CN107879450B - Water-soluble quaternary polymer molecular brush anionic dye capturing settling agent and preparation method and application thereof - Google Patents

Abstract

The invention relates to a water-soluble quaternary polymer molecular brush anionic dye capturing settling agent and a preparation method and application thereof, which are characterized in that the water-soluble quaternary polymer molecular brush anionic dye capturing settling agent is prepared by polymer main chain polyhydroxyethyl acrylamide, cationic polymethacryloxyethyl trimethyl ammonium chloride containing carboxyl at the tail end of a high molecular side chain, functional high molecular side chain precursor polymer containing carboxyl at the tail end of poly N-vinyl formamide, water, a catalyst, namely N-hydroxysuccinimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt, sodium hydroxide, 1, 2-cyclohexanediaminetetraacetic dianhydride and carbon disulfide, and the water-soluble quadripolymer molecular brush anionic dye capturing settling agent is used for treating dye wastewater or artistic coating wastewater discharged in the dye synthesis or dyeing and finishing process. The complex type heavy metal ion capture agent has the advantages of good capture capacity, high settling speed, capability of treating complex type heavy metal ions, capability of capturing anionic dye and complex type heavy metal ions within a few seconds, capability of rapidly growing large aggregate precipitates within 10 seconds, capability of rapidly separating dye and the like.

Description

Water-soluble quaternary polymer molecular brush anionic dye capture 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 in particular relates to a water-soluble quaternary polymer molecular brush anionic dye capture and sedimentation agent, a preparation method and an application thereof. It can be used in dye wastewater or art paint wastewater, and can simultaneously remove anionic dyes and complex heavy metal ions from 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%, and dye wastewater accounts for 35% of the total industrial wastewater discharge, and it is also increasing at a rate of 1% year by year. Dye wastewater mainly comes from dye synthesis and dye use enterprises, and consists of dyes and auxiliaries discharged during synthesis or dyeing and finishing. 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 dye production volume reaches ^1.5 × 105 tons, of which about 10% to 15% of the dyes will be directly The dye wastewater has become one of the important pollution sources of the water body when it is discharged into the water body with the wastewater. 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 jointly revised and issued the "Water Pollutant Discharge Standard for Textile Dyeing and Finishing Industry" (GB 4287-2012). According to the new discharge standard and traditional treatment technology, many printing and dyeing enterprises cannot meet the new national discharge standard. In general, the current dye wastewater treatment technology is still unable to meet the national discharge standards, and the research and development of new materials and new technologies is urgently needed to solve the current enterprise discharge problems. Dye wastewater has a strong sense of pollution, and colored water will affect sunlight exposure, which is not conducive to the growth of aquatic organisms, and it is difficult to treat it by general biochemical methods. The discharge of dye wastewater is also very large, and the discharge is intermittent, and the water quality is also unstable, which is difficult to treat wastewater.

Traditional wastewater treatment methods include physicochemical method, chemical coagulation method, physical adsorption method, biochemical method, electrochemical method, etc. The chemical coagulation method is to add a coagulant to the dye wastewater to make the pollutants form colloidal particles, and to remove the pollutants in the wastewater through coagulation sedimentation 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. The coagulants currently used mainly include inorganic coagulants and organic polymer coagulants. Inorganic coagulants are mainly aluminum salts and iron salts, which have a good coagulation effect on the dyes that exist in the wastewater in a colloidal or suspended state, but the coagulation effect is relatively small for the water-soluble dyes with smaller molecular weights. Difference. The organic polymer coagulant has a large molecular weight, disperses into a huge number of linear molecules after being dissolved in water, and has strong adsorption and bridging ability to colloidal suspended particles in water. Organic polymer coagulants have stable properties, less residue, and wider pH requirements. 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, and inability to deal with complex heavy metal ions.

SUMMARY OF THE INVENTION

The object of the present invention is to overcome the deficiencies of the prior art and provide a water-soluble quaternary polymer molecular brush anionic dye capture and sedimentation agent and its preparation method and application, which have good capturing ability, fast sedimentation speed, and can handle complex type Heavy metal ions can capture anionic dyes and complex heavy metal ions within a few seconds, quickly 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 quaternary polymer molecular brush anionic dye capture and sedimentation agent of the present invention is realized in this way, which is characterized in that it comprises 1-10 parts of the polymer main chain polyhydroxyethyl acrylamide (PHEMAA ), 20-100 parts of polymethacryloyloxyethyl trimethyl ammonium chloride (PDMC-COOH) containing carboxyl group at the end of cationic polymer side chain, 5-40 parts of functional polymer side chain precursor polymerization poly-N-vinylformamide (PNVF-COOH) with carboxyl group at the end of the product, 100-500 parts of water, 1-5 parts of catalyst, namely N-hydroxysuccinimide (NHS), 1-5 parts of 1- Ethyl-3-(3-dimethylaminopropyl)carbodiimide iodomethane salt (EDC·CH ₃ I), 1-10 parts of sodium hydroxide, 1-20 parts of 1,2-cyclohexane Diaminetetraacetic dianhydride (CDTAD) and 1-10 parts of carbon disulfide; the above are all parts by mass.

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

The cationic polymer side chain PDMC-COOH mainly uses azodicyanovaleric acid as the initiator to synthesize polymethacryloyloxyethyltrimethylammonium chloride (PDMC) containing carboxyl groups at the end by ordinary free radical polymerization method. -COOH) polymer;

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

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

In order to achieve the above purpose, the technical scheme of the water-soluble quaternary polymer molecular brush anionic dye capture and sedimentation agent preparation method of the present invention is realized in this way, which is characterized in that 1-10 parts of the polymer main chain polyhydroxyethyl propylene Amide (PHEMAA), 20-100 parts of cationic polymer side chain end containing carboxyl polymethacryloyloxyethyl trimethyl ammonium chloride (PDMC-COOH) and 5-40 parts of functional polymer side chain The poly-N-vinylformamide (PNVF-COOH) containing carboxyl groups at the end of the precursor polymer is mixed and dissolved in 100-500 parts of water, and 1-5 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 ℃, carry out esterification reaction for 10 ~70 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyN-vinylformamide) (PHEMAA-g-(PDMC- r-PNVF)); then add 1-10 parts of sodium hydroxide, control the temperature at 50-80 ° C, and carry out a hydrolysis reaction for 12-48 hours to obtain polyhydroxyethyl acrylamide-graft-(polymethacryloyl Oxyethyltrimethylammonium chloride-random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVA)); then add 1 to 20 parts of 1,2-cyclohexanediaminetetraacetic acid dianhydride (CDTAD), carry out acylation reaction for 5 to 24 hours, and the acylation degree range is controlled to be 60 to 99% to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride) -random-polyvinylaminocyclohexanediaminetetraacetate-random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVA)); then add 1-10 parts of carbon disulfide, The temperature is controlled at 20～40℃, and the addition reaction is carried out for 1～3 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylamine (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble quaternary polymer molecular brush Anionic dye capture sedimentation agent; the above are all parts by mass.

In this technical solution, the degree of polymerization of the polyhydroxyethyl acrylamide (PHEMAA) is 10-200, and the cationic polymer side chain PDMC-COOH and the functional polymer side chain precursor polymer PNVF-COOH have The degree of polymerization is 10-200, the grafting rate of the cationic polymer side chain PDMC is 1-70%, the grafting rate of the chelating polymer side chain PVACDTANa is 1-20%, and the assisted sedimentation polymer side chain PVACS ₂ The grafting ratio of Na is 1-5%.

In order to achieve the above-mentioned purpose, the technical scheme of the application of the water-soluble quaternary polymer molecular brush anionic dye capture and sedimentation agent of the present invention is realized in this way, which is characterized in that 0.1-1 part of the water-soluble quaternary polymer molecular brush an anionic dye The capture and sedimentation agent is added to 100-1000 parts of wastewater, stirred for 1 to 5 minutes at room temperature, and the pH is adjusted to 2 to 5. The anionic dye molecules and water-soluble quaternary polymer molecules in the wastewater are brushed with the cationic type of the anionic dye capture and sedimentation agent. The side chain PDMC is electrostatically adsorbed, and the heavy metal ions in the wastewater and the water-soluble quaternary polymer molecular brush anionic dye capture the chelating side chain PVACDTANa of the sedimentation agent. Stir for 1 minute, the metal ions of the sedimentation aid quickly react with the water-soluble quaternary polymer molecular brush anionic dye to capture the side chain PVACS ₂ Na of the sedimentation aid, and the flocs with a particle size greater than 100 μm are formed within 10 seconds. Precipitation can quickly remove anionic dyes and complex heavy metal ions in wastewater. The effluent is colorless and meets the national discharge standard. The above are all parts by mass.

In this technical scheme, the settling aid is any combination of one 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 capturing performance of traditional synthetic polymer dye flocculants. The present invention contains three kinds of polymer side chains with different functions, and the cationic polymer side chain PDMC has a good effect on anionic dyes. Electrostatic adsorption capacity, chelating side chain PVACDTANa chelates and adsorbs heavy metal ions, under the synergistic effect of PVACS ₂ Na polymer side chain PVACS ₂ Na, the polymer side chain of PVACS 2 Na and the metal ions of the deposition aid quickly undergo chemical precipitation reaction to achieve efficient capture and rapid sedimentation;

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

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

Detailed ways

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

Example 1

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

Step 1 Synthesis of PHEMAA polymer backbone

Take 2 parts of azobisisobutyronitrile initiator, 50 parts of hydroxyethyl acrylamide (HEMAA) and 400 parts of methanol, carry out polymerization reaction at 75°C for 1 hour under nitrogen protection, and obtain a degree of polymerization (DP) of 20 of polyhydroxyethyl acrylamide (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 , carried out radical polymerization at 70 °C for 16 hours under nitrogen protection to 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 Perform free radical polymerization 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)

9 parts of 1,2-cyclohexanediaminetetraacetic acid and 9 parts of acetic anhydride were dissolved in 10 parts of 2-picoline, controlled at 50°C, and reacted 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 polyhydroxyethyl acrylamide (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 compound PNVF-COOH was mixed and dissolved in 100 parts of water, and 1 part of the catalyst was N-hydroxysuccinimide (NHS) and 1 part of 1-ethyl-3-(3-dimethylaminopropyl) Carbodiimide methyl iodide (EDC·CH ₃ I), the temperature was controlled at 50 ° C, and the esterification reaction was carried out for 70 hours to obtain polyhydroxyethyl acrylamide-grafted-(polymethacryloyloxyethyl trimethylene ammonium chloride-random-polyN-vinylformamide) (PHEMAA-g-(PDMC-r-PNVF)); add 1 part of sodium hydroxide, control the temperature at 80 ° C, and graft on the polymer The functional polymer side chain precursor polymer (PNVF) of the main chain was hydrolyzed for 48 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride- Random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVA)); then add 8 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) synthesized in step 3, acylation reaction 24 hours, the degree of acylation is 80%, to obtain polyhydroxyethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediaminetetraacetic 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 carry out an addition reaction for 1 hour to obtain polyhydroxy Ethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediaminetetraacetate-sodium-random-polyvinylaminodithioamino Sodium formate) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent. The grafting rates of PDMC, PVACDTANa and PVACS ₂ Na side chains were determined by elemental analyzer and nuclear magnetic resonance analyzer, and they were 18%, 8% and 2%, respectively.

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

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

Embodiment 2

A water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent is prepared by the following steps:

Step 1 Synthesis of PHEMAA polymer backbone

Take 1 part of azobisisobutyronitrile initiator, 400 parts of hydroxyethyl acrylamide (HEMAA) and 40 parts of methanol, carry out polymerization reaction at 75°C for 1 hour under nitrogen protection, and obtain a degree of polymerization (DP) of 190 of polyhydroxyethyl acrylamide (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 , carried out radical polymerization at 70 °C for 8 hours under nitrogen protection to 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 Perform free radical polymerization 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)

15 parts of 1,2-cyclohexanediaminetetraacetic acid and 15 parts of acetic anhydride were dissolved in 20 parts of 2-picoline, controlled at 60°C, and reacted for 30 hours to obtain 1,2-cyclohexanediaminetetramine Acetic dianhydride;

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

Polymerize 2 parts of polyhydroxyethyl acrylamide (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 The compound PNVF-COOH was mixed and dissolved in 300 parts of water, and 4 parts of catalyst, namely N-hydroxysuccinimide (NHS) and 4 parts of 1-ethyl-3-(3-dimethylaminopropyl) Carbodiimide methyl iodide salt (EDC·CH ₃ I), the temperature was controlled at 60 ° C, and the esterification reaction was carried out for 40 hours to obtain polyhydroxyethyl acrylamide-grafted-(polymethacryloyloxyethyl trimethylene ammonium chloride-random-polyN-vinylformamide) (PHEMAA-g-(PDMC-r-PNVF)); add 5 parts of sodium hydroxide, control the temperature at 70 ° C, and graft on the polymer The functional polymer side chain precursor polymer (PNVF) of the main chain was hydrolyzed for 36 hours to obtain polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride- Random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVA)); then add 15 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) synthesized in step 3, acylation reaction 12 hours, the degree of acylation was 83%, and polyhydroxyethylacrylamide-grafted-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediaminetetraacetic acid was obtained Sodium-random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVA)); then add 6 parts of carbon disulfide, control the temperature at 30 ° C, and carry out an addition reaction for 2 hours to obtain polyhydroxy Ethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediaminetetraacetate-sodium-random-polyvinylaminodithioamino Sodium formate) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent. The grafting rates of PDMC, PVACDTANa and PVACS ₂ Na side chains were determined by elemental analyzer and nuclear magnetic resonance analyzer, and they were 65%, 19% and 4%, respectively.

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

Take the water-soluble quaternary polymer molecular brush anionic dye capture and sedimentation agent of this embodiment for dye wastewater test, take 500 parts containing methyl red 100 mg/L, Cu ²⁺ ions 3 mg/L and citric acid 0.2 mg/L L wastewater, add 0.5 part of water-soluble quaternary polymer molecular brush anion dye to capture sedimentation agent, stir at room temperature for 3 minutes, use 0.1 mol/L hydrochloric acid to adjust the pH value of wastewater to 3.0, and then add 0.05 part of magnesium chloride as a sedimentation aid, Stir for 1 minute at room temperature, and within 7 seconds, flocs with a particle size larger than 180 μm are formed. After filtration, the concentration of methyl red in the filtrate was determined by ultraviolet absorption spectrophotometer to be 0.08 mg/L, and the concentration of Cu ²⁺ in the filtrate was determined by atomic absorption spectrophotometer to be 0.02 mg/L, and the removal efficiency was greater than 99%.

Embodiment 3

A water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent is prepared by the following steps:

Step 1 Synthesis of PHEMAA polymer backbone

Take 2 parts of ethyl 2-bromoisobutyrate initiator, 3 parts of CuBr and 3 parts of 4,4-bi-2-methylpyridine (BPy), 200 parts of hydroxyethyl acrylamide (HEMAA), 200 parts of Parts of methanol were polymerized at 50 °C for 3 hours under nitrogen protection to obtain polyhydroxyethyl acrylamide (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 , carried out radical polymerization at 40 °C for 2 hours under nitrogen protection to 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 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)

20 parts of 1,2-cyclohexanediaminetetraacetic acid and 20 parts of acetic anhydride were dissolved in 30 parts of 2-picoline, controlled at 70°C, and reacted 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 polyhydroxyethyl acrylamide (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 The compound PNVF-COOH was mixed and dissolved in 500 parts of water, and 3 parts of catalyst, namely N-hydroxysuccinimide (NHS) and 3 parts of 1-ethyl-3-(3-dimethylaminopropyl) Carbodiimide methyl iodide salt (EDC·CH ₃ I), the temperature was controlled at 80 ° C, and the esterification reaction was carried out for 20 hours to obtain polyhydroxyethyl acrylamide-grafted-(polymethacryloyloxyethyl trimethylene ammonium chloride-random-polyN-vinylformamide) (PHEMAA-g-(PDMC-r-PNVF)); add 10 parts of sodium hydroxide, control the temperature at 50 ° C, and graft on the polymer The functional polymer side chain precursor polymer (PNVF) of the main chain was hydrolyzed for 12 hours to obtain polyhydroxyethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride- Random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVA)); then add 20 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) synthesized in step 3, acylation reaction 6 hours, the degree of acylation was controlled to 67%, and polyhydroxyethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediaminetetramine was obtained) 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 carry out an addition reaction for 3 hours to obtain polyhydroxy Ethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediaminetetraacetate-sodium-random-polyvinylaminodithioamino Sodium formate) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent. The grafting rates of PDMC, PVACDTANa and PVACS ₂ Na side chains were determined by elemental analyzer and nuclear magnetic resonance analyzer, and they were 48%, 10% and 5%, respectively.

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

Take the water-soluble quaternary polymer molecular brush anionic dye capture and sedimentation agent of this embodiment for dye wastewater test, take 1000 parts containing methyl orange 100 mg/L, Pb ²⁺ ion 3 mg/L and citric acid 0.2 mg/L Wastewater, add 1.0 part of water-soluble quaternary polymer molecular brush anion dye to capture 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 part of aluminum chloride as a sedimentation aid , stirred at room temperature for 1 minute, and within 3 seconds, flocs with a particle size greater than 400 μm were precipitated, filtered, and the concentration of methyl orange in the filtrate was determined by an ultraviolet absorption spectrophotometer to be 0.03 mg/L. The concentration of Pb ²⁺ was 0.01 mg/L, and the removal efficiency was greater than 99%.

The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.

Claims (5)

1. A water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent, characterized in that it comprises 1-10 parts of polymer backbone polyhydroxyethyl acrylamide (PHEMAA), 20-100 parts of cationic macromolecules Polymethacryloyloxyethyltrimethylammonium chloride (PDMC-COOH) with carboxyl group at the end of the side chain, 5-40 parts of functional polymer side chain precursor PolyN-vinyl methyl group with carboxyl group at the end of the polymer Amide (PNVF-COOH), 100-500 parts of water, 1-5 parts of catalyst namely N-hydroxysuccinimide (NHS), 1-5 parts of 1-ethyl-3-(3-dimethylamine) propyl) carbodiimide iodomethane salt (EDC·CH ₃ I), 1-10 parts of sodium hydroxide, 1-20 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD) and 1 ~10 parts of carbon disulfide; The polymer main chain polyhydroxyethyl acrylamide (PHEMAA) is synthesized by ordinary free radical polymerization or controlled living polymerization method to synthesize the PHEMAA polymer main chain; The cationic polymer side chain PDMC-COOH uses azodicyanovaleric acid as an initiator to synthesize polymethacryloyloxyethyltrimethylammonium chloride (PDMC- COOH) polymer; The functional polymer side chain precursor polymer PNVF-COOH uses azodicyanovaleric acid as an initiator to synthesize a poly-N-vinylformamide (PNVF-COOH) polymer containing carboxyl groups at the end by ordinary free radical polymerization; The method for synthesizing the 1,2-cyclohexanediaminetetraacetic acid dianhydride (CDTAD) is: dissolving 5-20 parts of 1,2-cyclohexanediaminetetraacetic acid and 5-20 parts of acetic anhydride in 10-30 parts of In part of 2-picoline, control at 50～70℃, and react for 20～40 hours to obtain 1,2-cyclohexanediaminetetraacetic dianhydride; The above are all parts by mass. 2. the application of the water-soluble quaternary polymer molecular brush anion dye catching sedimentation agent according to claim 1, is characterized in that adding 0.1～1 part of water-soluble quaternary polymer molecular brush anionic dye catching sedimentation agent to 100 In ~1000 parts of wastewater, stir at room temperature for 1 to 5 minutes, adjust the pH to 2 to 5, and the anionic dye molecules in the wastewater and the water-soluble quaternary polymer molecules brush the cationic side chain PDMC of the anionic dye to capture the sedimentation agent. Electrostatic adsorption occurs , the heavy metal ions in the wastewater and the water-soluble quaternary polymer molecular brush anionic dye capture the chelating type side chain PVACDTANa of the sedimentation agent chelate adsorption, and then add 0.01 to 0.1 parts of the sedimentation aid, and stir at room temperature for 1 minute to aid the sedimentation. The metal ions of the agent quickly react with the water-soluble quaternary polymer molecular brush anionic dye to capture the sedimentation-assisting side chain PVACS ₂ Na of the sedimentation agent, and generate flocs with a particle size larger than 100 μm within 10 seconds. The anionic dyes and complex heavy metal ions in the effluent are colorless and meet the national emission standards, and the above are all parts by mass. 3. the application of water-soluble quaternary polymer molecular brush anion dyes according to claim 2 to capture the sedimentation agent, it is characterized in that described sedimentation aid is calcium chloride, magnesium sulfate, ferrous chloride, ferric chloride , any combination of one or more of aluminum trichloride. 4. A method for preparing a water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent, characterized in that 1-10 parts of polymer backbone polyhydroxyethyl acrylamide (PHEMAA), 20-100 parts of cationic Polymethacryloyloxyethyltrimethylammonium chloride (PDMC-COOH) with carboxyl group at the end of the polymer side chain and 5-40 parts of functional polymer side chain precursor Vinylformamide (PNVF-COOH) is mixed and dissolved in 100-500 parts of water, and 1-5 parts of catalyst, N-hydroxysuccinimide (NHS) and 1-5 parts of 1-ethyl-3 are added. -(3-Dimethylaminopropyl)carbodiimide iodomethane salt (EDC·CH ₃ I), the temperature is controlled at 50-80° C., and the esterification reaction is carried out for 10-70 hours to obtain polyhydroxyethyl acrylamide -grafted-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyN-vinylformamide)(PHEMAA-g-(PDMC-r-PNVF)); then add 1～10 parts of sodium hydroxide, the temperature is controlled at 50-80 ° C, and the hydrolysis reaction is carried out for 12-48 hours to obtain polyhydroxyethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-no (regular-polyvinylamine) (PHEMAA-g-(PDMC-r-PVA)); then add 1-20 parts of 1,2-cyclohexanediaminetetraacetic dianhydride (CDTAD), and carry out acylation reaction 5-24 hours, the acylation degree range is controlled to 60-99%, and polyhydroxyethylacrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediol is obtained) Sodium amine tetraacetate-random-polyvinylamine) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVA)); then add 1-10 parts of carbon disulfide, control the temperature at 20-40 ℃, and carry out addition React for 1 to 3 hours to obtain polyhydroxyethyl acrylamide-graft-(polymethacryloyloxyethyltrimethylammonium chloride-random-polyvinylaminocyclohexanediaminetetraacetic acid sodium-random -Polyvinylamino dithiocarbamate sodium) (PHEMAA-g-(PDMC-r-PVACDTANa-r-PVACS ₂ Na)) is a water-soluble quaternary polymer molecular brush anion dye capture sedimentation agent; the above are parts by mass number. 5 . The preparation method of the water-soluble quaternary polymer molecular brush anionic dye capture sedimentation agent according to claim 4 , wherein the polymerization degree of the polyhydroxyethyl acrylamide (PHEMAA) is 10-200, and the The polymerization degree of cationic polymer side chain PDMC-COOH and functional polymer side chain precursor polymer PNVF-COOH are both 10-200, and the grafting rate of cationic polymer side chain PDMC is 1-70%, chelating The grafting rate of the side chain PVACDTANa of the type polymer is 1-20% and the grafting rate of the side chain PVACS ₂ Na of the assisted sedimentation polymer is 1-5%.