CN107879450A - Water-soluble ter-polymers molecular brush anionic dye catches sedimentation agent and preparation method thereof and its application - Google Patents

Abstract

The invention relates to a water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent and its preparation method and application. Polymethacryloyloxyethyltrimethylammonium chloride, functional polymer side chain precursor poly N-vinyl formamide with carboxyl group at the end of the polymer, water, catalyst namely N-hydroxysuccinimide, 1- Ethyl‑3‑(3‑dimethylaminopropyl)carbodiimide iodide, potassium hydroxide, 1,2‑cyclohexanediaminetetraacetic dianhydride and carbon disulfide to prepare water-soluble ternary polymer molecular brushes The anionic dye capture and sedimentation agent is used to treat the dye wastewater or art paint wastewater discharged from the dye synthesis or dyeing and finishing process. It has good trapping ability, fast settling speed, can handle complexed heavy metal ions, can capture anionic dyes and complexed heavy metal ions within a few seconds, quickly grow into large aggregates and precipitate within 10 seconds, and quickly realize the separation of dyes, etc. advantage.

Description

Water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent and preparation method thereof law and its application

technical field

The invention belongs to the field of water treatment technology and polymer functional materials, and specifically relates to a water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent and its preparation method and application. It is mainly discharged during the dye synthesis or dyeing and finishing process. It can be used in dye wastewater or art paint wastewater, and can simultaneously remove anionic dyes and complexed heavy metal ions in dye wastewater.

Background technique

In recent years, my country's annual sewage discharge has reached more than 39 billion tons, of which industrial sewage accounts for 51%, while dye wastewater accounts for 35% of the total industrial wastewater discharge, and it is increasing at a rate of 1% year by year. Dye wastewater mainly comes from dye synthesis and dye use enterprises, and is composed of dyes and auxiliaries discharged during the synthesis or dyeing and finishing process. With the rapid development of the printing and dyeing industry, China is a big country in textile production and processing. The export volume of textiles has ranked first in the world for many years. The annual production of dyes reaches 1.5×10 ⁵ tons, of which about 10% to 15% of the dyes will be directly produced. With the wastewater discharged into the water body, the dye wastewater has become one of the important pollution sources of the water body. In order to strengthen the control of water pollution in the textile dyeing and finishing industry, in 2012, the Ministry of Environmental Protection and the General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China jointly revised and issued the Discharge Standard of Water Pollutants in the Textile Dyeing and Finishing Industry (GB 4287-2012). According to the new discharge standards, many printing and dyeing enterprises could not meet the new national discharge standards by adopting traditional treatment technologies, and many illegal discharges occurred, resulting in serious water pollution incidents. Generally speaking, the current dye wastewater treatment technology cannot meet the national discharge standards, and the research and development of new materials and new technologies are urgently needed to solve the current discharge problems of enterprises. Dye wastewater has a strong sense of pollution, and the colored water will affect the sunlight, which is not conducive to the growth of aquatic organisms. It is difficult to treat it with general biochemical methods. The discharge of dye wastewater is also large, and the discharge is intermittent, and the water quality is unstable, which is difficult to treat.

Traditional wastewater treatment methods include physical and chemical methods, chemical coagulation methods, physical adsorption methods, biochemical methods, and electrochemical methods. The chemical coagulation method is to add a coagulant to the dye wastewater to make the pollutants form colloidal particles, and remove the pollutants in the wastewater through coagulation precipitation or air flotation. The coagulation-sedimentation method is the most widely used in practice. Coagulation can simultaneously remove dye pollutants and other macromolecular suspended pollutants. The treatment effect of wastewater mainly depends on the structural properties of the coagulant. Currently used coagulants mainly include inorganic coagulants and organic polymer coagulants. Inorganic coagulants are mainly aluminum salts and iron salts, which have a good coagulation effect on dyes that exist in colloidal or suspended states in wastewater, but for water-soluble dyes with small molecular weights, the coagulation effect is relatively low. Difference. The organic polymer coagulant has a large molecular weight and is dispersed into a huge number of linear molecules after being dissolved in water. It has a strong ability to adsorb and bridge colloidal suspended particles in water. The organic polymer coagulant has stable properties, less residue, and a wide range of pH requirements, and the most representative one is polyacrylamide. However, the chemical structure of polyacrylamide is relatively simple, and there are problems such as poor ability to capture dye molecules, slow sedimentation speed, and inability to deal with complexed heavy metal ions.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art and provide a water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent and its preparation method and application, which has good trapping ability, fast sedimentation speed, and can handle complex type Heavy metal ions can capture anionic dyes and complexed heavy metal ions in a few seconds, grow into large aggregates and precipitate within 10 seconds, and quickly realize the separation of dyes.

In order to achieve the above-mentioned purpose, the technical scheme of the water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent of the present invention is realized in this way, it is characterized in that including 1～10 parts of polymer main chain polyhydroxyethyl acrylamide (PHEMAA ), 20-100 parts of polymethacryloyloxyethyltrimethylammonium chloride (PDMC-COOH) containing carboxyl groups at the end of the cationic polymer side chain, 5-40 parts of functional polymer side chain precursor polymerization Carboxyl-containing poly N-vinylformamide (PNVF-COOH), 100 to 500 parts of water, 1 to 5 parts of catalyst N-hydroxysuccinimide (NHS), 1 to 5 parts of 1- Ethyl-3-(3-dimethylaminopropyl) carbodiimide iodomethane salt (EDC CH ₃ I), 1-10 parts of potassium hydroxide, 1-20 parts of 1,2-cyclohexyl Diaminetetraacetic dianhydride (CDTAD) and 1-10 parts of carbon disulfide; the above are parts by mass.

In this technical solution, the polymer main chain polyhydroxyethylacrylamide (PHEMAA) is synthesized by ordinary free radical polymerization or controlled living polymerization to synthesize the PHEMAA polymer main chain;

The cationic polymer side chain PDMC-COOH mainly uses azodicyanovaleric acid as an initiator to synthesize polymethacryloyloxyethyltrimethylammonium chloride (PDMC -COOH) polymer;

The functional polymer side chain precursor polymer PNVF-COOH mainly uses azodicyanovaleric acid as the initiator to synthesize poly N-vinylformamide (PNVF-COOH) polymer with carboxyl group at the end through ordinary free radical polymerization ;

The synthesis method of the 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) is: dissolving 5-20 parts of 1,2-cyclohexanediaminetetraacetic acid and 5-20 parts of acetic anhydride in 10-30 Parts of 2-picoline, controlled at 50-70°C, reacted for 20-40 hours to obtain 1,2-cyclohexanediaminetetraacetic dianhydride.

In order to achieve the above-mentioned purpose, the technical scheme of the preparation method of the water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent of the present invention is realized in this way, it is characterized in that 1～10 parts of polymer main chain polyhydroxyethyl propylene Amide (PHEMAA), 20-100 parts of polymethacryloyloxyethyltrimethylammonium chloride (PDMC-COOH) containing carboxyl groups at the end of cationic polymer side chains and 5-40 parts of functional polymer side chains The poly N-vinylformamide (PNVF-COOH) containing carboxyl groups at the end of the precursor polymer is mixed and dissolved in 100 to 500 parts of water, and 1 to 5 parts of the catalyst, namely N-hydroxysuccinimide (NHS) and 1-5 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide iodomethane salt (EDC CH ₃ I), temperature controlled at 50-80°C, carry out esterification reaction for 10 ~70 hours, polyhydroxyethylacrylamide-graft-(polymethacryloxyethyltrimethylammonium chloride-random-polyN-vinylformamide) (PHEMAA-g-(PDMC- r-PNVF)); then add 1 to 10 parts of potassium hydroxide, control the temperature at 50 to 80°C, and carry out the hydrolysis reaction for 12 to 48 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyl Oxyethyltrimethylammonium chloride-random-polyethyleneamine) (PHEMAA-g-(PDMC-r-PVA)); then add 1 to 20 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD), carry out the acylation reaction for 5 to 24 hours, and the range of the degree of acylation is controlled at 60 to 99%, to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride -random-polyethyleneaminocyclohexanediamine sodium tetraacetate-random-polyethyleneamine) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVA)); then add 1 to 10 parts of carbon disulfide, The temperature is controlled at 20-40°C, and the addition reaction is carried out for 1-3 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyethyleneamine Sodium cyclohexanediamine tetraacetate-random-sodium polyvinylaminodithiocarbamate) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble ternary polymer molecular brush Anionic dye capture and sedimentation agent; the above are parts by mass.

In this technical solution, the polymerization degree of the polyhydroxyethylacrylamide (PHEMAA) is 10-200, and the cationic polymer side chain PDMC-COOH and the functional polymer side chain precursor polymer PNVF-COOH The degree of polymerization is 10-200, the grafting rate of cationic polymer side chain PDMC is 1-70%, the grafting rate of chelating polymer side chain PVACDTANA is 1-20%, and the polymer side chain PVACS ₂ The grafting rate of Na is 1 to 5%.

In order to achieve the above-mentioned purpose, the technical scheme of the application of the water-soluble ternary polymer molecular brush anionic dye catching and sedimentation agent of the present invention is realized in this way, it is characterized in that 0.1～1 part of water-soluble ternary polymer molecular brush anionic dye The capture and sedimentation agent is added to 100 to 1000 parts of wastewater, stirred at room temperature for 1 to 5 minutes, and the pH is adjusted to 2 to 5. The anionic dye molecules in the wastewater and the water-soluble ternary polymer molecules brush the cationic dye capture and sedimentation agent. The side chain PDMC is electrostatically adsorbed, and the heavy metal ions in the wastewater and the chelating side chain PVACDTANA of the water-soluble ternary polymer molecular brush anionic dye capture the sedimentation agent undergo chelation adsorption, and then add 0.01 to 0.1 parts of the auxiliary sedimentation agent. Stir for 1 minute, the metal ions of the settling agent quickly react with the water-soluble ternary polymer molecular brush anionic dye to capture the settling side chain PVACS ₂ Na of the settling agent, and produce floc precipitation with a particle size greater than 100 μm within 10 seconds , can quickly realize the removal of anionic dyes and complexed heavy metal ions in wastewater, and the effluent is colorless, meeting the national discharge standards. The above are parts by mass.

In this technical solution, the settling aid is one or any combination of two or more of calcium chloride, magnesium sulfate, ferrous chloride, ferric chloride, and aluminum trichloride.

Compared with the prior art, the present invention has the following advantages and effects:

1. The present invention solves the defects of single structure and poor capture performance of traditional synthetic polymer dye flocculants. The present invention contains three polymer side chains with different functions, and the cationic polymer side chain PDMC has a good effect on anionic dyes. Electrostatic adsorption capacity, the chelating side chain PVCDTANa chelates and adsorbs heavy metal ions, and under the synergistic effect of the sedimentation-assisting polymer side chain PVACS ₂ Na, the PVACS ₂ Na polymer side chain and the sedimentation-assisting agent metal ions undergo rapid chemical precipitation reaction to achieve efficient capture and rapid sedimentation;

2. The present invention has the technical advantage of settling speed, and can produce a settling reaction with a small amount of auxiliary settling agent, quickly form large aggregates, and generate a small amount of sludge.

3. The invention has dual functions, which can simultaneously capture anionic dyes and complexed heavy metal ions, and solve the problem that traditional flocculants cannot treat complexed heavy metal ions in dye wastewater.

Detailed ways

The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto. The parts involved in the following examples are all parts by mass.

Embodiment one

It is a water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent, which is prepared by the following steps:

Synthesis of Step 1 PHEMAA Polymer Main Chain

Take 2 parts of azobisisobutyronitrile initiator, 50 parts of hydroxyethylacrylamide (HEMAA), and 400 parts of methanol, and carry out polymerization reaction at 75°C for 1 hour under the protection of nitrogen to obtain a degree of polymerization (DP) of 20 Polyhydroxyethylacrylamide (PHEMAA);

Step 2 Synthesis of cationic polymer side chain PDMC-COOH and functional polymer side chain precursor polymer PNVF-COOH

Synthesis of cationic polymer side chain PDMC-COOH: Take 2 parts of azodicyanovaleric acid initiator, 150 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) and 50 parts of water , under the protection of nitrogen, carry out free radical polymerization reaction at 70°C for 16 hours, and obtain PDMC-COOH with a degree of polymerization (DP) of 180;

Synthesis of functional polymer side chain precursor polymer PNVF-COOH: take 2 parts of azodicyanovaleric acid initiator, 100 parts of N-vinylformamide (NVF) and 40 parts of water, under nitrogen protection Free radical polymerization was carried out at 70°C for 13 hours to obtain PNVF-COOH with a degree of polymerization (DP) of 190;

Step 3 Synthesis of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD)

Dissolve 9 parts of 1,2-cyclohexanediamine tetraacetic acid and 9 parts of acetic anhydride in 10 parts of 2-picoline, control at 50°C, and react for 20 hours to obtain 1,2-cyclohexanediamine Tetraacetic dianhydride;

Step 4 Synthesis of PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)

Polymerize 1 part of polyhydroxyethylacrylamide (PHEMAA) obtained in step 1 with 20 parts of cationic polymer side chain PDMC-COOH and 10 parts of functional polymer side chain precursor obtained in step 2 The substance PNVF-COOH is mixed and dissolved in 100 parts of water, and 1 part of the catalyst is N-hydroxysuccinimide (NHS) and 1 part of 1-ethyl-3-(3-dimethylaminopropyl) Carbodiimide iodomethane salt (EDC·CH ₃ I), temperature controlled at 50°C, esterification reaction was carried out for 70 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethyl ammonium chloride-random-poly N-vinyl formamide) (PHEMAA-g-(PDMC-r-PNVF)); add 1 part of potassium hydroxide, control the temperature at 80°C, and graft on the polymerization The functional macromolecule side chain precursor polymer (PNVF) of the main chain of the substance was hydrolyzed for 48 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride- random-polyethyleneamine) (PHEMAA-g-(PDMC-r-PVA)); then add 8 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) synthesized in step 3, acylation reaction After 24 hours, the degree of acylation was 80%, and polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyethyleneaminocyclohexanediamine tetraacetic acid Sodium-random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVA)); then add 2 parts of carbon disulfide, control the temperature at 40°C, and perform addition reaction for 1 hour to obtain polyhydroxy Ethylacrylamide-graft-(polymethacryloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediamine tetraacetate sodium-random-polyvinylaminodithioamino Sodium formate) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble terpolymer molecular brush anionic dye capture and sedimentation agent. The grafting rates of side chains of PDMC, PVACDTANa and PVACS ₂ Na were determined by elemental analyzer and NMR to be 18%, 8% and 2%, respectively.

In this embodiment, the application of water-soluble ternary polymer molecular brush anionic dye capture sedimentation agent

Take the water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent of this embodiment to do the dye wastewater test, take 100 parts of waste water containing Congo red 100 mg/L, add 0.1 part of water-soluble ternary polymer molecular brush anionic dye Catch the sedimentation agent, stir for 1 minute at room temperature, adjust the pH value of the wastewater to 2.0 with 0.1 mol/L hydrochloric acid, then add 0.01 part of calcium chloride as a sedimentation aid, stir for 1 minute at room temperature, and generate particles with a particle size greater than 130 μm within 9 seconds floc precipitation. After filtration, the Congo red concentration in the filtrate was measured by an ultraviolet absorption spectrophotometer to be 0.04 mg/L, and the removal efficiency was greater than 99%.

Embodiment two

Its water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent is prepared by the following steps:

Synthesis of Step 1 PHEMAA Polymer Main Chain

Take 1 part of azobisisobutyronitrile initiator, 400 parts of hydroxyethylacrylamide (HEMAA), and 40 parts of methanol, and carry out polymerization reaction at 75°C for 1 hour under the protection of nitrogen to obtain a degree of polymerization (DP) of 190 Polyhydroxyethylacrylamide (PHEMAA);

Step 2 Synthesis of cationic polymer side chain PDMC-COOH and functional polymer side chain precursor polymer PNVF-COOH

Synthesis of cationic polymer side chain PDMC-COOH: Take 1 part of azodicyanovaleric acid initiator, 300 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) and 200 parts of water , under the protection of nitrogen, carry out free radical polymerization at 70°C for 8 hours, and obtain PDMC-COOH with a degree of polymerization (DP) of 110;

Synthesis of functional polymer side chain precursor polymer PNVF-COOH: take 1 part of azodicyanovaleric acid initiator, 300 parts of N-vinylformamide (NVF) and 100 parts of water, under nitrogen protection Free radical polymerization was carried out at 65°C for 5 hours to obtain PNVF-COOH with a degree of polymerization (DP) of 130;

Step 3 Synthesis of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD)

Dissolve 15 parts of 1,2-cyclohexanediamine tetraacetic acid and 15 parts of acetic anhydride in 20 parts of 2-picoline, control at 60°C, and react for 30 hours to obtain 1,2-cyclohexanediamine tetraacetic acid Acetic dianhydride;

Step 4 Synthesis of PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)

Polymerize 2 parts of polyhydroxyethylacrylamide (PHEMAA) obtained in step 1 with 50 parts of cationic polymer side chain PDMC-COOH and 20 parts of functional polymer side chain precursor obtained in step 2 Mix and dissolve PNVF-COOH in 300 parts of water, add 4 parts of catalyst, namely N-hydroxysuccinimide (NHS) and 4 parts of 1-ethyl-3-(3-dimethylaminopropyl) Carbodiimide iodomethane salt (EDC·CH ₃ I), temperature controlled at 60°C, esterification reaction was carried out for 40 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethyl ammonium chloride-random-poly N-vinyl formamide) (PHEMAA-g-(PDMC-r-PNVF)); add 5 parts of potassium hydroxide, control the temperature at 70°C, and graft on the polymerization The functional polymer side chain precursor polymer (PNVF) of the main chain was hydrolyzed for 36 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride- random-polyethyleneamine) (PHEMAA-g-(PDMC-r-PVA)); then add 15 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) synthesized in step 3, acylation reaction After 12 hours, the degree of acylation was 83%, and polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyethyleneaminocyclohexanediamine tetraacetic acid Sodium-random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVA)); then add 6 parts of carbon disulfide, control the temperature at 30°C, and perform addition reaction for 2 hours to obtain polyhydroxy Ethylacrylamide-graft-(polymethacryloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediamine tetraacetate sodium-random-polyvinylaminodithioamino Sodium formate) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble terpolymer molecular brush anionic dye capture and sedimentation agent. The grafting ratios of side chains of PDMC, PVACDTANa and PVACS ₂ Na were measured by elemental analyzer and nuclear magnetic resonance, respectively, to be 65%, 19% and 4%.

In this embodiment, the application of water-soluble terpolymer molecular brush anionic dye capture sedimentation agent

Take the water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent of this embodiment to do the dye wastewater test, get 500 parts of methyl red 100 mg/L, Cu ²⁺ ion 3 mg/L and citric acid 0.2 mg/L L waste water, add 0.5 parts of water-soluble ternary polymer molecular brush anionic dyes to catch and settle, stir at room temperature for 3 minutes, use 0.1 mol/L hydrochloric acid to adjust the pH value of the waste water to 3.0, then add 0.05 parts of auxiliary settling agent magnesium chloride, After stirring for 1 minute at room temperature, floc precipitation with a particle size greater than 180 μm is formed within 7 seconds. Filtration, the concentration of methyl red in the filtrate measured by ultraviolet absorption spectrophotometer was 0.08 mg/L, the concentration of Cu ²⁺ in the filtrate measured by atomic absorption spectrophotometer was 0.02 mg/L, and the removal efficiency was greater than 99%.

Embodiment Three

Its water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent is prepared by the following steps:

Synthesis of Step 1 PHEMAA Polymer Main Chain

Take 2 parts of ethyl 2-bromoisobutyrate initiator, 3 parts of CuBr and 3 parts of 4,4-linked 2-picoline (BPy), 200 parts of hydroxyethylacrylamide (HEMAA), 200 parts of Parts of methanol were polymerized at 50°C for 3 hours under the protection of nitrogen to obtain polyhydroxyethylacrylamide (PHEMAA) with a degree of polymerization (DP) of 100;

Step 2 Synthesis of cationic polymer side chain PDMC-COOH and functional polymer side chain precursor polymer PNVF-COOH

Synthesis of cationic polymer side chain PDMC-COOH: Take 2 parts of azodicyanovaleric acid initiator, 100 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) and 100 parts of water , carry out free radical polymerization at 40°C for 2 hours under the protection of nitrogen, and obtain PDMC-COOH with a degree of polymerization (DP) of 60;

Synthesis of functional polymer side chain precursor polymer PNVF-COOH: take 3 parts of azodicyanovaleric acid initiator, 200 parts of N-vinylformamide (NVF) and 200 parts of water, under nitrogen protection Free radical polymerization was carried out at 45°C for 7 hours to obtain PNVF-COOH with a degree of polymerization (DP) of 70;

Step 3 Synthesis of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD)

Dissolve 20 parts of 1,2-cyclohexanediaminetetraacetic acid and 20 parts of acetic anhydride in 30 parts of 2-picoline, control at 70°C, and react for 40 hours to obtain 1,2-cyclohexanediamine Tetraacetic dianhydride;

Step 4 Synthesis of PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)

Polymerize 3 parts of polyhydroxyethylacrylamide (PHEMAA) obtained in step 1 with 100 parts of cationic polymer side chain PDMC-COOH and 40 parts of functional polymer side chain precursor obtained in step 2 Mix and dissolve PNVF-COOH in 500 parts of water, add 3 parts of catalysts, namely N-hydroxysuccinimide (NHS) and 3 parts of 1-ethyl-3-(3-dimethylaminopropyl) Carbodiimide iodomethane salt (EDC·CH ₃ I), temperature controlled at 80°C, esterification reaction was carried out for 20 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethyl ammonium chloride-random-poly N-vinyl formamide) (PHEMAA-g-(PDMC-r-PNVF)); add 10 parts of potassium hydroxide, control the temperature at 50°C, and graft on the polymerization The functional macromolecule side chain precursor polymer (PNVF) of the main chain of the substance was hydrolyzed for 12 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride- random-polyethyleneamine) (PHEMAA-g-(PDMC-r-PVA)); then add 20 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) synthesized in step 3, acylation reaction After 6 hours, the degree of acylation was controlled at 67%, and polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyethyleneaminocyclohexanediamine tetra Sodium acetate-random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVA)); then add 10 parts of carbon disulfide, control the temperature at 20°C, and perform addition reaction for 3 hours to obtain polyhydroxy Ethylacrylamide-graft-(polymethacryloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediamine tetraacetate sodium-random-polyvinylaminodithioamino Sodium formate) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble terpolymer molecular brush anionic dye capture and sedimentation agent. The grafting ratios of side chains of PDMC, PVACDTANa and PVACS ₂ Na were determined by elemental analyzer and NMR to be 48%, 10% and 5%, respectively.

In this embodiment, the application of water-soluble ternary polymer molecular brush anionic dye capture sedimentation agent

Take the water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent of this embodiment to do the dye wastewater test, get 1000 parts containing methyl orange 100 mg/L, Pb ²⁺ ion 3 mg/L and citric acid 0.2 mg/L For wastewater, add 1.0 parts of water-soluble ternary polymer molecular brush anionic dye capture and sedimentation agent, stir at room temperature for 5 minutes, use 0.1 mol/L hydrochloric acid to adjust the pH value of wastewater to 5.0, and then add 0.1 parts of aluminum chloride as a sedimentation aid , stirred at normal temperature for 1 minute, and within 3 seconds, the floc precipitation with a particle size greater than 400 μm was generated, filtered, and the concentration of methyl orange in the filtrate was measured by an ultraviolet absorption spectrophotometer to be 0.03 mg/L, and the filtrate was measured by an atomic absorption spectrophotometer. The concentration of Pb ²⁺ in the medium is 0.01 mg/L, and the removal efficiency is greater than 99%.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (6)

1. a kind of water-soluble ter-polymers molecular brush anionic dye catches sedimentation agent, it is characterised in that including 1~10 part Main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）, 20~100 parts cationic high-molecular side chain terminal it is carboxylic Polymethyl acyloxyethyl trimethyl ammonium chloride（PDMC-COOH）, 5~40 parts of functional polymer side chain precursor polymer The carboxylic polyvinylformamide in end（PNVF-COOH）, 100~500 parts water, 1~5 part of catalyst be N- hydroxyls Succinimide (NHS), 1~5 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH₃I)、 1~10 part of potassium hydroxide, 1~20 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) and 1~10 part of carbon disulfide； It is mass fraction above.

2. water-soluble ter-polymers molecular brush anionic dye according to claim 1 catches sedimentation agent, its feature exists In：

The main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）Pass through general radical polymerization or controllable living polymerization Synthesize PHEMAA main polymer chains；

It is common free that the cationic high-molecular side chain PDMC-COOH mainly uses azo dicyano valeric acid to pass through for initiator Base polymerization synthesizes the carboxylic polymethyl acyloxyethyl trimethyl ammonium chloride in end（PDMC-COOH）Polymer；

The functional polymer side chain precursor polymer PNVF-COOH mainly uses azo dicyano valeric acid to pass through for initiator The general radical polymerization synthesis carboxylic polyvinylformamide in end（PNVF-COOH）Polymer；

The synthetic method of the 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) is：By 5~20 parts of 1,2- cyclohexanediamine tetrems Acid and 5~20 parts of acetic anhydrides are dissolved in 10~30 parts of 2- picolines, are controlled in 50~70 DEG C, are reacted 20~40 hours, Obtain 1,2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides.

3. a kind of water-soluble ter-polymers molecular brush anionic dye catches the preparation method of sedimentation agent, it is characterised in that by 1 ~10 parts of main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）, 20~100 parts of cationic high-molecular side chain terminal Carboxylic polymethyl acyloxyethyl trimethyl ammonium chloride（PDMC-COOH）Before 5~40 parts of functional polymer side chain Drive the carboxylic polyvinylformamide of body polymer ends（PNVF-COOH）Mixing is dissolved in 100~500 parts of water, is added Enter 1~5 part of catalyst i.e. n-hydroxysuccinimide (NHS) and 1~5 part 1- ethyls -3- (3- dimethylamino-propyls) carbon Diimine iodomethane salt (EDCCH₃I), temperature control carries out esterification 10~70 hours in 50~80 DEG C, obtains poly-hydroxyethyl Acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-polyvinylformamide）(PHEMAA- g-(PDMC-r-PNVF))；1~10 part of potassium hydroxide is added, it is small that reaction 12~48 is hydrolyzed in 50~80 DEG C in temperature control When, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-polyvinylamine） （PHEMAA-g-(PDMC-r-PVA）)；1~20 part of CDTA dianhydride (CDTAD) is added, carries out acyl group Change reaction 5~24 hours, acylation degree scope control is 60~99%, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethyl Acyloxyethyl trimethyl ammonium chloride-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyvinylamine）(PHEMAA-g- (PDMC-r-PVACDTANa-r-PVA))；1~10 part of carbon disulfide is added, temperature control carries out addition reaction in 20~40 DEG C 1~3 hour, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- second Enamine basic ring hexamethylene tetraacetic acid sodium-random-polyethylene amido nabam）(PHEMAA-g-(PDMC-r- PVACDTANa-r-PVACS₂Na it is)) that water-soluble ter-polymers molecular brush anionic dye catches sedimentation agent；It is matter above Measure number.

4. water-soluble ter-polymers molecular brush anionic dye according to claim 3 catches the preparation side of sedimentation agent Method, it is characterised in that the poly-hydroxyethyl acrylamide（PHEMAA）The degree of polymerization be 10~200, the cationic high-molecular Side chain PDMC-COOH and functional polymer side chain precursor polymer the PNVF-COOH degree of polymerization are 10~200, cation Type polymer side chain PDMC grafting rate is 1~70%, chelating type polymer side chain PVACDTANa grafting rate 1~20% and helped Settle polymer side chain PVACS₂Na grafting rate is 1~5%.

5. a kind of water-soluble ter-polymers molecular brush anionic dye catches the application of sedimentation agent, it is characterised in that by 0.1~1 The water-soluble ter-polymers molecular brush anionic dye of part catches sedimentation agent and is added in 100~1000 parts of waste water, normal temperature Lower stirring 1~5 minute, adjusts pH to 2~5, in waste water anionic dye molecule and water-soluble ter-polymers molecular brush the moon from Electrostatic Absorption occurs for the cationic side chain PDMC that sub- dyestuff catches sedimentation agent, and heavy metal ions in wastewater is gathered with water-soluble ternary Chelating absorption occurs for the chelating type side chain PVACDTANa that adduct molecule brush anionic dye catches sedimentation agent, add 0.01~ 0.1 part is helped sedimentation agent, is stirred 1 minute under normal temperature, help the metal ion of sedimentation agent quickly with water-soluble ter-polymers molecule Brush anionic dye catches helping for sedimentation agent and settles side chain PVACS₂Chemical precipitation reaction occurs for Na, and generation particle diameter is more than in 10 seconds 100 μm of flco precipitation, can quickly realize the anionic dye and solvay-type heavy metal ion removed in waste water, go out water colorless, Reach discharging standards, be mass fraction above.

6. water-soluble ter-polymers molecular brush anionic dye according to claim 5 catches the application of sedimentation agent, its Be characterised by it is described help sedimentation agent for calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, alchlor it is one or two kinds of with On any combination.