Super-crosslinked polymer as well as preparation method and application thereof

Abstract

The invention provides a super-crosslinked polymer as well as a preparation method and application thereof. The super-crosslinked polymer is prepared from the following raw materials: a combination of a halogen-modified super-crosslinked polymer and ethylenediamine-terminated polyethyleneimine, the halogen-modified super-crosslinked polymer is prepared from the following raw materials: a benzyl dihalide compound. The super-crosslinked polymer provided by the invention can generate electrostatic interaction and hydrogen bonds with glyphosate molecules, so that the super-crosslinked polymer can be used as a glyphosate adsorbent, and has high glyphosate adsorption capacity, rapid adsorption kinetics and excellent cycle performance; in addition, the synthesis raw materials of the super-crosslinked polymer provided by the invention are simple and low in price.

Description

Technical Field

[0001] The invention belongs to the technical field of adsorption materials, and in particular relates to a hyper-crosslinked polymer and a preparation method and application thereof. Background Art

[0002] Glyphosate, with the chemical name N-(phosphonomethyl)glycine, also known as Roundup, Glyphosate, etc., is the most widely used high-efficiency and low-toxic herbicide in the world today. The production methods of glyphosate mainly include the iminodiacetic acid method, the dimethylphosphonite method and the glycine method. Domestic enterprises mainly use the glycine method to produce glyphosate. It is reported that every ton of glyphosate produced produces about 4.5 tons of acidic phosphorus-containing mother liquor, which contains about 0.5-1.8% glyphosate, 3-5% glyphosate, about 5% phosphorous acid and 16% sodium chloride. If these organophosphorus compounds are not treated in time, they will cause serious harm to the natural environment and human health. The environmental protection treatment of glyphosate mother liquor is an international industry problem. Not only is the industrial treatment difficult but also the cost is high. Therefore, the development of efficient separation and recovery technology for high-value phosphorus compounds has become one of the current industrial problems that need to be solved urgently.

[0003] Over the past few decades, a variety of treatment methods for glyphosate in glyphosate wastewater have been developed, such as incineration, advanced oxidation, chemical precipitation, biochemical, membrane separation and adsorption. Among the many separation methods, considering the complexity of glyphosate wastewater, separation rate, stability, economic factors and feasibility, the adsorption method is most suitable for the separation and extraction of glyphosate in glyphosate wastewater. Polymers are increasingly used in the field of adsorption because they can be processed into different target shapes according to different application scenarios and the material surface is easy to modify. Since there are acidic groups such as carboxyl and phosphonic acid groups in the molecular structure of glyphosate, hydrogen bonds and acid-base interactions can be generated with amino groups, it is possible to consider using amino-functionalized adsorption materials to separate glyphosate.

[0004] Currently, amino-functionalized commercial resins have been used in the separation research of glyphosate, but there is still a problem that it is difficult to have high adsorption capacity, high selectivity, and fast adsorption rate. Therefore, it is of great significance to develop a new amino-functionalized adsorption material that has high adsorption capacity, fast adsorption kinetics, high selectivity, simple synthetic raw materials, and low price to efficiently adsorb and separate glyphosate. Summary of the invention

[0005] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a hyper-crosslinked polymer and a preparation method and application thereof. By designing the raw materials for preparing the hyper-crosslinked polymer, the obtained hyper-crosslinked polymer has a high adsorption capacity, fast adsorption kinetics and excellent cycle performance for glyphosate, while the synthetic raw materials are simple and inexpensive.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a hyper-crosslinked polymer, wherein the raw materials for preparing the hyper-crosslinked polymer include a combination of a halogen-modified hyper-crosslinked polymer and ethylenediamine-terminated polyethyleneimine; and the raw materials for preparing the halogen-modified hyper-crosslinked polymer include dihalobenzyl compounds.

[0008] The hyper-crosslinked polymer provided by the present invention is modified with polyethyleneimine terminated with ethylenediamine, and the synthetic raw materials thereof are inexpensive. The hyper-crosslinked polymer can generate electrostatic effects and hydrogen bonds between its own amino groups and the carboxyl groups and phosphonic acid groups in the molecular structure of glyphosate, thereby achieving excellent adsorption and separation performance and rapid adsorption kinetics, and has excellent prospects in the field of glyphosate separation and recovery. In addition, after the hyper-crosslinked polymer provided by the present invention completes the adsorption of glyphosate, the glyphosate can be eluted and recovered by an alkaline solution (such as sodium hydroxide, potassium hydroxide, etc.).

[0009] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0010] As a preferred technical solution, the dihalobenzyl compound includes 1,4-dichlorobenzyl and / or 1,4-dibromobenzyl.

[0011] Preferably, the number average molecular weight of the ethylenediamine-terminated polyethyleneimine is 400-800, for example, 400, 450, 500, 550, 600, 650, 700, 750, etc.

[0012] In the present invention, the ethylenediamine-terminated polyethyleneimine can be purchased, for example, from but not limited to Aladdin.

[0013] Preferably, the mass ratio of the halogen-modified hyper-crosslinked polymer to the ethylenediamine-terminated polyethyleneimine is (0.5-2):1, for example, it can be 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 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, 1.95:1, etc.

[0014] Preferably, the preparation method of the halogen-modified hyper-crosslinked polymer comprises:

[0015] The dihalobenzyl compound is subjected to Friedel-Crafts alkylation reaction to obtain the halogen-modified hyper-crosslinked polymer.

[0016] Preferably, the Friedel-Crafts alkylation reaction is carried out in the presence of a first catalyst.

[0017] Preferably, the first catalyst comprises anhydrous ferric chloride and / or anhydrous aluminum chloride.

[0018] Preferably, the mass ratio of the dihalobenzyl compound to the first catalyst is (0.5-2.5):1, for example, it can be 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 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, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, etc.

[0019] Preferably, the Friedel-Crafts alkylation reaction is carried out in the presence of a first organic solvent.

[0020] Preferably, the first organic solvent comprises ethylene dichloride and / or dichloromethane.

[0021] Preferably, based on the mass of the dihalobenzyl compound as 1 g, the volume of the first organic solvent is 10-40 mL, for example, 10 mL, 12 mL, 14 mL, 16 mL, 18 mL, 20 mL, 22 mL, 24 mL, 26 mL, 28 mL, 30 mL, 32 mL, 34 mL, 36 mL, 38 mL, etc.

[0022] Preferably, the Friedel-Crafts alkylation reaction is carried out under a nitrogen atmosphere.

[0023] Preferably, the Friedel-Crafts alkylation reaction includes a first stage reaction and a second stage reaction.

[0024] Preferably, the temperature of the first stage reaction is 18-25°C, for example, it can be 19°C, 19.5°C, 20°C, 20.5°C, 21°C, 21.5°C, 22°C, 22.5°C, 23°C, 23.5°C, 24°C, 24.5°C, 25°C, etc.

[0025] Preferably, the first stage reaction time is 1-2 h, for example, it can be 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, etc.

[0026] Preferably, the temperature of the second stage reaction is 25-90°C, for example, it can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc.

[0027] Preferably, the reaction time of the second stage is 1-24 h, for example, it can be 2 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, etc.

[0028] Preferably, the second stage reaction is carried out under the condition of a constant temperature oil bath.

[0029] Preferably, the first stage reaction and the second stage reaction are each independently carried out under a first stirring condition.

[0030] Preferably, the first stirring speed is 400-550 r / min, for example, 400 r / min, 420 r / min, 440 r / min, 460 r / min, 480 r / min, 500 r / min, 520 r / min, 540 r / min, 550 r / min, etc.

[0031] Preferably, after the Friedel-Crafts alkylation reaction is completed, the steps of washing and first drying are further performed in sequence.

[0032] Preferably, the first drying temperature is 60-100°C, for example, it can be 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 82°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C, etc.

[0033] Preferably, the first drying time is 12-24 hours, for example, it can be 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, etc.

[0034] Preferably, the raw materials for preparing the hyper-crosslinked polymer further include a second organic solvent.

[0035] Preferably, the second organic solvent comprises N,N-dimethylformamide and / or dimethyl sulfoxide.

[0036] Preferably, based on the mass of the ethylenediamine-terminated polyethyleneimine as 1 g, the volume of the second organic solvent is 150-1000 mL, for example, it can be 150 mL, 200 mL, 250 mL, 300 mL, 350 mL, 400 mL, 450 mL, 500 mL, 550 mL, 600 mL, 650 mL, 700 mL, 750 mL, 800 mL, 850 mL, 900 mL, 950 mL, 1000 mL, etc.

[0037] Preferably, the raw materials for preparing the hyper-crosslinked polymer further include a second catalyst.

[0038] Preferably, the second catalyst comprises potassium carbonate.

[0039] Preferably, the mass ratio of the ethylenediamine-capped polyethyleneimine to the second catalyst is (0.1-1):1, for example, it can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, etc.

[0040] In a second aspect, the present invention provides a method for preparing the hyper-crosslinked polymer as described in the first aspect, the preparation method comprising:

[0041] The halogen-modified hyper-crosslinked polymer reacts with ethylenediamine-terminated polyethyleneimine to obtain the hyper-crosslinked polymer.

[0042] The preparation method of the hyper-crosslinked polymer provided by the present invention is simple and easy to operate, and amino-functionalized hyper-crosslinked polymer with excellent performance can be obtained by performing substitution reaction between polyethyleneimine terminated with ethylenediamine and a halogen-modified hyper-crosslinked polymer.

[0043] Preferably, the reaction temperature is 80-100° C. For example, it may be 80° C., 82° C., 85° C., 88° C., 90° C., 91° C., 92° C., 93° C., 94° C., 95° C., 96° C., 97° C., 98° C., 99° C., etc.

[0044] Preferably, the reaction time is 2-24 h, for example, it can be 2 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, etc.

[0045] Preferably, the reaction is carried out in the presence of a second organic solvent and / or a second catalyst.

[0046] Preferably, the reaction is carried out under a nitrogen atmosphere.

[0047] Preferably, the reaction is carried out under the condition of a constant temperature oil bath.

[0048] Preferably, the reaction is carried out under a second stirring.

[0049] Preferably, the second stirring speed is 400-550 r / min, for example, 400 r / min, 420 r / min, 440 r / min, 460 r / min, 480 r / min, 500 r / min, 520 r / min, 540 r / min, 550 r / min, etc.

[0050] Preferably, after the reaction is completed, the steps of washing and second drying are further performed in sequence.

[0051] Preferably, the second drying temperature is 60-100°C, for example, 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 82°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C, etc.

[0052] Preferably, the second drying time is 12-24 hours, for example, it can be 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, etc.

[0053] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0054] In a third aspect, the present invention provides a use of the hyper-crosslinked polymer as described in the first aspect, wherein the hyper-crosslinked polymer is used as a glyphosate adsorbent.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] The hyper-crosslinked polymer provided by the present invention has high adsorption capacity and rapid adsorption kinetics for glyphosate, excellent adsorption separation performance, and excellent recycling performance; when the pH value of the glyphosate solution is 3, the adsorption capacity of the hyper-crosslinked polymer for glyphosate is the largest, which can reach 24.3-206.5 mg / g; under the condition that the pH value of the glyphosate solution is 3, the hyper-crosslinked polymer provided by the present invention is adsorbed for 120 seconds, and the adsorption amount of glyphosate is 14.5-195.8 mg / g, and the adsorption amount reaches a relatively high level after 600 seconds. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 are the infrared spectra of HCP-Cl, HCP-PEI, HCP-OH and HCP-EDA;

[0058] Figure 2 is the SEM image of HCP-PEI;

[0059] Figure 3 is the SEM image of HCP-EDA;

[0060] Figure 4 is the SEM image of HCP(Br)-PEI;

[0061] Figure 5 This is a scanning electron micrograph of HCP-OH. DETAILED DESCRIPTION

[0062] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0063] The sources of some components in the following examples and comparative examples are as follows:

[0064] (1) Ethylenediamine-terminated polyethyleneimine: purchased from Aladdin, with a number average molecular weight of 600 and a brand number of P121256.

[0065] Preparation Example 1

[0066] A chlorine-modified hyper-crosslinked polymer and a preparation method thereof, the preparation method comprising:

[0067] Under a nitrogen atmosphere, 7 g of 1,4-benzyl chloride and 5 g of anhydrous ferric chloride were added to 200 mL of dichloroethane, and the mixture was stirred for reaction at room temperature for 60 min at a speed of 400 r / min. Subsequently, the mixture was stirred for reaction at 40° C. for 1 h under a constant temperature oil bath. The reaction product was then poured into a Buchner funnel for suction filtration, washed with deionized water and anhydrous methanol until neutral, and finally dried in a vacuum drying oven at 60° C. for 24 h to obtain the chlorine-modified hyper-cross-linked polymer, and the obtained chlorine-modified hyper-cross-linked polymer was named HCP-Cl.

[0068] Preparation Example 2

[0069] A bromine-modified hyper-crosslinked polymer and a preparation method thereof, the preparation method comprising:

[0070] Under a nitrogen atmosphere, 10.6 g of 1,4-dibromobenzyl and 5 g of anhydrous ferric chloride were added to 200 mL of dichloroethane, and the mixture was stirred for reaction at room temperature for 60 min at a speed of 400 r / min. Subsequently, the mixture was stirred for reaction at 60° C. for 1 h under a constant temperature oil bath. The reaction product was then poured into a Buchner funnel for suction filtration, washed with deionized water and anhydrous methanol until neutral, and finally dried in a vacuum drying oven at 60° C. for 24 h to obtain the bromine-modified hyper-crosslinked polymer, which was named HCP-Br.

[0071] Example 1

[0072] A hyper-crosslinked polymer, wherein the raw materials for preparing the hyper-crosslinked polymer include the chlorine-modified hyper-crosslinked polymer HCP-Cl provided in Preparation Example 1 and polyethyleneimine terminated with ethylenediamine;

[0073] The preparation method of the hyper-crosslinked polymer comprises:

[0074] In a nitrogen atmosphere, 2.5 g HCP-Cl and 5 g ethylenediamine-terminated polyethyleneimine were added to 1000 mL N,N-dimethylformamide, and the mixture was stirred at room temperature for 20 min to dissolve and mix evenly. Then, 5 g anhydrous potassium carbonate was added as a catalyst to start the reaction under a constant temperature oil bath. The reaction was carried out at 80° C. for 24 h. The reaction product was poured into a Buchner funnel for suction filtration, and washed with deionized water and anhydrous methanol until neutral. The obtained product was subjected to Soxhlet extraction for 48 h, and finally placed in a vacuum drying oven and dried at 60° C. for 24 h to obtain the hyper-crosslinked polymer, which was named HCP-PEI.

[0075] Example 2

[0076] A hyper-crosslinked polymer, wherein the raw materials for preparing the hyper-crosslinked polymer include the bromine-modified hyper-crosslinked polymer HCP-Br provided in Preparation Example 2 and ethylenediamine-terminated polyethyleneimine;

[0077] The preparation method of the hyper-crosslinked polymer comprises:

[0078] In a nitrogen atmosphere, 5 g of HCP-Br and 5 g of polyethyleneimine terminated with ethylenediamine were added to 1000 mL of N,N-dimethylformamide, and the mixture was stirred at room temperature for 20 min to dissolve and mix evenly. Then, 5 g of anhydrous potassium carbonate was added as a catalyst to start the reaction under the condition of a constant temperature oil bath. The reaction was carried out at 90° C. for 24 h. The reaction product was poured into a Buchner funnel for suction filtration, and washed with deionized water and anhydrous methanol until neutral. The obtained product was subjected to Soxhlet extraction for 48 h, and finally placed in a vacuum drying oven and dried at 60° C. for 24 h to obtain the hyper-cross-linked polymer, which was named HCP(Br)-PEI.

[0079] Example 3

[0080] A hyper-crosslinked polymer HCP-PEI-A and a preparation method thereof, which differs from Example 1 only in that the amount of ethylenediamine-terminated polyethyleneimine used is 1 g, and the remaining raw materials, process parameters and steps are the same as those in Example 1.

[0081] Example 4

[0082] A hyper-crosslinked polymer HCP-PEI-B and a preparation method thereof, which differs from Example 1 only in that the amount of ethylenediamine-terminated polyethyleneimine used is 10 g, and the remaining raw materials, process parameters and steps are the same as those in Example 1.

[0083] Comparative Example 1

[0084] A hyper-crosslinked polymer and a preparation method thereof, which differs from Example 1 only in that the mass of polyethyleneimine capped with ethylenediamine is replaced by ethylenediamine, and the remaining raw materials, process parameters and steps are the same as those in Example 1. The obtained hyper-crosslinked polymer is named HCP-EDA.

[0085] Comparative Example 2

[0086] A hyper-crosslinked polymer and a preparation method thereof, the preparation method comprising:

[0087] In a nitrogen atmosphere, 2.5 g HCP-Cl and 5 g ethanolamine were added to 1000 mL N,N-dimethylformamide, and the mixture was stirred at room temperature for 20 min to dissolve and mix evenly. Then, 5 g anhydrous potassium carbonate was added as a catalyst to start the reaction under the condition of a constant temperature oil bath. The reaction was carried out at 80° C. for 24 h. The reaction product was poured into a Buchner funnel for suction filtration, and washed with deionized water and anhydrous methanol until neutral. The obtained product was subjected to Soxhlet extraction for 48 h, and finally placed in a vacuum drying oven and dried at 60° C. for 24 h to obtain the hyper-crosslinked polymer, which was named HCP-OH.

[0088] Product Characterization and Performance Testing

[0089] (1) Infrared spectrum test: The samples were tested using Bruker Tensor 27 (Bruker). The test method was as follows: the samples were mixed with potassium bromide and ground and then pressed into tablets. The wave number was 4000-400 cm -1 Range, select transmission mode, resolution is 2cm -1 The infrared spectra of HCP-Cl, HCP-PEI, HCP-OH and HCP-EDA are shown in Figure 1 As shown by Figure 1 It can be seen that 1607cm -1 The peak at 3426cm is the stretching vibration peak of the benzene ring skeleton, which indicates that HCP-Cl is successfully polymerized; -1 The peak at 2925cm is the -NH stretching vibration peak; -1 The peaks appearing near are related to the stretching vibration of methylene groups. The peaks of HCP-PEI and HCP-EDA are at 1088 cm -1 The peaks appearing nearby are related to the stretching vibration of CN, and the peak of HCP-OH at 3200 cm -1 The stretching vibration peak of -OH appears near Figure 1 It can be seen that compared with HCP-Cl, HCP-EDA and HCP-PEI have amino peaks, and HCP-OH has a hydroxyl peak, which proves that HCP-EDA, HCP-PEI and HCP-OH were successfully prepared.

[0090] (2) Scanning electron microscope image: The sample was tested using a Zeiss (sigma 300) in-situ ultra-high resolution field emission scanning electron microscope. The test method was as follows: the sample was placed in ethanol and ultrasonically dispersed evenly, 1 microliter was dropped onto aluminum foil, and gold was sprayed onto the aluminum foil to enhance the conductivity of the sample; the InLens mode was selected to test the sample. The test results are as follows: Figure 2-5 As shown, Figure 2-5 The scanning electron micrographs of HCP-PEI, HCP-EDA, HCP(Br)-PEI and HCP-OH are shown in Figure 1. Figure 2-5 It can be seen that the morphology of HCP-PEI, HCP-EDA, HCP(Br)-PEI and HCP-OH are all amorphous powders with a diameter of 20-30 nm.

[0091] (3) Adsorption test: 5 g of glyphosate powder was dissolved in 1 L of deionized water to prepare a glyphosate solution with a concentration of 5 g / L. The pH value of the glyphosate solution was adjusted to 1, 2, 3, 4, 5, 6, 7, and 8 with 0.1 M H3PO4 solution or 0.1 M NaOH solution. 5 mg of the hypercrosslinked polymer was weighed into a 10 mL centrifuge tube. 10 mL of glyphosate solution with different pH values ​​was added into the centrifuge tube. The tube was placed in a constant temperature shaking incubator (25°C, 220 rpm) and oscillated at constant temperature for 60 min to allow the tube to reach adsorption equilibrium. The supernatant was taken with a syringe and filtered with a 0.22 μm water filter. The glyphosate concentration before and after adsorption was determined by high performance liquid chromatography (HPLC) and the adsorption amount was calculated. The calculation formula for the adsorption amount is:

[0092] Where, C0 (mg / L) is the concentration of glyphosate in the initial solution; C e (mg / L) is the concentration of glyphosate in the solution at adsorption equilibrium; V (L) is the volume of the solution; m (g) is the mass of the added hypercross-linked polymer;

[0093] The above-mentioned high performance liquid chromatography test method is: 1260 Infinity II high performance liquid chromatography HPLC detection system (Aligent), equipped with a quaternary high pressure pump, a refractive index detector (RID) and a variable wavelength detector (VWD). The mobile phase is prepared by dissolving 0.54g of potassium dihydrogen phosphate, 60mL of chromatographic grade methanol and 10mL of phosphoric acid in 1940mL of ultrapure water; the detection wavelength is 195nm; the chromatographic column model is ZORBAX SAX (5μm, 4.6×250mm), the column temperature is 25℃, and the mobile phase flow rate is 0.5mL / min.

[0094] The hyper-crosslinked polymers provided in Examples 1-4 and Comparative Examples 1-2 were tested for adsorption according to the above method. The test results are shown in Table 1. The pH value in Table 1 is the pH value of the glyphosate solution added to the centrifuge tube.

[0095] Table 1

[0096]

[0097] The pK1, pK2, pK3 and pK4 dissociation constants of glyphosate are 0.78, 2.29, 5.96 and 10.98 respectively. Under different pH conditions, glyphosate will ionize to form different glyphosate ions. Since the adsorption process of glyphosate mainly depends on the electrostatic interaction and hydrogen bond interaction between glyphosate molecules and the amino groups on the surface of the hyper-cross-linked polymer, the pH value of the solution usually has a great influence on the adsorption performance of the adsorbent. Therefore, the pH of the glyphosate solution was adjusted in the range of 1-10 to study the influence of pH on the adsorption performance of the hyper-cross-linked polymer.

[0098] It can be seen from the test data in Table 1 that compared with HCP-EDA (Comparative Example 1), the hyper-crosslinked polymer HCP-PEI has a maximum adsorption amount of 206.5 mg / g when the pH of the glyphosate solution is 3. This is because the amino content of polyethyleneimine capped with ethylenediamine is higher than that of EDA per unit mass, indicating that increasing the amino content on the surface of the hyper-crosslinked polymer is beneficial to improving the adsorption performance.

[0099] The hyper-cross-linked polymer provided by the present invention replaces the Cl on the surface of HCP-Cl with polyethyleneimine terminated with ethylenediamine to complete the modification of the amino group on the surface of the hyper-cross-linked polymer. The mass ratio of polyethyleneimine terminated with ethylenediamine to HCP-Cl is controlled within a suitable range to enable the hyper-cross-linked polymer to have excellent adsorption performance. If the mass ratio of HCP-Cl to polyethyleneimine terminated with ethylenediamine is too large (Example 3) or too small (Example 4), the adsorption performance of the hyper-cross-linked polymer will be deteriorated.

[0100] From the comparison between Example 1 and Comparative Example 2, it can be seen that the hydroxyl functionalized hyper-crosslinked polymer HCP-OH provided in Comparative Example 2 cannot be protonated under acidic conditions and can only generate hydrogen bonding with glyphosate, so the adsorption amount is relatively small.

[0101] (4) Adsorption kinetics test: A glyphosate solution with a pH value of 3 and a concentration of 5 g / L was prepared, 5 mg of the hypercrosslinked polymer was weighed into a 10 mL centrifuge tube, 10 mL of the glyphosate solution was added to the centrifuge tube, and the tube was placed in a constant temperature shaking incubator (25° C., 220 rpm) and shaken at constant temperature for a period of time before being taken out. The shaking time was set to 10 s, 30 s, 60 s, 120 s, 180 s, 300 s, 600 s, and 1200 s, respectively. The supernatant was taken with a syringe and filtered with a 0.22 μm water filter. The glyphosate concentration before and after adsorption was determined using high performance liquid chromatography (HPLC) and the adsorption amount was calculated. The adsorption amount was calculated according to the above formula;

[0102] The hyper-crosslinked polymers provided in Examples 1-4 and Comparative Examples 1-2 were tested for adsorption capacity. The test results are shown in Table 2. The time in Table 2 is the adsorption time of glyphosate by the hyper-crosslinked polymers.

[0103] Table 2

[0104]

[0105] It can be seen from the test data in Table 2 that the adsorption rate of glyphosate by the hyper-crosslinked polymer HCP-PEI is much higher than that of several other hyper-crosslinked polymers. Since the hyper-crosslinked polymer provided by the present invention is itself polymerized by aromatic compounds and has strong hydrophobicity, the hydrophilicity of the material can be improved by introducing amino functional groups on the surface of the hyper-crosslinked polymer, promoting the diffusion of glyphosate molecules on the surface of the hyper-crosslinked polymer and improving the adsorption rate. HCP-PEI has a higher amino content than HCP-EDA and is more hydrophilic, so its adsorption kinetics are better than HCP-EDA. The hydroxyl functionalized hyper-crosslinked polymer HCP-OH in Comparative Example 2 cannot be protonated under acidic conditions and can only produce hydrogen bond interactions with glyphosate, so its adsorption kinetics for glyphosate are slow.

[0106] The applicant declares that the present invention uses the above embodiments to illustrate the hyper-crosslinked polymer and its preparation method and application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A hyper-crosslinked polymer, characterized in that: The raw materials for preparing the hyper-crosslinked polymer include a combination of a halogen-modified hyper-crosslinked polymer and ethylenediamine-terminated polyethyleneimine; The raw materials for preparing the halogen-modified hyper-crosslinked polymer include dihalobenzyl compounds.

2. The hypercrosslinked polymer according to claim 1, characterized in that The dihalobenzyl compounds include 1,4-dichlorobenzyl and / or 1,4-dibromobenzyl; Preferably, the number average molecular weight of the ethylenediamine-terminated polyethyleneimine is 400-800; Preferably, the mass ratio of the halogen-modified hyper-crosslinked polymer to the ethylenediamine-terminated polyethyleneimine is (0.5-2):

1.

3. The hypercrosslinked polymer according to claim 1 or 2, characterized in that The preparation method of the halogen-modified hyper-crosslinked polymer comprises: The dihalobenzyl compound is subjected to Friedel-Crafts alkylation reaction to obtain the halogen-modified hyper-crosslinked polymer.

4. The hypercrosslinked polymer according to claim 3, characterized in that The Friedel-Crafts alkylation reaction is carried out in the presence of a first catalyst; Preferably, the first catalyst comprises anhydrous ferric chloride and / or anhydrous aluminum chloride; Preferably, the mass ratio of the dihalobenzyl compound to the first catalyst is (0.5-2.5):

1.

5. The hypercrosslinked polymer according to claim 3 or 4, characterized in that The Friedel-Crafts alkylation reaction is carried out in the presence of a first organic solvent; Preferably, the first organic solvent comprises ethylene dichloride and / or dichloromethane; Preferably, based on the mass of the dihalobenzyl compound being 1 g, the volume of the first organic solvent is 10-40 mL.

6. The hypercrosslinked polymer according to any one of claims 3 to 5, characterized in that: The Friedel-Crafts alkylation reaction is carried out under a nitrogen atmosphere; Preferably, the Friedel-Crafts alkylation reaction comprises a first stage reaction and a second stage reaction; Preferably, the temperature of the first stage reaction is 18-25°C; Preferably, the first stage reaction time is 1-2h; Preferably, the temperature of the second stage reaction is 25-90°C; Preferably, the second stage reaction time is 1-24h; Preferably, the second stage reaction is carried out under the condition of a constant temperature oil bath; Preferably, the first stage reaction and the second stage reaction are each independently carried out under a first stirring condition; Preferably, the first stirring speed is 400-550r / min; Preferably, after the Friedel-Crafts alkylation reaction is completed, the method further comprises the steps of washing and first drying in sequence; Preferably, the first drying temperature is 60-100°C; Preferably, the first drying time is 12-24 hours.

7. The hypercrosslinked polymer according to any one of claims 1 to 6, characterized in that The raw materials for preparing the hyper-crosslinked polymer also include a second organic solvent; Preferably, the second organic solvent comprises N,N-dimethylformamide and / or dimethyl sulfoxide; Preferably, based on the mass of the ethylenediamine-terminated polyethyleneimine being 1 g, the volume of the second organic solvent is 150-1000 mL; Preferably, the raw materials for preparing the hyper-crosslinked polymer further include a second catalyst; Preferably, the second catalyst comprises potassium carbonate; Preferably, the mass ratio of the ethylenediamine-terminated polyethyleneimine to the second catalyst is (0.1-1):

1.

8. A method for preparing a hyper-crosslinked polymer according to any one of claims 1 to 7, characterized in that: The preparation method comprises: The halogen-modified hyper-crosslinked polymer reacts with ethylenediamine-terminated polyethyleneimine to obtain the hyper-crosslinked polymer.

9. The preparation method according to claim 8, characterized in that: The reaction temperature is 80-100°C; Preferably, the reaction time is 2-24h; Preferably, the reaction is carried out in the presence of a second organic solvent and / or a second catalyst; Preferably, the reaction is carried out under a nitrogen atmosphere; Preferably, the reaction is carried out under the condition of a constant temperature oil bath; Preferably, the reaction is carried out under a second stirring; Preferably, the second stirring speed is 400-550r / min; Preferably, after the reaction is completed, the steps of washing and second drying are also performed in sequence; Preferably, the second drying temperature is 60-100°C; Preferably, the second drying time is 12-24 hours.

10. A use of the hyper-crosslinked polymer according to any one of claims 1 to 7, characterized in that: The super cross-linked polymer is used for glyphosate adsorbent.

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