CN107828063B - Water-soluble quaternary chelate polymer molecular brush dye capture agent, and preparation method and application thereof - Google Patents
Water-soluble quaternary chelate polymer molecular brush dye capture agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a water-soluble quaternary chelating polymer molecular brush dye catching agent and a preparation method and application thereof, and is characterized in that the water-soluble quaternary chelating polymer molecular brush dye catching agent is prepared by polymer main chain polyhydroxyethylacrylamide, cationic polymethacryloxyethyltrimethylammonium chloride containing carboxyl at the tail end of a high molecular side chain, anionic polymethacrylic acid tert-butyl ester containing carboxyl at the tail end of a high molecular side chain precursor polymer, functional poly-N-vinylformamide containing carboxyl at the tail end of a high molecular side chain precursor polymer, dimethylformamide solvent, catalyst namely N-hydroxysuccinimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide iodomethane salt, potassium hydroxide and ethylene glycol diethyl ether diamine tetraacetic dianhydride, and the water-soluble quaternary chelating polymer molecular brush dye catching agent is used for treating dye wastewater and process wastewater discharged in the dye synthesis or dyeing and finishing process Coating waste water. The method has the advantages of strong trapping capacity, high settling speed, capability of treating complex heavy metal ions, capability of capturing dye molecules and complex heavy metal ions within seconds, rapid growth of large settling particles, realization of the purpose of rapid separation of dyes, simplicity and convenience in operation, low treatment cost, strong adaptability and the like.
Description
Technical Field
The invention belongs to the field of water treatment technology and high-molecular functional materials, and particularly relates to a quaternary chelate polymer molecular brush dye capturing agent, a preparation method and application thereof.
Background
In recent years, the annual sewage discharge amount of China reaches over 390 hundred million tons, wherein the industrial sewage accounts for 51 percent, and the dye wastewater accounts for 35 percent of the total industrial wastewater discharge amount, and is increased year by year at a speed of 1 percent, the dye wastewater mainly comes from dye synthesis and dye using enterprises and consists of dyes, additives and the like discharged in the synthesis or dyeing and finishing process, along with the rapid development of the printing and dyeing industry, China is a large country for textile production and processing, the export of textiles is listed in the first world for many years, and the annual dye production amount reaches 1.5 × 105And (3) ton of the dye is discharged into a water body directly along with waste water, wherein about 10 to 15 percent of the dye is discharged into the water body, and the dye waste water becomes one of important pollution sources of the water body. In 2012, the environmental protection department and the national quality supervision, inspection and quarantine bureau jointly revise and release the discharge standard of water pollutants for textile dyeing and finishing industry (GB 4287-. According to the new discharge standard, a plurality of printing and dyeing enterprises can not reach the new national discharge standard by adopting the traditional treatment technology, a plurality of emission stealing phenomena occur, and serious water body environmental pollution events occur. Generally, the current dye wastewater treatment technology cannot reach the national discharge standard, and the research and development of new materials and new technologies are urgently needed to solve the current enterprise discharge problem. Dye wastewater has extremely strong pollution, colored water can influence sunlight irradiation, aquatic organisms are not beneficial to growth, and the dye wastewater is difficult to treat by a common biochemical method. Discharge of dye wastewaterThe amount is also large, the discharge is intermittent, the water quality is not stable, and the method belongs to wastewater which is difficult to treat.
The traditional wastewater treatment methods include physical and chemical methods, chemical coagulation methods, physical adsorption methods, biochemical methods, electrochemical methods and the like. The chemical coagulation method is that coagulant is added into dye waste water to make pollutant form colloidal particles, and the pollutant in the waste water is removed through coagulating sedimentation or air flotation. The coagulation sedimentation method is the most widely used in practice. The coagulation method can simultaneously remove dye pollutants and other macromolecular suspended pollutants. The treatment effect on the wastewater mainly depends on the structural property of the coagulant. The currently used coagulants mainly include inorganic coagulants and organic polymer coagulants. The inorganic coagulant mainly takes aluminum salt and ferric salt as main materials, has good coagulation effect on dye existing in the wastewater in a colloid or suspension state, but has poor coagulation effect on water-soluble dye with smaller molecular weight. The organic polymer coagulant has large molecular weight, is dispersed into a great number of linear molecules after being dissolved in water, and has strong adsorption and bridging capacity on colloid suspended particles in the water. The organic polymer coagulant has stable property, less residue and wider requirement on pH value, wherein the most representative is polyacrylamide. But the polyacrylamide has a single chemical structure, and has the problems of poor capability of capturing dye molecules, low settling velocity, incapability of treating complex heavy metal ions and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a water-soluble quaternary chelating polymer molecular brush dye trapping agent, a preparation method and application thereof, the trapping agent has strong trapping capacity and high settling speed, can treat complex heavy metal ions, can trap dye molecules and complex heavy metal ions within seconds, can quickly grow into large settling particles, realizes the purpose of quickly separating dyes, and has the advantages of simple and convenient operation, low treatment cost and strong adaptability.
In order to achieve the purpose, the technical scheme of the water-soluble quaternary chelating polymer molecular brush dye trapping agent is realized by the following steps of 1-10 parts of polymer main chain Polyhydroxyethylacrylamide (PHEMAA) and 20-50 parts of cationic high-molecular-weight polymerPoly (methacryloyloxyethyl trimethyl ammonium chloride) (PDMC-COOH) containing carboxyl at molecular side chain end, 20-50 parts of poly (tert-butyl methacrylate) (PtBMA-COOH) containing carboxyl at anionic polymer side chain precursor polymer end, 5-30 parts of poly (N-vinyl formamide) (PNVF-COOH) containing carboxyl at functional polymer side chain precursor polymer end, 100-500 parts of dimethyl formamide (DMF) solvent, 1-5 parts of N-hydroxysuccinimide (NHS) serving as catalyst and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide iodomethane salt (EDC. CH) 13I) 1-10 parts of potassium hydroxide and 20-80 parts of ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD); the above are all parts by mass.
In the technical scheme, the PHEMAA polymer main chain is synthesized by the polymer main chain polyhydroxyethyl acrylamide (PHEMAA) through common free radical polymerization or a controllable activity polymerization method;
the cationic high molecular side chain PDMC-COOH is mainly prepared by adopting azodicyano valeric acid as an initiator and synthesizing a polymethacryloxyethyltrimethyl ammonium chloride (PDMC-COOH) polymer with a carboxyl group at the tail end through a common free radical polymerization method;
the anionic high-molecular precursor polymer PtBMA-COOH is mainly prepared by taking azobiscyanovaleric acid as an initiator and synthesizing a poly (tert-butyl methacrylate) (PtBMA-COOH) polymer with a carboxyl group at the tail end through a common free radical polymerization method;
the functional polymer side chain precursor polymer PNVF-COOH mainly adopts azodicyano valeric acid as an initiator to synthesize a poly N-vinyl formamide (PNVF-COOH) polymer with a carboxyl group at the tail end through common free radical polymerization;
the synthesis method of the ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD) comprises the following steps: dissolving 40-80 parts of ethylene glycol diethyl ether diamine tetraacetic acid and 40-80 parts of acetic anhydride in 50-100 parts of 2-methylpyridine, and reacting at 50-70 ℃ for 20-40 hours to obtain the ethylene glycol diethyl ether diamine tetraacetic dianhydride.
In order to achieve the above object, the technical solution of the method for preparing a water-soluble quaternary chelating polymer molecular brush dye catcher of the present invention is realized byIs characterized in that 1 to 10 portions of polymer main chain polyhydroxyethyl acrylamide (PHEMAA), 20 to 50 portions of cationic high molecular side chain end carboxyl-containing polymethacryloxyethyl trimethyl ammonium chloride (PDMC-COOH), 20 to 50 portions of anionic high molecular side chain precursor polymer end carboxyl-containing polymethacrylic acid tert-butyl ester (PtBMA-COOH) and 5 to 30 portions of functional high molecular side chain precursor polymer end carboxyl-containing poly N-vinyl formamide (PNVF-COOH) are mixed and dissolved in 100 to 500 portions of Dimethylformamide (DMF) solvent, 1 to 5 portions of catalyst, namely N-hydroxysuccinimide (NHS) and 1 to 5 portions of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide iodomethane salt (EDC. CH)3I) Controlling the temperature to be 50-80 ℃, and carrying out esterification reaction for 10-70 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-poly (tert-butyl methacrylate) -random-poly (N-vinylformamide) (PHEMAA-g- (PDMC-r-PtBMA-r-PNVF)); adding 1-10 parts of potassium hydroxide, controlling the temperature at 50-80 ℃, and carrying out hydrolysis reaction for 12-48 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); and then adding 20-80 parts of ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD) to perform an acylation reaction for 12-48 hours to obtain polyhydroxyethyl acrylamide-graft- (polymethacryloyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-random-polyvinylaminoethylene glycol diethyl ether diamine tetraacetic acid) (PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)) which is a water-soluble quaternary chelate polymer molecular brush dye trapping agent.
In the technical scheme, the polymerization degree of Polyhydroxyethylacrylamide (PHEMAA) is 10-200, the polymerization degrees of cationic high molecular side chain PDMC-COOH, anionic high molecular side chain precursor polymer PtBMA-COOH and functional high molecular side chain precursor polymer PNVF-COOH are 10-200, the grafting rate of cationic high molecular side chain PDMC is 1-80%, the grafting rate of anionic high molecular side chain PMAANa is 1-80%, and the grafting rate of chelating high molecular side chain PVAEGTANa is 1-20%.
In order to achieve the purpose, the application technical scheme of the water-soluble quaternary chelating polymer molecular brush dye catcher is realized by adding 0.1-1 part of the water-soluble quaternary chelating polymer molecular brush dye catcher into 100-1000 parts of waste water, stirring for 1-5 minutes at normal temperature, adjusting the pH to 2-9, enabling dye molecules in the waste water to be electrostatically adsorbed with cationic side chains PDMC and anionic PMAANa of the water-soluble quaternary chelating polymer molecular brush dye catcher, enabling heavy metal ions in the waste water to be chelated with chelating side chains PVAEGTANa of the water-soluble quaternary chelating polymer molecular brush dye catcher, adding 0.01-0.1 part of settling aid, stirring for 1 minute at normal temperature, enabling excessive metal ions of the settling aid to rapidly perform chelating and crosslinking precipitation reaction with chelating PVAEGTANa of the water-soluble quaternary chelating polymer molecular brush dye catcher, floc precipitates with the particle size of more than 100 mu m are generated within 10 seconds, and the cationic dye, the anionic dye and the complex type heavy metal ions in the wastewater can be rapidly removed, wherein the mass parts are all above.
In the technical scheme, the settling agent is one or any combination of more than two of calcium chloride, magnesium sulfate, ferrous chloride, ferric trichloride and aluminum trichloride.
Compared with the prior art, the invention has the following advantages and effects:
1. the flocculant comprises three polymer side chains with different functions, a cationic polymer side chain PDMC has good electrostatic adsorption capacity on anionic dyes, an anionic polymer side chain PMAANa has good electrostatic adsorption capacity on cationic dyes, a chelating side chain PVAEGTANa has chelating adsorption capacity on heavy metal ions, and the PVAEGTANa polymer side chain further rapidly undergoes chelating crosslinking precipitation reaction with excessive metal ions of a settling aid, so that the high-efficiency capturing and rapid settling functions are achieved, the effluent is basically colorless, and the national discharge standard is achieved;
2. the invention has the technical advantage of settling velocity, can generate chelation crosslinking precipitation reaction under the condition of a small amount of settling agent, quickly generate large aggregates within a few seconds, and generate less sludge;
3. the flocculant has double functions, can simultaneously capture dye and heavy metal ions, and solves the problem that the traditional flocculant cannot treat complex heavy metal ions in dye wastewater.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The parts referred to in the following examples are parts by mass.
Example one
The water-soluble quaternary chelating polymer molecular brush dye trapping agent is prepared by the following steps:
step one, synthesizing a PHEMAA polymer main chain
Taking 1 part of azodiisobutyronitrile initiator, 100 parts of hydroxyethyl acrylamide (HEMAA) and 200 parts of methanol, and carrying out polymerization reaction for 2 hours at 70 ℃ under the protection of nitrogen to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 45;
step two, synthesizing cationic high molecular side chain PDMC-COOH, anionic high molecular side chain precursor polymer PtBMA-COOH and functional high molecular side chain precursor polymer PNVF-COOH
Synthesizing a cationic polymer side chain PDMC-COOH: taking 2 parts of azodicyano valeric acid initiator, 100 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC) and 200 parts of water, and carrying out free radical polymerization reaction for 4 hours at 65 ℃ under the protection of nitrogen to obtain PDMC-COOH with the polymerization Degree (DP) of 35;
synthesis of anionic high-molecular side-chain precursor polymer PtBMA-COOH: taking 2 parts of azodicyano valeric acid initiator, 100 parts of tert-butyl methacrylate (tBMA) and 200 parts of toluene, and carrying out free radical polymerization reaction for 3 hours at 65 ℃ under the protection of nitrogen to obtain PtBMA-COOH with the polymerization Degree (DP) of 45;
synthesizing functional polymer side chain precursor polymer PNVF-COOH: taking 2 parts of azodicyano valeric acid initiator, 100 parts of N-vinyl formamide (NVF) and 300 parts of water, and carrying out free radical polymerization reaction for 3 hours at 55 ℃ under the protection of nitrogen to obtain PNVF-COOH with the polymerization Degree (DP) of 40;
step three, synthesizing ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD)
Dissolving 40 parts of ethylene glycol diethyl ether diamine tetraacetic acid and 40 parts of acetic anhydride in 50 parts of 2-methylpyridine, and reacting for 20 hours at 50 ℃ to obtain ethylene glycol diethyl ether diamine tetraacetic dianhydride;
step four, synthesizing PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)
Mixing 2 parts of polymer main chain PHEMAA obtained in the step one, 25 parts of cationic high molecular side chain PDMC-COOH obtained in the step two, 25 parts of anionic high molecular side chain precursor polymer PtBMA-COOH and 7 parts of functional high molecular side chain precursor polymer PNVF-COOH obtained in the step two, dissolving the mixture in 100 parts of Dimethylformamide (DMF) solvent, and adding 1 part of catalyst N-hydroxysuccinimide (NHS) and 1 part of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) Controlling the temperature to be 50 ℃, and carrying out esterification reaction for 70 hours to ensure that a hydroxyl functional group of each unit of a polymer main chain is randomly subjected to esterification reaction with a cationic polymer side chain PDMC-COOH with a carboxyl at the tail end, an anionic polymer side chain precursor polymer PtBMA with a carboxyl at the tail end and a functional polymer side chain precursor polymer PNVF with a carboxyl at the tail end to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethyl ammonium chloride-random-poly (tert-butyl methacrylate) -random-poly (N-vinylformamide) (PHEMAA-g- (PDMC-r-PtBMA-r-PNVF)); adding 2 parts of potassium hydroxide, controlling the temperature to 80 ℃, and carrying out hydrolysis reaction on the polymer PtBMA grafted on the polymer main chain anionic high molecular side chain precursor polymer and the functional high molecular side chain precursor polymer PNVF for 48 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); then 20 parts of ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD) synthesized in the step three is added, and the vinylamine and the ethylene glycol diethyl ether diamine tetraacetic dianhydride are subjected to acylation reaction for 24 hours to obtain polyhydroxyEthyl acrylamide-graft- (polymethacryloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-random-polyvinylamine ethylene glycol diethyl ether diamine tetrasodium acetate) (PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)) is a water-soluble quaternary chelate polymer molecular brush dye trapping agent, and the grafting rates of PDMC, PMAANa and PVAEGTANa side chains are respectively 23%, 22% and 6% by adopting a nuclear magnetic resonance spectrometer.
In this example, the application of the Water-soluble Quaternary chelate Polymer molecular Brush dye Capture agent
The water-soluble quaternary chelating polymer molecular brush dye catcher of the embodiment is used for dye wastewater test, 100 parts of wastewater containing 30 mg/L methylene blue and 30 mg/L methyl red is added into 0.1 part of water-soluble quaternary chelating polymer molecular brush dye catcher, stirring is carried out for 1 minute at normal temperature, 0.1 mol/L hydrochloric acid is adopted to adjust the pH value of the wastewater to 3.0, 0.01 part of magnesium sulfate serving as a settling aid is added, stirring is carried out for 1 minute at normal temperature, floc precipitation with the particle diameter larger than 160 mu m is generated within 10 seconds, filtering is carried out, an ultraviolet absorption spectrophotometer is adopted to determine that the concentration of the methylene blue in the filtrate is 0.03 mg/L, the concentration of the methyl red is 0.05 mg/L, and the removal efficiency is more than 99%.
Example two
The water-soluble quaternary chelating polymer molecular brush dye trapping agent is prepared by the following steps:
step one, synthesizing polymer main chain PHEMAA
Taking 2 parts of 2-bromoisobutyric acid ethyl ester initiator, 2 parts of CuBr, 2 parts of 4, 4-bis 2-methylpyridine (BPy), 100 parts of hydroxyethyl acrylamide (HEMAA) and 100 parts of methanol, and carrying out polymerization reaction for 2 hours at 60 ℃ under the protection of nitrogen to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 120;
step two, synthesizing cationic high molecular side chain PDMC-COOH, anionic high molecular side chain precursor polymer PtBMA-COOH and functional high molecular side chain precursor polymer PNVF-COOH
Synthesizing a cationic polymer side chain PDMC-COOH: taking 2 parts of azodicyano valeric acid initiator, 200 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC) and 200 parts of water, and carrying out free radical polymerization reaction for 7 hours at 60 ℃ under the protection of nitrogen to obtain cationic polymer side chain PDMC-COOH with the polymerization Degree (DP) of 110;
synthesis of anionic high-molecular side-chain precursor polymer PtBMA-COOH: taking 2 parts of azodicyano valeric acid initiator, 200 parts of tert-butyl methacrylate (tBMA) and 100 parts of toluene, and carrying out free radical polymerization reaction for 12 hours at 70 ℃ under the protection of nitrogen to obtain an anionic high-molecular side chain precursor polymer PtBMA-COOH with the polymerization Degree (DP) of 100;
synthesizing functional polymer side chain precursor polymer PNVF-COOH: taking 2 parts of azodicyano valeric acid initiator, 200 parts of N-vinyl formamide (NVF) and 200 parts of water, and carrying out free radical polymerization reaction for 8 hours at 70 ℃ under the protection of nitrogen to obtain a functional high molecular side chain precursor polymer PNVF-COOH with the polymerization Degree (DP) of 120;
step three, synthesizing ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD)
Dissolving 60 parts of ethylene glycol diethyl ether diamine tetraacetic acid and 60 parts of acetic anhydride in 80 parts of 2-methylpyridine, and reacting for 40 hours at 70 ℃ to obtain ethylene glycol diethyl ether diamine tetraacetic dianhydride;
step four, synthesizing PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)
Mixing 2 parts of Polyhydroxyethylacrylamide (PHEMAA) obtained in the first step, 35 parts of cationic high molecular side chain PDMC-COOH, 35 parts of anionic high molecular side chain precursor polymer PtBMA-COOH and 15 parts of functional high molecular side chain precursor polymer PNVF-COOH obtained in the second step, dissolving in 300 parts of Dimethylformamide (DMF) solvent, adding 3 parts of catalyst, namely N-hydroxysuccinimide (NHS) and 3 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) Controlling the temperature at 65 ℃ to carry out esterification reaction for 40 hours, so that the hydroxyl functional group of each unit of the polymer main chain randomly carries out esterification reaction with the cationic high molecular side chain PDMC-COOH containing carboxyl at the tail end, the anionic high molecular side chain precursor polymer PtBMA containing carboxyl at the tail end and the functional high molecular side chain precursor polymer PNVF containing carboxyl at the tail end, and poly (vinyl chloride-co-vinyl acetate) is obtainedHydroxyethyl acrylamide-graft- (polymethacryloxyethyltrimethyl ammonium chloride-random-poly (tert-butyl methacrylate) -random-poly (N-vinyl formamide)) (PHEMAA-g- (PDMC-r-PtBMA-r-PNVF)); adding 5 parts of potassium hydroxide, controlling the temperature at 60 ℃, and carrying out hydrolysis reaction on the polymer PtBMA grafted on the polymer main chain anionic high molecular side chain precursor polymer and the functional high molecular side chain precursor polymer PNVF for 24 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); and adding 50 parts of ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD) synthesized in the third step, and performing acylation reaction on vinylamine and the ethylene glycol diethyl ether diamine tetraacetic dianhydride for 12 hours to obtain polyhydroxyethyl acrylamide-graft- (polymethacryloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-random-polyvinylamine ethylene glycol diethyl ether diamine tetraacetic acid) (PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)) which is a water-soluble quaternary chelating polymer molecular brush dye capture agent, wherein the grafting ratios of side chains of PDMC, PMAANa and PVAEGTANa are respectively 38%, 36% and 12% by adopting a nuclear magnetic resonance apparatus.
In this example, the application of the Water-soluble Quaternary chelate Polymer molecular Brush dye Capture agent
Taking the water-soluble quaternary chelating polymer molecular brush dye catcher of the embodiment as a dye wastewater test, adding 500 parts of wastewater containing rhodamine B40 mg/L, Congo red 40 mg/L, cadmium ion 2 mg/L and citric acid 0.1 mg/L into 0.5 part of water-soluble quaternary chelating polymer molecular brush dye catcher, stirring for 3 minutes at normal temperature, adjusting the pH value of the wastewater to 6.0 by using 0.1 mol/L hydrochloric acid, adding 0.05 part of aluminum trichloride serving as a settling agent, stirring for 1 minute at normal temperature, generating floc precipitates with particle diameters larger than 300 mu m within 2 seconds, filtering, respectively measuring the concentration of rhodamine B in the filtrate to be 0.04 mg/L and the concentration of Congo red to be 0.06 mg/L and Cd in the filtrate by using an ultraviolet absorption spectrophotometer and an atomic absorption spectrophotometer2+The ion concentration is 0.02 mg/L, and the removal efficiency is high>99%。
EXAMPLE III
The water-soluble quaternary chelating polymer molecular brush dye trapping agent is prepared by the following steps:
step one, synthesizing polymer main chain PHEMAA
Taking 2 parts of 2-bromoisobutyric acid ethyl ester initiator, 2 parts of CuBr, 2 parts of 4, 4-bis-2-methylpyridine (BPy), 100 parts of hydroxyethyl acrylamide (HEMAA) and 100 parts of methanol, and carrying out polymerization reaction at 70 ℃ for 7 hours under the protection of nitrogen to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 190;
step two, synthesizing cationic high molecular side chain PDMC-COOH, anionic high molecular side chain precursor polymer PtBMA-COOH and functional high molecular side chain precursor polymer PNVF-COOH
Synthesizing a cationic polymer side chain PDMC-COOH: taking 2 parts of azodicyano valeric acid initiator, 200 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC) and 200 parts of water, and carrying out free radical polymerization reaction for 8 hours at 60 ℃ under the protection of nitrogen to obtain cationic polymer side chain PDMC-COOH with the polymerization Degree (DP) of 170;
synthesis of anionic high-molecular side-chain precursor polymer PtBMA-COOH: taking 2 parts of azodicyano valeric acid initiator, 200 parts of tert-butyl methacrylate (tBMA) and 100 parts of toluene, and carrying out free radical polymerization reaction for 10 hours at 70 ℃ under the protection of nitrogen to obtain an anionic high-molecular side chain precursor polymer PtBMA-COOH with the polymerization Degree (DP) of 180;
synthesizing functional polymer side chain precursor polymer PNVF-COOH: taking 2 parts of azodicyano valeric acid initiator, 300 parts of N-vinyl formamide (NVF) and 100 parts of water, and carrying out free radical polymerization reaction for 12 hours at 60 ℃ under the protection of nitrogen to obtain PNVF-COOH with the polymerization Degree (DP) of 150;
step three, synthesizing ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD)
Dissolving 80 parts of ethylene glycol diethyl ether diamine tetraacetic acid and 80 parts of acetic anhydride in 100 parts of 2-methylpyridine, and reacting for 30 hours at 60 ℃ to obtain ethylene glycol diethyl ether diamine tetraacetic dianhydride;
step four, synthesizing PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)
Mixing 1 part of Polyhydroxyethylacrylamide (PHEMAA) obtained in the first step with 50 parts of cationic high molecular side chain PDMC-COOH, 50 parts of anionic high molecular side chain precursor polymer PtBMA-COOH and 20 parts of functional high molecular side chain precursor polymer PNVF-COOH obtained in the second step, dissolving in 500 parts of Dimethylformamide (DMF) solvent, adding 5 parts of catalyst, namely N-hydroxysuccinimide (NHS) and 5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) Controlling the temperature to be 50 ℃, and carrying out esterification reaction for 10 hours to ensure that a hydroxyl functional group of each unit of a polymer main chain is randomly subjected to esterification reaction with a cationic polymer side chain PDMC-COOH with a carboxyl at the tail end, an anionic polymer side chain precursor polymer PtBMA with a carboxyl at the tail end and a functional polymer side chain precursor polymer PNVF with a carboxyl at the tail end to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethyl ammonium chloride-random-poly (tert-butyl methacrylate) -random-poly (N-vinylformamide) (PHEMAA-g- (PDMC-r-PtBMA-r-PNVF)); adding 10 parts of potassium hydroxide, controlling the temperature at 50 ℃, and carrying out hydrolysis reaction on the polymer PtBMA grafted on the polymer main chain anionic high molecular side chain precursor polymer and the functional high molecular side chain precursor polymer PNVF for 12 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); and adding 80 parts of ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD) synthesized in the step III, and performing acylation reaction on vinylamine and the ethylene glycol diethyl ether diamine tetraacetic dianhydride for 48 hours to obtain polyhydroxyethyl acrylamide-graft- (polymethacryloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-random-polyvinylamine ethylene glycol diethyl ether diamine tetraacetic acid) (PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)) which is a water-soluble quaternary chelating polymer molecular brush dye capture agent, wherein the grafting ratios of side chains of PDMC, PMAANa and PVAEGTANa are respectively 44%, 42% and 14% by adopting a nuclear magnetic resonance apparatus.
In this example, the application of the Water-soluble Quaternary chelate Polymer molecular Brush dye Capture agent
Taking the water-soluble quaternary chelating polymer molecular brush dye catcher of the embodiment as a dye wastewater test, adding 1000 parts of wastewater containing 20 mg/L of methyl violet, 20 mg/L of methyl orange, 2 mg/L of lead ions and 0.5 mg/L of citric acid into 1.0 part of water-soluble quaternary chelating polymer molecular brush dye catcher, stirring for 5 minutes at normal temperature, adjusting the pH value of the wastewater to 8.0 by using 0.1 mol/L of potassium hydroxide, adding 0.1 part of ferric trichloride as a settling agent, stirring for 1 minute at normal temperature, generating floc with a particle size of more than 500 mu m within 3 seconds, filtering, respectively measuring the methyl violet concentration of 0.04 mg/L, the methyl orange concentration of 0.08 mg/L and Pb in the filtrate by using an ultraviolet absorption spectrophotometer and an atomic absorption spectrophotometer2+The ion concentration is 0.02 mg/L, and the removal efficiency is high>99%。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A water-soluble quaternary chelating polymer molecular brush dye trapping agent is characterized by comprising 1-10 parts of polymer main chain Polyhydroxyethylacrylamide (PHEMAA), 20-50 parts of cationic high-molecular side chain terminal carboxyl-containing polymethacryloxyethyltrimethylammonium chloride (PDMC-COOH), 20-50 parts of anionic high-molecular side chain precursor polymer terminal carboxyl-containing poly tert-butyl methacrylate (PtBMA-COOH) and 5-30 parts of functional high-molecular side chain precursor polymer terminal carboxyl-containing poly N-vinyl formamide (PNVF-COOH), 100-500 parts of Dimethylformamide (DMF) solvent, 1-5 parts of catalyst namely N-hydroxysuccinimide (NHS) and 1-5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH).3I) 1-10 parts of potassium hydroxide and 20-80 parts of ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD); the above are all parts by mass;
the PHEMAA polymer main chain is synthesized by the polymer main chain polyhydroxyethyl acrylamide (PHEMAA) through common free radical polymerization or a controllable activity polymerization method;
the cationic high molecular side chain PDMC-COOH is mainly prepared by adopting azodicyano valeric acid as an initiator and synthesizing a polymethacryloxyethyltrimethyl ammonium chloride (PDMC-COOH) polymer with a carboxyl group at the tail end through a common free radical polymerization method;
the anionic high-molecular precursor polymer PtBMA-COOH is mainly prepared by taking azobiscyanovaleric acid as an initiator and synthesizing a poly (tert-butyl methacrylate) (PtBMA-COOH) polymer with a carboxyl group at the tail end through a common free radical polymerization method;
the functional polymer side chain precursor polymer PNVF-COOH mainly adopts azodicyano valeric acid as an initiator to synthesize a poly N-vinyl formamide (PNVF-COOH) polymer with a carboxyl group at the tail end through common free radical polymerization;
the synthesis method of the ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD) comprises the following steps: dissolving 40-80 parts of ethylene glycol diethyl ether diamine tetraacetic acid and 40-80 parts of acetic anhydride in 50-100 parts of 2-methylpyridine, and reacting at 50-70 ℃ for 20-40 hours to obtain the ethylene glycol diethyl ether diamine tetraacetic dianhydride.
2. The method for preparing a water-soluble quaternary chelating polymer molecular brush dye scavenger according to claim 1, the method is characterized by mixing and dissolving 1-10 parts of Polyhydroxyethylacrylamide (PHEMAA) of a polymer main chain, 20-50 parts of polymethacryloxyethyltrimethylammonium chloride (PDMC-COOH) containing carboxyl at the tail end of a cationic polymer side chain, 20-50 parts of polymethacrylic acid tert-butyl ester (PtBMA-COOH) containing carboxyl at the tail end of an anionic polymer side chain precursor polymer and 5-30 parts of poly N-vinyl formamide (PNVF-COOH) containing carboxyl at the tail end of a functional polymer side chain precursor polymer in 100-500 parts of a Dimethylformamide (DMF) solvent, and adding 1-5 parts of a catalyst, namely N-hydroxysuccinimide (NHS) and 1-5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide iodomethane salt (EDC. CH).3I) Controlling the temperature to be 50-80 ℃, and carrying out esterification reaction for 10-70 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloyloxy)Ethyltrimethyl ammonium chloride-random-poly (tert-butyl methacrylate) -random-poly (N-vinylformamide) (PHEMAA-g- (PDMC-r-PtBMA-r-PNVF)); adding 1-10 parts of potassium hydroxide, controlling the temperature at 50-80 ℃, and carrying out hydrolysis reaction for 12-48 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); then adding 20-80 parts of ethylene glycol diethyl ether diamine tetraacetic dianhydride (EGTAD), and carrying out acylation reaction for 12-48 hours to obtain polyhydroxyethyl acrylamide-graft- (polymethacryloyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-random-polyvinylaminoethylene glycol diethyl ether diamine tetraacetic acid sodium salt) (PHEMAA-g- (PDMC-r-PMAANa-r-PVAEGTANa)) which is a water-soluble quaternary chelate polymer molecular brush dye catcher; the above are all parts by mass.
3. The method for preparing the water-soluble quaternary chelating polymer molecular brush dye catcher according to claim 2, characterized in that the polymerization degree of Polyhydroxyethylacrylamide (PHEMAA) is 10-200, the polymerization degrees of the cationic high molecular side chain PDMC-COOH, the anionic high molecular side chain precursor polymer PtBMA-COOH and the functional high molecular side chain precursor polymer PNVF-COOH are 10-200, the grafting ratio of the cationic high molecular side chain PDMC is 1-80%, the grafting ratio of the anionic high molecular side chain PMAANa is 1-80%, and the grafting ratio of the chelating high molecular side chain PVAEGTANa is 1-20%.
4. The application of the water-soluble quaternary chelating polymer molecular brush dye scavenger according to claim 1, wherein 0.1-1 part of the water-soluble quaternary chelating polymer molecular brush dye scavenger is added into 100-1000 parts of wastewater, stirred for 1-5 minutes at normal temperature, pH is adjusted to 2-9, dye molecules in the wastewater are electrostatically adsorbed with cationic side chain PDMC and anionic PMAANa of the water-soluble quaternary chelating polymer molecular brush dye scavenger, heavy metal ions in the wastewater are chelated with chelating side chain PVAEGTANa of the water-soluble quaternary chelating polymer molecular brush dye scavenger, 0.01-0.1 part of settling aid is added, stirred for 1 minute at normal temperature, excess metal ions of the settling aid rapidly react with the chelating side chain PVAEGTANa of the water-soluble quaternary chelating polymer molecular brush dye scavenger to form floc precipitates with particle diameters larger than 100 μm within 10 seconds, can rapidly remove cationic dye, anionic dye and complex heavy metal ions in the wastewater, which are in parts by mass.
5. The use of the water-soluble quaternary chelating polymer molecular brush dye scavenger according to claim 4, wherein the settling agent is one or more of calcium chloride, magnesium sulfate, ferrous chloride, ferric chloride and aluminum chloride.
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| US20120225025A1 (en) * | 2011-03-01 | 2012-09-06 | Basf Se | Dye transfer inhibiting polymers with improved storage stability and processability for laundry detergents and cleaners |
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