Functionalized styryl copolymer / metal ion hybrid material and preparation method thereof

Abstract

The invention belongs to the field of styryl copolymer materials, and relates to a functionalized styryl copolymer / metal ion hybrid material and a preparation method thereof. The hybrid material is composed of a styryl copolymer main chain A and a side group functional group, wherein the side group functional group comprises a proton-containing acidic substituent group B and a proton-containing acid amination metal ion complexing crown ether group C; wherein the molar content of the B is 1-55 mol% and the molar content of the C is 0.01-1.0 mol% based on 100 mol% of the total molar content of the structural unit of the A. According to the functionalized styryl copolymer / metal ion hybrid material, the proton-containing acidic substituent group B and the proton-containing acid aminated metal ion complexing crown ether group C are introduced, so that compared with a styryl copolymer material, the mechanical property and the optical property are obviously improved.

Description

Technical Field

[0001] This invention belongs to the field of styrene-based copolymer materials, specifically, it relates to a functionalized styrene-based copolymer / metal ion hybrid material and its preparation method. Background Technology

[0002] Styrene-based copolymer materials, such as styrene-ethylene copolymers, styrene-propylene copolymers, styrene-butene copolymers, styrene-isobutylene copolymers, α-methylstyrene-isobutylene copolymers, styrene-ethylene / propylene terpolymers, and styrene-ethylene / butene terpolymers, such as: polystyrene-b-polybutadiene-b-polystyrene (SBS), polystyrene-b-polyisoprene-b-polystyrene (SIS), hydrogenated SIS or polystyrene-b-poly(ethylene-co-propylene)-b-polystyrene (SEPS), hydrogenated SBS or polystyrene-b-poly(ethylene-co-propylene)-b-polystyrene. Polystyrene-co-α-methylstyrene (SEBS), polystyrene-β-polyisobutylene-β-polystyrene (SIBS), poly(styrene-co-α-methylstyrene)-β-polyisobutylene-β-poly(styrene-co-α-methylstyrene), and poly(α-methylstyrene)-β-polyisobutylene-β-poly(α-methylstyrene) triblock copolymers possess excellent strength and elongation, acid and alkali resistance, barrier properties, processability and reprocessability, shock absorption properties, and water and air barrier properties. These copolymers can be applied in adhesives, asphalt modification, plastic modification, and biomedicine. Introducing polar groups into the side groups of the styrene-based copolymer macromolecular chain can yield new properties while maintaining the original excellent characteristics.

[0003] Polymer polar functionalization includes sulfonic acid functionalization, phosphoric acid functionalization, carboxylic acid functionalization, acetyl functionalization, and halomethyl functionalization, which can significantly improve the compatibility of copolymers. This results in compositions containing the copolymer and polar copolymers exhibiting superior mechanical properties, anti-slip properties, and heat generation properties, expanding into new application areas. Polar functionalized styrene-based copolymers have potential application value in multiple fields such as seawater desalination separation membranes, optical membranes, biological protective clothing and electrolyte membranes, and breathable membranes. See: CN117986463A; CN114561034A; CN1192221A; CN116535801A; CN111875720A; CN1636036A.

[0004] Polar functionalized styrene copolymers can be further chemically modified through efficient acid-base reactions, such as by forming strong interactions between basic compounds containing amino (-NH2) groups and acidic compounds containing carboxylic acids, sulfonic acids, or phosphonic acids. See: *Inorganic Chemistry* (3rd Edition), Higher Education Press, pp. 281-289; RSC Advance, 2023, 13, 28729-28735; CN101896540B; *Journal of Applied Polymer Science*, 2021, 138, 50034.

[0005] In addition, composite materials can be prepared by blending functionalized polymer solutions with solutions containing metal ions. For example, rare earth metal salt aqueous solutions (cerium acetate aqueous solution or lanthanum acetate aqueous solution, etc.) can be directly added to sulfonated SEBS solutions, or sulfonated SEBS-based rare earth ionomers can be obtained through melt extrusion blending. However, these methods are difficult to mix and retain metal ions in the polymer matrix, and also suffer from severe side reactions at high temperatures. See: CN112876588B. To solve the problem of metal ion dispersion in the polymer matrix, a composite film can be prepared by uniformly mixing perfluorosulfonic acid resin with alizarin red cerium complex (ARS / Ce) in a solvent and then removing the solvent. However, the problem of metal ion migration is still difficult to solve. See: CN114276573B. DSPAEK-CRE was synthesized by reacting bissulfonated 3,3-diphenylpropylamine (DSDPA) and aminomethyl-15-crown-5-ether (CRE) with polyaryletherketone (PAEK). Cerium nitrate hexahydrate was then introduced into DSPAEK-CRE to mitigate Ce ion migration. However, the inevitable interaction between cerium ions and sulfonic acid groups when introduced into the sulfonated matrix material leads to material instability. See: Molecular Systems Design & Engineering, 2019, 4, 901-911.

[0006] In summary, existing technologies, such as directly introducing metal ions into the polymer matrix or modifying polymers by blending with metal ion complexes, struggle to address the issues of uniform dispersion of metal ions within the polymer and migration of metal ions out of the polymer matrix. Furthermore, no publicly available reports to date have described a polar functionalized styrene-based copolymer / metal ion hybrid material or its preparation method. Summary of the Invention

[0007] The purpose of this invention is to solve the above-mentioned problems existing in the prior art and to provide a functionalized styrene-based copolymer / metal ion hybrid material and its preparation method. By introducing a proton-containing acidic substituent B and a proton-containing acid-amined metal ion complex crown ether group C as a side group functional group, the mechanical and optical properties are significantly improved compared to styrene-based copolymers.

[0008] To achieve the above objectives, a first aspect of the present invention provides a functionalized styrene-based copolymer / metal ion hybrid material, the hybrid material being composed of a styrene-based copolymer backbone A and side functional groups, wherein the side functional groups include a proton-containing acidic substituent B and a proton-containing acid-amined metal ion complex crown ether group C;

[0009] Wherein, with the total molar content of structural unit A being 100%, the molar content of B is 1-55%, preferably 2-50%, more preferably 2.5-47%; and the molar content of C is 0.01-1.0%, preferably 0.03-0.85%, more preferably 0.10-0.60%.

[0010] A second aspect of the present invention provides a method for preparing the aforementioned functionalized styrene-based copolymer / metal ion hybrid material, comprising the following steps:

[0011] (1) Obtaining a functionalized styrene-based copolymer;

[0012] (2) Preparation of metal ion complex solution: The amino crown ether compound is mixed with the first organic medium, and an equimolar metal ion compound is added to carry out a complexation reaction to obtain the metal ion complex solution;

[0013] (3) Preparation of functionalized styrene copolymer / metal ion hybrid material: Dissolve the functionalized styrene copolymer described in step (1) in a second organic medium, add the metal ion complex solution described in step (2) to react, remove the solvent, and obtain the functionalized styrene copolymer / metal ion hybrid material.

[0014] The technical solution of this invention can bring the following beneficial effects:

[0015] 1. Functionalized styrene-based copolymer metal ion hybrid materials containing proton acidic substituent side group functional groups and proton acid amination metal ion complex crown ether groups were designed and synthesized, and the degree of proton acid amination can be adjusted according to the material properties.

[0016] 2. Functionalized styrene-based copolymers / metal ion hybrid materials were prepared by forming hydrogen bonds or chemical bonds through efficient acid-base reactions between proton-containing functional groups and amino groups. The tensile strength of the materials can reach 34 MPa, the light transmittance can be as high as 94.9%, the haze can be as low as 3.4%, the refractive index can be as high as 1.56, and the hydrophilicity and hydrophobicity of the materials can be adjusted.

[0017] 3. Compared with styrene-based copolymers, the functionalized styrene-based copolymer / metal ion hybrid materials exhibit significantly improved mechanical and optical properties. Tensile strength increases by approximately 79%, elongation at break by approximately 211%, light transmittance by approximately 7%, haze by approximately 79%, and the refractive index increases by 0.0097. The prepared sulfonated styrene-based copolymer / metal ion hybrid materials show improved surface hydrophilicity, with a water contact angle reduction of approximately 45%, even transforming from hydrophobic to hydrophilic materials.

[0018] 4. Compared with functionalized styrene-based copolymers, the mechanical properties, optical properties and surface hydrophilicity of functionalized styrene-based copolymer / metal ion hybrid materials are further improved. For example, the tensile strength is increased by about 8%, the elongation at break is increased by about 51%, the haze is reduced by about 44%, and the water contact angle is reduced by about 19%.

[0019] 5. Styrene-based copolymers / metal ion hybrid materials can be prepared by polar functionalization and acid-base reactions. The process is simple, the reaction efficiency is high, and the materials have excellent comprehensive performance. They have potential applications in seawater desalination separation membranes, optical membranes, biological protective clothing, and isolation materials.

[0020] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0021] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0022] To achieve the above objectives, a first aspect of the present invention provides a functionalized styrene-based copolymer / metal ion hybrid material, the hybrid material being composed of a styrene-based copolymer backbone A and side functional groups, wherein the side functional groups include a proton-containing acidic substituent B and a proton-containing acid-amined metal ion complex crown ether group C;

[0023] Wherein, with the total molar content of structural unit A being 100%, the molar content of B is 1-55%, preferably 2-50%, more preferably 2.5-47%; and the molar content of C is 0.01-1.0%, preferably 0.03-0.85%, more preferably 0.10-0.60%.

[0024] According to the present invention, preferably, the styrene-based copolymer backbone A is a copolymer segment of styrene or its derivatives with an olefin, wherein the copolymer of styrene or its derivatives with an olefin is selected from at least one of styrene-ethylene copolymer, styrene-propylene copolymer, styrene-butene copolymer, styrene-isobutylene copolymer, α-methylstyrene-isobutylene copolymer, styrene-ethylene / propylene terpolymer, and styrene-ethylene / butene terpolymer, preferably selected from styrene-isobutylene random copolymer, α-methylstyrene-isobutylene random copolymer, polystyrene-b-(polyethylene-co-polypropylene) diblock copolymer, polystyrene-b-(polyethylene-co-polypropylene)-b-polystyrene triblock copolymer, polystyrene-b-poly(ethylene-co-butene) diblock copolymer, polystyrene-b-poly(ethylene-co-butene)-b-polystyrene triblock copolymer, polystyrene-b-polyisobutylene diblock copolymer, polystyrene-b-polyisobutylene-b-polystyrene At least one of poly(styrene-co-α-methylstyrene) triblock copolymer, poly(styrene-co-α-methylstyrene)-b-polyisobutylene-b-poly(styrene-co-α-methylstyrene) triblock copolymer, poly(α-methylstyrene)-b-polyisobutylene diblock copolymer, and poly(α-methylstyrene)-b-polyisobutylene-b-poly(α-methylstyrene) triblock copolymer, more preferably polystyrene-b-poly(ethylene-co-α-methylstyrene) triblock copolymer. At least one of the following: poly(styrene-co-α-methylstyrene)-b-polystyrene triblock copolymer, polystyrene-b-poly(ethylene-co-butene)-b-polystyrene triblock copolymer, polystyrene-b-polyisobutylene-b-polystyrene triblock copolymer, poly(styrene-co-α-methylstyrene)-b-polyisobutylene-b-poly(styrene-co-α-methylstyrene) triblock copolymer, and poly(α-methylstyrene)-b-polyisobutylene-b-poly(α-methylstyrene) triblock copolymer.

[0025] Preferably, the number-average molecular weight of the copolymer of styrene or its derivatives with olefins is 10-200 kg / mol, more preferably 20-150 kg / mol, and even more preferably 25-90 kg / mol.

[0026] Preferably, based on the total weight of the main chain A of the styrene copolymer, the mass content of styrene is 10-75%, more preferably 15-70%, and even more preferably 20-67%.

[0027] According to the present invention, preferably, the proton-containing acidic substituent B is at least one of a sulfonic acid group, a phosphate group, and a carboxylic acid group, preferably a sulfonic acid group and / or a phosphate group.

[0028] According to the present invention, preferably, the proton-containing acid-amined metal ion complexed crown ether group C is composed of a proton-containing acidic substituent B and a metal ion complexed amino crown ether.

[0029] Preferably, the metal ion is selected from at least one of sodium ion, potassium ion, magnesium ion, aluminum ion, calcium ion, scandium ion, titanium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, zirconium ion, molybdenum ion, indium ion, tin ion, antimony ion, cerium ion, praseodymium ion, neodymium ion, samarium ion, europium ion, gadolinium ion, ytterbium ion, hafnium ion, mercury ion, and lead ion, more preferably selected from at least one of sodium ion, potassium ion, magnesium ion, aluminum ion, calcium ion, scandium ion, titanium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, zirconium ion, molybdenum ion, tin ion, cerium ion, praseodymium ion, neodymium ion, samarium ion, hafnium ion, mercury ion, and lead ion, and more preferably selected from at least one of titanium ion, vanadium ion, chromium ion, cerium ion, manganese ion, iron ion, cobalt ion, nickel ion, and copper ion.

[0030] Preferably, the amino crown ether is selected from 2-aminomethyl-15-crown ether-5, 4'-aminobenzo-15-crown ether-5, 4'-(2”,4”-dinitro-6”-trifluoromethylphenyl)-aminobenzo-15-crown ether-5, 2-(aminomethyl)-18-crown ether-6, 4'-aminobenzo-18-crown ether-6, 4'-aminodibenzo-18-crown ether-6, 4'-aminobenzo-15-crown ether-5 hydrochloride, 4'-aminodibenzo-18-crown ether-6 hydrochloride, 4'-aminodibenzo-18-crown ether-6 hydrochloride, 4'-aminobenzo-18-crown ether-6. At least one of ether-6 and 4-aminobenzo-18-crown ether-6 sesquihydrate hydrochloride, preferably selected from at least one of 2-aminomethyl-15-crown ether-5, 4'-aminobenzo-15-crown ether-5, 2-(aminomethyl)-18-crown ether-6, 4'-aminobenzo-18-crown ether-6 and 4'-aminodibenzo-18-crown ether-6, more preferably selected from at least one of 2-aminomethyl-15-crown ether-5, 4'-aminobenzo-15-crown ether-5 and 4'-aminobenzo-18-crown ether-6.

[0031] A second aspect of the present invention provides a method for preparing the aforementioned functionalized styrene-based copolymer / metal ion hybrid material, comprising the following steps:

[0032] (1) Obtaining functionalized styrene-based copolymers;

[0033] (2) Preparation of metal ion complex solution: The amino crown ether compound is mixed with the first organic medium, and an equimolar metal ion compound is added to carry out a complexation reaction to obtain the metal ion complex solution;

[0034] (3) Preparation of functionalized styrene copolymer / metal ion hybrid material: The functionalized styrene copolymer described in step (1) is dissolved in a second organic medium to obtain a functionalized styrene copolymer solution. The metal ion complex solution described in step (2) is added to react and the solvent is removed to obtain the functionalized styrene copolymer / metal ion hybrid material.

[0035] According to the present invention, preferably, the first organic medium and the second organic medium are the same or different, and each is independently selected from at least one of isopropanol, n-hexanol, tetrahydrofuran, toluene, xylene, phenol, o-dichlorobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, preferably selected from at least one of isopropanol, n-hexanol, N,N-dimethylformamide and N,N-dimethylacetamide, more preferably selected from at least one of isopropanol, toluene and N,N-dimethylacetamide.

[0036] According to the present invention, preferably, the metal ion compound is selected from at least one salt of sodium, potassium, magnesium, aluminum, calcium, yttrium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, indium, tin, antimony, cerium, praseodymium, neodymium, samarium, europium, gadolinium, ytterbium, hafnium, mercury, and lead; more preferably, it is selected from at least one salt of sodium, potassium, magnesium, aluminum, calcium, yttrium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, tin, cerium, praseodymium, neodymium, samarium, hafnium, mercury, and lead; and more preferably, it is selected from at least one salt of titanium, vanadium, chromium, cerium, manganese, iron, cobalt, nickel, and copper.

[0037] According to the present invention, preferably, in step (1), the functionalized styrene-based copolymer is obtained by a functionalization reaction, preferably by a sulfonation, phosphorylation or carboxylation reaction.

[0038] The functionalized styrene-based copolymer has a molar functionality of 1–56%, preferably 2–51%, and more preferably 2.5–46%.

[0039] In this invention, functionality (SP) refers to the molar ratio of proton-containing acidic substituents (B) and proton-containing acid-amined metal ion complexed crown ether groups (C) to all structural units of the styrene copolymer molecular backbone (A).

[0040] The functionalization reactions of the styrene-based copolymers described in this invention, namely sulfonation, phosphorylation, or carboxylation, can be referred to the prior art, see: Polymer, 2004, 45(9):3037-3043; CN117487047A; ACS Applied Energy Materials, 2024, 7, 1080-1091.

[0041] Taking polymer sulfonation reaction as an example, the preparation can be carried out by referring to the following steps.

[0042] A. Under nitrogen protection and stirring at -10℃, a solvent (such as dichloromethane or dichloroethane) is added to the reactor. After adding acetic anhydride, concentrated sulfuric acid is slowly added. After the reaction, an acetylsulphate solution is obtained.

[0043] B. Under nitrogen protection and stirring, a styrene-based copolymer (e.g., SIBS, SEPS, or SEBS) and a solvent (e.g., dichloromethane or dichloroethane) are added to a reactor and dissolved to obtain a polymer solution. The dissolution temperature is 20–70°C, preferably 35–65°C, more preferably 45–60°C; the dissolution time is 0.5–24 h, preferably 1–12 h, more preferably 2–6 h; the polymer solution concentration is 2–100 g / L, preferably 5–60 g / L, more preferably 8–30 g / L. Given a specific polymer, the dissolution temperature is correlated with the time required; higher temperatures result in shorter dissolution times, and lower temperatures result in longer dissolution times.

[0044] C. Under nitrogen protection and stirring, add an appropriate amount of the above acetyl sulfate solution to the above polymer solution and mix thoroughly.

[0045] D. Under nitrogen protection and stirring, the above mixture undergoes further sulfonation, and methanol is finally added to terminate the sulfonation reaction. The reaction temperature is 30–70°C, preferably 35–65°C, more preferably 45–60°C; the reaction time is 1–24 h, preferably 2–12 h, more preferably 3–8 h. The sulfonation reaction temperature and time are also correlated; a higher reaction temperature results in a shorter sulfonation reaction time, while a lower reaction temperature results in a longer sulfonation reaction time.

[0046] E. Separate the above sulfonation reaction solution to obtain the initial sulfonated polymer solid product. Add an organic solvent (such as ethanol or isopropanol) and stir to dissolve. Filter to remove insoluble impurities to obtain the filtrate. The dissolution temperature is 30–70°C, preferably 35–65°C, more preferably 45–60°C; the dissolution time is 0.5–24 h, preferably 1–12 h, more preferably 1.5–5 h. The polymer dissolution temperature is related to the time; a higher dissolution temperature results in a shorter dissolution time, and a lower dissolution temperature results in a longer dissolution time.

[0047] F. Add long-chain alkane compounds to the obtained filtrate to precipitate sulfonated polymers.

[0048] G. Repeat the purification process three times to obtain the purified sulfonated polymer; then vacuum dry at 45°C to obtain the dried sulfonated polymer solid product.

[0049] In this invention, the phosphorylating agent is selected from at least one of the following: phosphorus oxychloride, dialkyl chlorophosphate, dimethyl iodophosphate, orthophosphoric acid, phosphorous acid, polyphosphoric acid, and sodium tripolyphosphate.

[0050] In this invention, the carboxylating agent is selected from at least one of the following: formic acid, acetic acid, oxalic acid, acetic anhydride, succinic anhydride, maleic anhydride, acetyl chloride, acetyl bromide, p-methylbenzoyl chloride, trifluoroacetyl chloride, and trifluoroacetyl bromide.

[0051] According to the present invention, preferably, in step (2), the conditions of the complexation reaction include: a reaction temperature of -20 to 50°C, preferably -10 to 40°C, more preferably 0 to 30°C, and a reaction time of 1 to 24 hours, preferably 1.5 to 12 hours, more preferably 2 to 5 hours.

[0052] Preferably, the mass concentration of the metal ion complex in the metal ion complex solution is 1-10%, more preferably 2-8%, and even more preferably 3-6%.

[0053] According to the present invention, preferably, in step (3), the mass concentration of the functionalized styrene copolymer in the functionalized styrene copolymer solution is 1-30%, more preferably 2-20%, and more preferably 3-10%. Too low a concentration will consume a large amount of solvent, increasing the cost, while too high a concentration will make the viscosity of the sulfonated styrene copolymer solution too high, which is not conducive to the uniform dispersion of organometallic ion complexes.

[0054] Preferably, in step (3), the reaction conditions include: a reaction temperature of -20 to 50°C, preferably -10 to 40°C, more preferably 0 to 30°C; and a reaction time of 0.5 to 24 h, preferably 1 to 12 h, more preferably 1.5 to 6 h.

[0055] The present invention will be further described below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0056] In this embodiment, a Buker Advance-AV400 nuclear magnetic resonance spectrometer was used to determine the chemical structure and composition of the functionalized polymer, and optical properties were tested according to GB / T 2410-2008 standard. Thickness measurements were performed using a thickness gauge with an accuracy of at least 0.1 μm, with three measurements taken and the median value recorded as the film thickness. The water contact angle of the polymer film in a horizontal state was measured using a JC2000D2M contact angle meter in an air atmosphere. The mechanical properties of the material were characterized using a universal testing machine according to GB / T 1040-2006.

[0057] Example 1

[0058] (1) Preparation of sulfonated styrene polymer

[0059] Under nitrogen atmosphere and stirring at -10℃, 42 mL of dichloroethane (DCE), 5.5 mL of acetic anhydride and 2.5 mL of concentrated sulfuric acid were added to a 100 mL reactor. After reacting for 30 min, an acetylsulphate solution was obtained.

[0060] Under nitrogen protection and stirring, 5g of SIBS (M) was added to a 250mL reactor. n =30.6 kg / mol, St mass content = 60.0%) and 100 mL DCE were dissolved to obtain SIBS solution (mass concentration = 3.8%); at room temperature, an appropriate amount of the above acetylsulphate solution was added to the above SIBS solution, mixed evenly, and further reacted at 55 °C for 4 h; 50 mL methanol was added to terminate the sulfonation reaction; the sulfonated SIBS (SSIBS) primary product was separated; the SSIBS primary product was dissolved in ethanol / isopropanol and precipitated with hexane three times to obtain purified SSIBS product; the SSIBS product was vacuum dried at 45 °C to constant weight.

[0061] The yield of SSIBS was 86.8%. The degree of sulfonation functionalization (SP) in SSIBS was 3.62%, denoted as SSIBS-3.62.

[0062] (2) Preparation of metal ion complex solution

[0063] A solution of a metal ion complex (A-CRE5·Ce) (mass concentration = 5%) was obtained after reacting 0.28 g of 4'-aminobenzo-15-crown-5, 13.49 g of N,N-dimethylacetamide (DMA) with 0.43 g of Ce(NO3)3·6H2O for 3 h at room temperature and with stirring.

[0064] (3) Preparation of functionalized styrene copolymers / metal ion hybrid materials

[0065] Under stirring and at room temperature, 0.8 g of SSIBS-3.62, 15.2 g of DMAc from step (1) and 0.48 g of the above metal ion complex solution from step (2) were reacted for 2 h. After solvent removal, the SSIBS / A-CRE5·Ce hybrid material was obtained, wherein: the molar content of the proton-containing acidic substituent (B) was 3.30%, and the molar content of the proton-containing acid-amined metal ion complex crown ether group (C) was 0.32%.

[0066] The film was prepared by removing the solvent. The film thickness was 118 μm, the tensile strength was 34.0 MPa, the elongation at break was 140%, the light transmittance was 94.9%, the haze was 3.4%, the refractive index was 1.5552, and the surface water contact angle was 99.9°, indicating that it is a hydrophobic material.

[0067] Compared with SIBS in Comparative Example 1, the SSIBS / A-CRE5·Ce hybrid material prepared by Example 1 showed an increase of 78.9% in tensile strength, 211% in elongation at break, 7.0% in light transmittance, 76.5% in haze, and 0.0042 in refractive index; and a decrease of 18.9% in water contact angle.

[0068] Compared with SSIBS-3.62 in Comparative Example 4, the SSIBS / A-CRE5·Ce hybrid material prepared by Example 1 showed a 2.4% increase in tensile strength and a 2.2% increase in elongation at break; the transmittance remained relatively unchanged, while the haze decreased by 18.9% and the refractive index increased by 0.0026; the water contact angle remained relatively unchanged.

[0069] The above results indicate that the SSIBS / A-CRE5·Ce hybrid material prepared by Example 1 has superior mechanical, optical, and hydrophilic properties.

[0070] Example 2

[0071] The preparation process is the same as described in Example 1, except that:

[0072] The yield of SSIBS was 89.9%, and the functionalization degree was 9.84%, denoted as SSIBS-9.84.

[0073] 0.48 g of the A-CRE5·Ce solution from Example 1 was added to the SSIBS-9.84 / DMAc solution. The resulting hybrid material had a B molar content of 9.52% and a C molar content of 0.32%.

[0074] The film prepared by Example 2 has a thickness of 116 μm, a tensile strength of 24.2 MPa, an elongation at break of 88%, a light transmittance of 93.9%, a haze of 4.5%, a refractive index of 1.5551, and a water contact angle of 85.6°, indicating it is a hydrophilic material.

[0075] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 2 showed an increase in tensile strength of 26.3%, an increase in elongation at break of 96%, an increase in light transmittance of 5.9%, a decrease in haze of 68.7%, an increase in refractive index of 0.0041, and a decrease in water contact angle of 30.5%.

[0076] Compared with SSIBS-9.84 in Comparative Example 5, the hybrid material prepared by Example 2 showed an increase in tensile strength of 3.7%, an increase in elongation at break of 8.6%, a decrease in haze of 15.2%, an increase in refractive index of 0.0022, and a decrease in water contact angle of 10.2%.

[0077] The results above indicate that the hybrid material prepared by Example 2 has superior mechanical, optical and hydrophilic properties.

[0078] Example 3

[0079] The preparation process is the same as described in Example 1, except that:

[0080] The yield of SSIBS was 90.8%, and the functionalization degree was 13.37%, denoted as SSIBS-13.37.

[0081] 0.48 g of the A-CRE5·Ce solution from Example 1 was added to the SSIBS-13.37 / DMAc solution. The resulting hybrid material had a B molar content of 13.05% and a C molar content of 0.32%.

[0082] The film prepared by Example 3 has a thickness of 121 μm, a tensile strength of 26.3 MPa, an elongation at break of 88%, a light transmittance of 92.3%, a haze of 4.8%, a refractive index of 1.5570, and a water contact angle of 84.6°, indicating it is a hydrophilic material.

[0083] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 3 showed an increase in tensile strength of 36.8%, an increase in elongation at break of 96%, an increase in light transmittance of 4.0%, a decrease in haze of 66.5%, an increase in refractive index of 0.0060, and a decrease in water contact angle of 31.3%.

[0084] Compared with SSIBS-13.37 in Comparative Example 6, the hybrid material prepared by Example 3 showed an increase in tensile strength of 7.0%, an increase in elongation at break of 14.3%, a decrease in haze of 10.9%, an increase in refractive index of 0.0029, and a decrease in water contact angle of 4.5%.

[0085] The above results indicate that the hybrid material prepared by Example 3 has superior mechanical, optical, and hydrophilic properties.

[0086] Example 4

[0087] The preparation process is the same as described in Example 1, except that:

[0088] The SSIBS yield was 91.0%, and the functionalization degree was 16.51 mol%, denoted as SSIBS-16.51. 0.48 g of the A-CRE5·Ce solution from Example 1 was added to the SSIBS-16.51 / DMAc solution. The resulting hybrid material had a B molar content of 16.19% and a C molar content of 0.32%.

[0089] The film prepared by Example 4 has a thickness of 120 μm, a tensile strength of 17.4 MPa, an elongation at break of 48%, a light transmittance of 90.6%, a haze of 5.9%, a refractive index of 1.5591, and a surface water contact angle of 63.6°, making it a hydrophilic material.

[0090] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 4 showed a decrease in tensile strength of 8.4%, an increase in elongation at break of 6.7%, an increase in light transmittance of 2.1%, a decrease in haze of 59.0%, an increase in refractive index of 0.0081, and a decrease in water contact angle of 48.4%.

[0091] Compared with SSIBS-16.51 in Comparative Example 8, the hybrid material prepared by Example 4 showed an 8.7% increase in tensile strength, a 9.1% increase in elongation at break, a 4.8% decrease in haze, a 0.0026 increase in refractive index, and an 18.5% decrease in water contact angle.

[0092] The above results indicate that the hybrid material prepared by Example 4 has superior optical and hydrophilic properties.

[0093] Example 5

[0094] The preparation process is the same as described in Example 1, except that:

[0095] The yield of SSIBS was 97.0%, and the functionalization degree was 44.68%, denoted as SSIBS-44.68.

[0096] 0.48 g of the A-CRE5·Ce solution from Example 1 was added to the SSIBS-44.68 / DMAc solution. The resulting hybrid material had a B molar content of 44.36% and a C molar content of 0.32%.

[0097] The film prepared by Example 5 has a thickness of 127 μm, a tensile strength of 5.2 MPa, an elongation at break of 16%, a light transmittance of 88.7%, a haze of 7.3%, and a refractive index of 1.5607. The water contact angle of the film surface is 23.4°, indicating that it is a hydrophilic material.

[0098] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 5 showed a 72.6% reduction in tensile strength, a 65.1% reduction in elongation at break, a 49.3% reduction in haze, a 0.0097 increase in refractive index, and an 81.0% reduction in water contact angle.

[0099] Compared with SSIBS-44.68 in Comparative Example 9, the hybrid material prepared by Example 5 showed an increase in tensile strength of 4.0%, an increase in elongation at break of 4.7%, a decrease in haze of 13.4%, an increase in refractive index of 0.0019, and a decrease in water contact angle of 8.9%.

[0100] The above results indicate that the hybrid material prepared by Example 5 has superior optical and hydrophilic properties.

[0101] Example 6

[0102] The preparation process is the same as described in Example 3, except that:

[0103] 4'-Aminobenzo-15-crown-5 was replaced with 4'-aminobenzo-18-crown-6, and 0.33 g of 4'-aminobenzo-18-crown-6 was added to 14.44 g of DMAc, followed by the addition of 0.43 g of Ce(NO3)3·6H2O to prepare a metal ion complex (A-CRE6·Ce) solution. 0.16 g of the A-CRE6·Ce solution was added to the SSIBS-13.37 solution described in Example 3. The resulting hybrid material had a B molar content of 13.26% and a C molar content of 0.11%.

[0104] The film prepared by Example 6 has a thickness of 117 μm, a tensile strength of 18.4 MPa, an elongation at break of 116%, a light transmittance of 94.4%, a haze of 4.0%, a refractive index of 1.5537, and a water contact angle of 84.8°, indicating that it is a hydrophilic material.

[0105] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 6 showed a 3.2% decrease in tensile strength, a 157.8% increase in elongation at break, a 6.4% increase in light transmittance, a 72.5% decrease in haze, a 0.0027 increase in refractive index, and a 31.1% decrease in water contact angle.

[0106] Compared with SSIBS-13.40 in Comparative Example 6, the hybrid material prepared by Example 6 showed a 24.3% increase in tensile strength, a 50.6% increase in elongation at break, little change in light transmittance, a 26.8% decrease in haze, and a 4.3% decrease in water contact angle.

[0107] The results above indicate that the hybrid material prepared by Example 6 has superior mechanical, optical, and hydrophilic properties.

[0108] Example 7

[0109] The preparation process is the same as described in Example 6, except that:

[0110] 0.64 g of A-CRE6·Ce solution was mixed thoroughly with SSIBS-13.37 solution. The resulting hybrid material contained 12.93% B molar and 0.44% C molar.

[0111] The film prepared in Example 7 has a thickness of 118 μm, a tensile strength of 21.3 MPa, an elongation at break of 77%, a light transmittance of 93.5%, a haze of 4.9%, and a refractive index of 1.5571. The water contact angle of the film surface is 81.4°, indicating that it is a hydrophilic material.

[0112] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 7 showed an increase in tensile strength of 10.5%, an increase in elongation at break of 71.1%, an increase in light transmittance of 5.4%, a decrease in haze of 66.1%, an increase in refractive index of 0.0061, and a decrease in water contact angle of 33.9%.

[0113] Compared with SSIBS-13.37 in Comparative Example 6, the hybrid material prepared by Example 7 showed the same elongation at break; haze decreased by 9.8%; refractive index increased by 0.0030; and water contact angle decreased by 8.1%.

[0114] The above results indicate that the hybrid material prepared by Example 7 has superior mechanical, optical, and hydrophilic properties.

[0115] Example 8

[0116] The preparation process is the same as described in Example 6, except that:

[0117] 0.8 g of A-CRE6·Ce solution was added to SSIBS-13.37 solution. In the resulting hybrid material, the molar content of B was 12.82%, and the molar content of C was 0.55%.

[0118] The film prepared in Example 8 has a thickness of 123 μm, a tensile strength of 24.4 MPa, an elongation at break of 82%, a light transmittance of 93.4%, a haze of 4.9%, a refractive index of 1.5582, and a water contact angle of 79.8°, indicating that it is a hydrophilic material.

[0119] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 8 showed an increase in tensile strength of 26.3%, an increase in elongation at break of 82.2%, an increase in light transmittance of 5.3%, a decrease in haze of 66.3%, an increase in refractive index of 0.0072, and a decrease in water contact angle of 35.2%.

[0120] Compared with SSIBS-13.37 in Comparative Example 6, the hybrid material prepared by Example 8 showed an increase in elongation at break of 6.5%; a decrease in haze of 10.2%; an increase in refractive index of 0.0041; and a decrease in water contact angle of 9.9%.

[0121] The above results indicate that the material prepared by Example 8 has superior mechanical, optical, and hydrophilic properties.

[0122] Example 9

[0123] The preparation process is the same as described in Example 3, except that:

[0124] Replace the DMAc solvent with isopropanol.

[0125] In the prepared hybrid material, the molar content of B is 13.05% and the molar content of C is 0.32%.

[0126] The film prepared in Example 9 has a thickness of 124 μm, a tensile strength of 24.4 MPa, and an elongation at break of 78%. It has a light transmittance of 90.2%, a haze of 5.8%, and a refractive index of 1.5539. The water contact angle of the film surface is 85.1°, indicating it is a hydrophilic material.

[0127] Compared with SIBS in Comparative Example 1, the hybrid material prepared by Example 13 showed an increase in tensile strength of 26.3%, an increase in elongation at break of 73.3%, an increase in light transmittance of 1.7%, a decrease in haze of 59.7%, an increase in refractive index of 0.0029, and a decrease in water contact angle of 30.9%.

[0128] Compared with SSIBS-13.37 in Comparative Example 7, the hybrid material prepared by Example 9 showed an increase in tensile strength of 3.9% and an increase in elongation at break of 8.3%; the light transmittance remained relatively unchanged, the haze decreased by 6.9%, the refractive index increased by 0.0009, and the water contact angle decreased by 2.0%.

[0129] The results above indicate that the hybrid material prepared by Example 9 has superior mechanical, optical, and hydrophilic properties.

[0130] Example 10

[0131] The preparation process is the same as described in Example 1, except that:

[0132] The SIBS used n The concentration was 48.0 kg / mol, and the styrene content was 60.0%. The SSIBS yield was 89.0%, and the functionality was 13.45%, denoted as SSIBS-13.45.

[0133] The hybrid material obtained contains 13.13% B molar content and 0.32% C molar content.

[0134] The film prepared in Example 10 has a thickness of 114 μm, a tensile strength of 28.6 MPa, and an elongation at break of 98%. It has a light transmittance of 93.6%, a haze of 5.5%, and a refractive index of 1.5472. The water contact angle of the film surface is 82.7°, indicating it is a hydrophilic material.

[0135] Compared with SIBS in Comparative Example 2, the SSIBS / A-CRE5·Ce metal hybrid material prepared by Example 10 showed an increase in tensile strength of 24.2%, an increase in elongation at break of 71.5%, an increase in light transmittance of 5.0%, a decrease in haze of 54.4%, an increase in refractive index of 0.0055, and a decrease in water contact angle of 37.3%.

[0136] Compared with SSIBS-13.40 in Comparative Example 10, the hybrid material prepared by Example 10 showed a 7.8% increase in tensile strength, a 6.8% decrease in haze, a 0.0017 increase in refractive index, and a 3.1% decrease in water contact angle.

[0137] The above results indicate that the hybrid material prepared by Example 10 has superior mechanical, optical, and hydrophilic properties.

[0138] Example 11

[0139] The preparation process is the same as described in Example 1, except that the M of the polystyrene-b-poly(ethylene-co-butene)-b-polystyrene (SEBS) used is... nThe yield was 82.8 kg / mol, and the styrene content was 30.0%. The yield of sulfonated SEBS (SSEBS) was 86.4%, and the functionality was 3.22%, denoted as SSEBS-3.22.

[0140] The resulting hybrid material has a B molar content of 2.85% and a C molar content of 0.37%.

[0141] The film prepared by Example 11 has a thickness of 118 μm, a tensile strength of 22.4 MPa, an elongation at break of 357%, a light transmittance of 89.6%, a haze of 13.5%, and a refractive index of 1.5326; the water contact angle of the film surface is 109.7°, indicating that it is a hydrophobic material.

[0142] Compared with SEBS in Comparative Example 3, the hybrid material prepared by Example 11 showed little change in tensile strength, a 16.8% decrease in elongation at break, a 0.6% increase in light transmittance, an 18.0% increase in haze, a 0.0014 increase in refractive index, and a 19.1% decrease in water contact angle.

[0143] Compared with SSEBS-3.22 in Comparative Example 11, the hybrid material prepared by Example 11 showed an increase in tensile strength of 1.9%, an increase in elongation at break of 13.3%, an increase in light transmittance of 8.4%, an increase in haze of 2.4%, an increase in refractive index of 0.0004, and a decrease in water contact angle of 3.0%.

[0144] The results above indicate that the hybrid material prepared by Example 11 has superior mechanical, optical and hydrophilic properties.

[0145] Example 12

[0146] The preparation process is the same as described in Example 1, except that:

[0147] M of poly(α-methylstyrene)-b-polyisobutylene-b-poly(α-methylstyrene) triblock copolymer (ASIBS) n =36.3 kg / mol, α-methylstyrene mass = 65.1%. The yield of sulfonated ASIBS (S-ASIBS) was 87.3%, the functionalization degree was 12.71%, and it was denoted as S-ASIBS-12.71.

[0148] 0.48 g of the A-CRE5·Ce solution from Example 1 was added to the S-ASIBS-12.71 solution. The resulting hybrid material contained 12.27% B molar content and 0.43% C molar content. The film prepared by Example 1 had a thickness of 119 μm, a tensile strength of 26.8 MPa, an elongation at break of 79%, a transmittance of 91.7%, a haze of 5.1%, a refractive index of 1.5563, and a water contact angle of 85.1°, indicating it was a hydrophilic material.

[0149] Compared with ASIBS in Comparative Example 12, the hybrid material prepared by Example 1 showed an increase in tensile strength of 29.5%, an increase in elongation at break of 83.7%, an increase in light transmittance of 2.6%, a decrease in haze of 62.8%, an increase in refractive index of 0.0052, and a decrease in water contact angle of 34.7%.

[0150] Compared with S-ASIBS-12.71 in Comparative Example 13, the hybrid material prepared by Example 1 showed an increase in tensile strength of 7.6%, an increase in elongation at break of 8.2%, a decrease in haze of 12.0%, an increase in refractive index of 0.0022, and a decrease in water contact angle of 4.0%.

[0151] The above results indicate that the hybrid material prepared by Example 1 has superior mechanical, optical, and hydrophilic properties.

[0152] Comparative Example 1

[0153] The polystyrene-b-polyisobutylene-b-polystyrene (SIBS) is the same as in Example 1, with a film thickness of 118 μm, a tensile strength of 19.0 MPa, an elongation at break of 45%, a light transmittance of 88.7%, a haze of 14.4%, a refractive index of 1.5510, and a water contact angle of 123.2° on the film surface, making it a hydrophobic material.

[0154] Comparative Example 2

[0155] The polystyrene-b-polyisobutylene-b-polystyrene (SIBS) is the same as in Example 10, with a film thickness of 120 μm, a tensile strength of 22.54 MPa, an elongation at break of 57%, a light transmittance of 89.2%, a haze of 12.1%, a refractive index of 1.5417, and a water contact angle of 131.9° on the film surface, making it a hydrophobic material.

[0156] Comparative Example 3

[0157] The polystyrene-b-poly(ethylene-co-butene)-b-polystyrene (SEBS) is the same as in Example 11, with a film thickness of 120 μm, a tensile strength of 21.8 MPa, an elongation at break of 430%, a light transmittance of 89.1%, a haze of 11.4%, and a refractive index of 1.5311. The water contact angle of the film surface is 135.6°, making it a hydrophobic material.

[0158] Comparative Example 4

[0159] The experimental procedure was the same as in Example 1. The film was prepared by solution film formation. The SSIBS-3.62 film thickness was 115 μm, the tensile strength was 33.2 MPa, the elongation at break was 137%, the light transmittance was 95.11%, the haze was 4.17%, the refractive index was 1.5526, and the water contact angle of the film surface was 100.5°, indicating that it is a hydrophobic material.

[0160] Comparative Example 5

[0161] The experimental procedure was the same as in Example 2. The film was prepared by solution film formation. The SSIBS-9.84 film thickness was 118 μm, the tensile strength was 23.14 MPa, the elongation at break was 81%, the light transmittance was 94.86%, the haze was 5.32%, the refractive index was 1.5528, and the water contact angle on the film surface was 95.3°, indicating that it is a hydrophobic material.

[0162] Comparative Example 6

[0163] The experimental procedure was the same as in Example 3. The film was prepared by solution deposition. The SSIBS-13.37 film had a thickness of 118 μm, a tensile strength of 24.3 MPa, and an elongation at break of 77%. The light transmittance was 94.2%, the haze was 5.41%, and the refractive index was 1.5541. The water contact angle of the film surface was 88.6°, indicating that it is a hydrophilic material.

[0164] Comparative Example 7

[0165] The experimental procedure was the same as in Example 9. The film was prepared by solution film formation. The SSIBS-13.37 film had a thickness of 122 μm, a tensile strength of 23.1 MPa, an elongation at break of 72%, a light transmittance of 89.5%, a haze of 6.2%, and a refractive index of 1.5530. The water contact angle of the film surface was 86.8°, indicating that it is a hydrophilic material.

[0166] Comparative Example 8

[0167] The SSIBS-16.19 membrane has a water contact angle of 78.0°, making it a hydrophilic material.

[0168] Comparative Example 9

[0169] The SSIBS-44.36 membrane has a water contact angle of 25.7°, making it a hydrophilic material.

[0170] Comparative Example 10

[0171] The experimental procedure was the same as in Example 10. The film was prepared by solution film formation method. The film thickness was 115 μm, the tensile strength was 26.5 MPa, the elongation at break was 100%, the light transmittance was 97.7%, the haze was 5.9%, the refractive index was 1.5455, and the water contact angle of the film surface was 85.4°, indicating that it is a hydrophilic material.

[0172] Comparative Example 11

[0173] The experimental procedure was the same as in Example 11. The SSEBS-3.22 film thickness was 115 μm, the tensile strength was 21.6 MPa, the elongation at break was 315%, the light transmittance was 82.7%, the haze was 13.2%, the refractive index was 1.5322, and the water contact angle on the film surface was 113.4°, indicating that it is a hydrophobic material.

[0174] Comparative Example 12

[0175] The poly(α-methylstyrene)-b-polyisobutylene-b-poly(α-methylstyrene) (ASIBS) is the same as in Example 12, with a film thickness of 121 μm, a tensile strength of 20.7 MPa, an elongation at break of 43%, a light transmittance of 89.4%, a haze of 13.8%, a refractive index of 1.5512, and a water contact angle of 130.4° on the film surface, making it a hydrophobic material.

[0176] Comparative Example 13

[0177] The experimental procedure was the same as in Example 12. The film was prepared by solution deposition. The S-ASIBS-12.71 film had a thickness of 115 μm, a tensile strength of 24.9 MPa, and an elongation at break of 73%. The light transmittance was 93.6%, the haze was 5.8%, and the refractive index was 1.5541. The water contact angle of the film surface was 88.6°, indicating that it is a hydrophilic material.

[0178] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A functionalized styrene-based copolymer / metal ion hybrid material, characterized in that, The hybrid material is composed of a styrene-based copolymer backbone A and side functional groups, wherein the side functional groups include a proton-containing acidic substituent B and a proton-containing acid-amined metal ion complex crown ether group C; Wherein, with the total molar content of structural unit A being 100%, the molar content of B is 1-55%, preferably 2-50%, more preferably 2.5-47%; and the molar content of C is 0.01-1.0%, preferably 0.03-0.85%, more preferably 0.10-0.60%.

2. The functionalized styrene-based copolymer / metal ion hybrid material according to claim 1, wherein, The styrene-based copolymer backbone A is a copolymer segment of styrene or its derivatives with an olefin. The copolymer of styrene or its derivatives with an olefin is selected from at least one of styrene-ethylene copolymer, styrene-propylene copolymer, styrene-butene copolymer, styrene-isobutylene copolymer, α-methylstyrene-isobutylene copolymer, styrene-ethylene / propylene terpolymer, and styrene-ethylene / butene terpolymer, preferably selected from styrene-isobutylene random copolymer, α-methylstyrene-isobutylene random copolymer, polystyrene-b-poly(ethylene-co-propylene) diblock copolymer, polystyrene-b-poly(ethylene-co-propylene)-b-polystyrene triblock copolymer, polystyrene-b-poly(ethylene-co-butene) diblock copolymer, polystyrene-b-poly(ethylene-co-butene)-b-polystyrene triblock copolymer, polystyrene-b-polyisobutylene diblock copolymer, polystyrene-b-polyisobutylene-b-polystyrene triblock copolymer, etc. At least one of the following: (styrene-co-α-methylstyrene)-b-polyisobutylene diblock copolymer, poly(styrene-co-α-methylstyrene)-b-polyisobutylene-b-poly(styrene-co-α-methylstyrene) triblock copolymer, poly(α-methylstyrene)-b-polyisobutylene diblock copolymer, and poly(α-methylstyrene)-b-polyisobutylene-b-poly(α-methylstyrene) triblock copolymer; more preferably, at least one of the following: polystyrene-b-poly(ethylene-co-propylene)-b-polystyrene triblock copolymer, polystyrene-b-poly(ethylene-co-butene)-b-polystyrene triblock copolymer, polystyrene-b-polyisobutylene-b-polystyrene triblock copolymer, poly(styrene-co-α-methylstyrene)-b-polyisobutylene-b-poly(styrene-co-α-methylstyrene) triblock copolymer, and poly(α-methylstyrene)-b-polyisobutylene-b-poly(α-methylstyrene) triblock copolymer; Preferably, the number average molecular weight of the copolymer of styrene or its derivatives with olefins is 10-200 kg / mol, more preferably 20-150 kg / mol, and even more preferably 25-90 kg / mol; Preferably, based on the total weight of the main chain A of the styrene copolymer, the mass content of styrene is 10-75%, more preferably 15-70%, and even more preferably 20-67%.

3. The functionalized styrene-based copolymer / metal ion hybrid material according to claim 1, wherein, The proton-containing acidic substituent B is at least one of a sulfonic acid group, a phosphate group, and a carboxylic acid group, preferably a sulfonic acid group and / or a phosphate group.

4. The functionalized styrene-based copolymer / metal ion hybrid material according to claim 1, wherein, The proton-containing acid-amined metal ion complexed crown ether group C is composed of a proton-containing acidic substituent B and a metal ion complexed amino crown ether. Preferably, the metal ion is selected from at least one of sodium ion, potassium ion, magnesium ion, aluminum ion, calcium ion, scandium ion, titanium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, zirconium ion, molybdenum ion, indium ion, tin ion, antimony ion, cerium ion, praseodymium ion, neodymium ion, samarium ion, europium ion, gadolinium ion, ytterbium ion, hafnium ion, mercury ion, and lead ion; more preferably selected from at least one of sodium ion, potassium ion, magnesium ion, aluminum ion, calcium ion, scandium ion, titanium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, zirconium ion, molybdenum ion, tin ion, cerium ion, praseodymium ion, neodymium ion, samarium ion, hafnium ion, mercury ion, and lead ion; more preferably selected from at least one of titanium ion, vanadium ion, chromium ion, cerium ion, manganese ion, iron ion, cobalt ion, nickel ion, and copper ion. Preferably, the amino crown ether is selected from 2-aminomethyl-15-crown ether-5, 4'-aminobenzo-15-crown ether-5, 4'-(2”,4”-dinitro-6”-trifluoromethylphenyl)-aminobenzo-15-crown ether-5, 2-(aminomethyl)-18-crown ether-6, 4'-aminobenzo-18-crown ether-6, 4'-aminodibenzo-18-crown ether-6, 4'-aminobenzo-15-crown ether-5 hydrochloride, 4'-aminodibenzo-18-crown ether-6 hydrochloride, 4'-aminodibenzo-18-crown ether-6 hydrochloride, 4'-aminobenzo-18-crown ether-6. At least one of ether-6 and 4-aminobenzo-18-crown ether-6 sesquihydrate hydrochloride, preferably selected from at least one of 2-aminomethyl-15-crown ether-5, 4'-aminobenzo-15-crown ether-5, 2-(aminomethyl)-18-crown ether-6, 4'-aminobenzo-18-crown ether-6 and 4'-aminodibenzo-18-crown ether-6, more preferably selected from at least one of 2-aminomethyl-15-crown ether-5, 4'-aminobenzo-15-crown ether-5 and 4'-aminobenzo-18-crown ether-6.

5. The method for preparing the functionalized styrene-based copolymer / metal ion hybrid material according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Obtaining functionalized styrene-based copolymers; (2) Preparation of metal ion complex solution: The amino crown ether compound is mixed with the first organic medium, and an equimolar metal ion compound is added to carry out a complexation reaction to obtain the metal ion complex solution; (3) Preparation of functionalized styrene copolymer / metal ion hybrid material: Dissolve the functionalized styrene copolymer described in step (1) in a second organic medium, add the metal ion complex solution described in step (2) to react, remove the solvent, and obtain the functionalized styrene copolymer / metal ion hybrid material.

6. The preparation method according to claim 5, wherein, The first organic medium and the second organic medium may be the same or different, and each is independently selected from at least one of isopropanol, n-hexanol, tetrahydrofuran, toluene, xylene, phenol, o-dichlorobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, preferably selected from at least one of isopropanol, n-hexanol, N,N-dimethylformamide and N,N-dimethylacetamide, more preferably selected from at least one of isopropanol, toluene and N,N-dimethylacetamide.

7. The preparation method according to claim 5, wherein, The metal ion compound is selected from at least one salt of sodium, potassium, magnesium, aluminum, calcium, yttrium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, indium, tin, antimony, cerium, praseodymium, neodymium, samarium, europium, gadolinium, ytterbium, hafnium, mercury, and lead, preferably from at least one salt of sodium, potassium, magnesium, aluminum, calcium, yttrium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, tin, cerium, praseodymium, neodymium, samarium, hafnium, mercury, and lead, and more preferably from at least one salt of titanium, vanadium, chromium, cerium, manganese, iron, cobalt, nickel, and copper.

8. The preparation method according to claim 5, wherein, In step (1), the functionalized styrene copolymer is obtained through a functionalization reaction, preferably through sulfonation, phosphorylation or carboxylation reaction; The functionalized styrene-based copolymer has a molar functionality of 1–56%, preferably 2–51%, and more preferably 2.5–46%.

9. The preparation method according to claim 5, wherein, In step (2), the conditions for the complexation reaction include: a reaction temperature of -20 to 50°C, preferably -10 to 40°C, more preferably 0 to 30°C; and a reaction time of 1 to 24 hours, preferably 1.5 to 12 hours, more preferably 2 to 5 hours. In the metal ion complex solution, the mass concentration of the metal ion complex is 1-10%, preferably 2-8%, and more preferably 3-6%.

10. The preparation method according to claim 5, wherein, In step (3), the functionalized styrene copolymer solution has a mass concentration of 1-30%, preferably 2-20%, and more preferably 3-10%. The reaction conditions include: a reaction temperature of -20 to 50°C, preferably -10 to 40°C, more preferably 0 to 30°C; and a reaction time of 0.5 to 24 hours, preferably 1 to 12 hours, more preferably 1.5 to 6 hours.