A method for immobilizing phosphonobetaine and phosphonic acid on polystyrene

Abstract

The present invention provides a method for immobilizing phosphonic acid betaine and phosphonic acid on polystyrene, wherein a quaternary ammonium cation containing glycidyl ether is used as a spacer arm, phosphite undergoes a ring-opening reaction with glycidyl ether connected to a polystyrene side chain under an alkali reagent catalyst, phosphonic acid ester is grafted on the polystyrene, and then the phosphonic acid ester is hydrolyzed by acid catalysis to obtain phosphonic acid and phosphonic acid betaine immobilized on the surface of the polystyrene. The method produces the effect of introducing phosphonic acid and phosphonic acid betaine on the polystyrene; the method can not only be used for the adsorption, enrichment and separation of rare earth ions and heavy metal ions, but also has an anion exchange function.

Description

Technical Field

[0001] The present invention relates to a method for preparing an ion exchange resin, and in particular to a method for immobilizing phosphonic acid betaine and phosphonic acid on polystyrene. The polystyrene-based phosphonic acid type ion exchange resin material prepared according to the method of the present invention has high phosphonic acid content, good hydrophilicity, and anion and cation dual exchange function, and belongs to the field of functional polymer materials. Technical Background

[0002] Small molecule organic phosphoric acid and its esters, or organic phosphonic acid and its esters have strong affinity and high coordination ability for rare earth ions, and are the most widely used solvent extractants in the rare earth hydrometallurgy industry. However, the selectivity, loading capacity, stripping efficiency, water dispersibility, emulsification phenomenon, chemical stability, recycling and regeneration, and process loss of small molecule organic phosphonic acid and its derivatives as liquid extractants determine their industrial use value for extracting and separating rare earths. In order to solve the defects of traditional organic phosphonic acid extractants such as volatility, easy loss, emulsified third phase, flammability, and toxicity, scientists immobilize organic phosphonic acid and its derivatives on the surface of macroporous polystyrene resin, silica gel and other materials by bonding to form chelating resins or bonded leaching resins with the function of extracting and adsorbing rare earth ions from solutions. Among them, the most successful is polystyrene-based phosphonic acid resin, which has demonstrated high adsorption performance, high selectivity, simple operation, efficient solid-liquid separation, no loss in the elution process, and clean environment in the fields of rare earth hydrometallurgy, extraction and enrichment of heavy metal ions in dilute solutions, and uranium extraction from seawater.

[0003] There are three main types of immobilized phosphonic acid on polystyrene in the form of covalent bonds: ① Chlorophosphonylation of polystyrene with phosphorus trichloride, followed by oxidative hydrolysis. This method was used in the preparation of phosphonic acid resins in the early stage. However, due to the high toxicity of phosphorus trichloride, the production environment is harsh and the equipment requirements are high; at the same time, the exchange capacity of phosphonic acid resins is not high and the surface hydrophilicity of phosphonic acid resins is also low, so it has lost its value. ② The Michaelis–Arbuzov reaction of chloromethylated polystyrene with phosphite is followed by acid-catalyzed hydrolysis. In this method, the active site of chloromethylated polystyrene is relatively single, and the number of introduced phosphonic acid groups is not high, so the exchange capacity of phosphonic acid resin is not high. In addition, the Michaelis–Arbuzov reaction temperature of chloromethylated polystyrene with phosphite is completed at a relatively high temperature, which has an adverse effect on the stability of the resin itself. ③ After the amination reaction of polystyrene, the obtained ammoniated polystyrene is heated with formaldehyde and phosphorous acid together by Mannich reaction to obtain styrene-loaded aminophosphonic acid. In this method, the amount of phosphonic acid loaded on polystyrene is relatively high, but the Mannich reaction product is complex, and the obtained aminomethylphosphonic acid unit structure is also required to be relatively stable, otherwise the Mannich reaction will proceed in the reverse direction. Other types of phosphoric acid resins or phosphonic acid resins (including phosphoric acid-epoxy resin, phosphoric acid-polyacrylate, phosphoric acid-polyvinyl alcohol, phosphite-polyvinyl chloride, etc.) that have been reported and disclosed have not been recognized because of their low structural stability, poor absorption and desorption recycling effect, and high raw material costs. Summary of the invention

[0004] In order to overcome the defects of the prior art, combined with the technical requirements and application specifications of polystyrene-based phosphonic acid resin or surface-bonded phosphonate-type polystyrene-based leaching resin, the present invention provides a method for immobilizing phosphonic acid betaine and phosphonic acid on polystyrene, and the specific method is achieved by the following steps:

[0005] Step 1: Preparation of quaternary ammonium cationized polystyrene containing glycidyl groups on the surface

[0006] The solvent and chloromethylated polystyrene material are weighed into a reaction kettle, swelled at room temperature for 24 hours under N2 protection, and then N, N-diglycidyl-N-alkylamine is added, the material temperature in the reaction kettle is adjusted to 40-60°C, stirred and reacted for 6-16 hours, then the reaction temperature is increased to 60-90°C, and the stirring reaction is continued for 2-16 hours. After filtering, washing and drying, a quaternary ammonium cationic polystyrene material containing glycidyl groups on the surface is obtained.

[0007] The amount of the solvent used is 2 to 20 times the mass of the chloromethylated polystyrene material, and the amount of the N,N-diglycidyl-N-alkylamine used is 1.0 to 2.0 times the molar amount of chlorine contained in the chloromethylated polystyrene material.

[0008] The polystyrene material refers to cross-linked or non-cross-linked polystyrene resin balls, cross-linked or non-cross-linked polystyrene fibers, cross-linked or non-cross-linked polystyrene filter membranes, or cross-linked or non-cross-linked polystyrene open-cell foams.

[0009] The hydrocarbon group in the N,N-diglycidyl-N-hydrocarbon amine refers to C1 to C 18 Hydrocarbon.

[0010] The solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, chloroform, dichloromethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, decahydronaphthalene, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide. Step 2: Preparation of quaternary ammonium cationic polystyrene containing phosphonate on the surface

[0011] Phosphate is added to a reactor filled with an organic solvent, and an alkali reagent is slowly added under stirring. After stirring evenly, the quaternary ammonium cationized polystyrene containing glycidyl groups on the surface prepared in step 1 is added to the reactor, the reaction temperature is adjusted to 40-90° C., and the reaction is stirred for 6-16 hours; then the quaternary ammonium cationized polystyrene containing phosphonate on the surface is prepared through cooling, filtering, washing, and centrifugal drying.

[0012] The amount of the phosphate ester is 3.0 to 5.5 times the molar amount of glycidyl groups contained in the quaternary ammonium cationized polystyrene containing glycidyl groups on the surface, the amount of the alkaline reagent is 2 to 12% of the mass of the phosphate ester, and the amount of the organic solvent is 0.5 to 5 times the mass of the quaternary ammonium cationized polystyrene containing glycidyl groups on the surface.

[0013] The alkaline reagent is one of sodium hydride, calcium hydride, sodium methoxide, sodium ethoxide, sodium propoxide and sodium tert-butoxide, preferably sodium ethoxide and sodium tert-butoxide.

[0014] The organic solvent refers to one or more of phosphate, N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

[0015] The phosphate ester has a structure shown in the general formula (I):

[0016]

[0017] Wherein R1 in the general formula (Ⅰ) is selected from C1~C 18 Hydroxyl or C1~C 18 Hydrocarbon, R2 is selected from C1~C 18 Hydrocarbon.

[0018] Step 3: Preparation of immobilized phosphonobetaine and phosphonic acid polystyrene

[0019] The quaternary ammonium cationized polystyrene material containing phosphonate on the surface obtained in step 2 is put into hydrochloric acid, the temperature is controlled at 80-90° C., and stirred for acid-catalyzed hydrolysis for 6-16 hours. The polystyrene with immobilized phosphonic acid betaine and phosphonic acid is obtained by filtering, washing, and centrifuging to obtain the polystyrene with immobilized phosphonic acid betaine and phosphonic acid, that is, the polystyrene with surface grafted phosphonic acid betaine and phosphonic acid of the present invention.

[0020] The hydrochloric acid mentioned herein refers to a molar concentration of 1.0 to 11.5 mol·L -1 Aqueous solution of hydrogen chloride, wherein the amount of hydrochloric acid used is 1.0 to 6.0 times the mass of the quaternary ammonium cationized polystyrene containing phosphonate on the surface.

[0021] Reaction formula 1 schematically expresses the preparation method and process of the polystyrene-immobilized phosphonic acid betaine and phosphonic acid:

[0022]

[0023] Among them, the reaction formula-1 Refers to polystyrene materials, wherein the polystyrene materials refer to cross-linked or non-cross-linked polystyrene resin balls, cross-linked or non-cross-linked polystyrene fibers, cross-linked or non-cross-linked polystyrene filter membranes, or cross-linked or non-cross-linked polystyrene open-cell foams; R is selected from C1 to C 18 Hydrocarbon, R1 is selected from C1~C 18 Hydroxyl or C1~C 18 Hydrocarbon, R2 is selected from C1~C 18 Hydrocarbon.

[0024] The alkaline reagent refers to one of sodium hydride, calcium hydride, sodium methoxide, sodium ethoxide, sodium propoxide, and sodium tert-butoxide, preferably sodium ethoxide and sodium tert-butoxide.

[0025] The hydrochloric acid refers to a molar concentration of 1.0 to 11.5 mol·L -1 Aqueous hydrogen chloride solution.

[0026] The present invention provides a polystyrene-immobilized phosphonic acid betaine and phosphonic acid, which have the following beneficial effects:

[0027] ① The polystyrene-immobilized phosphonobetaine and phosphonic acid of the present invention not only include phosphonobetaine and phosphonic acid functional groups with zwitterionic properties, which endow the polystyrene material with high hydrophilicity, can be quickly miscible in a metal salt aqueous solution to extract rare earth metal ions or heavy metal ions therefrom, but also have the characteristics of anion exchange function and antibacterial function.

[0028] ② The methods for preparing the polystyrene-immobilized phosphonobetaine and phosphonic acid of the present invention all adopt classical chemical reactions; the required raw materials are all industrial products with low cost; and the process is safe and efficient.

[0029] ③ The polystyrene-immobilized phosphonobetaine and phosphonic acid of the present invention have high extraction chemical stability, so that the performance of extracting rare earth metal ions is long-lasting and stable, and is particularly suitable for recycling in the process of extraction, separation or enrichment and recovery of precious metal ions or rare earth ions, or in the field of uranium extraction from seawater. DETAILED DESCRIPTION

[0030] The method for immobilizing phosphono-betaine and phosphonic acid on polystyrene of the present invention is further described by the following examples, the purpose of which is to provide a better understanding of the present invention.

[0031] Example 1 Preparation of immobilized phosphonic acid betaine and phosphonic acid polystyrene resin sphere-1

[0032] Step 1: Preparation of quaternary ammonium cationic polystyrene resin sphere-1 containing glycidyl groups on the surface

[0033] Weigh 200 grams of N, N-dimethylformamide and 17.3 grams of washed and vacuum-dried chloromethylated cross-linked polystyrene macroporous hollow resin balls (Nankai University Chemical Plant, commonly known as chlorine balls, particle size 0.45-0.65 mm, cross-linking degree 4.7%, Cl content 17.34%) into a reactor, swell at room temperature for 24 hours under N2 protection, then add 20.5 grams of N, N-diglycidylethylamine, adjust the temperature of the material in the reactor to 40-60°C, stir and react for 8 hours, then increase the reaction temperature to 70-90°C, continue to stir and react for 8 hours, then filter, wash with acetone, extract with Soxhlet for 24 hours, and vacuum dry to obtain 30.5 grams of quaternary ammonium cationized polystyrene resin balls-1 containing glycidyl groups on the surface.

[0034] The grafting rate of quaternary ammonium cationized polystyrene resin sphere-1 containing glycidyl groups on the surface grafted with N,N-diglycidylethylamine was calculated to be 39.8% by mass increase method, and the quaternary ammonium salt rate of the chlorine sphere was deduced to be 89.5%. The mass percentage of epoxy groups of quaternary ammonium cationized polystyrene resin sphere-1 containing glycidyl groups on the surface was calculated to be 22.64% by hydrochloric acid acetone method according to GB1677-81, and the grafting rate of quaternary ammonium cationized polystyrene resin sphere-1 containing glycidyl groups on the surface grafted with N,N-diglycidylethylamine was calculated to be 41.4%; the detection and calculation results of the two grafting rates are basically close, indicating that the preparation of quaternary ammonium cationized polystyrene resin sphere-1 containing glycidyl groups on the surface is successful, and it has the following schematic structure:

[0035]

[0036] Step 2: Preparation of quaternary ammonium cationized polystyrene resin sphere-1 containing diethyl phosphonate on the surface

[0037] 138 g of diethyl phosphite was added to the reactor at room temperature, 2.75 g of sodium ethoxide was slowly added under stirring, and then 30.5 g of quaternary ammonium cationized polystyrene resin balls-1 containing glycidyl groups on the surface obtained in step 1 were added to the reactor, and the temperature was slowly raised to 40-50° C., stirred for reaction for 4 hours, and then gradually raised to 70-80° C., stirred for reaction for another 4 hours, and then cooled and filtered, and washed with ethanol; the resin balls washed with ethanol were centrifuged and dried for 5 minutes at a constant speed of 2000±200 rpm to obtain 52.7 g of quaternary ammonium cationized polystyrene resin balls-1 containing diethoxyphosphonic acid on the surface, which has the following schematic structure:

[0038]

[0039] Thermogravimetric analysis revealed that the quaternary ammonium cationized polystyrene resin sphere-1 containing diethoxyphosphonic acid on the surface contained 11.7% of volatile matter, indicating that the weight gain rate of the resin was 33.59%. The weight gain rate was calculated by the weight gain of the quaternary ammonium cationized polystyrene resin sphere-1 containing diethoxyphosphonic acid on the surface / the mass of the quaternary ammonium cationized polystyrene resin sphere-1 containing diethoxyphosphonic acid on the surface.

[0040] Step 3: Preparation of immobilized phosphonic acid betaine and phosphonic acid polystyrene resin sphere-1

[0041] 52.7 g of quaternary ammonium cationic polystyrene resin beads-1 containing diethoxyphosphonic acid on the surface prepared in step 2 were added into 250 g of 5.5 mol·L -1 The mixture was hydrolyzed in hydrochloric acid at a temperature of 80-90°C for 12 hours with stirring, and then filtered and washed with water until neutral. The neutral resin balls were centrifuged at a constant speed of 2000±200 rpm for 5 minutes to obtain 137.6 g of immobilized phosphonic acid betaine and phosphonic acid polystyrene resin balls-1.

[0042] Thermogravimetric analysis showed that the volatile matter contained in the immobilized phosphonic acid betaine and phosphonic acid polystyrene resin ball-1 was 62.8%. The water content of the immobilized phosphonic acid betaine and phosphonic acid polystyrene resin ball-1 was 67.7% by using the GB / T 5757-2008 ion exchange resin water content determination method. The water contents of the immobilized phosphonic acid betaine and phosphonic acid polystyrene resin ball-1 measured by the two methods were basically close.

[0043] The infrared spectrum of the immobilized phosphonic acid betaine and phosphonic acid polystyrene resin ball-1 FT-IR (cm -1 , KBr tablet) include: 3453cm-1 The characteristic absorption peaks of hydroxyl group OH are 1647 and 1436 cm -1 The characteristic absorption peak of benzene nucleus is 1334cm -1 It is the characteristic absorption peak of CN, 1259cm -1 It is the characteristic absorption peak of P=O double bond, 936cm -1 The above analysis results show that the styrene resin ball-1 has successfully bonded and immobilized phosphonic acid betaine and phosphonic acid with the following schematic structure:

[0044]

[0045] Example 2 Preparation of immobilized phosphonic acid betaine and phosphonic acid polystyrene resin sphere-2

[0046] According to the method and steps of Example 1, the N,N-diglycidylethylamine in step 1 of Example 1 was replaced with N,N-diglycidylbenzylamine to obtain quaternary ammonium cationized polystyrene resin sphere-2 containing glycidyl groups on the surface. The quaternary ammonium cationized polystyrene resin sphere-2 containing glycidyl groups on the surface was confirmed to have the following schematic structure:

[0047]

[0048] The grafting rate of N, N-diglycidyl benzylamine grafted on the quaternary ammonium cationized polystyrene resin ball-2 containing glycidyl groups on the surface was calculated to be 32.2% by the mass increase method. It can be seen that the grafting rate of N, N-diglycidyl benzylamine grafted on the quaternary ammonium cationized polystyrene resin ball-2 containing glycidyl groups on the surface is lower than that of the quaternary ammonium cationized polystyrene resin ball-1 containing glycidyl groups on the surface in Example 1, indicating that the volume of the hydrocarbon group in the N, N-diglycidyl alkylamine increases, reducing its reaction probability with the chlorine ball. It may be that after the chlorine ball undergoes quaternary ammonium salt reaction, the micropore diameter becomes narrow, which hinders the N, N-diglycidyl alkylamine from further penetrating into the resin ball to react; secondly, it may also be because some of the micropore diameters of the chlorine ball are intrinsically narrow, and the chemical sites are built-in deeply, which is not conducive to the quaternary ammonium salt reaction of N, N-diglycidyl alkylamine with a larger molecular volume.

[0049] According to the method and steps of Example 1, the diethyl phosphite in step 2 of Example 1 was replaced with ethyl phosphite to obtain quaternary ammonium cationized polystyrene resin sphere-2 containing ethoxyethyl phosphonic acid on the surface. After analysis, it was confirmed that the quaternary ammonium cationized polystyrene resin sphere-2 containing ethoxyethyl phosphonic acid on the surface had the following schematic structure:

[0050]

[0051] According to the method and steps of Example 1, the method and procedure of step 3 of Example 1 were used to prepare surface grafted phosphonic acid betaine phosphonic acid polystyrene resin sphere-2. Analysis confirmed that the immobilized phosphonic acid betaine and phosphonic acid polystyrene resin sphere-2 had the following schematic structure:

[0052]

[0053] Example 3 Preparation of immobilized phosphonic acid betaine and phosphonic acid polystyrene resin sphere-3

[0054] According to the method and steps of Example 1, the N,N-diglycidylethylamine in step 1 of Example 1 was replaced with N,N-diglycidylbenzylamine to obtain quaternary ammonium cationized polystyrene resin sphere-2 containing glycidyl groups on the surface. The quaternary ammonium cationized polystyrene resin sphere-2 containing glycidyl groups on the surface was confirmed to have the following schematic structure:

[0055]

[0056] According to the method and steps of Example 1, the diethyl phosphite in step 2 of Example 1 was replaced with ethyl phenyl phosphite to obtain quaternary ammonium cationized polystyrene resin sphere-3 containing ethoxyphenylphosphonic acid on the surface. Analysis confirmed that the quaternary ammonium cationized polystyrene resin sphere-3 containing ethoxyphenylphosphonic acid on the surface has the following schematic structure:

[0057]

[0058] According to the method and steps of Example 1, the method and procedure of step 3 of Example 1 were used to prepare surface-grafted phosphonic acid betaine and phosphonic acid polystyrene resin sphere-3. Analysis confirmed that the immobilized phosphonic acid betaine and phosphonic acid polystyrene resin sphere-3 had the following schematic structure:

[0059]

[0060] Example 4 Preparation of bonded immobilized phosphonic acid betaine and phosphonic acid polystyrene microspheres-1

[0061] According to the method and steps of Example 1, the chloromethylated cross-linked polystyrene macroporous hollow resin spheres (Nankai University Chemical Plant, commonly known as chlorine spheres, particle size 0.45-0.65 mm, cross-linking degree 4.7%, Cl content 17.34%) in step 1 of Example 1 were replaced with chloromethylated cross-linked polystyrene microspheres (Xi'an Qiyue Biotechnology Co., Ltd., particle size 25-80 μm, cross-linking degree 5.0%, Cl content 18.25%). Quaternary ammonium cationized polystyrene microspheres-1 containing glycidyl groups on the surface were obtained.

[0062] The grafting rate of quaternary ammonium cationized polystyrene microspheres-1 grafted with glycidyl groups on the surface was calculated to be 21.3% by mass increase method, and the quaternary ammonium salt rate of microspheres-1 was deduced to be 67.7%. The mass percentage of epoxy groups of quaternary ammonium cationized polystyrene microspheres-1 grafted with glycidyl groups on the surface was calculated to be 15.34% by hydrochloric acid acetone method according to GB1677-81, and the grafting rate of quaternary ammonium cationized polystyrene microspheres-1 grafted with N,N-diglycidylethylamine was calculated to be 22.8% by mass increase method; the detection and calculation results of the two grafting rates were close, indicating that the preparation of quaternary ammonium cationized polystyrene microspheres-1 grafted with glycidyl groups on the surface was successful, and it has the following schematic structure:

[0063]

[0064] Under the condition that other technical conditions are basically the same, compared with the quaternary ammonium cationized polystyrene resin ball-1 containing glycidyl groups on the surface in step 1 of Example 1, the grafting rate of N,N-diglycidylethylamine of the quaternary ammonium cationized polystyrene microsphere-1 containing glycidyl groups on the surface drops sharply, so the quaternization rate of microsphere-1 is also relatively low. This may be because part of the chloromethyl groups of microsphere-1 are submerged in the microsphere and cannot show chemical activity in the quaternization reaction.

[0065] Then, according to the method of Example 1 and the procedures of Step 2 and Step 3, the immobilized phosphonic acid betaine and phosphonic acid polystyrene microsphere-1 was prepared. After analysis and determination, it was shown that the microsphere-1 had successfully immobilized phosphonic acid betaine and phosphonic acid, and had the following schematic structure:

[0066]

[0067] Example 5 Characteristics of the immobilized phosphonic acid betaine and phosphonic acid polystyrene of Examples 1 to 4

[0068] Weigh the bonded immobilized phosphonic acid betaine and phosphonic acid polystyrene of Examples 1 to 4, add them to 4 mol / L hydrochloric acid or 10% caustic soda aqueous solution, heat and reflux for 24 hours at normal pressure, filter, wash with water until the washing water is neutral, centrifuge and dry the washed neutral resin balls at a constant speed of 2000±200 rpm for 5 minutes, and obtain the immobilized phosphonic acid betaine and phosphonic acid polystyrene of Examples 1 to 4 after acid / base solution treatment. After elemental analysis and water content determination, the phosphorus content and water content of the immobilized phosphonic acid betaine and phosphonic acid polystyrene of Examples 1 to 4, as well as before and after acid and base treatment are shown in Table 1.

[0069] Table 1 Properties of immobilized phosphonic acid betaine and phosphonic acid polystyrene in Examples 1 to 4

[0070]

[0071] It can be seen from Table 1 that the phosphorus content and water content of the immobilized phosphonic acid betaine and phosphonic acid polystyrene in Examples 1 to 4 of the present invention are substantially unchanged after being refluxed with an acid / base aqueous solution, indicating that each has high chemical stability in an acid / base solution.

Claims

1. A method for immobilizing phosphonobetaine and phosphonic acid on polystyrene, characterized in that This is accomplished using the following steps: Step 1: Preparation of quaternary ammonium cationized polystyrene containing glycidyl groups on the surface Weigh the solvent and chloromethylated polystyrene material in a reaction kettle, swell at room temperature for 24 hours under N2 protection, then add N,N-diglycidyl-N-alkylamine, adjust the temperature of the material in the reaction kettle to 20-60°C, stir and react for 6-16 hours, then increase the reaction temperature to 60-90°C, continue to stir and react for 2-12 hours, and then filter, wash and dry to obtain quaternary ammonium cationic polystyrene containing glycidyl groups on the surface; The polystyrene material refers to cross-linked or non-cross-linked polystyrene resin balls, cross-linked or non-cross-linked polystyrene fibers, cross-linked or non-cross-linked polystyrene filter membranes, or cross-linked or non-cross-linked polystyrene open-cell foams; The hydrocarbon group in the N,N-diglycidyl-N-hydrocarbon amine refers to C1 to C 18 Hydrocarbon; The amount of the solvent is 2 to 20 times the mass of the chloromethylated polystyrene material, and the amount of the N,N-diglycidyl-N-alkylamine is 1.0 to 2.0 times the molar amount of chlorine contained in the chloromethylated polystyrene material; Step 2: Preparation of quaternary ammonium cationized polystyrene containing phosphonate on the surface Phosphate is added to a reactor filled with an organic solvent at room temperature, and an alkali reagent is slowly added under stirring. After stirring evenly, the quaternary ammonium cationized polystyrene material containing glycidyl groups on the surface prepared in step 1 is added to the reactor, the reaction temperature is adjusted to 40-90° C., the reaction is stirred for 6-16 hours, the temperature is lowered to terminate the reaction, and the quaternary ammonium cationized polystyrene containing phosphonate on the surface is obtained through filtering, washing, and centrifugal drying; The amount of the phosphate ester is 1.0 to 1.5 times the molar amount of glycidyl groups contained in the quaternary ammonium cationized polystyrene material containing glycidyl groups on the surface, the amount of the alkaline reagent is 2 to 20% of the mass of the quaternary ammonium cationized polystyrene material containing glycidyl groups on the surface, and the amount of the organic solvent is 2 to 20 times the mass of the quaternary ammonium cationized polystyrene material containing glycidyl groups on the surface; The phosphate ester has a structure shown in the general formula (I): Wherein R1 in the general formula (Ⅰ) is selected from C1~C 18 Hydroxyl or C1~C 18 Hydrocarbon, R2 is selected from C1~C 18 Hydrocarbon; Step 3: Preparation of immobilized phosphonobetaine and phosphonic acid polystyrene The quaternary ammonium cationic polystyrene material containing phosphonate on the surface obtained in step 2 is put into hydrochloric acid, the temperature is controlled at 20-90° C., stirred for acid-catalyzed hydrolysis for 6-16 hours, and then filtered, washed with water until neutral, and centrifuged to obtain polystyrene immobilized with phosphono betaine and phosphonic acid; The hydrochloric acid mentioned herein refers to a molar concentration of 1.0 to 11.5 mol·L -1 Aqueous solution of hydrogen chloride, wherein the amount of hydrochloric acid used is 1.0 to 6.0 times the mass of the quaternary ammonium cationized polystyrene material containing phosphonate on the surface.

2. A method for immobilizing phosphonobetaine and phosphonic acid on polystyrene according to claim 1, characterized in that The solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, chloroform, dichloromethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, decahydronaphthalene, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

3. A method for immobilizing phosphonobetaine and phosphonic acid on polystyrene according to claim 1, characterized in that The alkaline reagent refers to one of sodium hydride, calcium hydride, sodium methoxide, sodium ethoxide, sodium propoxide, and sodium tert-butoxide.

4. A method for immobilizing phosphonobetaine and phosphonic acid on polystyrene according to claim 1, characterized in that The organic solvent refers to one or more of phosphate, N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide; The phosphate ester has the structure shown in the general formula (I): Wherein R1 in the general formula (Ⅰ) is selected from C1~C 18 Hydroxyl or C1~C 18 Hydrocarbon, R2 is selected from C1~C 18 Hydrocarbon.

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