CN107892372B - Water-soluble five-membered polymer molecular brush dye capturing settling agent, and preparation method and application thereof - Google Patents
Water-soluble five-membered polymer molecular brush dye capturing settling agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a water-soluble five-membered polymer molecular brush dye capturing settling agent and a preparation method and application thereof, and is characterized in that the water-soluble five-membered polymer molecular brush dye capturing settling agent is prepared by polymer main chain polyhydroxyethylacrylamide, cationic polymethacryloxyethyltrimethylammonium chloride containing carboxyl at the tail end of a high molecular side chain, polymethacrylic acid tert-butyl ester 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 (DMF) solvent, catalyst, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide salt, sodium hydroxide, 1, 2-cyclohexanediaminetetraacetic dianhydride and carbon disulfide, and the water-soluble five-membered polymer molecular brush dye capturing settling agent is used for treating dye wastewater discharged in the dye synthesis or dyeing and finishing process and is coated with art And (4) material waste water. The method has the advantages of simple and convenient operation, low treatment cost, strong adaptability, good trapping capacity and high settling speed, can treat complex heavy metal ions, and can trap cationic dyes, anionic dyes and complex heavy metal ions within seconds.
Description
Technical Field
The invention belongs to the field of water treatment technology and high molecular functional materials, and particularly relates to a five-membered polymer molecular brush dye capturing settling agent, and a preparation method and application thereof. The method is mainly applied to dye wastewater and artistic paint wastewater discharged in the dye synthesis or dyeing and finishing process, and can simultaneously remove cationic dye, anionic dye and complex heavy metal ions in the dye wastewater.
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 provides a water-soluble five-membered polymer molecular brush dye capturing settling agent, a preparation method and application thereof, wherein the water-soluble five-membered polymer molecular brush dye capturing settling agent is simple and convenient to operate, low in treatment cost, strong in adaptability, good in capturing capacity and high in settling speed, can be used for treating complex heavy metal ions, can capture cationic dyes, anionic dyes and complex heavy metal ions within seconds, can quickly grow large aggregate particles, and can realize quick separation of the dyes and the complex heavy metal ions.
In order to achieve the purpose, the technical scheme of the water-soluble five-membered polymer molecular brush dye capturing settling agent is realized by the following steps of 1-10 parts of polymer main chain Polyhydroxyethylacrylamide (PHEMAA), 20-50 parts of cationic high-molecular side chain terminal carboxyl-containing polymethacryloxyethyltrimethyl ammonium chloride (PDMC-COOH), 20-50 parts of anionic high-molecular side chain precursor polymer terminal carboxyl-containing poly tert-butyl methacrylate (PtBMA-COOH) and 5-15 parts of functional high-molecular side chainThe precursor polymer is prepared from poly-N-vinyl formamide (PNVF-COOH) containing carboxyl at the tail end, 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 sodium hydroxide, 1-20 parts of 1, 2-cyclohexanediaminetetraacetic dianhydride (CDTAD) and 1-10 parts of carbon disulfide; 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 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD) 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 five-membered polymer molecular brush dye capturing sedimentation agent is realized by the following steps of 1-10 parts of polymer main chain polyhydroxyethyl acrylamide (PHEMAA), 20-50 parts of cationic polymethacryloxyethyl trimethyl ammonium chloride (PDMC-COOH) with carboxyl at the tail end of a side chain of a high polymer, and 20-50 parts of anionic polymer before the side chain of the high polymerMixing and dissolving poly (tert-butyl methacrylate) (PtBMA-COOH) containing carboxyl at the tail end of a precursor polymer and 5-15 parts of functional polymer side chain precursor polymer N-vinylformamide (PNVF-COOH) containing carboxyl at the tail end into 100-500 parts of Dimethylformamide (DMF) solvent, adding 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) 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 sodium hydroxide, controlling the temperature at 50-80 ℃, and carrying out hydrolysis reaction for 12-48 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloyloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); adding 1-20 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD), and carrying out acylation reaction for 5-24 hours, wherein the acylation degree range is controlled to be 60-99%, so as to obtain polyhydroxyethyl acrylamide-graft- (polymethacryloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-random-polyvinylamido cyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDDANA-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 polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamidocyclohexanediamine sodium tetraacetate-random-polyvinylamido sodium dithiocarbamate) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)), namely a water-soluble five-membered polymer molecular brush dye capturing settling agent, in parts by mass.
In the technical scheme, the polymerization degree of Polyhydroxyethylacrylamide (PHEMAA) is 10-500, 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 10-500, and the polymerization degrees of cationic high molecular side chain precursor polymer PDMC-COOH and anionic high molecular side chain precursor polymer PtBMA-COOH are 10-500The grafting rate of the polymer side chain PDMC is 1-40%, the grafting rate of the cationic polymer side chain PMAANa is 1-40%, the grafting rate of the chelating side chain PVACDTANA is 1-15%, and the settling-assisted 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 five-membered polymer molecular brush dye catching sedimentation agent is realized, it is characterized in that 0.1 to 1 part of water-soluble five-membered polymer molecular brush dye capturing settling agent is added into 100 to 1000 parts of wastewater, stirring for 1-5 minutes at normal temperature, adjusting the pH value to 2-9, performing electrostatic adsorption on dye molecules in the wastewater and cationic side chains PDMC and anionic side chains PMAANa of the water-soluble five-membered polymer molecular brush dye capture settling agent, performing chelate adsorption on heavy metal ions in the wastewater and chelate side chains PVACDTANA of the water-soluble five-membered polymer molecular brush dye capture settling agent, adding 0.01-0.1 part of settling aid, stirring for 1 minute at normal temperature, and rapidly mixing the metal ions of the settling aid with the settling aid side chains PVACS of the water-soluble five-membered polymer molecular brush dye capture settling agent.2Na is subjected to chemical precipitation reaction, floc precipitation with the particle size of more than 100 mu m is generated within 10 seconds, the removal of cationic dye, anionic dye and complex heavy metal ions in wastewater can be rapidly realized, the effluent is colorless and reaches the national discharge standard, and the above are all in parts by mass.
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 four polymer side chains with different functions, wherein the cationic polymer side chain has good electrostatic adsorption capacity on anionic dye, the anionic polymer side chain PMAANa has good electrostatic adsorption capacity on cationic dye, and the chelating side chain PVACDTANA carries out chelating adsorption on heavy metal ions and has good settling-assisting side chain PVACS2Under the synergistic effect of Na, PVACS2The Na high molecular side chain and metal ions of the settling aid rapidly generate chemical precipitation reaction to achieve the functions of efficient capture and rapid settling, and the effluent is basically colorless and reaches the national discharge standard;
2. the invention has the technical advantage of settling velocity, 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;
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 dye catching settling agent is a water-soluble five-membered polymer molecular brush dye catching settling agent and 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 400 parts of methanol, and carrying out polymerization reaction for 1 hour at 80 ℃ under the protection of nitrogen to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 30;
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 1 part of azodicyano valeric acid initiator, 100 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC) and 300 parts of water, and carrying out free radical polymerization reaction for 2 hours at 60 ℃ under the protection of nitrogen to obtain PDMC-COOH with the polymerization Degree (DP) of 30;
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 1 hour at 60 ℃ under the protection of nitrogen to obtain PtBMA-COOH with the polymerization Degree (DP) of 30;
synthesizing functional polymer side chain precursor polymer PNVF-COOH: taking 1 part of azodicyano valeric acid initiator, 100 parts of N-vinyl formamide (NVF) and 600 parts of water, and carrying out free radical polymerization reaction for 1 hour at 50 ℃ under the protection of nitrogen to obtain PNVF-COOH with the polymerization Degree (DP) of 20;
step three, synthesizing 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD)
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- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)
Mixing 1 part of Polyhydroxyethylacrylamide (PHEMAA) obtained in the first step with 20 parts of cationic high molecular side chain PDMC-COOH, 20 parts of anionic high molecular side chain precursor polymer PtBMA-COOH and 5 parts of functional high molecular side chain precursor polymer PNVF-COOH obtained in the second step, dissolving in 100 parts of Dimethylformamide (DMF) solvent, adding 1 part of catalyst, namely 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 1 part of sodium hydroxide, controlling the temperature at 80 ℃, and carrying out hydrolysis reaction on the anionic macromolecular side chain precursor polymer PtBMA grafted on the main chain of the polymer and the functional macromolecular side chain precursor polymer PNVF for 48 hours to obtain polyhydroxyethylAcrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (phema-g- (PDMC-r-pmaaana-r-PVA)); then 5 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD) synthesized in the third step is added, and the acylation reaction is carried out for 24 hours, wherein the acylation degree is 80 percent, and polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACTANa-r-PVA)); adding 1 part of carbon disulfide, controlling the temperature at 40 ℃, and carrying out addition reaction for 1 hour to finally obtain water-soluble polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyethyleneaminocyclohexanediamine sodium tetraacetate-random-polyethyleneaminodithiocarbamic acid sodium salt) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)) i.e. a water-soluble five-membered polymer molecular brush dye trapping settling agent. Measuring PDMC, PMAANa, PVACDTANA and PVACS with nuclear magnetic resonance apparatus2The grafting ratios of the Na side chains were 17%, 18%, 4% and 1%, respectively.
In this example, the application of the water-soluble five-membered polymer brush dye trapping settling agent
Taking the water-soluble five-membered polymer molecular brush dye capturing settling agent of the embodiment as a dye wastewater test, taking 100 parts of wastewater containing 50 mg/L of methylene blue and 20 mg/L of methyl red, adding 0.1 part of water-soluble five-membered polymer molecular brush dye capturing settling agent, stirring for 1 minute at normal temperature, adjusting the pH value of the wastewater to 2.0 by using 0.1 mol/L hydrochloric acid, adding 0.01 part of settling assistant agent calcium chloride, stirring for 1 minute at normal temperature, generating floc precipitation with a particle size of more than 110 mu m within 10 seconds, filtering, measuring the concentration of the methylene blue in the filtrate to be 0.04 mg/L and the concentration of the methyl red to be 0.03mg/L by using an ultraviolet absorption spectrophotometer, and the removal efficiency is more than 99%.
Example two
The dye catching settling agent is a water-soluble five-membered polymer molecular brush dye catching 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-bipyridine (BPy), 100 parts of hydroxyethyl acrylamide (HEMAA) and 100 parts of methanol at 60 ℃ under the protection of nitrogen for 5 hours to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 200;
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 1 part of azodicyano valeric acid initiator, 200 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC) and 100 parts of water, and carrying out free radical polymerization reaction for 10 hours at 60 ℃ under the protection of nitrogen to obtain PDMC-COOH with the polymerization Degree (DP) of 120;
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 20 hours at 70 ℃ under the protection of nitrogen to obtain PtBMA-COOH with the polymerization Degree (DP) of 130;
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 10 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 (CDTAD)
Dissolving 10 parts of 1, 2-cyclohexanediaminetetraacetic acid and 10 parts of acetic anhydride in 30 parts of pyridine, and reacting for 40 hours at 70 ℃ to obtain 1, 2-cyclohexanediaminetetraacetic dianhydride;
step four, synthesizing PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)
2 parts of Polyhydroxyethylacrylamide (PHEMAA) obtained in the step one, 40 parts of cationic high molecular side chain PDMC-COOH obtained in the step two and 40 parts of anionic high molecular side chain precursor polymer PtBMA-COOH and 10 parts of functional polymer side chain precursor polymer PNVF-COOH were mixed and dissolved in 300 parts of Dimethylformamide (DMF) solvent, 3 parts of catalyst, N-hydroxysuccinimide (NHS), and 3 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide methyl iodide (EDC. CH)3I) Controlling the temperature to 65 ℃, and carrying out esterification reaction for 40 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 high-molecular side chain PDMC-COOH with a carboxyl at the tail end, an anionic high-molecular side chain precursor polymer PtBMA with a carboxyl at the tail end and a functional high-molecular side chain precursor polymer PNVF with a carboxyl at the tail end to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-poly-tert-butyl methacrylate-random-poly-N-vinylformamide) (PHEMAA-g- (PDMC-r-PtBMA-r-PNVF)); adding 5 parts of sodium 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)); then 10 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD) synthesized in the third step is added, and the acylation reaction is carried out for 12 hours, wherein the acylation degree is 75 percent, and polyhydroxyethylacrylamide-graft- (polymethacryloyloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACCTANa-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- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyethyleneaminocyclohexanediamine sodium tetraacetate-random-polyethyleneaminodithiocarbamic acid sodium salt) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)) i.e. a water-soluble five-membered polymer molecular brush dye trapping settling agent. Measuring PDMC, PMAANa, PVACDTANA and PVACS with nuclear magnetic resonance apparatus2The grafting ratios of the Na side chains were 26%, 24%, 6% and 2%, respectively.
In this example, the application of the water-soluble five-membered polymer brush dye trapping settling agent
Taking the water-soluble five-membered polymer molecular brush dye capturing settling agent of the embodiment as a dye wastewater test, adding 500 parts of wastewater containing 60 mg/L rhodamine B, 60 mg/L Congo red, 3mg/L cadmium ion and 0.5 mg/L citric acid into 0.5 part of water-soluble five-membered polymer molecular brush dye capturing settling agent, stirring for 3 minutes at normal temperature, adjusting the pH value of the wastewater to 5.0 by using 0.1 mol/L hydrochloric acid, adding 0.05 part of settling agent ferric trichloride, stirring for 1 minute at normal temperature, generating floc precipitation with the particle size of more than 420 mu m within 2 seconds, filtering, respectively measuring the concentration of the rhodamine B in the filtrate to be 0.05 mg/L, the concentration of the Congo red to be 0.03mg/L and the concentration of the Cd in the filtrate by using an ultraviolet absorption spectrophotometer2+The ion concentration is 0.03mg/L, and the removal efficiency is high>99%。
EXAMPLE III
The dye catching settling agent is a water-soluble five-membered polymer molecular brush dye catching 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-bipyridine (BPy), 400 parts of hydroxyethyl acrylamide (HEMAA) and 100 parts of methanol at 70 ℃ for 10 hours under the protection of nitrogen to obtain polyhydroxyethyl acrylamide (PHEMAA) with the polymerization Degree (DP) of 300;
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 1 part of azodicyano valeric acid initiator, 300 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC) and 100 parts of water, and carrying out free radical polymerization reaction for 12 hours at 60 ℃ under the protection of nitrogen to obtain PDMC-COOH with the polymerization Degree (DP) of 190;
synthesis of anionic high-molecular side-chain precursor polymer PtBMA-COOH: taking 1 part of azodicyano valeric acid initiator, 400 parts of tert-butyl methacrylate (tBMA) and 100 parts of toluene, and carrying out free radical polymerization reaction for 15 hours at 70 ℃ under the protection of nitrogen to obtain PtBMA-COOH with the polymerization Degree (DP) of 250;
synthesizing functional polymer side chain precursor polymer PNVF-COOH: taking 1 part of azodicyano valeric acid initiator, 400 parts of N-vinyl formamide (NVF) and 100 parts of water, and carrying out free radical polymerization reaction for 18 hours at 60 ℃ under the protection of nitrogen to obtain PNVF-COOH with the polymerization Degree (DP) of 350;
step three, synthesizing 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD)
Dissolving 20 parts of 1, 2-cyclohexanediaminetetraacetic acid and 20 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- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)
Mixing 3 parts of Polyhydroxyethylacrylamide (PHEMAA) obtained in the first step, 50 parts of cationic high molecular side chain PDMC-COOH, 50 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 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 sodium hydroxide, controlling the temperature at 50 ℃, and grafting the precursor polymer PtBMA grafted on the anionic macromolecular side chain of the main chain of the polymer and the precursor polymer of the functional macromolecular side chainPerforming hydrolysis reaction on PNVF for 12 hours to obtain polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); then 20 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD) synthesized in the third step is added, and the acylation reaction is carried out for 5 hours, the acylation degree is controlled to be 69 percent, thus obtaining polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamidocyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANA-r-PVA)); then 10 parts of carbon disulfide is added, the temperature is controlled at 20 ℃, addition reaction is carried out for 3 hours, and finally water-soluble polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyethyleneaminocyclohexanediamine sodium tetraacetate-random-polyethyleneaminodithiocarbamic acid sodium salt) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)) i.e. a water-soluble five-membered polymer molecular brush dye trapping settling agent. Measuring PDMC, PMAANa, PVACDTANA and PVACS with nuclear magnetic resonance apparatus2The grafting ratios of the Na side chains were 35%, 36%, 11% and 5%, respectively.
In this example, the application of the water-soluble five-membered polymer brush dye trapping settling agent
Taking the water-soluble five-membered polymer molecular brush dye capturing settling agent of the embodiment as a dye wastewater test, taking 1000 parts of wastewater containing 30 mg/L of methyl violet, 30 mg/L of methyl orange, 4mg/L of lead ions and 0.2mg/L of citric acid, adding 1.0 part of water-soluble five-membered polymer molecular brush dye capturing settling 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 assisting agent aluminum trichloride, stirring for 1 minute at normal temperature, generating floc precipitation with the particle size of more than 200 mu m within 5 seconds, filtering, respectively measuring the methyl violet concentration of 0.06 mg/L, the methyl orange concentration of 0.05 mg/L and Pb in the filtrate by using an ultraviolet absorption spectrophotometer2+The ion concentration is 0.04 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 five-membered polymer molecular brush dye capturing settling 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 polymethacryloxyethyltrimethyl ammonium chloride (PDMC-COOH), 20-50 parts of anionic high-molecular side chain precursor polymer terminal carboxyl-containing poly tert-butyl methacrylate (PtBMA-COOH) and 5-15 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 sodium hydroxide, 1-20 parts of 1, 2-cyclohexanediaminetetraacetic dianhydride (CDTAD) and 1-10 parts of carbon disulfide;
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;
synthesizing a polymethacryloxyethyltrimethyl ammonium chloride (PDMC-COOH) polymer with a carboxyl at the tail end by using azodicyano valeric acid as an initiator through a common free radical polymerization method;
synthesizing an anionic high-molecular precursor polymer PtBMA-COOH into a poly (tert-butyl methacrylate) (PtBMA-COOH) polymer with a carboxyl at the tail end by using azodicyano valeric acid as an initiator through 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 (CDTAD) 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 five-membered polymer brush dye capturing and settling agent as claimed in claim 1, wherein 0.1-1 part of the water-soluble five-membered polymer brush dye capturing and settling agent is added to 100-1000 parts of wastewater, the wastewater is stirred at normal temperature for 1-5 minutes, the pH is adjusted to 2-9, the dye molecules in the wastewater and the cationic side chain PDMC and the anionic side chain PMAANa of the water-soluble five-membered polymer brush dye capturing and settling agent are electrostatically adsorbed, the heavy metal ions in the wastewater and the chelating side chain PVACDTANA of the water-soluble five-membered polymer brush dye capturing and settling agent are chelated and adsorbed, 0.01-0.1 part of the settling aid agent is added, the wastewater is stirred at normal temperature for 1 minute, and the metal ions of the settling aid agent rapidly react with the settling aid side chain PVACS of the water-soluble five-membered polymer brush dye capturing and settling agent2Na is subjected to chemical precipitation reaction, floc precipitation with the particle size of more than 100 mu m is generated within 10 seconds, the removal of cationic dye, anionic dye and complex heavy metal ions in wastewater can be rapidly realized, the effluent is colorless and reaches the national discharge standard, and the above are all in parts by mass.
3. The use of the water-soluble five-membered polymer brush dye capture settling agent of claim 2, wherein the settling aid is one or more of calcium chloride, magnesium sulfate, ferrous chloride, ferric chloride, and aluminum chloride.
4. A preparation method of a water-soluble five-membered polymer molecular brush dye capturing sedimentation agent is characterized in that 1-10 parts of polymer main chain polyhydroxyethyl acrylamide (PHEMAA) and 20-50 parts of cationic polymethacryloyloxyethyl ether with carboxyl at the tail end of a side chain of a high polymerTrimethyl ammonium chloride (PDMC-COOH), 20-50 parts of anionic high-molecular side chain precursor polymer terminal carboxyl-containing poly (tert-butyl methacrylate) (PtBMA-COOH) and 5-15 parts of functional high-molecular side chain precursor polymer terminal carboxyl-containing poly (N-vinyl formamide) (PNVF-COOH) are mixed and dissolved in 100-500 parts of dimethyl formamide (DMF) solvent, 1-5 parts of 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- (polymethacryloxyethyltrimethylammonium chloride-random-poly (tert-butyl methacrylate) -random-poly (N-vinylformamide) (PHEMAA-g- (PDMC-r-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- (polymethacryloyloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVA)); adding 1-20 parts of 1, 2-cyclohexanediamine tetraacetic dianhydride (CDTAD), and carrying out acylation reaction for 5-24 hours, wherein the acylation degree range is controlled to be 60-99%, so as to obtain polyhydroxyethyl acrylamide-graft- (polymethacryloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-random-polyvinylamido cyclohexanediamine tetrasodium acetate-random-polyvinylamine) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDDANA-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 polyhydroxyethylacrylamide-graft- (polymethacryloxyethyltrimethylammonium chloride-random-sodium polymethacrylate-random-polyvinylamidocyclohexanediamine sodium tetraacetate-random-polyvinylamido sodium dithiocarbamate) (PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANA-r-PVACS)2Na)), namely a water-soluble five-membered polymer molecular brush dye capturing settling agent, in parts by mass.
5. The method for preparing water-soluble five-membered polymer molecular brush dye capture setting agent according to claim 4, wherein said polyhydroxyethylacryloyl is used as a dye capture setting agentThe polymerization degree of amine (PHEMAA) is 10-500, 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 10-500, the grafting rate of cationic high molecular side chain PDMC is 1-40%, the grafting rate of cationic high molecular side chain PMAANa is 1-40%, the grafting rate of chelating type side chain PVACDTANA is 1-15%, and the polymerization degree of settling-assistant type side chain PVACS is 10-5002The grafting ratio of Na is 1-5%.
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| CN105498726A (en) * | 2015-12-17 | 2016-04-20 | 山东大学 | High-adsorptivity heavy metal ion chelating agent containing dithiocar-bamate structure and preparation method thereof |
| CN106467327A (en) * | 2016-09-28 | 2017-03-01 | 顺德职业技术学院 | The preparation method of ter-polymers molecular brush heavy metal chelating agent |
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| CN101397354A (en) * | 2007-09-30 | 2009-04-01 | 中国科学院理化技术研究所 | Hydrophobic modified cationic block polyacrylamide and synthesis method and application thereof |
| CN105498726A (en) * | 2015-12-17 | 2016-04-20 | 山东大学 | High-adsorptivity heavy metal ion chelating agent containing dithiocar-bamate structure and preparation method thereof |
| CN106467327A (en) * | 2016-09-28 | 2017-03-01 | 顺德职业技术学院 | The preparation method of ter-polymers molecular brush heavy metal chelating agent |
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