Hydrophilic metal chelating resin as well as preparation method and application thereof

Abstract

The invention provides hydrophilic metal chelating resin as well as a preparation method and application thereof. The hydrophilic metal chelate resin has a structure represented by formula (1): # imgabs0, in which R1 represents # imgabs1 #, R2 represents # imgabs2 # and # imgabs3 # or a single bond, R3 represents # imgabs4 #, and z represents an integer of 1-3. M1 and M2 independently represent alkali metal; n represents an integer of 6-50; x and y are the same or different, x represents an integer of 1-12, and y represents an integer of 1-12. The hydrophilic metal chelating resin disclosed by the invention is insoluble in water and can be dispersed in a water phase, so that trace metal ions can be favorably adsorbed, and particularly, the adsorption capacity on iron ions is strong.

Description

Technical Field

[0001] The present invention relates to a hydrophilic metal chelating resin, a preparation method thereof and uses thereof, belonging to the field of resin preparation. Background Art

[0002] Citric acid is an organic acid produced by microbial fermentation and is widely used in semiconductor chip cleaning solutions. The use of citric acid has no impact on the environment, is relatively easy to degrade under the action of microorganisms and heat, and has relatively strong chelating ability itself. Citric acid in semiconductor chip cleaning solutions also has certain corrosion inhibition properties. As an important link in chemical cleaning, compared with inorganic acids, citric acid has relatively weak acidity, so the corrosion it causes to equipment is relatively small. The safety and reliability of citric acid cleaning are relatively strong, and the waste liquid is relatively easy to handle and does not cause harm to the human body. Therefore, citric acid is often used as a chelating agent, corrosion inhibitor or organic acid in semiconductor chip cleaning solutions and is one of the chemicals with a large consumption in the field of semiconductor chip cleaning.

[0003] Currently, the fermentation method has become the main method for producing citric acid. After extracting the fermentation broth by advanced chromatography or traditional calcium salt method, the citric acid solution still contains a large amount of metal ions such as ferric ions. If citric acid containing ferric ions is added to the semiconductor chip cleaning solution, metal ions will be introduced into the cleaning solution. The presence of metal ions is likely to corrode the chip and cause chip short circuits. Therefore, it is very necessary to purify citric acid before adding it to the semiconductor chip cleaning solution to remove metal ions in the citric acid. Summary of the Invention

[0004] Problems to be Solved by the Invention

[0005] In view of the technical problems existing in the prior art, the present invention first provides a hydrophilic metal chelating resin. The hydrophilic metal chelating resin of the present invention is insoluble in water and can be dispersed in the aqueous phase, which is beneficial to adsorb trace metal ions, especially has a strong adsorption ability for iron ions.

[0006] Furthermore, the present invention also provides a preparation method of the hydrophilic metal chelating resin. The synthesis process of this preparation method is simple, the raw materials are easy to obtain, and it can be mass-produced in kilograms.

[0007] Solutions for Solving the Problems

[0008] [1], A hydrophilic metal chelating resin, wherein the hydrophilic metal chelating resin has a structure shown in the following formula (1):

[0009]

[0010] Wherein, R 1 represents

[0011] R 2 represents or a single bond,

[0012] R 3 represents z represents an integer from 1 to 3;

[0013] M 1 、M 2 each independently represents an alkali metal;

[0014] n represents an integer from 6 to 50;

[0015] x and y are the same or different, and x represents an integer from 1 to 12, and y represents an integer from 1 to 12.

[0016] [2]. The hydrophilic metal chelating resin according to [1] above, wherein the alkali metal is selected from Li, Na or K.

[0017] [3]. A method for preparing the hydrophilic metal chelating resin according to [1] or [2] above, which comprises the following steps:

[0018] In an organic solvent, a nitrogen-containing heterocyclic compound is subjected to a halogenation reaction with a halogenating reagent to obtain a dihalogenated product;

[0019] Using the dihalogenated product and a phenylenediamine compound as reaction monomers, an intermediate polymer is obtained after a polymerization reaction;

[0020] Subjecting the intermediate polymer to an aminomethylation reaction to obtain an aminomethylated product;

[0021] Subjecting the aminomethylated product to a nucleophilic addition reaction with a hydroxide and CS 2 to obtain a hydrophilic metal chelating resin; wherein, the hydroxide has an alkali metal.

[0022] [4]. The preparation method according to [3] above, wherein the molar ratio of the nitrogen-containing heterocyclic compound to the halogenating reagent is 1:(2 - 8), preferably 1:(2.5 - 5);

[0023] The organic solvent includes one or a combination of two or more of absolute ethanol, absolute methanol, acetone, N-methylpyrrolidone or N,N-dimethylformamide;

[0024] The halogenating reagent includes N-bromosuccinimide and / or N-chlorosuccinimide;

[0025] The temperature of the halogenation reaction is 50 - 100 °C, and the time of the halogenation reaction is 30 - 180 s.

[0026] [5]. The preparation method according to [3] or [4] above, wherein the nitrogen-containing heterocyclic compound includes one or a combination of two or more of pyrimidine compounds, pyridine compounds, or pyrazine compounds;

[0027] Preferably, the nitrogen-containing heterocyclic compound includes one or a combination of two or more of pyrazine-2-methanamine oxime, 2-pyridylamidoxime, 3-pyridylamidoxime, pyridine amide, 5-aminopyrimidine, or 3-aminopyridine.

[0028] [6]. The preparation method according to any one of [3]-[5] above, wherein the molar ratio of the nitrogen-containing heterocyclic compound to the benzene diamine compound is greater than or equal to 2:1, preferably (2-5):1; and / or,

[0029] The temperature of the polymerization reaction is 25-100 °C, and the time of the polymerization reaction is 6-12 h;

[0030] Preferably, the benzene diamine compound includes one or a combination of two or more of m-phenylenediamine, p-phenylenediamine, or o-phenylenediamine.

[0031] [7]. The preparation method according to any one of [3]-[6] above, wherein in the presence of an aldehyde compound, the intermediate polymer is subjected to an aminomethylation reaction with a polyamine compound to obtain the aminomethylation product;

[0032] Preferably, the aldehyde compound includes one or a combination of two or more of formaldehyde, acetaldehyde, propionaldehyde, or 2-methylbutyraldehyde;

[0033] Preferably, the polyamine compound is NH 2 -(CH 2 ) x -NH-(CH 2 ) y -NH 2 , wherein x and y are the same or different, and x represents an integer from 1 to 12, and y represents an integer from 1 to 12.

[0034] [8]. The preparation method according to [7] above, wherein the molar ratio of the nitrogen-containing heterocyclic compound to the aldehyde compound is (1.2-2.2):1;

[0035] The molar ratio of the nitrogen-containing heterocyclic compound to the polyamine compound is (1-2.2):1;

[0036] The temperature of the aminomethylation reaction is 25-55 °C, and the time of the aminomethylation reaction is 4-12 h.

[0037] [9]. The preparation method according to any one of [3] - [8] above, wherein the molar ratio of the nitrogen-containing heterocyclic compound to the hydroxide is (1 - 3.3):1;

[0038] The molar ratio of the nitrogen-containing heterocyclic compound to the CS 2 is (1 - 2.5):1;

[0039] The temperature of the nucleophilic addition reaction is 25 - 60 °C, and the time of the nucleophilic addition reaction is 2 - 9 h.

[0040]

[10] . Use of the hydrophilic metal chelating resin according to [1] or [2] above in removing metal ions from citric acid. Preferably, the metal ions include Fe 3+ , Cu 2+ , Pb 2+ , Zn 2+ , Co 2+ , Ni 2+ or a combination of two or more of them.

[0041] Effects of the Invention

[0042] The hydrophilic metal chelating resin of the present invention is insoluble in water and can be dispersed in the aqueous phase, which is beneficial to adsorb trace metal ions, especially has a strong adsorption ability for iron ions.

[0043] Furthermore, the synthesis process of the preparation method of the present invention is simple, the raw materials are easy to obtain, and it can be mass-produced in kilograms. Description of the Drawings

[0044] Figure 1 It is the infrared spectrogram of the hydrophilic metal chelating resin prepared in Example 1. Detailed Embodiments

[0045] The following will detail various exemplary embodiments, features, and aspects of the present invention. The special word "exemplary" here means "serving as an example, embodiment, or illustration". Any embodiment described as "exemplary" here does not have to be interpreted as superior to or better than other embodiments.

[0046] In addition, to better illustrate the present invention, numerous specific details are given in the following detailed embodiments. Those skilled in the art should understand that the present invention can be implemented without some specific details. In other instances, methods, means, equipment, and steps well-known to those skilled in the art are not described in detail to highlight the gist of the present invention.

[0047] Unless otherwise specified, the units used in this specification are all international standard units, and the numerical values and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0048] In this specification, the meaning expressed by "may" includes the meanings of both performing a certain process and not performing a certain process.

[0049] In this specification, the "some specific / preferred embodiments", "some other specific / preferred embodiments", "embodiments", etc. mentioned refer to the specific elements (e.g., features, structures, properties, and / or characteristics) related to the embodiment, which are included in at least one of the embodiments described herein, and may or may not exist in other embodiments. Additionally, it should be understood that the elements can be combined in various embodiments in any suitable manner.

[0050] In this specification, the numerical range expressed by "numerical value A to numerical value B" refers to the range including the endpoint numerical values A and B.

[0051] <The first aspect>

[0052] The first aspect of the present invention provides a hydrophilic metal chelating resin, and the hydrophilic metal chelating resin has a structure shown in the following formula (1):

[0053]

[0054] Wherein, R 1 represents Specifically, R 1 represents

[0055] R 2 represents or a single bond;

[0056] R 3 represents z represents an integer from 1 to 3;

[0057] M 1 and M 2 each independently represent an alkali metal;

[0058] n represents an integer from 6 to 50;

[0059] x and y are the same or different, and x represents an integer from 1 to 12, and y represents an integer from 1 to 12.

[0060] Specifically, the first aspect of the present invention provides a hydrophilic metal chelating resin, and the hydrophilic metal chelating resin has a structure shown in the following formula (1-1) - formula (1-3):

[0061]

[0062]

[0063] In formulas (1-1) to (1-3), R 1 , R 2 , R 3 , z, M 1 , M 2 , n, x, y are exactly the same as those in formula (1).

[0064] The hydrophilic metal chelating resin of the present invention is insoluble in water and can be dispersed in the aqueous phase, which is beneficial to adsorb trace metal ions, especially has a strong adsorption capacity for iron ions.

[0065] In the present invention, the alkali metal can be selected from Li, Na or K.

[0066] In the present invention, n represents an integer from 6 to 50, and for example, it can be 6, 8, 10, 11, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 50, etc.

[0067] In the present invention, x and y are the same or different. x represents an integer from 1 to 12, preferably an integer from 2 to 4. x can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc., and y represents an integer from 1 to 12, preferably an integer from 2 to 4. y can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0068] In the present invention, z represents an integer from 1 to 3, and for example, it can be 1, 2, 3.

[0069] <Second aspect>

[0070] The second aspect of the present invention provides a preparation method of the hydrophilic metal chelating resin according to the first aspect of the present invention, which includes the following steps:

[0071] In an organic solvent, a nitrogen-containing heterocyclic compound is subjected to a halogenation reaction with a halogenating reagent to obtain a dihalogenated product;

[0072] Using the dihalogenated product and a phenylenediamine compound as reaction monomers, an intermediate polymer is obtained after a polymerization reaction;

[0073] The intermediate polymer is subjected to an aminomethylation reaction to obtain an aminomethylated product;

[0074] The aminomethylated product is reacted with a hydroxide and CS 2A nucleophilic addition reaction is carried out to obtain a hydrophilic metal chelating resin; wherein, the hydroxide has an alkali metal.

[0075] The synthesis process of the preparation method of the present invention is simple, the raw materials are easy to obtain, and it can be mass-produced in kilograms.

[0076] Halogenation reaction

[0077] In an organic solvent, a nitrogen-containing heterocyclic compound is subjected to a halogenation reaction with a halogenating reagent to obtain a dihalogenated product.

[0078] In some specific embodiments, after the nitrogen-containing heterocyclic compound and the organic solvent are mixed evenly, a halogenating reagent is added for a halogenation reaction to obtain a dihalogenated product.

[0079] Furthermore, the molar ratio of the nitrogen-containing heterocyclic compound to the halogenating reagent is 1:(2-8), preferably 1:(2.5-5), for example: 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, etc. When the molar ratio of the nitrogen-containing heterocyclic compound to the halogenating reagent is 1:(2-8), the halogenation reaction can proceed more effectively.

[0080] Specifically, the temperature of the halogenation reaction is 50-100 °C, for example: 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, etc., and the time of the halogenation reaction is 30-180 s, for example: 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s, 130 s, 140 s, 150 s, 160 s, 170 s, 180 s, etc.

[0081] In some specific embodiments, the nitrogen-containing heterocyclic compound and the organic solvent are mixed evenly, and at a temperature of 50-100 °C, a halogenating reagent is added, and the reaction is carried out by microwave heating for 30-180 s to obtain a dihalogenated product.

[0082] In some specific embodiments, the nitrogen-containing heterocyclic compound includes one or a combination of two or more of pyrimidine compounds, pyridine compounds or pyrazine compounds; preferably, the nitrogen-containing heterocyclic compound includes one or a combination of two or more of pyrazine-2-methanamine oxime, 2-pyridylamidoxime, 3-pyridylamidoxime, pyridine amide, 5-aminopyrimidine or 3-aminopyridine.

[0083] Specifically, the organic solvent includes one or a combination of two or more selected from absolute ethanol, absolute methanol, acetone, N-methylpyrrolidone, or N,N-dimethylformamide. The halogenating agent includes N-bromosuccinimide and / or N-chlorosuccinimide.

[0084] In the present invention, halogen can be introduced through a halogenation reaction. By introducing halogen, a polymerization reaction can be carried out with a phenylenediamine compound.

[0085] Polymerization reaction

[0086] The present invention uses a dihalogenated product and a phenylenediamine compound as reaction monomers, and an intermediate polymer is obtained after a polymerization reaction.

[0087] In the present invention, the temperature of the polymerization reaction is 25 to 100 °C, for example: 25 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 75 °C, 80 °C, 90 °C, 100 °C, etc.; the time of the polymerization reaction is 6 to 12 h, for example: 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, etc. When the temperature of the polymerization reaction is 25 to 100 °C and the time of the polymerization reaction is 6 to 12 h, the polymerization reaction can proceed more effectively.

[0088] In some specific embodiments, under nitrogen protection, a phenylenediamine compound is dissolved in an organic solvent in a reactor, and the dihalogenated product is gradually added to the reactor, and the reaction is carried out at a temperature of 25 to 100 °C for 6 to 12 h, and the excess organic solvent is removed by vacuum distillation to obtain an intermediate polymer.

[0089] Specifically, the molar ratio of the nitrogen-containing heterocyclic compound to the phenylenediamine compound is greater than or equal to 2:1, preferably: (2 to 5):1, more preferably 2 to 3.3:1, for example: 2:1, 2.2:1, 2.3:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.3:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 5:1, etc. When the molar ratio of the nitrogen-containing heterocyclic compound to the phenylenediamine compound is greater than or equal to 2:1, it is beneficial to obtain the intermediate polymer of the present application.

[0090] Furthermore, the phenylenediamine compound includes one or a combination of two or more selected from m-phenylenediamine, p-phenylenediamine, or o-phenylenediamine.

[0091] Aminomethylation reaction

[0092] In the present invention, an aminated methylated product is obtained by subjecting the intermediate polymer to an aminated methylation reaction; specifically, in the presence of an aldehyde compound, the intermediate polymer is subjected to an aminated methylation reaction with the polyamine compound to obtain the aminated methylated product.

[0093] In some specific embodiments, the intermediate polymer can be mixed with an aldehyde compound and then with a polyamine compound for an aminomethylation reaction. Specifically, after mixing the intermediate polymer with the aldehyde compound for 0.2 to 2 hours, it is then mixed with the polyamine compound for an aminomethylation reaction.

[0094] Furthermore, the molar ratio of the nitrogen-containing heterocyclic compound to the aldehyde compound is (1.2 to 2.2):1, preferably (1.2 to 1.3):1, such as: 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, etc.; the molar ratio of the nitrogen-containing heterocyclic compound to the polyamine compound is (1 to 2.2):1, preferably (1 to 1.7):1, such as: 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, etc. When the molar ratio of the nitrogen-containing heterocyclic compound to the aldehyde compound is (1.2 to 2.2):1 and the molar ratio of the nitrogen-containing heterocyclic compound to the polyamine compound is (1 to 2.2):1, the polymerization reaction can proceed effectively.

[0095] In some specific embodiments, the temperature of the aminomethylation reaction is 25 to 55 °C, such as: 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, etc.; the time of the aminomethylation reaction is 4 to 12 h, such as: 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, etc. When the temperature of the aminomethylation reaction is 25 to 55 °C and the time of the aminomethylation reaction is 4 to 12 h, the aminomethylation reaction can proceed more effectively.

[0096] In some specific embodiments, the aldehyde compound includes one or more combinations of formaldehyde, acetaldehyde, propionaldehyde, or 2-methylbutyraldehyde. Preferably, the aldehyde compound is formaldehyde.

[0097] In some specific embodiments, the polyamine compound is NH 2 -(CH 2 ) x -NH-(CH 2 ) y -NH 2, wherein x and y are the same or different, x represents an integer from 1 to 12, and y represents an integer from 1 to 12. Preferably, the polyamine compound is one or a combination of two or more of diethylenetriamine, 3,3'-diaminodipropylamine (CAS No.: 56-18-8), and spermidine (CAS No.: 124-20-9). More preferably, the polyamine compound is diethylenetriamine.

[0098] Nucleophilic addition reaction

[0099] The present invention makes the aminomethylated product react with a hydroxide and CS 2 to carry out a nucleophilic addition reaction to obtain a hydrophilic metal chelating resin, wherein the hydroxide has an alkali metal.

[0100] Specifically, in the present invention, the hydroxide can be NaOH, KOH, LiOH, etc.

[0101] In some specific embodiments, the molar ratio of the nitrogen-containing heterocyclic compound to the hydroxide is (1 to 3.3):1, preferably (1 to 1.7):1, for example: 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.3:1, etc. When the molar ratio of the nitrogen-containing heterocyclic compound to the hydroxide is (1 to 3.3):1, it is easier to obtain the desired hydrophilic metal chelating resin.

[0102] In some specific embodiments, the molar ratio of the nitrogen-containing heterocyclic compound to the CS 2 is (1 to 2.5):1, preferably (1 to 1.7):1, for example: 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.5:1, etc. When the molar ratio of the nitrogen-containing heterocyclic compound to CS 2 is (1 to 2.5):1, the reaction can proceed more effectively.

[0103] Specifically, the temperature of the nucleophilic addition reaction is 25 to 60 °C, for example: 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, etc.; the time of the nucleophilic addition reaction is 2 to 9 h, for example: 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, etc.

[0104] Furthermore, the nucleophilic addition reaction of the present invention can be carried out step by step. Specifically, after mixing the hydroxide and the aminomethylated product, CS can be added dropwise 2After performing a one-step reaction, the temperature is raised to continue the two-step reaction, thereby obtaining a hydrophilic metal chelating resin. Preferably, during the reaction process, the temperature of the one-step reaction can be 20-35 °C, for example: 20 °C, 22 °C, 25 °C, 28 °C, 30 °C, 32 °C, 35 °C, etc.; the time of the one-step reaction is 0.5-6 h, for example: 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, etc. The temperature of the two-step reaction can be 36-60 °C, for example: 36 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, etc.; the time of the two-step reaction is 0.5-3 hours, for example: 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, etc. Through the stepwise reaction, it is more conducive to obtaining a hydrophilic metal chelating resin.

[0105] Furthermore, a precipitating agent can be added to the reaction product (stop adding the precipitating agent when precipitation appears) to precipitate the hydrophilic metal chelating resin to obtain a precipitate (white floc). The present invention does not particularly limit the precipitating agent, and it can be a commonly used precipitating agent in the art, for example: acetone, etc.

[0106] Finally, the precipitate is washed and then dried to obtain a hydrophilic metal chelating resin. Regarding the temperature and time of drying, the present invention does not make a particular limitation, and specifically, it can be dried at a temperature of 30-100 °C for 5-20 hours.

[0107] <The third aspect>

[0108] The third aspect of the present invention provides a use of the hydrophilic metal chelating resin according to the first aspect of the present invention in removing metal ions in citric acid. Preferably, the metal ions include Fe 3+ 、Cu 2+ 、Pb 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ or a combination of two or more of them.

[0109] Specifically, removing metal ions in citric acid can include the following steps:

[0110] (1) Pretreatment of the hydrophilic chelating resin;

[0111] Place the hydrophilic metal chelating resin of the present invention in an ion exchange column and rinse it with pure water until there is no turbidity, add dilute hydrochloric acid with a mass percentage content of 3-6% and soak it for 6-12 h, and rinse it with pure water until the conductivity of the outlet and the inlet is the same, and set it aside;

[0112] (2) Treat citric acid;

[0113] Mix 0.5 - 20 wt% citric acid with the resin treated in step (1), and let it flow out of the ion exchange column at a rate of 0.2 - 1 ml / min, preferably 0.5 ml / min, with a treatment time of 0.5 - 2 h.

[0114] The inventors of the present invention found that the hydrophilic chelating resin of the present invention has good adsorption effects on Fe, Cu, Pb, Zn, Co, Ni and other ions.

[0115] Examples

[0116] The following will describe the embodiments of the present invention in detail in conjunction with the examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those not specified in the examples, they are carried out under conventional conditions or conditions recommended by the manufacturer. For reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0117] In the examples, the degree of polymerization is calculated by measuring the molecular weight of the polymer through GPC.

[0118] Examples 1 - 9

[0119] Examples 1 - 9 contain the components and molar ratios as shown in Table 1. And the hydrophilic metal chelating resin is prepared according to the following preparation method:

[0120] S1: Prepare the dihalogenated product

[0121] Add the nitrogen-containing heterocyclic compound into 1200 ml of N,N-dimethylformamide and mix evenly. At a temperature of 70 °C, add the halogenating reagent and react by microwave heating for 60 s. After centrifugation and drying, the dihalogenated product is obtained.

[0122] S2: Prepare the intermediate polymer

[0123] Under nitrogen protection, dissolve the phenylenediamine compound in 1200 ml of absolute ethanol in the reactor. Add the dihalogenated product to the reactor in 4 portions and react at a temperature of 75 °C for 8 h. Remove the excess solvent by vacuum distillation to obtain the intermediate polymer.

[0124] S3: Synthesize the hydrophilic chelating resin

[0125] At a temperature of 50 °C, add the aldehyde compound to the intermediate polymer prepared in step S2 and stir for 1 h. Then add the polyamine compound and carry out the aminomethylation reaction under stirring for 4 h to obtain the aminomethylated product. Cool the obtained aminomethylated product and keep it at room temperature for further use.

[0126] Add the hydroxide of an alkali metal to the above-prepared aminomethylated product, stir in a water bath at 25 °C, and then add CS dropwise 2 , and continue the reaction for 4 h. Then, raise the temperature to 55 °C and continue the reaction for 1.5 h to obtain a reaction product. Subsequently, add an excess of acetone to the reaction product to precipitate the hydrophilic metal chelating resin, obtaining a precipitate. Wash the precipitate 3 times with absolute ethanol and dry the precipitate in an oven at 100 °C for 12 h to obtain the hydrophilic metal chelating resin.

[0127] Table 1 Examples 1-9

[0128]

[0129] Comparative Examples 1-7

[0130] The components and molar ratios included in Comparative Examples 1-7 are shown in Table 2. And they are prepared according to the preparation method of Examples 1-9.

[0131] Table 2 Comparative Examples 1-7

[0132]

[0133] Performance test

[0134] 1. Infrared test

[0135] To prove the correctness of the above structure, the hydrophilic metal chelating resin prepared in Example 1 was subjected to infrared spectrum structure verification, and the test results are shown in Figure 1 as shown.

[0136] From Figure 1 it can be seen that the peak at about 3453 cm -1 is the stretching vibration peak of N-H in methylamine oxime, and the peaks at about 2923 cm -1 and about 2857 cm -1 are caused by the asymmetric stretching vibration of C-H of -CH 3 and the symmetric stretching vibration of C-H of -CH 2 . The peak at about 1643 cm -1 is the stretching vibration peak of C=N in methylamine oxime, the peak at about 1400 cm -1 is the stretching vibration peak of C-N in methylamine oxime, the peak at 1022 cm -1 is the stretching vibration peak of C=S, and the peak at about 948 cm -1 is the stretching vibration peak of N-O in methylamine oxime.

[0137] 2. Performance verification of the resin

[0138] Resin pretreatment: Take 30 ml of hydrophilic metal chelating resin as 1 BV volume, place it in an ion exchange column and rinse with pure water until there is no turbidity. Then dilute it 5 - 10 times with electronic grade hydrochloric acid, soak the hydrophilic metal chelating resin with the diluted hydrochloric acid for 8 h, and then rinse the hydrophilic metal chelating resin with pure water until the conductivity of the outlet and inlet is the same. The treatment of the hydrophilic metal chelating resin is completed.

[0139] Dynamic adsorption experiment: Take 60 ml of citric acid solution, pour it into the treated hydrophilic metal chelating resin, let it flow out of the ion exchange column at a speed of 0.5 ml / min, and take samples. Detect the situation of other metal ions in citric acid by ICP-MS, and the test results are shown in Table 3.

[0140] Table 3

[0141] Raw material <![CDATA[Fe 3+ (%)]]> <![CDATA[Co 2+ (%)]]> <![CDATA[Ni 2+ (%)]]> <![CDATA[Cu 2+ (%)]]> <![CDATA[Zn 2+ (%)]]> <![CDATA[Pb 2+ (%)]]> Citric acid (CA) 50.92 0.56 0.43 0.26 5.27 0.07 Example 1 0.33 0 0 0 0 0 Example 2 4.72 0.12 0.02 0.02 0.62 0 Example 3 2.98 0.14 0.01 0.03 0.56 0.01 Example 4 3.62 0.09 0.01 0 0.15 0 Example 5 20.52 0.11 0 0 0.60 0 Example 6 19.83 0.15 0 0 0.59 0 Example 7 1.83 0 0 0 0.03 0 Example 8 1.88 0 0 0 0.08 0 Example 9 1.73 0 0 0 0.05 0 Comparative example 1 43.92 0.47 0.38 0.25 5.12 0.05 Comparative example 2 40.62 0.45 0.35 0.21 4.03 0.03 Comparative example 3 39.03 0.31 0.31 0.19 4.14 0.06 Comparative example 4 37.14 0.44 0.29 0.18 4.20 0.05 Comparative example 5 37.14 0.44 0.29 0.18 4.20 0.05 Comparative example 6 38.56 0.42 0.32 0.12 4.07 0.07 Comparative example 7 38.56 0.42 0.32 0.12 4.07 0.07

[0142] As can be seen from Table 3, the hydrophilic metal chelating resin prepared in the examples of this application has good adsorption effects on Fe, Cu, Pb, Zn, Co, Ni and other ions.

[0143] Compared with Example 1, in Comparative Example 1, since no halogenated reagent was added in Comparative Example 1, the polymerization reaction could not occur, resulting in a decrease in the adsorption effects on Fe, Cu, Pb, Zn, Co, Ni and other ions.

[0144] Compared with Example 1, in Comparative Example 2, since the content of the halogenated reagent in Comparative Example 2 was not excessive, only a small amount of monohalogenated product was obtained, and no dihalogenated product was formed. And the formed monohalogenated product could not polymerize normally, resulting in a decrease in the adsorption effects on Fe, Cu, Pb, Zn, Co, Ni and other ions.

[0145] Compared with Example 1, in Comparative Example 3, since the effect of adding 3 - pyridinemethanol compound in Comparative Example 3 was not as obvious as that of pyrazine - 2 - methanamine oxime, the adsorption effects on Fe, Cu, Pb, Zn, Co, Ni and other ions decreased.

[0146] Compared with Example 1, in Comparative Example 4, since no formaldehyde was added in Comparative Example 4, the aminomethylation reaction could not be carried out, resulting in a decrease in the adsorption effects on Fe, Cu, Pb, Zn, Co, Ni and other ions.

[0147] Compared with Example 1, in Comparative Example 5, since no polyamine compound was added in Comparative Example 5, the adsorption effects on Fe, Cu, Pb, Zn, Co, Ni and other ions decreased.

[0148] For Comparative Example 6 and Comparative Example 7, since NaOH and CS were not added 2, which leads to the inability to carry out the nucleophilic addition reaction and results in a decrease in the adsorption effect on ions such as Fe, Cu, Pb, Zn, Co, and Ni.

[0149] It should be noted that although the technical solutions of the present invention are introduced by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.

[0150] The embodiments of the present invention have been described above. The above description is exemplary and not exhaustive, and is also not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The choice of terms used herein is intended to best explain the principles of the embodiments, practical applications, or improvements to technologies in the market, or to enable other ordinary skill in the art to understand the disclosed embodiments.

Claims

1. A hydrophilic metal chelate resin, characterized in that, The hydrophilic metal chelate resin has a structure as shown in the following formula (1): Among them, R1 represents R2 means or single key, R3 means z represents an integer from 1 to 3; M1 and M2 each independently represent an alkali metal; n represents an integer from 6 to 50; x and y are the same or different, and x represents an integer of 1 to 12, and y represents an integer of 1 to 12.

2. The hydrophilic metal chelate resin according to claim 1, wherein The alkali metal is selected from Li, Na or K.

3. A method for preparing a hydrophilic metal chelate resin according to claim 1 or 2, characterized in that: The following steps are involved: In an organic solvent, a nitrogen-containing heterocyclic compound is subjected to a halogenation reaction with a halogenation reagent to obtain a dihalogenated product; Using dihalogenated products and phenylenediamine compounds as reaction monomers, an intermediate polymer is obtained after polymerization reaction; subjecting the intermediate polymer to an amine methylation reaction to obtain an amine methylation product; The amine methylation product is subjected to a nucleophilic addition reaction with a hydroxide and CS2 to obtain a hydrophilic metal chelate resin; wherein the hydroxide contains an alkali metal.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the nitrogen-containing heterocyclic compound to the halogenating agent is 1:(2-8), preferably 1:(2.5-5); The organic solvent includes one or a combination of two or more of anhydrous ethanol, anhydrous methanol, acetone, N-methylpyrrolidone or N,N-dimethylformamide; The halogenating agent includes N-bromosuccinimide and / or N-chlorosuccinimide; The temperature of the halogenation reaction is 50-100° C., and the time of the halogenation reaction is 30-180 seconds.

5. The preparation method according to claim 3 or 4, characterized in that: The nitrogen-containing heterocyclic compound includes one or a combination of two or more of pyrimidine compounds, pyridine compounds or pyrazine compounds; Preferably, the nitrogen-containing heterocyclic compound includes one or a combination of two or more of pyrazine-2-methylamine oxime, 2-pyridyl amidoxime, 3-pyridyl amidoxime, pyridine amide, 5-aminopyrimidine or 3-aminopyridine.

6. The preparation method according to any one of claims 3 to 5, characterized in that: The molar ratio of the nitrogen-containing heterocyclic compound to the phenylenediamine compound is greater than or equal to 2:1, preferably (2-5):1; and / or, The polymerization reaction temperature is 25 to 100° C., and the polymerization reaction time is 6 to 12 hours; Preferably, the phenylenediamine compound includes one or a combination of two or more of m-phenylenediamine, p-phenylenediamine or o-phenylenediamine.

7. The preparation method according to any one of claims 3 to 6, characterized in that: In the presence of an aldehyde compound, the intermediate polymer is subjected to an amine methylation reaction with a polyamine compound to obtain the amine methylation product; Preferably, the aldehyde compound includes one or a combination of two or more of formaldehyde, acetaldehyde, propionaldehyde or 2-methylbutyraldehyde; Preferably, the polyamine compound is NH2-(CH2) x -NH-(CH2) y -NH2, wherein x and y are the same or different, and x represents an integer of 1 to 12, and y represents an integer of 1 to 12.

8. The preparation method according to claim 7, characterized in that: The molar ratio of the nitrogen-containing heterocyclic compound to the aldehyde compound is (1.2-2.2):1; The molar ratio of the nitrogen-containing heterocyclic compound to the polyamine compound is (1-2.2):1; The temperature of the amine methylation reaction is 25 to 55° C., and the time of the amine methylation reaction is 4 to 12 hours.

9. The preparation method according to any one of claims 3 to 8, characterized in that: The molar ratio of the nitrogen-containing heterocyclic compound to the hydroxide is (1-3.3):1; The molar ratio of the nitrogen-containing heterocyclic compound to the CS2 is (1-2.5):1; The temperature of the nucleophilic addition reaction is 25 to 60° C., and the time of the nucleophilic addition reaction is 2 to 9 hours.

10. A use of the hydrophilic metal chelate resin according to claim 1 or 2 in removing metal ions from citric acid, preferably, the metal ions include Fe 3+ , Cu 2+ , Pb 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ One or a combination of two or more.

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