Maleamic acid-tragacanth copolymer as well as preparation method and application thereof

Abstract

The invention discloses a maleamic acid-tragacanth copolymer as well as a preparation method and application thereof, and the maleamic acid-tragacanth copolymer is prepared from the following raw materials in parts by weight: 3-7 parts of maleic anhydride, 90-110 parts of an absolute ethyl alcohol solvent, 10-15 parts of polyethyleneimine, 8-10 parts of polyethylene polyamine and 40-60 parts of an alcohol-water solution, and 15-30 parts by weight of a tragacanth modified derivative. A tragacanth modified derivative is introduced into maleic anhydride amidation in a ring-opening grafting blending manner, so that two adsorption materials have a synergistic effect, the characteristics of biodegradability, a macromolecular porous structure and the like are retained, and a large number of functional groups such as hydroxyl, carboxyl, amido, carbon-carbon double bonds and the like are introduced; toxic substances such as heavy metals, medical intermediates, dyes and pesticides in the wastewater are removed by virtue of comprehensive effects of electrostatic force, hydrogen bonds, Van der Waals force, inclusion and the like.

Description

Technical Field

[0001] The invention relates to the technical field of adsorbents, and in particular to a maleamic acid-tragacanth copolymer and a preparation method and application thereof. Background Art

[0002] With the acceleration of industrialization and urbanization, the problem of wastewater discharge is becoming increasingly serious, especially wastewater containing toxic substances such as heavy metal ions, pharmaceutical intermediates, dyes and pesticides, which poses a huge threat to the environment and human health. Although traditional wastewater treatment methods such as chemical precipitation, ion exchange, membrane separation, etc. can effectively remove pollutants to a certain extent, they often have problems such as high cost, high energy consumption, complex operation and easy to cause secondary pollution. Therefore, it is particularly important to develop efficient, low-cost, green and environmentally friendly wastewater treatment materials and technologies.

[0003] In the related technology, tragacanth gum, as a natural biopolysaccharide material, has shown good adsorption performance in the field of wastewater treatment due to its structure containing active functional groups such as hydroxyl, carboxylic acid and epoxy groups. However, the adsorption capacity and selectivity of single tragacanth gum are limited, which is difficult to meet the needs of complex wastewater treatment. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the present invention provides a maleamic acid-tragacanth gum copolymer and a preparation method and application thereof. The copolymer introduces a modified derivative of tragacanth gum in the amidation of maleic anhydride through an open-loop graft blending method, so that the two adsorption materials are synergistically enhanced, and not only retains the characteristics of its own biodegradability and macromolecular porous structure, but also introduces a large number of functional groups such as hydroxyl groups, carboxyl groups, amide groups, carbon-carbon double bonds, etc., and relies on the comprehensive effects of electrostatic force, hydrogen bond, van der Waals force and inclusion complexation to remove heavy metals, pharmaceutical intermediates, dyes, pesticides and other toxic substances in wastewater. The copolymer is a one-dose multi-effect, low-cost, green and environmentally friendly polymer adsorption material, which can be widely used in treating various industrial wastewaters and domestic sewage.

[0005] The first aspect of the present invention provides a maleamic acid-tragacanth copolymer, which is prepared from the following raw materials in parts by weight: 3-7 parts by weight of maleic anhydride, 90-110 parts by weight of anhydrous ethanol solvent, 10-15 parts by weight of polyethyleneimine, 8-10 parts by weight of polyethylene polyamine, 40-60 parts by weight of alcohol-water solution, and 15-30 parts by weight of a modified tragacanth derivative.

[0006] In the present invention, as a preferred embodiment, the maleamic acid-tragacanth copolymer is prepared from the following raw materials in parts by weight: 5 parts by weight of maleic anhydride, 100 parts by weight of anhydrous ethanol solvent, 10-15 parts by weight of polyethyleneimine, 8-10 parts by weight of polyethylene polyamine, 50 parts by weight of alcohol-water solution, and 15-30 parts by weight of a modified tragacanth derivative.

[0007] In the present invention, as a preferred embodiment, the maleamic acid-tragacanth gum copolymer is prepared from the following raw materials by weight: 5 parts by weight of maleic anhydride, 100 parts by weight of anhydrous ethanol solvent, 12 parts by weight of polyethyleneimine, 10 parts by weight of polyethylene polyamine, 50 parts by weight of alcohol-water solution, and 25 parts by weight of tragacanth gum modified derivative. Preferably, in the alcohol-water solution, the volume percentage of alcohol is 20%, and the alcohol is ethanol or methanol.

[0008] In the present invention, as a preferred embodiment, the modified tragacanth gum derivative is prepared from the following raw materials in parts by weight: 10-20 parts by weight of tragacanth gum, 30-50 parts by weight of an alcohol aqueous solution, 0.1-0.25 parts by weight of an initiator, 10-15 parts by weight of an N-vinyl caprolactam monomer, and 5-10 parts by weight of an N-(3-dimethylaminopropyl)methacrylamide monomer.

[0009] In the present invention, as a preferred embodiment, the modified tragacanth gum derivative is prepared from the following raw materials in parts by weight: 10 parts by weight of tragacanth gum, 40 parts by weight of an alcohol aqueous solution, 0.1 parts by weight of an initiator, 10 parts by weight of an N-vinyl caprolactam monomer, and 8 parts by weight of an N-(3-dimethylaminopropyl)methacrylamide monomer.

[0010] In the present invention, as a preferred embodiment, the initiator is potassium persulfate.

[0011] The second aspect of the present invention also provides a method for preparing a maleamic acid-tragacanth copolymer, comprising the following steps: adding a formula amount of maleic anhydride to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, passing nitrogen for 20 minutes to deoxygenate, adding a formula amount of anhydrous ethanol solvent, stirring until the solution is clarified, and then dripping a formula amount of polyethyleneimine and polyethylene polyamine in sequence, heating to 40°C with stirring, reacting for 2-4 hours, and cooling to room temperature after the reaction is completed; then continuing to pass nitrogen for protection, adding a formula amount of alcohol-water solution for dilution, and then adding a formula amount of a modified tragacanth derivative, first stirring at 50°C until completely dissolved, heating to 80-90°C, reacting for 4-6 hours, and cooling to room temperature to obtain a maleamic acid-tragacanth copolymer.

[0012] In the present invention, as a preferred embodiment, the preparation method of the modified tragacanth gum derivative comprises the following steps: adding a formula amount of tragacanth gum to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, adding a formula amount of alcohol aqueous solution, stirring to completely dissolve, dropping a formula amount of initiator, and then sequentially adding a formula amount of N-vinyl caprolactam monomer and N-(3-dimethylaminopropyl) methacrylamide monomer, heating to 50-70°C, reacting for 6-8h, cooling to room temperature, washing the precipitated product three times with anhydrous ethanol and acetone solvents alternately, vacuum drying and grinding the powder to obtain a modified tragacanth gum derivative.

[0013] In the present invention, as a preferred embodiment, in the preparation method of the modified tragacanth gum derivative, before heating to 50-70° C., stirring is first performed at room temperature for 0.5 h to fully mix.

[0014] The third aspect of the present invention also provides an application of a maleamic acid-tragacanth gum copolymer, which is used as an adsorbent to remove heavy metal ions, pharmaceutical intermediates or dyes in wastewater.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] The maleamic acid-tragacanth gum copolymer prepared by the present invention, on the one hand, tragacanth gum belongs to natural biological polysaccharide materials, and contains active functional groups such as hydroxyl, carboxylic acid and epoxy groups in the structure. By utilizing the characteristics of these functional groups, a larger network structure is formed by grafting, blending and the like to improve the functionality of tragacanth gum itself, so that it can undergo mutual adsorption with various substances in wastewater to achieve the purpose of purifying water quality; on the other hand, maleic anhydride is grafted with modified polyamines to synthesize maleamic acid, and the structure contains a large number of active groups such as amide groups and carboxyl groups, and heavy metal ions, pharmaceutical intermediates, dyes and other harmful substances in the wastewater are removed through adsorption, exchange or chelation reaction. In summary, the modified derivatives of tragacanth gum were introduced into the amidation of maleic anhydride by means of open-ring grafting and blending, so that the two adsorbent materials can enhance their synergy, which not only retains the characteristics of their own biodegradability and macromolecular porous structure, but also introduces a large number of functional groups such as hydroxyl, carboxyl, amide, carbon-carbon double bonds, etc., and relies on the comprehensive effects of electrostatic force, hydrogen bond, van der Waals force and inclusion complexation to remove heavy metals, pharmaceutical intermediates, dyes, pesticides and other toxic substances in wastewater. It is a one-dose multi-effect, low-cost, green and environmentally friendly polymer adsorbent material, which can be widely used to treat various industrial wastewater and domestic sewage, solve the problems of high cost and energy consumption of traditional treatment methods, and lay the foundation for the research and application of natural adsorbent materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic diagram showing the effect of the copolymer of Example 3 and the market comparison sample on the decolorization rate of the methylene blue MB solution under different addition amounts;

[0018] Figure 2 This is a comparison diagram of the effects of the homemade copolymer prepared in Example 3 on the deoiling and flocculation of produced water from oilfields under different addition amounts;

[0019] Figure 3 This is a comparison chart of the effects of market comparison samples on oilfield produced water deoiling and flocculation under different dosage conditions. DETAILED DESCRIPTION

[0020] The invention is further described below in conjunction with the accompanying drawings and specific implementation methods. It should be noted that, under the premise of no conflict, the various embodiments or technical features described below can be arbitrarily combined to form a new embodiment. Unless otherwise specified, the materials and equipment used in this embodiment can be purchased from the market.

[0021] The embodiment of the present invention provides a maleamic acid-tragacanth copolymer, which is prepared from the following raw materials in parts by weight: 3-7 parts by weight of maleic anhydride, 90-110 parts by weight of anhydrous ethanol solvent, 10-15 parts by weight of polyethyleneimine, 8-10 parts by weight of polyethylene polyamine, 40-60 parts by weight of alcohol-water solution, and 15-30 parts by weight of a modified tragacanth derivative.

[0022] Polyethylene polyamines are the co-products of lower polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. These lower polyamines are linked together through a specific chemical reaction to form polyethylene polyamines.

[0023] The polyethylene polyamine of this embodiment can be purchased directly from the market, including but not limited to Tosoh of Japan, Dow of the United States, BASF, and Huntsman. In addition, polyethylene polyamine is also produced and sold by many domestic companies such as Fuchen, Blue Duke, Jinan Liyang Chemical, Jinan Jiao Chemical, Shandong Xinheng Chemical, Shandong Jinyueyuan New Materials, Jinan Century Tongda Chemical, and Jinan Leqi Chemical.

[0024] As a preferred embodiment, the maleamic acid-tragacanth copolymer is prepared from the following raw materials in parts by weight: 5 parts by weight of maleic anhydride, 100 parts by weight of anhydrous ethanol solvent, 10-15 parts by weight of polyethyleneimine, 8-10 parts by weight of polyethylene polyamine, 50 parts by weight of alcohol-water solution, and 15-30 parts by weight of a modified tragacanth derivative.

[0025] As a preferred embodiment, the maleamic acid-tragacanth gum copolymer is prepared from the following raw materials in parts by weight: 5 parts by weight of maleic anhydride, 100 parts by weight of anhydrous ethanol solvent, 12 parts by weight of polyethyleneimine, 10 parts by weight of polyethylene polyamine, 50 parts by weight of alcohol-water solution, and 25 parts by weight of a modified derivative of tragacanth gum. Preferably, in the alcohol-water solution, the volume percentage of alcohol is 20%, and the alcohol is ethanol or methanol.

[0026] As a preferred embodiment, the modified tragacanth gum derivative is prepared from the following raw materials in parts by weight: 10-20 parts by weight of tragacanth gum, 30-50 parts by weight of an alcohol aqueous solution, 0.1-0.25 parts by weight of an initiator, 10-15 parts by weight of N-vinyl caprolactam monomer, and 5-10 parts by weight of N-(3-dimethylaminopropyl) methacrylamide monomer.

[0027] The English name of N-vinylcaprolactam: N-Vinylcaprolactam, CAS number: 2235-00-9, molecular formula: C8H13NO, molecular weight: about 139.19, EINECS number: 218-787-6, N-vinylcaprolactam molecule contains vinyl groups, which makes it have strong reactivity and can participate in a variety of chemical reactions, such as polymerization reaction, cross-linking reaction, etc.

[0028] The English name of N-(3-dimethylaminopropyl)methacrylamide is Dimethylamino propylmethacrylamide, CAS number: 5205-93-6, molecular formula: C9H18N2O, molecular weight: 170.25 (or 170.25200), EINECS registration number: 226-002-3. N-(3-dimethylaminopropyl)methacrylamide is an unsaturated tertiary amine, and its molecular structure contains tertiary amine groups and polymerizable vinyl groups, which makes it chemically active and can further undergo homopolymerization, copolymerization and quaternization reactions. The monomer activity is high, and the product molecular weight of the polymer is large, and it is alkaline and has cationic properties.

[0029] As a preferred embodiment, the modified derivative of tragacanth gum is prepared from the following raw materials by weight: 10 parts by weight of tragacanth gum, 40 parts by weight of alcohol aqueous solution, 0.1 parts by weight of initiator, 10 parts by weight of N-vinyl caprolactam monomer, and 8 parts by weight of N-(3-dimethylaminopropyl)methacrylamide monomer. Preferably, in the alcohol aqueous solution, the volume percentage of alcohol is 20%, and the alcohol is ethanol or methanol.

[0030] As a preferred embodiment, the initiator is potassium persulfate.

[0031] The second aspect of the present invention also provides a method for preparing a maleamic acid-tragacanth copolymer, comprising the following steps: adding a formula amount of maleic anhydride to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, passing nitrogen for 20 minutes to deoxygenate, adding a formula amount of anhydrous ethanol solvent, stirring until the solution is clarified, and then dripping a formula amount of polyethyleneimine and polyethylene polyamine in sequence, heating to 40°C with stirring, reacting for 2-4 hours, and cooling to room temperature after the reaction is completed; then continuing to pass nitrogen for protection, adding a formula amount of alcohol-water solution for dilution, and then adding a formula amount of a modified tragacanth derivative, first stirring at 50°C until completely dissolved, heating to 80-90°C, reacting for 4-6 hours, and cooling to room temperature to obtain a maleamic acid-tragacanth copolymer.

[0032] In the present invention, as a preferred embodiment, the preparation method of the modified tragacanth gum derivative comprises the following steps: adding a formula amount of tragacanth gum to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, adding a formula amount of alcohol aqueous solution, stirring to completely dissolve, dropping a formula amount of initiator, and then sequentially adding a formula amount of N-vinyl caprolactam monomer and N-(3-dimethylaminopropyl) methacrylamide monomer, heating to 50-70°C, reacting for 6-8h, cooling to room temperature, washing the precipitated product three times with anhydrous ethanol and acetone solvents alternately, vacuum drying and grinding the powder to obtain a modified tragacanth gum derivative.

[0033] As a preferred embodiment, in the preparation method of the modified derivative of tragacanth gum, before heating to 50-70° C., stirring is first performed at room temperature for 0.5 h to fully dissolve. In this way, not only can the uniformity of the reaction system be ensured and the reaction efficiency be improved, but also the occurrence of side reactions can be reduced, thereby improving the quality and yield of the product.

[0034] The third aspect of the present invention also provides an application of a maleamic acid-tragacanth gum copolymer, which is used as an adsorbent to remove heavy metal ions, pharmaceutical intermediates or dyes in wastewater.

[0035] The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, but should not be understood as limiting the present application.

[0036] Embodiment 1:

[0037] This embodiment provides a method for preparing a modified derivative of tragacanth gum, comprising the following preparation steps:

[0038] To a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, 15 parts by weight of tragacanth gum was added, and 30 parts by weight of an alcohol aqueous solution was added, and the mixture was stirred to completely dissolve. 0.16 parts by weight of an initiator was added dropwise, and then 10 parts by weight of N-vinyl caprolactam monomer and 10 parts by weight of N-(3-dimethylaminopropyl)methacrylamide monomer were added in sequence. The mixture was stirred at room temperature for 0.5 h to fully mix, and the mixture was heated to 60° C. and reacted for 6 h. The mixture was cooled to room temperature, and the precipitated product was washed three times with anhydrous ethanol and acetone solvents alternately. The powder was vacuum dried and ground to obtain a modified tragacanth gum derivative.

[0039] This embodiment also provides a method for preparing a maleamic acid-tragacanth copolymer, comprising:

[0040] Weigh 5 parts by weight of maleic anhydride, add it to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, pass nitrogen for 20 minutes to deoxygenate, add 100 parts by weight of anhydrous ethanol solvent, stir until the solution is clear, slowly drop 12 parts by weight of polyethyleneimine and 10 parts by weight of polyethylene polyamine in sequence at low temperature, slowly raise the temperature to 40°C while stirring, react for 2 hours, wait for the reaction to be completed, and cool to room temperature; then continue to pass nitrogen for protection, add 50 parts by weight of alcohol-water solution to dilute, and then add 30 parts by weight of the modified tragacanth gum derivative prepared above, first stir at 50°C for 1 hour to dissolve completely, raise the temperature to 90°C for reaction for 6 hours, and cool to room temperature to obtain a maleamic acid-tragacanth gum copolymer.

[0041] Wherein, in the alcohol aqueous solution or alcohol-water solution, the volume percentage of alcohol is 20%, and the alcohol is ethanol. The initiator is potassium persulfate.

[0042] Embodiment 2:

[0043] This embodiment provides a method for preparing a modified derivative of tragacanth gum, comprising the following preparation steps:

[0044] To a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, 20 parts by weight of tragacanth gum was added, and 50 parts by weight of an alcohol aqueous solution was added, and the mixture was stirred to completely dissolve. 0.25 parts by weight of an initiator was added dropwise, and then 15 parts by weight of N-vinyl caprolactam monomer and 5 parts by weight of N-(3-dimethylaminopropyl)methacrylamide monomer were added in sequence. The mixture was stirred at room temperature for 0.5 h to fully mix, and the mixture was heated to 70° C. and reacted for 8 h. The mixture was cooled to room temperature, and the precipitated product was washed three times with anhydrous ethanol and acetone solvents alternately. The powder was vacuum dried and ground to obtain a modified tragacanth gum derivative.

[0045] This embodiment also provides a method for preparing a maleamic acid-tragacanth copolymer, comprising the following preparation steps:

[0046] Weigh 5 parts by weight of maleic anhydride and add it to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser. Pass nitrogen for 20 minutes to deoxygenate, add 100 parts by weight of anhydrous ethanol solvent, stir until the solution is clear, slowly drop 10 parts by weight of polyethyleneimine and 8 parts by weight of polyethylene polyamine in sequence at low temperature, slowly raise the temperature to 40°C while stirring, react for 3 hours, wait for the reaction to end, and cool to room temperature; then continue to pass nitrogen for protection, add 50 parts by weight of an alcohol-water solution (alcohol content 20%) to dilute, then add 15 parts by weight of the modified tragacanth gum derivative prepared above, first stir at 50°C for 1 hour to dissolve completely, raise the temperature to 80°C for reaction for 5 hours, and cool to room temperature to obtain a maleamic acid-tragacanth gum copolymer.

[0047] Wherein, in the alcohol aqueous solution or alcohol-water solution, the volume percentage of alcohol is 20%, and the alcohol is ethanol. The initiator is potassium persulfate.

[0048] Embodiment 3:

[0049] This embodiment provides a method for preparing a modified derivative of tragacanth gum, comprising the following preparation steps:

[0050] To a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, 10 parts by weight of tragacanth gum was added, and 40 parts by weight of an alcohol aqueous solution was added, and the mixture was stirred to completely dissolve. 0.1 parts by weight of an initiator was added dropwise, and then 10 parts by weight of N-vinyl caprolactam monomer and 8 parts by weight of N-(3-dimethylaminopropyl)methacrylamide monomer were added in sequence. The mixture was stirred at room temperature for 0.5 h to fully mix, and the mixture was heated to 65° C. and reacted for 6 h. The mixture was cooled to room temperature, and the precipitated product was washed three times with anhydrous ethanol and acetone solvents alternately. The powder was vacuum dried and ground to obtain a modified tragacanth gum derivative.

[0051] This embodiment also provides a method for preparing a maleamic acid-tragacanth copolymer, comprising the following preparation steps:

[0052] Weigh 5 parts by weight of maleic anhydride, add it to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, pass nitrogen for 20 minutes to deoxygenate, add 100 parts by weight of anhydrous ethanol solvent, stir until the solution is clear, slowly drop 12 parts by weight of polyethyleneimine and 10 parts by weight of polyethylene polyamine in sequence at low temperature, slowly raise the temperature to 40°C while stirring, react for 3 hours, wait for the reaction to end, and cool to room temperature; then continue to pass nitrogen for protection, add 50 parts by weight of alcohol-water solution to dilute, and then add 25 parts by weight of the modified tragacanth gum derivative prepared above, first stir at 50°C for 1 hour to dissolve completely, raise the temperature to 80°C for reaction for 5 hours, and cool to room temperature to obtain a maleamic acid-tragacanth gum copolymer.

[0053] Wherein, in the alcohol aqueous solution or alcohol-water solution, the volume percentage of alcohol is 20%, and the alcohol is ethanol. The initiator is potassium persulfate.

[0054] Embodiment 4:

[0055] This embodiment provides a method for preparing a modified derivative of tragacanth gum, comprising the following preparation steps:

[0056] To a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, 15 parts by weight of tragacanth gum was added, and 50 parts by weight of an alcohol aqueous solution was added, and the mixture was stirred to completely dissolve. 0.2 parts by weight of an initiator was added dropwise, and 10 parts by weight of N-vinyl caprolactam monomer and 5 parts by weight of N-(3-dimethylaminopropyl)methacrylamide monomer were added in sequence. The mixture was stirred at room temperature for 0.5 h to fully mix, and the mixture was heated to 50° C. and reacted for 6 h. The mixture was cooled to room temperature, and the precipitated product was washed three times with anhydrous ethanol and acetone solvents alternately. The powder was vacuum dried and ground to obtain a modified tragacanth gum derivative.

[0057] This embodiment also provides a method for preparing a maleamic acid-tragacanth copolymer, comprising the following preparation steps:

[0058] Weigh 5 parts by weight of maleic anhydride, add it to a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, pass nitrogen for 20 minutes to deoxygenate, add 100 parts by weight of anhydrous ethanol solvent, stir until the solution is clear, slowly drop 10 parts by weight of polyethyleneimine and 8 parts by weight of polyethylene polyamine in sequence at low temperature, slowly raise the temperature to 40°C while stirring, react for 4 hours, wait for the reaction to be completed, and cool to room temperature; then continue to pass nitrogen for protection, add 50 parts by weight of alcohol-water solution to dilute, and then add 20 parts by weight of the modified tragacanth gum derivative prepared above, first stir at 50°C for 1 hour to completely dissolve, raise the temperature to 90°C to react for 4 hours, and cool to room temperature to obtain a maleamic acid-tragacanth gum copolymer.

[0059] Wherein, in the alcohol aqueous solution or alcohol-water solution, the volume percentage of alcohol is 20%, and the alcohol is ethanol. The initiator is potassium persulfate.

[0060] In summary, the maleamic acid-tragacanth gum copolymer prepared by the present invention, on the one hand, tragacanth gum belongs to a natural biopolysaccharide material, and contains active functional groups such as hydroxyl, carboxylic acid and epoxy groups in its structure. By utilizing the characteristics of these functional groups, a larger network structure is formed by grafting, blending and the like to improve the functionality of tragacanth gum itself, so that it can undergo mutual adsorption with various substances in wastewater to achieve the purpose of purifying water quality; on the other hand, maleic anhydride is synthesized by grafting modified polyamines to synthesize maleamic acid, and the structure contains a large number of active groups such as amide groups and carboxyl groups, and heavy metal ions, pharmaceutical intermediates, dyes and other harmful substances in wastewater are removed through adsorption, exchange or chelation reaction. In summary, the modified derivatives of tragacanth gum were introduced into the amidation of maleic anhydride by means of open-ring grafting and blending, so that the two adsorbent materials can enhance their synergy, which not only retains the characteristics of their own biodegradability and macromolecular porous structure, but also introduces a large number of functional groups such as hydroxyl, carboxyl, amide, carbon-carbon double bonds, etc., and relies on the comprehensive effects of electrostatic force, hydrogen bond, van der Waals force and inclusion complexation to remove heavy metals, pharmaceutical intermediates, dyes, pesticides and other toxic substances in wastewater. It is a one-dose multi-effect, low-cost, green and environmentally friendly polymer adsorbent material, which can be widely used to treat various industrial wastewater and domestic sewage, solve the problems of high cost and energy consumption of traditional treatment methods, and lay the foundation for the research and application of natural adsorbent materials.

[0061] Performance Test:

[0062] The maleamic acid-tragacanth gum copolymer prepared in Example 3 of the present invention has the characteristics of active functional groups such as hydroxyl, amide, carboxyl, and amino in its structure, and has amphoteric functional groups such as cations and anions, and has multiple effects in one dose. It has a good application effect in industrial wastewater, domestic wastewater, oilfield produced water and other industrial wastewater.

[0063] (i) 100 mL of 50 mg / L metal ion solution of Cd(II), Mn(II), Cr(VI), Ni(II) etc. was taken in a 250 mL conical flask, and a certain amount of maleamic acid-tragacanth copolymer prepared in Example 3 of the present invention and a market comparison sample (DTCR heavy metal scavenger of Futianbao Environmental Protection Technology Co., Ltd.) was added. The initial pH value of the system was adjusted with nitric acid or sodium hydroxide, and the mixture was oscillated at a constant temperature of 25° C. for 2 h. After the solution was allowed to stand, the supernatant was taken, and the absorbance of the supernatant was measured by a spectrophotometer to calculate the metal ion concentration. The adsorption amount Qe (mg / g) and the adsorption rate E (%) were calculated according to formulas (1) and (2).

[0064]

[0065] Where: C0—metal ion concentration in the original solution, mg / L;

[0066] C1—metal ion concentration in the adsorption solution, mg / L;

[0067] V—volume of metal ion solution, L;

[0068] m—adsorbent mass, g.

[0069] Table 1 Optimal dosage of various metal ions for the homemade copolymers prepared in Example 3 and the market comparison samples

[0070]

[0071] Table 2 Adsorption of various metal ions by the homemade copolymers prepared in Example 3 and the market comparison samples

[0072]

[0073] Table 3 Adsorption rates of various metal ions of the homemade copolymers prepared in Example 3 and the market comparison samples

[0074]

[0075] It can be seen from Table 1, Table 2 and Table 3 that the adsorption effect of the homemade copolymer prepared in Example 3 on metal ions is generally better than that of the market comparison sample, especially for Cr (VI) and Ni (II), the adsorption effect is more significant, and the adsorption rate is as high as more than 90%. This is because the homemade copolymer prepared in Example 3 has looser pores and can provide more active sites for heavy metals with large ion radius. The active groups such as hydroxyl, amide, carboxyl, and amino in the molecular structure react with heavy metal ions to form inner and outer orbital complexes. Therefore, the homemade copolymer prepared in Example 3 has good adsorption performance for heavy metal ions.

[0076] (ii) Under certain conditions (room temperature), a series of gradient equal 100 mL methylene blue MB solution (50 mg / L) was taken and added to a 150 mL conical flask, and the pH value was adjusted to 10.0. A series of gradient homemade copolymers prepared in Example 3 (30 mg, 40 mg, 50 mg, 60 mg, 70 mg, 80 mg) were added to the conical flask. After stirring at room temperature for 60 min, the upper clear liquid was taken and the absorbance A1 of the solution was measured at the maximum absorption wavelength of the dye by spectrophotometry. The decolorization rate was calculated. The effects of the dosage of the homemade copolymers of different Examples 3 and the market comparison sample (LSD decolorization flocculant of Wuxi Tianxin Chemical Co., Ltd.) on the decolorization of the methylene blue MB solution were investigated respectively. The calculation formula is as follows and the results are shown in Figure 1 shown.

[0077]

[0078] Where: A0 is the absorbance of the solution before decolorization; A1 is the absorbance of the supernatant after decolorization.

[0079] Depend on Figure 1 It can be seen that as the dosage of the homemade copolymer prepared in Example 3 and the market comparison sample increases, the decolorization rate of the methylene blue MB solution shows a trend of first increasing and then stabilizing. However, the homemade copolymer prepared in Example 3 has a higher decolorization rate than the market comparison sample methylene blue MB solution under the same dosage, with a maximum value of 94.1%. This is due to the characteristics of the homemade copolymer structure molecules prepared in Example 3 containing a large number of active functional groups such as hydroxyl, amide, carboxyl, and amino groups, and the use of electrical neutralization and roll-up adsorption to remove a large number of dye ions. Comprehensive actual cost-effectiveness, the homemade copolymer prepared in Example 3 has more practical application value, and the optimal dosage of the methylene blue MB solution is 50 mg.

[0080] (III) Take 3L of oilfield produced water (oil content 367mg / L) as the test water sample, then take 100mL quantitatively and dispense it into a series of 150mL conical bottles, adjust the pH to 8, add a certain amount of the homemade copolymer prepared in Example 3 and a market comparison sample (TM water purifier of Tianjin Keweijinhong Environmental Protection Technology Co., Ltd.), seal the test bottle, stir rapidly for 1min to fully mix it, disperse the agent in the wastewater, let it stand for 10min, take the clear liquid, and detect the oil content, turbidity and COD Cr The removal rate was used to investigate the oil removal flocculation effect of the homemade copolymer prepared in Example 3 and the market comparison sample. Figure 2 and Figure 3 shown.

[0081] Depend on Figure 2 and Figure 3 It can be seen that the homemade copolymer prepared in Example 3 and the market comparison sample both have an oil removal and flocculation effect on oil field produced water. Within a certain dosage range, as the dosage increases, the oil content, turbidity and COD of the oil field produced water Cr The removal rate showed a trend of first increasing and then decreasing, but the oil content, turbidity and COD Cr The removal rates of the self-made copolymers prepared in Example 3 are much higher than those of the market comparison samples, with the maximum value reaching 96%. This is because the functional groups on the structure of the self-made copolymer prepared in Example 3 bridge with the organic matter in the wastewater to form a huge network of supramolecular floccules, which collide violently under stirring and adsorb more colloidal particles, thereby achieving a significant oil removal and flocculation effect. However, if the dosage is further increased, the removal rate will decrease, mainly due to destabilization. At the same time, the agent itself also has small molecular solvents, which will cause the oil removal and flocculation effect to decrease. Therefore, considering the actual operating cost-effectiveness, the optimal dosage of the self-made copolymer prepared in Example 3 for oilfield produced water is 40 mg.

[0082] The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present invention shall fall within the scope of protection required by the present invention.

Claims

1. A maleamic acid-tragacanth copolymer, characterized in that The invention is prepared from the following raw materials in parts by weight: 3-7 parts by weight of maleic anhydride, 90-110 parts by weight of anhydrous ethanol solvent, 10-15 parts by weight of polyethyleneimine, 8-10 parts by weight of polyethylene polyamine, 40-60 parts by weight of alcohol-water solution, and 15-30 parts by weight of a modified derivative of tragacanth gum.

2. The maleamic acid-tragacanth copolymer according to claim 1, characterized in that The invention is prepared from the following raw materials in parts by weight: 5 parts by weight of maleic anhydride, 100 parts by weight of anhydrous ethanol solvent, 10-15 parts by weight of polyethyleneimine, 8-10 parts by weight of polyethylene polyamine, 50 parts by weight of alcohol-water solution, and 15-30 parts by weight of a modified derivative of tragacanth gum.

3. The maleamic acid-tragacanth copolymer according to claim 2, characterized in that The invention is prepared from the following raw materials in parts by weight: 5 parts by weight of maleic anhydride, 100 parts by weight of anhydrous ethanol solvent, 12 parts by weight of polyethyleneimine, 10 parts by weight of polyethylene polyamine, 50 parts by weight of alcohol-water solution, and 25 parts by weight of a modified derivative of tragacanth gum.

4. The maleamic acid-tragacanth copolymer according to claim 1, characterized in that The modified tragacanth gum derivative is prepared from the following raw materials in parts by weight: 10-20 parts by weight of tragacanth gum, 30-50 parts by weight of an alcohol aqueous solution, 0.1-0.25 parts by weight of an initiator, 10-15 parts by weight of an N-vinyl caprolactam monomer, and 5-10 parts by weight of an N-(3-dimethylaminopropyl)methacrylamide monomer.

5. The maleamic acid-tragacanth copolymer according to claim 4, characterized in that The modified tragacanth gum derivative is prepared from the following raw materials in parts by weight: 10 parts by weight of tragacanth gum, 40 parts by weight of an alcohol aqueous solution, 0.1 parts by weight of an initiator, 10 parts by weight of an N-vinyl caprolactam monomer, and 8 parts by weight of an N-(3-dimethylaminopropyl)methacrylamide monomer.

6. The maleamic acid-tragacanth copolymer according to claim 4, characterized in that The initiator is potassium persulfate.

7. A method for preparing the maleamic acid-tragacanth copolymer according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: adding a formula amount of maleic anhydride into a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condensing device, passing nitrogen for 20 minutes to remove oxygen, adding a formula amount of anhydrous ethanol solvent, stirring until the solution is clarified, sequentially adding a formula amount of polyethyleneimine and polyethylene polyamine dropwise, heating to 40°C under stirring, reacting for 2-4 hours, cooling to room temperature after the reaction is completed; then continuing to pass nitrogen for protection, adding a formula amount of alcohol-water solution for dilution, and then adding a formula amount of tragacanth gum modified derivative, stirring at 50°C until completely dissolved, heating to 80-90°C, reacting for 4-6 hours, cooling to room temperature, and obtaining a maleamic acid-tragacanth gum copolymer.

8. The method for preparing the maleamic acid-tragacanth copolymer according to claim 7, characterized in that: The preparation method of the modified tragacanth gum derivative comprises the following steps: adding a formula amount of tragacanth gum into a four-necked flask equipped with a mechanical stirring device, nitrogen, a thermometer and a reflux condenser, adding a formula amount of alcohol aqueous solution, stirring to completely dissolve, dropping a formula amount of initiator, and then sequentially adding a formula amount of N-vinyl caprolactam monomer and N-(3-dimethylaminopropyl) methacrylamide monomer, heating to 50-70°C, reacting for 6-8h, cooling to room temperature, washing the precipitated product three times with anhydrous ethanol and acetone solvents alternately, vacuum drying and grinding the powder to obtain the modified tragacanth gum derivative.

9. The method for preparing the maleamic acid-tragacanth copolymer according to claim 8, characterized in that: In the preparation method of the modified derivative of tragacanth gum, before heating to 50-70° C., the mixture is first stirred at room temperature for 0.5 h to fully dissolve.

10. A use of the maleamic acid-tragacanth copolymer according to any one of claims 1 to 6, characterized in that: It is used as an adsorbent to remove heavy metal ions, pharmaceutical intermediates or dyes from wastewater.

Images