CN107879451B - Water-soluble quaternary polymer molecular brush cationic dye capturing settling agent and preparation method and application thereof - Google Patents
Water-soluble quaternary polymer molecular brush cationic dye capturing settling agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a water-soluble quaternary polymer molecular brush cationic dye capturing settling agent and a preparation method and application thereof, which are characterized in that the water-soluble quaternary polymer molecular brush cationic dye capturing settling agent is prepared by polymer main chain polyhydroxyethylacrylamide, poly tert-butyl methacrylate containing carboxyl at the tail end of an anionic high molecular side chain precursor polymer, poly N-vinylformamide containing carboxyl at the tail end of a functional high molecular side chain precursor polymer, dimethylformamide, 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 quaternary polymer molecule brush cationic dye catching settling agent is used for treating dye wastewater and artistic paint wastewater discharged in the dye synthesis or dyeing and finishing process. The method has the advantages of good trapping capacity, high and low settling speed, capability of treating defects of complex heavy metal ions and the like, capability of trapping cationic dyes and complex heavy metal ions within a few seconds, rapid growth of large aggregates, realization of the purpose of rapid dye separation 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 polymer molecular brush cationic dye capturing settling 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. The discharge amount of dye wastewater is also large, the discharge is intermittent, the water quality is unstable, and the dye wastewater belongs to wastewater 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 provide a water-soluble quaternary polymer molecular brush cationic dye capturing settling agent, a preparation method and application thereof, which have the advantages of good capturing capacity, high settling speed, capability of treating the defects of complex heavy metal ions and the like, capability of capturing cationic dye and complex heavy metal ions within seconds, rapid growth of large aggregates, realization of the purpose of rapid dye separation and high-efficiency capturing and rapid settling functions.
In order to achieve the purpose, the technical scheme of the water-soluble quaternary polymer molecular brush cationic dye capturing settling agent is realized by the following steps of 1-10 parts of polymer main chain Polyhydroxyethylacrylamide (PHEMAA), 20-100 parts of anionic high-molecular side chain precursor polymer terminal carboxyl-containing poly tert-butyl methacrylate (PtBMA-COOH) and 5-30 parts of functional polymerThe polymer comprises macromolecule side chain precursor polymer, carboxyl-containing poly-N-vinylformamide (PNVF-COOH) at the tail end, 100-500 parts of Dimethylformamide (DMF), 1-5 parts of catalyst, namely N-hydroxysuccinimide (NHS), and 1-5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide (EDC. CH)3I) 1-10 parts of sodium hydroxide, 1-20 parts of 1, 2-Cyclohexanediaminetetraacetic Dianhydride (CDTA) and 1-10 parts of carbon disulfide; the above are all parts by mass.
In the technical scheme, the polymer main chain polyhydroxyethyl acrylamide (PHEMAA) is synthesized into the PHEMAA polymer main chain by common free radical polymerization or controllable activity polymerization;
the anionic high molecular side chain precursor polymer PtBMA-COOH and the functional high molecular side chain precursor polymer PNVF-COOH mainly adopt azodicyano valeric acid as an initiator to synthesize a poly tert-butyl methacrylate (PtBMA-COOH) polymer with a carboxyl group at the tail end by 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 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA) comprises the following steps: dissolving 5-20 parts of 1, 2-cyclohexanediamine tetraacetic acid and 5-20 parts of acetic anhydride in 10-30 parts of pyridine, controlling the temperature to be 50-70 ℃, and reacting for 20-40 hours to obtain 1, 2-cyclohexanediamine tetraacetic dianhydride.
In order to achieve the purpose, the technical scheme of the preparation method of the water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent is realized by mixing and dissolving 1-10 parts of polymer main chain polyhydroxyethyl acrylamide (PHEMAA), 20-100 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) in 100-500 parts of dimethyl formamide (DMF) solvent, and adding 1-5 parts of catalyst, namely N-hydroxysuccinylImine (NHS) and 1-5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) Controlling the temperature to be 50-80 ℃, and carrying out esterification reaction for 10-70 hours to obtain polyhydroxyethylacrylamide-graft- (poly (tert-butyl methacrylate) -random-poly (N-vinylformamide) (PHEMAA-g- (PtBMA-r-PNVF)); adding 1-10 parts of sodium hydroxide, controlling the temperature at 50-80 ℃, and carrying out hydrolysis reaction for 12-48 hours to obtain polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVA)); adding 1-20 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA) into the mixture, carrying out acylation reaction for 5-24 hours, and controlling the acylation degree range to be 60-99%, thereby obtaining polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVA)); adding 1-10 parts of carbon disulfide, controlling the temperature at 20-40 ℃, and carrying out addition reaction for 1-3 hours to finally obtain water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamido sodium dithiocarbamate) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) a water-soluble tetrapolymer molecular brush cationic dye capture settling agent; the above are all parts by mass.
In the technical scheme, the polymerization degree of Polyhydroxyethylacrylamide (PHEMAA) is 10-200, the polymerization degrees of 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 rate of the cationic high-molecular side chain PMAANa is 1-80%, the grafting rate of the chelating high-molecular side chain PVACDTANA is 1-20%, and the settling-assisting high-molecular side chain PVACS2The grafting ratio of Na is 1-5%.
In order to achieve the purpose, the technical scheme of the application of the water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent is realized by the following steps of preparing 0.1-1 part of water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyethylene amino cyclohexanediamine sodium tetraacetate-random-polyethylene amino sodium dithiocarbamate) (PHEMAA-g-(PMAANa-r-PVACDTANa-r-PVACS2Na)) is added into 100-1000 parts of wastewater, the mixture is stirred for 1-5 minutes at normal temperature, the pH is adjusted to 6-9, and the cationic dye molecules in the wastewater and the water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamido sodium dithiocarbamate) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)), and heavy metal ions in the wastewater and the quaternary polymer molecular brush (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) to generate chelate adsorption, adding 0.01-0.1 part of settling agent, stirring for 1 minute at normal temperature, and enabling metal ions of the settling agent to rapidly react with a water-soluble quaternary polymer molecular brush (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) on the subsiding side chain PVACS2Na is subjected to chemical precipitation reaction, floc precipitation with the particle size of more than 100 mu m is generated within 10 seconds, and the cationic dye and the complex type heavy metal ions in the wastewater can be rapidly removed, wherein the mass parts are 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.
In the technical scheme, 1-5 parts of floc precipitate is taken, 1-5 parts of water is added, the pH is adjusted to 2, and the floc precipitate can be reversibly dissolved in the water, so that the aims of recovering and concentrating the dye and the heavy metal ions are fulfilled.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention solves the defects of single structure and poor capturing performance of the traditional synthetic macromolecular dye flocculating agent, and the flocculating agent contains three macromolecular side chains with different functions, namely an anionic macromolecular side chain PMAANa, a chelating side chain PVACDTANA and a settling-assisting side chain PVACS2Na; the anionic polymer side chain PMAANa has good electrostatic adsorption capacity on cationic dye, the chelating side chain PVACDTANA performs chelating adsorption on heavy metal ions, and the side chain PVACS helps to settle2Under the synergistic effect of Na, PVACS2Na macromolecule side chain and settling aid metalIons rapidly generate chemical precipitation reaction to achieve the functions of efficient capture and rapid sedimentation, the water-soluble quaternary polymer molecular brush cationic dye capture sedimentation agent has the capacity of efficiently capturing cationic dye, and the effluent is basically colorless;
2. the invention can generate chelation precipitation reaction under the condition of a small amount of settling agent, quickly generate large aggregates within a few seconds and generate less sludge. The generated floc precipitate can be reversibly dissolved by further adjusting the pH value, so that the aims of recovering and concentrating the dye and the heavy metal ions are fulfilled;
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 cationic dye capturing settling agent is a water-soluble quaternary polymer molecular brush cationic dye capturing settling agent and is prepared by the following steps:
step one, synthesizing a PHEMAA polymer main chain
Taking 1 part of azodiisobutyronitrile initiator, 200 parts of hydroxyethyl acrylamide (HEMAA) and 400 parts of methanol, and carrying out polymerization reaction for 2 hours at 80 ℃ under the protection of nitrogen to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 30;
step two, synthesizing an anionic high-molecular side chain precursor polymer PtBMA-COOH and a functional high-molecular side chain precursor polymer PNVF-COOH
Synthesis of anionic high-molecular side-chain precursor polymer PtBMA-COOH: taking 1 part of azodicyano valeric acid initiator, 100 parts of tert-butyl methacrylate (tBMA) and 300 parts of toluene, and carrying out free radical polymerization reaction for 10 hours at 60 ℃ under the protection of nitrogen to obtain PtBMA-COOH with the polymerization Degree (DP) of 50;
synthesizing functional polymer side chain precursor polymer PNVF-COOH: taking 1 part of azodicyano valeric acid initiator, 300 parts of N-vinyl formamide (NVF) and 600 parts of water, and carrying out free radical polymerization reaction for 4 hours at 50 ℃ under the protection of nitrogen to obtain PNVF-COOH with the polymerization Degree (DP) of 40;
step three, synthesizing 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA)
Dissolving 5 parts of 1, 2-cyclohexanediaminetetraacetic acid and 5 parts of acetic anhydride in 10 parts of pyridine, and reacting for 20 hours at 50 ℃ to obtain 1, 2-cyclohexanediaminetetraacetic dianhydride;
step four, synthesizing PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)
Mixing 1 part of polyhydroxyethylacrylamide PHEMAA obtained in the step one, 20 parts of anionic high molecular side chain precursor polymer PtBMA-COOH obtained in the step two and 5 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 then adding 1 part of N-hydroxysuccinimide (NHS) and 1 part of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) Reacting for 10 hours at 50 ℃ to obtain a water-soluble quaternary polymer molecular brush PHEMAA-g- (PtBMA-r-PNVF); then adding 1 part of sodium hydroxide, controlling the temperature at 50 ℃, and carrying out hydrolysis reaction for 48 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacrylic acid sodium-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVA)); adding 5 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA) obtained in the third step, controlling the temperature at 50 ℃, and carrying out acylation reaction for 24 hours, wherein the acylation degree is 80%, so as to obtain polyhydroxyethyl acrylamide-graft- (sodium polymethacrylate-random-polyvinylamido cyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVA)); adding 1 part of carbon disulfide, controlling the temperature at 20 ℃, and carrying out addition reaction for 1 hour to finally obtain water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine sodium tetraacetate-random-polyvinylamidodithiocarbamic acid sodium salt) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)), namely a water-soluble quaternary polymer molecular brush cationic dye capturing settling agent, and PMAANa and PVACDTA are measured by a nuclear magnetic resonance spectrometerNa and PVACS2The grafting ratio of the Na side chain was 19%, 4% and 1%, respectively.
In this example, the use of a water-soluble tetrapolymer molecular brush cationic dye trapping settling agent
Taking the water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent of the embodiment as a dye wastewater test, adding 100 parts of wastewater containing 50 mg/L of methylene blue into 0.1 part of water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent, stirring for 1 minute at normal temperature, adjusting the pH value of the wastewater to 6.0 by using 0.1 mol/L hydrochloric acid, adding 0.01 part of sedimentation assisting agent calcium chloride, stirring for 1 minute at normal temperature, generating floc sediment with the particle diameter of more than 120 mu m within 10 seconds, filtering, measuring the concentration of the methylene blue in the filtrate by using an ultraviolet absorption spectrophotometer to be 0.01 mg/L, and the removal efficiency is more than 99%.
And (3) taking 1 part of the generated floc precipitate, adding 1 part of water, adjusting the pH to 2, and reversibly dissolving the floc precipitate in the water, thereby achieving the purposes of recovering and concentrating methylene blue.
Example two
The cationic dye capturing settling agent is a water-soluble quaternary polymer molecular brush cationic dye capturing settling agent and is prepared by the following steps:
step one, synthesizing a PHEMAA polymer main chain
Taking 2 parts of 2-bromoisobutyric acid ethyl ester initiator, 3 parts of CuBr, 3 parts of 4, 4-bipyridine (BPy), 100 parts of hydroxyethyl acrylamide (HEMAA) and 200 parts of methanol, and carrying out polymerization reaction at 60 ℃ for 10 hours under the protection of nitrogen to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 100;
step two, synthesizing an anionic high-molecular side chain precursor polymer PtBMA-COOH and a functional high-molecular side chain precursor polymer PNVF-COOH
Synthesis of anionic high-molecular side-chain precursor polymer PtBMA-COOH: taking 3 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 20 hours at 60 ℃ under the protection of nitrogen to obtain PtBMA-COOH with the polymerization Degree (DP) of 110;
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 7 hours at 70 ℃ under the protection of nitrogen to obtain PNVF-COOH with the polymerization Degree (DP) of 110;
step three, synthesizing 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA)
Dissolving 10 parts of 1, 2-cyclohexanediamine tetraacetic acid and 10 parts of acetic anhydride in 30 parts of pyridine, and reacting for 40 hours at 70 ℃ to obtain 1, 2-cyclohexanediamine tetraacetic dianhydride;
step four, synthesizing PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)
Mixing 3 parts of polyhydroxyethylacrylamide PHEMAA obtained in the step one, 40 parts of anionic high molecular side chain precursor polymer PtBMA-COOH obtained in the step two and 15 parts of functional high molecular side chain precursor polymer PNVF-COOH obtained in the step two, dissolving the mixture in 300 parts of Dimethylformamide (DMF) solvent, and then adding 3 parts of N-hydroxysuccinimide (NHS) and 3 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide iodomethane salt (EDC. CH)3I) Reacting for 50 hours at 70 ℃ to obtain a water-soluble quaternary polymer molecular brush PHEMAA-g- (PtBMA-r-PNVF); (ii) a Then adding 5 parts of sodium hydroxide, controlling the temperature at 70 ℃, and carrying out hydrolysis reaction for 36 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacrylic acid sodium-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVA)); then 10 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA) obtained in the third step is added, the temperature is controlled at 70 ℃, the acylation reaction is carried out for 12 hours, the acylation degree is 70 percent, and the polyhydroxyethyl acrylamide-graft- (sodium polymethacrylate-random-polyethylene amino cyclohexanediamine tetrasodium acetate-random-polyethylene amine) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVA)); adding 5 parts of carbon disulfide, controlling the temperature at 30 ℃, and carrying out addition reaction for 2 hours to finally obtain water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine sodium tetraacetate-random-polyvinylamidodithiocarbamic acid sodium salt) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) i.e. water-soluble tetrapolymer molecular brush cationic dye trapping sinkReducing agent is selected from PMAANa, PVACTTANA and PVACS2The grafting ratio of the Na side chain was 32%, 7% and 3%, respectively.
In this example, the use of a water-soluble tetrapolymer molecular brush cationic dye trapping settling agent
Taking the water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent of the embodiment as a dye wastewater test, adding 500 parts of wastewater containing 60 mg/L of rhodamine B, 5mg/L of cadmium ions and 0.5 mg/L of citric acid into 0.5 part of water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent, stirring for 3 minutes at normal temperature, adjusting the pH value of the wastewater to 8.0 by using 0.1 mol/L of sodium hydroxide, adding 0.05 part of ferrous dichloride serving as a settling aid, stirring for 1 minute at normal temperature, generating floc with the particle size of more than 320 mu m within 6 seconds for precipitation, filtering, respectively measuring the concentration of the rhodamine B and the 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%。
Taking 2 parts of generated floc precipitate, adding 2 parts of water, adjusting the pH to 2, and reversibly dissolving the floc precipitate in the water, thereby realizing the recovery and concentration of rhodamine B dye and Cd2+The purpose of the ions is.
EXAMPLE III
The cationic dye capturing settling agent is a water-soluble quaternary polymer molecular brush cationic dye capturing settling agent and is prepared by the following steps:
step one, synthesizing a PHEMAA polymer main chain
Carrying out polymerization reaction on 1 part of 2-bromoisobutyric acid ethyl ester initiator, 1 part of CuBr, 1 part of 4, 4-bipyridyl (BPy), 100 parts of hydroxyethyl acrylamide (HEMAA) and 100 parts of methanol at 70 ℃ for 5 hours under the protection of nitrogen to obtain polyhydroxyethyl acrylamide PHEMAA with the polymerization Degree (DP) of 195;
step two, synthesizing an anionic high-molecular side chain precursor polymer PtBMA-COOH and a functional high-molecular side chain precursor polymer PNVF-COOH
Synthesis of anionic high-molecular side-chain precursor polymer PtBMA-COOH: taking 1 part of azodicyano valeric acid initiator, 300 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 PtBMA-COOH with the polymerization Degree (DP) of 190;
synthesizing functional polymer side chain precursor polymer PNVF-COOH: taking 1 part of azodicyano valeric acid initiator, 200 parts of N-vinyl formamide (NVF) and 100 parts of water, and carrying out free radical polymerization reaction for 15 hours at 60 ℃ under the protection of nitrogen to obtain PNVF-COOH with the polymerization Degree (DP) of 180;
step three, synthesizing 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA)
Dissolving 8 parts of 1, 2-cyclohexanediaminetetraacetic acid and 8 parts of acetic anhydride in 20 parts of pyridine, and reacting for 30 hours at 60 ℃ to obtain 1, 2-cyclohexanediaminetetraacetic dianhydride;
step four, synthesizing PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)
Mixing 5 parts of polyhydroxyethylacrylamide PHEMAA obtained in the step one, 100 parts of anionic high molecular side chain precursor polymer PtBMA-COOH obtained in the step two and 30 parts of functional high molecular side chain precursor polymer PNVF-COOH obtained in the step two, dissolving the mixture in 300 parts of Dimethylformamide (DMF) solvent, and then adding 5 parts of N-hydroxysuccinimide (NHS) and 5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) Reacting for 70 hours at 80 ℃ to obtain a water-soluble quaternary polymer molecular brush PHEMAA-g- (PtBMA-r-PNVF); (ii) a Then 10 parts of sodium hydroxide is added, the temperature is controlled at 80 ℃, and hydrolysis reaction is carried out for 12 hours to obtain polyhydroxyethyl acrylamide-graft- (poly (sodium methacrylate-random-polyvinylamine)) (PHEMAA-g- (PMAANa-r-PVA)); adding 20 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA) obtained in the third step, controlling the temperature at 80 ℃, and carrying out acylation reaction for 5 hours, wherein the acylation degree is 71%, so as to obtain polyhydroxyethyl acrylamide-graft- (sodium polymethacrylate-random-polyvinylamido cyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVA)); then 10 parts of carbon disulfide is added, the temperature is controlled at 40 ℃, addition reaction is carried out for 3 hours, and finally the water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyethylene) is obtainedAmino cyclohexanediamine tetrasodium acetate-random-sodium polyethylenimine dithiocarbamate) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)), namely a water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent, and adopting nuclear magnetic resonance instruments PMAANa, PVACDTANA and PVACS2The grafting ratio of the Na side chain was 67%, 12% and 5%, respectively.
In this example, the use of a water-soluble tetrapolymer molecular brush cationic dye trapping settling agent
Taking the water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent of the embodiment as a dye wastewater test, adding 1000 parts of wastewater containing 30 mg/L of methyl violet, 2mg/L of lead ions and 0.2mg/L of citric acid into 1.0 part of water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent, stirring for 5 minutes at normal temperature, adjusting the pH value of the wastewater to 9.0 by using 0.1 mol/L of sodium hydroxide, adding 0.1 part of settling assistant agent aluminum trichloride, stirring for 1 minute at normal temperature, generating floc sediment with the particle size of more than 300 mu m within 3 seconds, filtering, respectively measuring the methyl violet concentration of 0.04 mg/L and the Pb concentration 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%。
4 parts of generated floc precipitate is taken, 4 parts of water is added, the pH is adjusted to 2, and the floc precipitate can be reversibly dissolved in the water, so that the methyl violet dye and Pb can be recovered and concentrated2+The purpose of the ions is.
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 (6)
1. A water-soluble quaternary polymer molecular brush cationic dye capturing settling agent is characterized by comprising 1-10 parts of polymer main chain polyhydroxyethyl acrylamide (PHEMAA) and 20-100 parts of carboxyl-containing poly (tert-butyl methacrylate) (P) at the tail end of an anionic high-molecular side chain precursor polymertBMA-COOH), 5-30 parts of functional polymer side chain precursor polymer terminal carboxyl-containing poly N-vinyl formamide (PNVF-COOH), 100-500 parts of dimethyl formamide (DMF), 1-5 parts of catalyst namely N-hydroxysuccinimide (NHS), 1-5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) 1-10 parts of sodium hydroxide, 1-20 parts of 1, 2-Cyclohexanediaminetetraacetic Dianhydride (CDTA) and 1-10 parts of carbon disulfide;
the polymer main chain polyhydroxyethyl acrylamide (PHEMAA) is synthesized into a PHEMAA polymer main chain by common free radical polymerization or a controllable activity polymerization method;
the anionic high molecular side chain precursor polymer PtBMA-COOH and the functional high molecular side chain precursor polymer PNVF-COOH adopt azodicyano valeric acid as an initiator to synthesize a poly tert-butyl methacrylate (PtBMA-COOH) polymer with a carboxyl group at the tail end by a common free radical polymerization method;
the functional polymer side chain precursor polymer PNVF-COOH 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 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA) comprises the following steps: dissolving 5-20 parts of 1, 2-cyclohexanediamine tetraacetic acid and 5-20 parts of acetic anhydride in 10-30 parts of pyridine, controlling the temperature to be 50-70 ℃, and reacting for 20-40 hours to obtain 1, 2-cyclohexanediamine tetraacetic dianhydride;
the above are all parts by mass.
2. The application of the water-soluble quaternary polymer molecular brush cationic dye capturing and settling agent as claimed in claim 1, wherein 0.1-1 part of water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine sodium tetraacetate-random-polyvinylamido sodium dithiocarbamate) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) is added into 100-1000 parts of wastewater, the mixture is stirred for 1-5 minutes at normal temperature, the pH is adjusted to 6-9, and cationic dye molecules in the wastewater are connected with water-soluble polyhydroxyethyl acrylamideBranch- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine sodium tetraacetate-random-polyvinylamidodithiocarbamic acid sodium salt) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)), and heavy metal ions in the wastewater and the quaternary polymer molecular brush (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) to generate chelate adsorption, adding 0.01-0.1 part of settling agent, stirring for 1 minute at normal temperature, and enabling metal ions of the settling agent to rapidly react with a water-soluble quaternary polymer molecular brush (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) on the subsiding side chain PVACS2Na is subjected to chemical precipitation reaction, floc precipitation with the particle size of more than 100 mu m is generated within 10 seconds, and the cationic dye and the complex type heavy metal ions in the wastewater can be rapidly removed, wherein the mass parts are above.
3. The use of the water-soluble quaternary polymer molecular brush cationic dye capturing and settling agent as claimed in claim 2, wherein the settling agent is one or more of calcium chloride, magnesium sulfate, ferrous chloride, ferric chloride, and aluminum trichloride.
4. The application of the water-soluble quaternary polymer molecular brush cationic dye capturing settling agent as claimed in claim 2, is characterized in that 1-5 parts of floc precipitate is taken, 1-5 parts of water is added, the pH is adjusted to 2, and the floc precipitate can be reversibly dissolved in the water, so that the purposes of recovering and concentrating the dye and heavy metal ions are achieved.
5. A preparation method of a water-soluble quaternary polymer molecular brush cationic dye capturing sedimentation agent is characterized by mixing and dissolving 1-10 parts of polymer main chain polyhydroxyethyl acrylamide (PHEMAA), 20-100 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) in 100-500 parts of dimethyl formamide (DMF) solvent, and adding1-5 parts of catalyst, namely N-hydroxysuccinimide (NHS) and 1-5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt (EDC. CH)3I) Controlling the temperature to be 50-80 ℃, and carrying out esterification reaction for 10-70 hours to obtain polyhydroxyethylacrylamide-graft- (poly (tert-butyl methacrylate) -random-poly (N-vinylformamide) (PHEMAA-g- (PtBMA-r-PNVF)); adding 1-10 parts of sodium hydroxide, controlling the temperature at 50-80 ℃, and carrying out hydrolysis reaction for 12-48 hours to obtain polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVA)); adding 1-20 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTA) into the mixture, carrying out acylation reaction for 5-24 hours, and controlling the acylation degree range to be 60-99%, thereby obtaining polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVA)); adding 1-10 parts of carbon disulfide, controlling the temperature at 20-40 ℃, and carrying out addition reaction for 1-3 hours to finally obtain water-soluble polyhydroxyethylacrylamide-graft- (sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamido sodium dithiocarbamate) (PHEMAA-g- (PMAANa-r-PVACDTANA-r-PVACS)2Na)) a water-soluble tetrapolymer molecular brush cationic dye capture settling agent; the above are all parts by mass.
6. The preparation method of the water-soluble quaternary polymer molecular brush cationic dye capturing and settling agent as claimed in claim 5, wherein the polymerization degree of Polyhydroxyethylacrylamide (PHEMAA) is 10-200, the polymerization degrees of 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 rate of the cationic high molecular side chain PMAANa is 1-80%, the grafting rate of the chelating high molecular side chain PVACDTANA is 1-20%, and the settling-assisting high molecular side chain PVACS2The grafting ratio of Na is 1-5%.
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