polar hydrophilic side group is a carboxylbenzene compound, a sulfonic acid benzene compound, or a hydroxybenzene compound.

[0061] Specifically, the benzene-polycarboxylic acid containing at least three polar functional groups is 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2-hydroxyterephthalic acid, 4-hydroxyphthalic acid, 3-hydroxyphthalic anhydride, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2,5-dihydroxyterephthalic acid, 2-aminoterephthalic acid, 4-aminophthalic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 4-aminoisophthalic acid, and pyromellitic dianhydride. 4-hydroxy-1,8-naphthalenedicarboxylic anhydride, 3-hydroxy-1,8-naphthalenedicarboxylic anhydride, 3-amino-4-hydroxy-1,8-naphthalenedicarboxylic anhydride, or 4-amino-3-sulfo-1,8-naphthalenedicarboxylic anhydride; the salicylic acid containing at least three polar functional groups is 5-aminosalicylic acid, 4-aminosalicylic acid, 3-aminosalicylic acid, 3,5-diaminosalicylic acid, 3,6-diaminosalicylic acid, 2,5-diaminoterephthalic acid, p-hydroxysalicylic acid, m-hydroxysalicylic acid, o-hydroxysalicylic acid, or 5-sulfosalicylic acid;

[0062] Preferably, the multifunctional active aromatic acid compound is 1,2,4-benzenetricarboxylic acid, pyromellitic dianhydride, or 4-hydroxyphthalic acid.

[0063] Furthermore, zirconium phosphate is a novel multifunctional mesoporous material and one of the layered solid acid materials. Zirconium phosphate exists in two structural types, α and γ, is a white powder, insoluble in water and organic solvents, and is resistant to strong acids and certain alkalis. It also possesses a large specific surface area and surface charge, making it a relatively strong solid acid with excellent ion exchange properties. Zirconium phosphate shares the common characteristics of layered compounds, exhibiting high chemical stability. It possesses both ion exchange properties similar to ion exchange resins and shape-selective adsorption and catalytic properties similar to zeolites, while also exhibiting high thermal stability and resistance to acids and alkalis.

[0064] Meanwhile, the soluble zirconium salt is zirconium acetate, zirconium nitrate, or zirconium oxychloride. The sulfide is sodium sulfide, sodium hydrosulfide, or hydrogen sulfide.

[0065] Furthermore, the polymerization monomers used in preparing the active polyaryl sulfide are p-dihalobenzene and monomers containing polar hydrophilic side groups; preferably, p-dihalobenzene is p-dichlorobenzene; and the monomers containing polar hydrophilic side groups are 2,5-dichlorohydroquinone or 2,5-dichloroterephthalic acid.

[0066] In various embodiments of the present invention, the synthetic route for active carboxyl polyarylene sulfides is as follows: .

[0067] Furthermore, the synthetic route for active sulfonic acid-based polyarylene sulfides is as follows: .

[0068] Furthermore, the synthetic route for active hydroxyl polyarylene sulfides is as follows: .

[0069] Meanwhile, during the preparation of the complex, the active polyarylene sulfide and the aromatic zirconium acid compound have a corresponding relationship: when the free active functional group of the aromatic zirconium acid compound is hydroxyl or amino, the polar group of the active polyarylene sulfide is carboxyl; when the free active functional group of the aromatic zirconium acid compound is carboxyl or sulfonic acid, the polar group of the active polyarylene sulfide is hydroxyl; when the aromatic zirconium acid compound is a poly(zirconium polybenzoate) chain compound or a poly(zirconium polysalicylate) chain compound, the active polyarylene sulfide is compatible with it when the polar group is carboxyl or hydroxyl.

[0070] The present invention will be further illustrated below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field.

[0071] Example 1:

[0072] A hydrophilic complex of aromatic zirconium acid-zirconium phosphate / polyarylene sulfide is prepared by the following steps:

[0073] S1, 2.1 kg of 1,2,4-benzenetricarboxylic acid ( ) and 1.2 kg of guanidine carbonate were added to 10 L of 55 °C deionized water to obtain a mixed solution, and then 1.6 kg of zirconium oxychloride (Cl2H) was added. 16 O9Zr (octahydrate) was dissolved in 5 L of deionized water and added to the mixed solution. The mixture was stirred for 0.5 h, filtered, and the precipitate was washed 5 times with deionized water. Water was added and stirred evenly. The mixture was transferred to a 50 L autoclave, and the air was replaced with nitrogen. The autoclave was then hydrothermally treated in water at 0.4-0.5 MPa and 130 °C for 6 h. After cooling to room temperature, the mixture was filtered to obtain aromatic zirconium acid compounds (zirconium carboxybenzoate).

[0074] S2. Add 1.15 kg of phosphoric acid (H3PO4, 85%) and 1.2 kg of guanidine carbonate to 10 L of deionized water at 55 °C, then add 3.27 kg of zirconium acetate (C8H4PO4). 12 Zirconium phosphate (Zr) was dissolved in 5 L of deionized water and added to a phosphoric acid solution. The mixture was stirred for 0.5 h, filtered, and the precipitate was washed 5 times with deionized water. Water was added and stirred until homogeneous. The mixture was then transferred to a 50 L autoclave, and the air was replaced with nitrogen. The autoclave was then hydrothermally treated in water at 0.4-0.5 MPa and 130 °C for 6 h. The mixture was cooled to room temperature and filtered to obtain zirconium phosphate.

[0075] S3. In a 100 L reactor equipped with an anchor frame and screw ribbon, add 50 L of N-pyrrolidone and 13 kg of sodium sulfide. Under nitrogen protection and stirring, gradually increase the temperature at a stirring speed of 80 rpm, gradually raising the temperature to 150 °C to begin dehydration, and then raising the temperature to 196 °C to complete dehydration; then cool down to 130 °C, and add 13.96 kg of p-dichlorobenzene and 0.9 kg of 2,5-dichlorohydroquinone (DHC). Under nitrogen protection and stirring, the mixture was stirred at 100 rpm and heated to 220 °C for 3 h, with the polymerization temperature controlled at 220-235 °C. The temperature was then increased to 250 °C and reacted for another 3 h, with the polymerization temperature controlled at 245-255 °C. The stirring speed was 85 rpm. 30 L of solvent was flash-evaporated, cooled to 120 °C, and 40 L of deionized water was added. The mixture was washed 6 times with deionized water at 80 °C and dried in an oven at 100 °C for 10 h to obtain active polyarylene sulfide (active hydroxyl polyarylene sulfide).

[0076] S4. Co-extrusion: 0.6 kg of aromatic zirconium acid compound (zirconium carboxybenzoate) and 0.4 kg of zirconium phosphate are vacuum dried at 100℃, then 100 g of silane coupling agent KH650 is added, followed by 9 kg of active polyarylene sulfide, and mixed using a high-speed mixer; extruded through an extruder at 280-356℃ with a screw speed between 200 rpm, plasticizing time maintained at 4 min, cooled with high-purity deionized water, and cut into granules with a diameter of 2-3 mm and a length of 3-5 mm, and then dried in a vacuum drying oven for 6-12 min to obtain an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic composite, which is used as masterbatch for injection molding of various products and test strips;

[0077] Preparation of zirconium compound / active hydroxyl polyarylene sulfide: The masterbatch is melt-spun at 280-330 ℃ with a spinning diameter of 10-20 μm. The resulting continuous fibers are then wound to form a uniform mesh structure and sprayed with bis(amino) silicone oil for shaping, resulting in a polyphenylene sulfide composite nonwoven fabric with a thickness of 100-500 μm.

[0078] Performance testing:

[0079] The hydrophilicity angle of the products obtained in Examples 1-10 and Comparative Examples 1-5 was tested using nonwoven fabric according to the national standard injection molding test strips.

[0080] The test items and standards are as follows: (1) Density (g / cm³) 3(1) Test method: GB / T 1033; (2) Tensile strength (MPa), test method GB / T 1040; (3) Elongation at break (%), test method GB / T 1040; (4) Flexural strength (MPa), test method GB / T 9341; (5) Flexural modulus (GPa), test method GB / T 9341; (6) Melting point (°C), test method GB / T4608; (7) Hydrophilic angle: GB / T30693-2014, pore size (SEM), porosity (SEM).

[0081] The testing method is as follows:

[0082] Melt flow index test: 315℃, 5kg load, mass of grams flowing out in 10 minutes; g / 10min.

[0083] Porosity: Electron microscopy: By observing the internal structure of the material under test with an electron microscope, the porosity of the material can be directly measured.

[0084] Thin film / sheet thickness: Electronic calipers (electronic thickness gauge): direct testing.

[0085] Polarity - Water Contact Angle:

[0086] Samples were fabricated into 2 cm × 2 cm films for water contact angle testing. Test conditions included room temperature, a seated drop method with a droplet volume of 2 µL, and six parallel measurements for each film sample. Statistical analysis was performed using OriginPro 2022b. All data are expressed as mean ± standard deviation. Normality was tested using the Kolmogorov-Smirnov method, homogeneity of variance was tested using the Levene method, and mean comparisons were performed using the Scheffe test in One Way ANOVA.

[0087] The test results are as follows:

[0088] (1) Melt index (g / 10min): Hydroxy polyarylene sulfide: 210; Aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex (also written as zirconium compound / hydroxy polyarylene sulfide): 170. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 120. (4) Elongation at break (%): 12. (5) Flexural strength (MPa): 151. (6) Flexural modulus (GPa): 6.5. (7) Melting point (°C): Zirconium compound / hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 43. (9) Pore size (μm): 5-11, Porosity (%): 52.

[0089] Example 2:

[0090] The preparation method of Example 2 is the same as that of Example 1, except that: an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex is prepared by in-situ composite, and the preparation method includes the following steps:

[0091] S1, 2.1 kg of 1,2,4-benzenetricarboxylic acid ( ) and 1.2 kg of guanidine carbonate were added to 10 L of 55 °C deionized water to obtain a mixed solution, and then 1.6 kg of zirconium oxychloride (Cl2H) was added. 16 O9Zr (octahydrate) was dissolved in 5 L of deionized water and added to the mixed solution. The mixture was stirred for 0.5 h, filtered, and the precipitate was washed 5 times with deionized water. Water was added and stirred evenly. The mixture was transferred to a 50 L autoclave, and the air was replaced with nitrogen. The autoclave was then hydrothermally treated in water at 0.4-0.5 MPa and 130 °C for 6 h. After cooling to room temperature, the mixture was filtered to obtain aromatic zirconium acid compounds (zirconium carboxybenzoate).

[0092] S2. Add 1.15 kg of phosphoric acid (H3PO4, 85%) and 1.2 kg of guanidine carbonate to 10 L of deionized water at 55 °C, then add 3.27 kg of zirconium acetate (C8H4PO4). 12 Zirconium phosphate (Zr) was dissolved in 5 L of deionized water and added to a phosphoric acid solution. The mixture was stirred for 0.5 h, filtered, and the precipitate was washed 5 times with deionized water. Water was added and stirred until homogeneous. The mixture was then transferred to a 50 L autoclave, and the air was replaced with nitrogen. The autoclave was then hydrothermally treated in water at 0.4-0.5 MPa and 130 °C for 6 h. The mixture was cooled to room temperature and filtered to obtain zirconium phosphate.

[0093] S3. In a 100 L reactor equipped with an anchor frame and ribbon, add 50 L of N-pyrrolidone and 13 kg of sodium sulfide. Under nitrogen protection and stirring, gradually increase the temperature at a stirring speed of 80 rpm, gradually raising the temperature to 150 °C to begin dehydration, and then raising the temperature to 196 °C to complete dehydration; then cool down to 130 °C, and add 13.96 kg of p-dichlorobenzene and 0.90 kg of 2,5-dichlorohydroquinone (DHC). Under nitrogen protection and stirring, the mixture was stirred at 100 rpm and heated to 220 °C for 3 h, with the polymerization temperature controlled at 220-235 °C. The temperature was then increased to 250 °C and reacted for another 3 h, with the polymerization temperature controlled at 245-255 °C. The stirring speed was 85 rpm. 30 L of solvent was flash-evaporated, cooled to 120 °C, and 40 L of deionized water was added. The mixture was washed 6 times with deionized water at 80 °C and dried in an oven at 100 °C for 10 h to obtain active polyarylene sulfide (active hydroxyl polyarylene sulfide).

[0094] S4. In-situ composite: 2 kg of aromatic zirconium acid compound (zirconium carboxybenzoate, undried, 50% water content) and 1 kg of zirconium phosphate (undried, 60% water content) were added to 10 L of NMP. The mixture was heated to 195 °C under nitrogen protection to dehydrate, and then added to active polyarylene sulfide. The mixture was reacted at 220-225 °C for 2.5 h under nitrogen protection, then heated to 250-270 °C for 3 h. After cooling to below 150 °C, the mixture was filtered, deionized water was added and the pH was adjusted to 4.5-6.5. The mixture was washed with hot deionized water until the pH was around 7 and the conductivity of the wash water was less than 5 S / m. The mixture was then vacuum dried to obtain an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic composite.

[0095] The product was tested using the test method described in Example 1, and the test results are as follows:

[0096] (1) Melt index (g / 10min): Zirconium compound / hydroxyl polyarylene sulfide: 150. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 125. (4) Elongation at break (%): 15. (5) Flexural strength (MPa): 155. (6) Flexural modulus (GPa): 7.0. (7) Melting point (°C): Zirconium compound / hydroxy polyarylene sulfide: 285. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 41. (9) Pore size (μm): 5-11, Porosity (%): 53.

[0097] Example 3:

[0098] The preparation method of Example 3 is the same as that of Example 1, except that in step S1, 1.1 kg of pyromellitic dianhydride ( It can replace 1,2,4-benzenetricarboxylic acid.

[0099] The product was tested using the test method described in Example 1, and the test results are as follows:

[0100] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 210; Zirconium compound / hydroxyaryl sulfide: 160. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 119. (4) Elongation at break (%): 11. (5) Flexural strength (MPa): 153. (6) Flexural modulus (GPa): 6.8. (7) Melting point (°C): Hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 45. (9) Pore size (μm): 5-15, Porosity (%): 52.

[0101] Example 4:

[0102] The preparation method of Example 4 is the same as that of Example 1, except that: in step S1, 1.8 kg of 4-hydroxyphthalic acid is used instead of 1,2,4-benzenetricarboxylic acid; in step S3, 1.2 kg of 2,5-dichlorobenzoic acid is used instead of 2,5-dichlorophenol.

[0103] The product was tested using the test method described in Example 1, and the test results are as follows:

[0104] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 180; Zirconium compound / hydroxyaryl sulfide: 150. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 122. (4) Elongation at break (%): 11. (5) Flexural strength (MPa): 155. (6) Flexural modulus (GPa): 6.9. (7) Melting point (°C): Hydroxy polyarylene sulfide: 285. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 41. (9) Pore size (μm): 5-15, Porosity (%): 56.

[0105] Example 5:

[0106] The preparation method of Example 5 is the same as that of Example 1, except that in step S3, 13.6 kg of p-dichlorobenzene and 1.3 kg of 2,5-dichlorohydroquinone are added to prepare active polyarylene sulfide (active hydroxyl polyarylene sulfide), and its hydroxyl content is different from that of Example 1.

[0107] The product was tested using the test method described in Example 1, and the test results are as follows:

[0108] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 220; Zirconium compound / hydroxyaryl sulfide: 160. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 112. (4) Elongation at break (%): 12. (5) Flexural strength (MPa): 149. (6) Flexural modulus (GPa): 6.8. (7) Melting point (°C): Hydroxy polyarylene sulfide: 285. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 41. (9) Pore size (μm): 3-15, Porosity (%): 50.

[0109] Example 6:

[0110] The preparation method of Example 6 is the same as that of Example 1, except that in step S4, 0.6 kg of aromatic zirconium acid compound (zirconium carboxybenzoate) and 0.4 kg of zirconium phosphate are replaced with 0.5 kg of aromatic zirconium acid compound (zirconium carboxybenzoate) and 0.5 kg of zirconium phosphate, that is, the mass ratio of aromatic zirconium acid compound to zirconium phosphate is 5:5.

[0111] The product was tested using the test method described in Example 1, and the test results are as follows:

[0112] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 210; Zirconium compound / hydroxyaryl sulfide: 149. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 119. (4) Elongation at break (%): 12. (5) Flexural strength (MPa): 150. (6) Flexural modulus (GPa): 7.0. (7) Melting point (°C): Hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 40. (9) Pore size (μm): 3-12, Porosity (%): 51.

[0113] Example 7:

[0114] The preparation method of Example 7 is the same as that of Example 1, except that in step S4, 0.6 kg of aromatic zirconium acid compound (zirconium carboxybenzoate) and 0.4 kg of zirconium phosphate are replaced with 0.4 kg of aromatic zirconium acid compound (zirconium carboxybenzoate) and 0.6 kg of zirconium phosphate, that is, the mass ratio of aromatic zirconium acid compound to zirconium phosphate is 4:6.

[0115] The product was tested using the test method described in Example 1, and the test results are as follows:

[0116] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 210; Zirconium compound / hydroxyaryl sulfide: 155. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 110. (4) Elongation at break (%): 10. (5) Flexural strength (MPa): 145. (6) Flexural modulus (GPa): 7.0. (7) Melting point (°C): Hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 43. (9) Pore size (μm): 3-15, Porosity (%): 49.

[0117] Example 8:

[0118] The preparation method of Example 8 is the same as that of Example 1, except that in step S4, the total mass of aromatic zirconium acid compound and zirconium phosphate (0.6 kg + 0.4 kg): active polyarylene sulfide (0.9 kg) = 1:9 is replaced by the total mass of aromatic zirconium acid compound and zirconium phosphate (0.9 kg + 0.6 kg): active polyarylene sulfide (8.5 kg) = 15:85.

[0119] The product was tested using the test method described in Example 1, and the test results are as follows:

[0120] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 210; Zirconium compound / hydroxyaryl sulfide: 150. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 121. (4) Elongation at break (%): 11. (5) Flexural strength (MPa): 155. (6) Flexural modulus (GPa): 7.2. (7) Melting point (°C): Hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 339. (9) Pore size (μm): 3-15, Porosity (%): 47.

[0121] Example 9:

[0122] The preparation method of Example 9 is the same as that of Example 1, except that in step S4, the total mass of aromatic zirconium acid compound and zirconium phosphate (0.6 kg + 0.4 kg): active polyarylene sulfide (0.9 kg) = 1:9 is replaced by the total mass of aromatic zirconium acid compound and zirconium phosphate (1.2 kg + 0.8 kg): active polyarylene sulfide (8 kg) = 2:8.

[0123] The product was tested using the test method described in Example 1, and the test results are as follows:

[0124] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 210; Zirconium compound / hydroxyaryl sulfide: 130. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 125. (4) Elongation at break (%): 10. (5) Flexural strength (MPa): 158. (6) Flexural modulus (GPa): 7.5. (7) Melting point (°C): Hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 36. (9) Pore size (μm): 3-15, Porosity (%): 46.

[0125] Example 10:

[0126] The preparation method of Example 10 is the same as that of Example 2, except that in step S4, the total mass of the aromatic zirconium acid compound and zirconium phosphate is increased by 50% compared with Example 2. Specifically, the total mass of the aromatic zirconium acid compound and zirconium phosphate (3 g + 1.5 kg) has a zirconium compound content of 18%, which is the same as that in Example 2.

[0127] Step S4 is as follows:

[0128] 3 g of aromatic zirconium acid compound (zirconium carboxybenzoate, undried, 50% water content) and 1.5 kg of zirconium phosphate (undried, 60% water content) were added to 10 L of NMP. The mixture was heated to 195 °C under nitrogen protection to remove water, and then added to an active polyarylene sulfide. The mixture was reacted at 220-225 °C for 2.5 h under nitrogen protection, then heated to 250-270 °C for 3 h. After cooling to below 150 °C, the mixture was filtered, deionized water was added, and the pH was adjusted to 4.5-6.5. The mixture was washed with hot deionized water until the pH was around 7 and the conductivity of the wash water was less than 5 S / m. The mixture was then vacuum dried to obtain an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex.

[0129] The product was tested using the test method described in Example 1, and the test results are as follows:

[0130] (1) Melt index (g / 10min): Zirconium compound / hydroxy polyarylene sulfide: 110. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 125. (4) Elongation at break (%): 15. (5) Flexural strength (MPa): 158. (6) Flexural modulus (GPa): 7.7. (7) Melting point (°C): Hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / hydroxy polyarylene sulfide composite nonwoven fabric: 35. (9) Pore size (μm): 3-15, Porosity (%): 49.

[0131] Comparative Example 1:

[0132] A conventional polyphenylene sulfide is prepared by the following steps:

[0133] In a 100 L reactor equipped with an anchor frame and ribbon, 50 L of N-pyrrolidone and 13 kg of sodium sulfide were added. Under nitrogen protection and stirring, the temperature was gradually increased at a stirring speed of 80 rpm. Dehydration began at 150 °C and was completed at 196 °C. The temperature was then lowered to 130 °C, and 14.7 kg of p-dichlorobenzene was added. Under nitrogen protection and stirring at a stirring speed of 100 rpm, the temperature was increased to 220 °C and reacted for 3 h, with the polymerization temperature controlled at 220-235 °C. The temperature was then increased to 250 °C and reacted for 3 h, with the polymerization temperature controlled at 245-255 °C and the stirring speed at 85 rpm. The mixture was flash-evaporated to remove 30 L of solvent, cooled to 120 °C, and 40 L of deionized water was added. The mixture was washed 6 times with deionized water at 80 °C and dried in an oven at 100 °C for 10 h to obtain polyphenylene sulfide.

[0134] The product was tested using the test method described in Example 1, and the test results are as follows:

[0135] (1) Melt index (g / 10min): Polyphenylene sulfide: 290. (2) Density (g / cm³) 3 ): 1.33. (3) Tensile strength (MPa): 70. (4) Elongation at break (%): 8. (5) Flexural strength (MPa): 105. (6) Flexural modulus (GPa): 3.7. (7) Melting point (°): hydroxyl polyarylene sulfide: 283. (8) Hydrophilic angle (°): polyphenylene sulfide: 98. (9) Pore size (μm): 3-15, porosity (%): 55.

[0136] As can be seen from the above, polyphenylene sulfide is highly hydrophobic, difficult to wet, and cannot be used for ion exchange and ion transport.

[0137] Comparative Example 2:

[0138] A complex, the preparation method of which includes the following steps:

[0139] The polyphenylene sulfide obtained in Comparative Example 1 (9 kg) and zirconia powder (1 kg) were combined and prepared by the method in step S4 of Example 1.

[0140] The product was tested using the test method described in Example 1, and the test results are as follows:

[0141] (1) Melt index (g / 10min): Zirconia / polyphenylene sulfide: 180. (2) Density (g / cm³) 3): 1.45. (3) Tensile strength (MPa): 85. (4) Elongation at break (%): 5. (5) Flexural strength (MPa): 160. (6) Flexural modulus (GPa): 5.1. (7) Melting point (°): 283 for active polyarylene sulfide. (8) Hydrophilic angle (°): 67 for polyarylene sulfide composite nonwoven fabric. (9) Pore size (μm): 3-20, porosity (%): 50.

[0142] As can be seen from the above, the strength and hydrophilicity of the composite obtained from polyphenylene sulfide and zirconium oxide powder are significantly different from those in the examples, and it cannot be used for ion exchange and ion transport.

[0143] Comparative Example 3:

[0144] The preparation method of Comparative Example 3 is the same as that of Example 1, except that in step S4, zirconium phosphate is not added, but only aromatic zirconium compounds are added.

[0145] The product was tested using the test method described in Example 1, and the test results are as follows:

[0146] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 210; Aromatic zirconium / hydroxyaryl sulfide: 160. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 105. (4) Elongation at break (%): 15. (5) Flexural strength (MPa): 138. (6) Flexural modulus (GPa): 5.8. (7) Melting point (°C): Hydroxy polyarylene sulfide: 283. (8) Hydrophilic angle (°): Aromatic zirconium acid / hydroxy polyarylene sulfide composite nonwoven fabric: 51. (9) Pore size (μm): 5-20, Porosity (%): 55.

[0147] As can be seen from the above, the strength and hydrophilicity both decreased after removing zirconium phosphate, and the performance deteriorated compared with Example 1.

[0148] Comparative Example 4:

[0149] The preparation method of Comparative Example 4 is the same as that of Example 1, except that in step S4, no aromatic zirconium acid compound is added, only zirconium phosphate is added.

[0150] The product was tested using the test method described in Example 1, and the test results are as follows:

[0151] (1) Melt index (g / 10min): Hydroxyaryl sulfide: 210; Zirconium phosphate / hydroxyaryl sulfide: 150. (2) Density (g / cm³) 3(3) Tensile strength (MPa): 101. (4) Elongation at break (%): 6. (5) Flexural strength (MPa): 130. (6) Flexural modulus (GPa): 5.5. (7) Melting point (°C): 283. (8) Hydrophilic angle (°): 5. (9) Pore size (μm): 5-20, Porosity (%): 50.

[0152] As can be seen from the above, after removing the aromatic zirconium acid with hydrophilic groups, both the strength and hydrophilicity decrease, and the performance deteriorates compared with Example 1.

[0153] Comparative Example 5:

[0154] The preparation method of Comparative Example 5 is the same as that of Example 1, except that: in step S3, no polar hydrophilic monomer (2,5-dichlorohydroquinone) is added, so the resulting polyarylene sulfide is a traditional polyphenylene sulfide.

[0155] The product was tested using the test method described in Example 1, and the test results are as follows:

[0156] (1) Melt index (g / 10min): Polyphenylene sulfide: 290; Zirconium compound / polyphenylene sulfide: 180. (2) Density (g / cm³) 3 (3) Tensile strength (MPa): 112. (4) Elongation at break (%): 6 (5) Flexural strength (MPa): 129. (6) Flexural modulus (GPa): 5.9. (7) Melting point (°C): Hydroxyaryl sulfide: 283. (8) Hydrophilic angle (°): Zirconium compound / polyphenylene sulfide composite nonwoven fabric: 53. (9) Pore size (μm): 5-20, Porosity (%): 51.

[0157] As can be seen from the above, after removing the aromatic structural unit with hydrophilic groups, the interfacial bonding between polyphenylene sulfide and zirconium compound is poor, and both strength and hydrophilicity decrease. Compared with Example 1, the performance is worse.

[0158] It should be noted that while the preferred embodiments of the present invention are provided in this specification, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. These embodiments are not intended to impose additional limitations on the content of the present invention; their purpose is to provide a more thorough and comprehensive understanding of the disclosure of the present invention. Furthermore, the above-described technical features can be combined with each other to form various embodiments not listed above, all of which are considered to be within the scope of the present invention. Moreover, those skilled in the art can make various improvements, substitutions, or modifications based on common technical knowledge and conventional methods without departing from the above-described technical concept of the present invention, and all such improvements, substitutions, or modifications should fall within the protection scope of the appended claims.

Claims

1. A method for preparing an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic composite, characterized in that, The preparation method is as follows: aromatic zirconium compounds are prepared by chemical synthesis using multifunctional active aromatic acid compounds and soluble zirconium salts; then, active polyarylene sulfides are prepared by polymerization reaction using sulfides and polymeric monomers; finally, the aromatic zirconium compounds and zirconium phosphate are compounded or blended with the active polyarylene sulfides in situ or extruded to obtain a hydrophilic complex of aromatic zirconium-zirconium phosphate / polyarylene sulfides. The multifunctional active aromatic acid compound is a benzenepolycarboxylic acid containing at least three polar functional groups or a salicylic acid containing at least three polar functional groups; the polymerization monomer is a p-dihalobenzene and a monomer containing a polar hydrophilic side group, wherein the monomer containing a polar hydrophilic side group is a carboxylbenzene compound, a sulfonic acid benzene compound, or a hydroxybenzene compound.

2. The method for preparing a zirconium-phenylate / polyarylene sulfide hydrophilic complex of aromatic acid according to claim 1, characterized by, The phenylpolycarboxylic acid containing at least three polar functional groups is selected from: 1,2,4-phenyltricarboxylic acid, 1,2,3-phenyltricarboxylic acid, 1,3,5-phenyltricarboxylic acid, 2-hydroxyterephthalic acid, 4-hydroxyphthalic acid, 3-hydroxyphthalic anhydride, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2,5-dihydroxyterephthalic acid, 2-aminoterephthalic acid, 4-aminophthalic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 4-aminoisophthalic acid, pyromellitic dianhydride, 4-hydroxy-1,8-naphthalic anhydride, 3-hydroxy-1,8-naphthalic anhydride, 3-amino-4-hydroxy-1,8-naphthalic anhydride, or 4-amino-3-sulfo-1,8-naphthalic anhydride; Furthermore, the salicylic acid containing at least three polar functional groups is selected from: 5-aminosalicylic acid, 4-aminosalicylic acid, 3-aminosalicylic acid, 3,5-diaminosalicylic acid, 3,6-diaminosalicylic acid, 2,5-diaminoterephthalic acid, p-hydroxysalicylic acid, m-hydroxysalicylic acid, o-hydroxysalicylic acid, or 5-sulfosalicylic acid; Furthermore, the multifunctional active aromatic acid compound is 1,2,4-benzenetricarboxylic acid, pyromellitic dianhydride, or 4-hydroxyphthalic acid; Furthermore, the soluble zirconium salt is zirconium acetate, zirconium nitrate, or zirconium oxychloride; Furthermore, the sulfide is sodium sulfide, sodium hydrosulfide, or hydrogen sulfide.

3. The method for preparing a zirconium-phenylate / phosphonium-phenylate / polyarylene sulfide hydrophilic complex according to claim 1, wherein the polar hydrophilic side group-containing monomer is 、 or ; X is F, Cl, B or I, and R is H, a hydroxyl group, a carboxyl group or a sulfonic acid group. Preferably, the monomer containing the polar hydrophilic side group is 2,5-dichlorohydroquinone or 2,5-dichloroterephthalic acid; Furthermore, in the p-dihalobenzene, the halogen is F, Cl, B, or I; Preferably, the p-dihalobenzene is p-dichlorobenzene.

4. The method for preparing a zirconium- phosphorous acid zirconate / polyarylene sulfide hydrophilic composite according to any one of claims 1 to 3, characterized by, The preparation method includes the following steps: S1. Dissolve soluble zirconium salt in deionized water, then add it to a deionized aqueous solution of a multifunctional active aromatic acid compound and guanidine carbonate, stir to dissolve, filter, wash, add water and stir evenly, then transfer to an autoclave and perform hydrothermal pressure treatment to obtain aromatic zirconium compounds. S2. Dissolve the soluble organic zirconium salt in deionized water, then add it to a deionized aqueous solution of phosphoric acid and guanidine carbonate, stir to dissolve, filter, wash, add water, stir evenly, transfer to an autoclave, and perform hydrothermal pressure treatment to obtain zirconium phosphate. S3. Place the sulfide in a polar aprotic solvent, dehydrate and cool it down, then add p-dihalobenzene and monomers containing polar hydrophilic side groups, polymerize, cool and filter, wash and dry to obtain active polyarylethers. S4. Add the aromatic zirconium acid compound and zirconium phosphate to a polar aprotic solvent for dehydration, then add them to an active polyarylene sulfide for in-situ composite formation. After cooling, filter, wash, and dry to obtain an aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex. Alternatively, aromatic zirconium compounds and zirconium phosphate are dried, then a coupling agent is added, followed by co-extrusion with active polyarylene sulfide, followed by cooling and drying to obtain an aromatic zirconium-zirconium phosphate / polyarylene sulfide hydrophilic complex.

5. The method for preparing a zirconium-phenylate / polyarylene sulfide hydrophilic complex of aromatic acid according to claim 4, characterized by, In step S1, the molar ratio of the multifunctional active aromatic acid compound to the soluble zirconium salt is 0.9-2.1:1, and the molar ratio of guanidine carbonate to the soluble zirconium salt is 2.1-2.5:

1. Furthermore, when the synthesized aromatic zirconium acid compound is a benzoic acid or salicylic acid containing an active functional group, the molar ratio of the multifunctional active aromatic acid compound to the soluble zirconium salt is 1.9-2.1:1; when the synthesized aromatic zirconium acid compound is polybenzoic acid or polysalicylic acid zirconium, the molar ratio of the multifunctional active aromatic acid compound to the soluble zirconium salt is 0.9-1.1:

1. Furthermore, during the hydrothermal pressurization process, nitrogen is used to replace the air, and the water is subjected to hydrothermal treatment at 0.4-0.5 MPa and 120-150 ℃ for 3-8 hours, followed by cooling to room temperature.

6. The method for preparing a zirconium- phosphorous acid zirconate / polyarylene sulfide hydrophilic composite of the aromatic acid according to claim 4, characterized by, In step S2, the soluble organic zirconium salt is zirconium acetate; Furthermore, the molar ratio of the phosphoric acid to the soluble organic zirconium salt is 0.9-1.1:1; Furthermore, the molar ratio of guanidine carbonate to soluble organic zirconium salt is 0.9-1.1:1; Furthermore, during the hydrothermal pressurization process, nitrogen is used to replace the air, and the water is subjected to hydrothermal treatment at 0.4-0.5 MPa and 120-150 ℃ for 3-8 hours, followed by cooling to room temperature.

7. The method for preparing a zirconium- phosphorous acid zirconate / polyarylene sulfide hydrophilic composite of the aromatic acid according to claim 4, characterized by, In step S3, the sulfide is sodium sulfide, sodium hydrosulfide, or hydrogen sulfide; Furthermore, the sulfide contains less than 15 ppm of iron and less than 20 ppm of heavy metal ions. Furthermore, the polar aprotic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone (MI) lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane. Furthermore, the molar ratio of the p-dihalobenzene to the monomer containing the polar hydrophilic side group is 80-97.5:20-2.5; Furthermore, the total molar ratio of the p-dihalobenzene and monomers containing polar hydrophilic side groups to the molar ratio of sulfides is 0.95-1.05:1; Furthermore, the total molar amount of the p-dihalobenzene and monomers containing polar hydrophilic side groups is: polar aprotic solvent volume = 1 mol : 0.3-1 L; Furthermore, the polymerization reaction is carried out at 180-280 °C for 3-16 h, and after the polymerization is stopped, the temperature is cooled to below 150 °C.

8. The method for preparing the aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex according to claim 4, characterized in that, In step S4, during in-situ recombination, the mass ratio of the aromatic zirconium acid compound to zirconium phosphate is 10-20:10-20; Furthermore, the total mass of the aromatic zirconium acid compound and zirconium phosphate is equal to the volume of the polar aprotic solvent (100 g : 500-1000 mL). Furthermore, the total mass of the aromatic zirconium acid compound and zirconium phosphate: the molar mass of the active polyarylene sulfide = 5-30 g : 1 mol; Furthermore, the polar aprotic solvent is N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1,3-dimethyl-2-imidazolone, hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylamide, N-ethylcaprolactam, N,N-vinylpyrrolidone, 1,3-dimethyl-2-imidazolinone (MI) lactam, tetramethylurea, dimethyl sulfoxide, or sulfolane.

9. The method for preparing the aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex according to claim 4, characterized in that, In step S4, during the blending extrusion, the extrusion temperature is 280-356 ℃, the screw speed is 100-300 rpm, and the plasticizing time is 1-5 min; Furthermore, the total mass of the aromatic zirconium acid compound and zirconium phosphate: the mass of the active polyarylene sulfide = 5-30: 70-95; Furthermore, the amount of the coupling agent is 1-6 wt% of the total mass of the aromatic zirconium acid compound and zirconium phosphate; Furthermore, the coupling agent is KH550, KH560, or KH570.

10. A hydrophilic complex of aromatic zirconium acid-zirconium phosphate / polyaryl sulfide, characterized in that, The aromatic zirconium acid-zirconium phosphate / polyarylene sulfide hydrophilic complex was prepared by any one of claims 1-9.

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