CN107162148B - Chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant and preparation method thereof - Google Patents
Chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant and preparation method thereof Download PDFInfo
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- CN107162148B CN107162148B CN201710506710.5A CN201710506710A CN107162148B CN 107162148 B CN107162148 B CN 107162148B CN 201710506710 A CN201710506710 A CN 201710506710A CN 107162148 B CN107162148 B CN 107162148B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention discloses a chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant, which is prepared by firstly synthesizing dendritic macromolecules with four amino end groups by taking ethylenediamine and methyl acrylate as raw materials; taking 2-mercaptopropionic acid as a chain transfer agent, participating in the polymerization reaction of N-isopropylacrylamide to prepare a poly N-isopropylacrylamide carboxylic acid derivative, and reacting a terminal carboxylic acid group of the poly N-isopropylacrylamide carboxylic acid derivative with chitosan and an amino group of a dendritic macromolecule under the action of a dehydrating agent to obtain the temperature-sensitive polymeric flocculant. The surface of the flocculant material contains a large number of active amino and imino groups, and protonation or deprotonation can be carried out so as to change the positive charge density of the surface, realize adsorption on negatively charged pollutants and realize high-efficiency flocculation.
Description
Technical Field
The invention relates to the field of temperature-sensitive materials, in particular to a chitosan/poly (N-isopropylacrylamide) graft copolymerization temperature-sensitive polymeric flocculant and a preparation method thereof.
Background
The upper critical temperature (LCST) in temperature-sensitive polymers is represented by the ability of macromolecules to transition from a hydrophilic linear state to a hydrophobic spherical state. The transformation process is reversible, reflecting the phenomenon of polymer shrinkage. When the temperature of the polymer solution is higher than the LCST, the polymer form is changed from a linear state to a spherical state, and conversely, when the temperature of the polymer solution is lower than the LCST, the polymer is changed from a spherical state to a linear state.
Compared with the traditional linear temperature-sensitive polymer, the low critical solution temperature of the tree-shaped temperature-sensitive polymer and the hyperbranched temperature-sensitive polymer which are newly developed at present and have a compact spherical or sphere-like structure is more sensitive to the change of the self structure and the external environment. Therefore, it is expected that the tree-shaped temperature sensitive polymer and the hyperbranched temperature sensitive polymer can fill or improve the deficiency of the linear temperature sensitive polymer.
The chitosan and the derivatives thereof have the property of cationic polyelectrolyte along with protonation of amino group after being dissolved under proper conditions, almost every unit of the chitosan and the derivatives thereof has an amino group with high charge density, when the conditions are proper, the chitosan and the derivatives thereof can not only adsorb negative charge particles in water, but also can be chelated with a plurality of heavy metal ions, and the chitosan and the derivatives thereof have the characteristics of small addition amount, high settling speed, high removal efficiency, easy sludge treatment, no secondary pollution and the like, and can be widely applied to the aspects of textile, printing and dyeing, papermaking, biochemistry, food, medical treatment, daily chemical industry, agriculture, environmental protection and the like as a flocculating agent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a chitosan/poly (N-isopropylacrylamide) graft copolymerization temperature-sensitive polymeric flocculant and a preparation method thereof.
A chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant is prepared by synthesizing dendritic macromolecules with four amino groups as end groups by using ethylenediamine and methyl acrylate as raw materials; taking 2-mercaptopropionic acid as a chain transfer agent, participating in the polymerization reaction of N-isopropylacrylamide to prepare a poly N-isopropylacrylamide carboxylic acid derivative, and reacting a terminal carboxylic acid group of the poly N-isopropylacrylamide carboxylic acid derivative with chitosan and an amino group of a dendritic macromolecule under the action of a dehydrating agent to obtain the temperature-sensitive polymeric flocculant.
The method comprises the following specific steps:
(1) synthesizing a terminal amino dendritic macromolecule:
adding 3-5 parts by weight of ethylenediamine into a three-necked bottle with a magnetic stirrer, a reflux condenser tube and a thermometer, adding methyl acrylate and 14-22 parts by weight of methanol in an ethylenediamine-methyl acrylate molar ratio of 1:8, stirring and mixing uniformly, stirring and reacting for 5-7 hours at 20-30 ℃, and carrying out reduced pressure distillation to obtain a light yellow liquid;
secondly, adding the light yellow liquid, 16-25 parts of methanol and 32-46 parts of ethylenediamine into a three-necked bottle in sequence, stirring and mixing uniformly, reacting for 20-26 hours at 20-30 ℃, and distilling under reduced pressure to obtain a light yellow transparent viscous liquid product;
(2) preparation of poly-N-isopropylacrylamide carboxylic acid derivative:
adding 80-150 parts of methanol into a three-necked bottle, heating to 60-70 ℃ under the protection of nitrogen, slowly adding 55-70 parts of N-isopropylacrylamide, 1-4 parts of azobisisobutyronitrile and 10-21 parts of 2-mercaptopropionic acid, continuously introducing nitrogen, continuously stirring for 20-24 hours at 60-70 ℃, distilling under reduced pressure to remove the solvent, dissolving the mixture by using acetone, dropwise adding N-hexane for recrystallization, filtering, and vacuum-drying the solid product at 35-45 ℃ to obtain the poly-N-isopropylacrylamide carboxylic acid derivative;
(3) dissolving 10-15 parts of chitosan into 65-80 parts of hydrochloric acid solution, adding the terminal amino dendritic macromolecule prepared in the step (1) under the condition of stirring, sequentially adding the aqueous solution of the poly-N-isopropylacrylamide carboxylic acid derivative and 7-14 parts of dicyclohexylcarbodiimide, then dropwise adding 0.02-0.1 part of tetramethylethylenediamine, stirring at room temperature for reacting for 3-4 days, filtering, putting the filtrate into a dialysis bag, dialyzing with distilled water for 4 days, changing the distilled water every 1 day, and freeze-drying the solution left in the dialysis bag to obtain the chitosan/N-isopropylacrylamide aqueous solution.
Wherein, the concentration of the hydrochloric acid solution used in the step (3) is 1-3%, preferably 2%.
Wherein, the concentration of the aqueous solution of the poly N-isopropylacrylamide carboxylic acid derivative in the step (3) is 20 to 40 percent.
Compared with the prior art, the invention has the following advantages:
(1) the invention takes 2-mercaptopropionic acid as a chain transfer agent to participate in the polymerization reaction of N-isopropylacrylamide to prepare a poly N-isopropylacrylamide carboxylic acid derivative, the terminal carboxylic acid group of the poly N-isopropylacrylamide carboxylic acid derivative reacts with chitosan and the amino group of a dendritic macromolecule under the action of a dehydrating agent to obtain a temperature-sensitive macromolecular flocculant, and the dendritic macromolecule is introduced at the same time, so that the temperature-sensitive flocculant disclosed by the invention combines the excellent performances of the dendritic macromolecule and the temperature-sensitive polymer, and has the excellent performances of narrow phase change temperature, small hysteresis effect and the like.
(2) The flocculant material of the invention is introduced with amine-terminated dendritic macromolecules, the branched chains of the amine-terminated dendritic macromolecules contain a large amount of active amine groups and imino groups, so that the flocculant material not only has higher reaction activity, but also can ensure that the surface of the flocculant containing amine groups is protonated or deprotonated by adjusting the pH value of the adsorption environment so as to change the positive charge density of the surface of the flocculant and realize the adsorption of pollutants with negative charges, and meanwhile, the introduction of chitosan molecules has high charge density, so that the flocculant material not only can adsorb negative charge particles in water, but also can be chelated with a plurality of heavy metal ions to realize high-efficiency flocculation.
Detailed Description
A chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant is prepared by synthesizing dendritic macromolecules with four amino groups as end groups by using ethylenediamine and methyl acrylate as raw materials; taking 2-mercaptopropionic acid as a chain transfer agent, participating in the polymerization reaction of N-isopropylacrylamide to prepare a poly N-isopropylacrylamide carboxylic acid derivative, and reacting a terminal carboxylic acid group of the poly N-isopropylacrylamide carboxylic acid derivative with chitosan and an amino group of a dendritic macromolecule under the action of a dehydrating agent to obtain the temperature-sensitive polymeric flocculant.
The method comprises the following specific steps:
(1) synthesizing a terminal amino dendritic macromolecule:
adding 5 parts by weight of ethylenediamine into a three-necked bottle with a magnetic stirrer, a reflux condenser tube and a thermometer, adding methyl acrylate and 20 parts by weight of methanol according to the molar ratio of the ethylenediamine to the methyl acrylate of 1:8, stirring and mixing uniformly, stirring and reacting for 6 hours at 25 ℃, and carrying out reduced pressure distillation to obtain a light yellow liquid;
secondly, adding the light yellow liquid, 19 parts of methanol and 38 parts of ethylenediamine into a three-necked bottle in sequence, stirring and mixing uniformly, stirring and reacting for 24 hours at 25 ℃, and carrying out reduced pressure distillation to obtain a light yellow transparent viscous liquid product;
(2) preparation of poly-N-isopropylacrylamide carboxylic acid derivative:
adding 100 parts of methanol into a three-necked bottle, heating to 65 ℃ under the protection of nitrogen, slowly adding 60 parts of N-isopropylacrylamide, 2 parts of azobisisobutyronitrile and 16 parts of 2-mercaptopropionic acid, continuously introducing nitrogen, continuously stirring for 24 hours at 65 ℃, removing the solvent by reduced pressure distillation, dissolving the mixture by acetone, dropwise adding N-hexane for recrystallization, filtering, and drying the solid product at 45 ℃ in vacuum to obtain the poly-N-isopropylacrylamide carboxylic acid derivative;
(3) dissolving 13 parts of chitosan into 70 parts of hydrochloric acid solution, adding the terminal amino dendritic macromolecule prepared in the step (1) under the stirring condition, sequentially adding the aqueous solution of the poly-N-isopropylacrylamide carboxylic acid derivative and 11 parts of dicyclohexylcarbodiimide, then dropwise adding 0.08 part of tetramethylethylenediamine, stirring at room temperature for reacting for 4 days, filtering, putting the filtrate into a dialysis bag, dialyzing for 4 days with distilled water, changing the distilled water every 1 day, and freeze-drying the solution remained in the dialysis bag to obtain the chitosan/chitosan composite material.
Wherein, the concentration of the hydrochloric acid solution used in the step (3) is 1-3%, preferably 2%.
Wherein the concentration of the aqueous solution of the poly-N-isopropylacrylamide carboxylic acid derivative in the step (3) is 40%.
Claims (3)
1. A chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant is characterized in that firstly, ethylenediamine and methyl acrylate are used as raw materials to synthesize dendritic macromolecules with four amido end groups; taking 2-mercaptopropionic acid as a chain transfer agent, participating in the polymerization reaction of N-isopropylacrylamide to prepare a poly N-isopropylacrylamide carboxylic acid derivative, and reacting a terminal carboxylic acid group of the poly N-isopropylacrylamide carboxylic acid derivative with chitosan and an amino group of a dendritic macromolecule under the action of a dehydrating agent to obtain a temperature-sensitive polymeric flocculant;
the preparation method of the chitosan/poly (N-isopropylacrylamide) graft copolymerization temperature-sensitive polymeric flocculant comprises the following specific steps:
(1) synthesizing a terminal amino dendritic macromolecule: adding 3-5 parts by weight of ethylenediamine into a three-necked bottle with a magnetic stirrer, a reflux condenser tube and a thermometer, adding methyl acrylate and 14-22 parts by weight of methanol in an ethylenediamine-methyl acrylate molar ratio of 1:8, stirring and mixing uniformly, stirring and reacting for 5-7 hours at 20-30 ℃, and carrying out reduced pressure distillation to obtain a light yellow liquid; secondly, sequentially adding the light yellow liquid, 16-25 parts of methanol and 32-46 parts of ethylenediamine into a three-necked bottle, stirring and mixing uniformly, reacting for 20-26 hours at 20-30 ℃, and distilling under reduced pressure to obtain a light yellow transparent viscous liquid product;
(2) preparation of poly-N-isopropylacrylamide carboxylic acid derivative: adding 80-150 parts of methanol into a three-necked bottle, heating to 60-70 ℃ under the protection of nitrogen, slowly adding 55-70 parts of N-isopropylacrylamide, 1-4 parts of azobisisobutyronitrile and 10-21 parts of 2-mercaptopropionic acid, continuously introducing nitrogen, continuously stirring for 20-24 hours at 60-70 ℃, distilling under reduced pressure to remove the solvent, dissolving the mixture by using acetone, dropwise adding N-hexane for recrystallization, filtering, and vacuum-drying the solid product at 35-45 ℃ to obtain the poly-N-isopropylacrylamide carboxylic acid derivative;
(3) dissolving 10-15 parts of chitosan into 65-80 parts of hydrochloric acid solution, adding the terminal amino dendritic macromolecule prepared in the step (1) under the condition of stirring, sequentially adding the aqueous solution of the poly-N-isopropylacrylamide carboxylic acid derivative and 7-14 parts of dicyclohexylcarbodiimide, then dropwise adding 0.02-0.1 part of tetramethylethylenediamine, stirring at room temperature for reacting for 3-4 days, filtering, putting the filtrate into a dialysis bag, dialyzing with distilled water for 4 days, changing the distilled water every 1 day, and freeze-drying the solution left in the dialysis bag to obtain the chitosan/N-isopropylacrylamide aqueous solution.
2. The chitosan/poly (N-isopropylacrylamide) -graft copolymerization temperature-sensitive polymeric flocculant according to claim 1, wherein the concentration of the hydrochloric acid solution used in the step (3) is 1-3%.
3. The chitosan/poly (N-isopropylacrylamide) graft copolymerization temperature-sensitive polymeric flocculant of claim 1, wherein the concentration of the aqueous solution of the poly (N-isopropylacrylamide carboxylic acid) derivative in the step (3) is 20-40%.
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| CN113322073B (en) * | 2021-04-30 | 2022-07-01 | 上海工程技术大学 | Degradable dendritic soil conditioner and preparation method thereof |
| CN115010878B (en) * | 2022-06-30 | 2023-05-16 | 四川农业大学 | Hydrophilic-hydrophobic switchable flocculant and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010074358A1 (en) * | 2008-12-24 | 2010-07-01 | Korea Institute Of Energy Research | Chitosan-nipam thermosensitive polymer coagulant and method for the preparation therefor |
| CN104774290A (en) * | 2015-03-27 | 2015-07-15 | 南京师范大学 | PH and temperature dual-sensitive chitosan flocculating agent, and preparation method and application thereof |
| CN105037736A (en) * | 2015-06-05 | 2015-11-11 | 青岛科技大学 | Chitosan grafted hyperbranched polymer polyamide-amine (PAMAM), and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010074358A1 (en) * | 2008-12-24 | 2010-07-01 | Korea Institute Of Energy Research | Chitosan-nipam thermosensitive polymer coagulant and method for the preparation therefor |
| CN104774290A (en) * | 2015-03-27 | 2015-07-15 | 南京师范大学 | PH and temperature dual-sensitive chitosan flocculating agent, and preparation method and application thereof |
| CN105037736A (en) * | 2015-06-05 | 2015-11-11 | 青岛科技大学 | Chitosan grafted hyperbranched polymer polyamide-amine (PAMAM), and preparation method and application thereof |
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Effective date of registration: 20220919 Address after: Baiping Village Sewage Treatment Plant, Ansai District, Yan'an City, Shaanxi Province 717400 Patentee after: Ansai Biaoyuan Environmental Protection Technology Co.,Ltd. Address before: 246133 No. 1318 Jixian North Road, Anqing City, Anhui Province Patentee before: ANQING NORMAL University |