CN107162148A - A kind of chitosan/poly- (N N-isopropylacrylamides) graft copolymerization thermosensitive polymer flocculant and preparation method thereof - Google Patents
A kind of chitosan/poly- (N N-isopropylacrylamides) graft copolymerization thermosensitive polymer flocculant and preparation method thereof Download PDFInfo
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- CN107162148A CN107162148A CN201710506710.5A CN201710506710A CN107162148A CN 107162148 A CN107162148 A CN 107162148A CN 201710506710 A CN201710506710 A CN 201710506710A CN 107162148 A CN107162148 A CN 107162148A
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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 kind of chitosan/poly- (N N-isopropylacrylamides) graft copolymerization thermosensitive polymer flocculant, it has prepared first using ethylenediamine and methyl acrylate as Material synthesis the dendritic macromole that end group is four amidos；Chain-transferring agent is used as using 2 mercaptopropionic acids, participate in the polymerisation of N N-isopropylacrylamides, poly- N N-isopropylacrylamides carboxylic acid derivates are prepared, its terminal carboxylic acid group is reacted under dehydrating agent effect with the amido of chitosan and dendritic macromole, obtains thermosensitive polymer flocculant.A large amount of active amido, imino groups are contained in flocculant material surface of the present invention, can occur protonation or deprotonation to change the positive charge density on its surface, realize the absorption to negatively charged pollutant, realize efficient flocculating.
Description
Technical field
The present invention relates to a kind of temperature sensing material field, and in particular to a kind of chitosan/NIPA connects
Branch copolymerization thermosensitive polymer flocculant and preparation method thereof.
Background technology
The upper critical temperature in responsive to temperature type polymer（LCST）Showing as macromolecule can be from hydrophilic line style state
It is transformed into hydrophobic ball-type state.The transition process is reversible, has reacted the phenomenon of macromolecule contraction.When polymer solution temperature
Degree be higher than LCST when Form of Polymer by line style state become spheroiding state, conversely when solution temperature be less than LCST when macromolecule again
Wire is become again by spherical, using this characteristic of temperature sensing material, as flocculant in use, heated solution makes its temperature high
The floc sedimentation of responsive to temperature type polymer formation, which is known from experience, when LCST shrinks close agglomerating, accelerates its settlement action, so as to reach wadding
Solidifying effect.
Compared with traditional line style temperature sensitive polymer, the tree-like temperature with compact spherical or spherical structure emerging at present
Change of the lower critical solution temperature of quick macromolecule and hyperbranched temperature sensitive polymer to self structure and external environment is more sensitive.Cause
This, it is contemplated that line style temperature sensitive polymer can be filled up or improved to tree-like temperature sensitive macromolecule and hyperbranched temperature sensitive polymer not
Foot.
Contain amino in chitosan molecule, this is the basic reason that Chitosan-phospholipid complex has adsorptivity, is used as one
Individual linear polyamine, Chitosan-phospholipid complex is after suitable condition dissolving, with the protonation of amino, that is, shows cation and gather
The property of electrolyte is closed, almost each unit has an amino to Chitosan-phospholipid complex, there is high charge density, when condition is suitable
When preferably, it can not only adsorb the negative electrical charge particulate in water, and can also with many heavy metal ion chelatings, with dosage
Few, sinking speed is fast, and removal efficiency is high, and sludge is disposable, the features such as non-secondary pollution, can as flocculant weaving, printing and dyeing,
Extensive use is obtained in terms of papermaking, biochemistry, food, medical treatment, daily-use chemical industry, agricultural and environmental protection.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of chitosan/NIPA graft copolymerization
Thermosensitive polymer flocculant and preparation method thereof.
A kind of chitosan/NIPA graft copolymerization thermosensitive polymer flocculant, it is prepared first
End group is the dendritic macromole of four amidos using ethylenediamine and methyl acrylate as Material synthesis；Using 2 mercaptopropionic acid as
Chain-transferring agent, participates in the polymerisation of NIPA, prepares poly-N-isopropyl acrylamide carboxylic acid derivates,
Its terminal carboxylic acid group is reacted under dehydrating agent effect with the amido of chitosan and dendritic macromole, obtains thermosensitive polymer
Flocculant.
Comprise the following steps that：
（1）Hold the synthesis of amido dendritic macromole：
1., 3-5 parts by weight ethylenediamines are added in the three-necked bottle with magnetic stir bar, reflux condensing tube and thermometer, with
Ethylenediamine and methyl acrylate mol ratio are 1:8 amount adds methyl acrylate and 14-22 parts of methanol, is uniformly mixed,
In stirring reaction 5-7 hours at 20-30 DEG C, vacuum distillation obtained weak yellow liquid；
2., it will be added sequentially in above-mentioned weak yellow liquid with 16-25 parts of methanol, 32-46 parts of ethylenediamines in three-necked bottle, stirring is mixed
Close uniform, in stirring reaction 20-26 hours at 20-30 DEG C, vacuum distillation obtained pale yellow transparent viscous liquid product；
（2）The preparation of poly-N-isopropyl acrylamide carboxylic acid derivates：
80-150 parts of methanol are added in three-necked bottle, 60-70 DEG C is warming up under nitrogen protection, 55-70 parts of N- isopropyls are slowly added to
Base acrylamide, 1-4 part azodiisobutyronitrile and 10-21 parts of 2 mercaptopropionic acids, continue to be passed through nitrogen, and at 60-70 DEG C continue
Stirring 20-24 hours, vacuum distillation removes solvent, and n-hexane recrystallization, filtering, by solid is added dropwise in mixture acetone solution
Poly-N-isopropyl acrylamide carboxylic acid derivates are made in 35-45 DEG C of vacuum drying in product；
（3）Take 10-15 parts of chitosans to be dissolved in 65-80 parts of hydrochloric acid solutions, step is added under stirring condition（1）The end amine of preparation
Base dendritic macromole, sequentially adds the aqueous solution, the ring of 7-14 parts two of above-mentioned poly-N-isopropyl acrylamide carboxylic acid derivates
Hexyl carbodiimides, is added dropwise 0.02-0.1 parts of tetramethylethylenediamines afterwards, reaction 3-4 days is stirred at room temperature, by filtrate after filtering
It is placed in bag filter and is dialysed 4 days with distilled water, often crosses and change first water in 1 day, the solution that will be left in bag filter is freezed
Processing, is produced.
Wherein, the step（3）The middle concentration of hydrochloric acid solution used is 1-3%, preferably 2%.
Wherein, the step（3）The concentration of the aqueous solution of middle poly-N-isopropyl acrylamide carboxylic acid derivates is 20-40%.
Compared with prior art, the present invention has advantages below：
（1）The present invention is participated in the polymerisation of NIPA, prepared using 2 mercaptopropionic acid as chain-transferring agent
Poly-N-isopropyl acrylamide carboxylic acid derivates, its terminal carboxylic acid group is divided greatly under dehydrating agent effect with chitosan and dendroid
The amido reaction of son, obtains thermosensitive polymer flocculant, while introducing amine dendrimer, makes temperature sensitive type flocculant knot of the present invention
The premium properties of amine dendrimer and temperature sensitive polymer is closed, with the excellent properties such as phase transition temperature is narrow, hysteresis effect is small.
（2）Introduced in flocculant material of the present invention on end amido dendritic macromole, its side chain containing a large amount of active amine
Base, imino group, not only with higher reactivity, and can make the wadding of amino-contained by the pH value for adjusting absorption environment
Protonation or deprotonation occur for solidifying agent surface to change the positive charge density on its surface, realize to negatively charged pollutant
Absorption, while the introducing of chitosan molecule, with high charge density, can not only adsorb the negative electrical charge particulate in water, and
Efficient flocculating can also be realized with many heavy metal ion chelatings.
Embodiment
A kind of chitosan/NIPA graft copolymerization thermosensitive polymer flocculant, it is prepared first
End group is the dendritic macromole of four amidos using ethylenediamine and methyl acrylate as Material synthesis；Using 2 mercaptopropionic acid as
Chain-transferring agent, participates in the polymerisation of NIPA, prepares poly-N-isopropyl acrylamide carboxylic acid derivates,
Its terminal carboxylic acid group is reacted under dehydrating agent effect with the amido of chitosan and dendritic macromole, obtains thermosensitive polymer
Flocculant.
Comprise the following steps that：
（1）Hold the synthesis of amido dendritic macromole：
1., 5 parts by weight ethylenediamines are added in the three-necked bottle with magnetic stir bar, reflux condensing tube and thermometer, with second
Diamines and methyl acrylate mol ratio are 1:8 amount adds methyl acrylate and 20 parts of methanol, is uniformly mixed, in 25 DEG C
Lower stirring reaction 6 hours, vacuum distillation obtains weak yellow liquid；
2., it will be added sequentially in above-mentioned weak yellow liquid with 19 parts of methanol, 38 parts of ethylenediamines in three-necked bottle, stirring mixing is equal
It is even, in stirring reaction 24 hours, vacuum distillation at 25 DEG C, obtain pale yellow transparent viscous liquid product；
（2）The preparation of poly-N-isopropyl acrylamide carboxylic acid derivates：
100 parts of methanol are added in three-necked bottle, 65 DEG C are warming up under nitrogen protection, 60 parts of N- isopropyl acrylamides are slowly added to
Amine, 2 parts of azodiisobutyronitriles and 16 parts of 2 mercaptopropionic acids, continue to be passed through nitrogen, and are persistently stirred 24 hours at 65 DEG C, and decompression is steamed
Solvent is removed in distillation, and n-hexane recrystallization, filtering, by solid product in 45 DEG C of vacuum drying, system is added dropwise in mixture acetone solution
Obtain poly-N-isopropyl acrylamide carboxylic acid derivates；
（3）Take 13 parts of chitosans to be dissolved in 70 parts of hydrochloric acid solutions, step is added under stirring condition（1）The end amido branch of preparation
Shape macromolecular, sequentially adds the aqueous solution of above-mentioned poly-N-isopropyl acrylamide carboxylic acid derivates, 11 parts of dicyclohexyls and is carbonized
Diimine, is added dropwise 0.08 part of tetramethylethylenediamine afterwards, and reaction 4 days is stirred at room temperature, filtrate is placed in bag filter after filtering and used
Distilled water is dialysed 4 days, is often crossed and is changed first water in 1 day, the solution that will be left in bag filter carries out frozen dried, produces.
Wherein, the step（3）The middle concentration of hydrochloric acid solution used is 1-3%, preferably 2%.
Wherein, the step（3）The concentration of the aqueous solution of middle poly-N-isopropyl acrylamide carboxylic acid derivates is 40%.
Claims (4)
1. a kind of chitosan/NIPA graft copolymerization thermosensitive polymer flocculant, it is characterised in that its
The dendritic macromole that end group is four amidos has been prepared first using ethylenediamine and methyl acrylate as Material synthesis；With 2- sulfydryls
Propionic acid participates in the polymerisation of NIPA, prepares poly-N-isopropyl acrylamide carboxylic as chain-transferring agent
Acid derivative, its terminal carboxylic acid group is reacted under dehydrating agent effect with the amido of chitosan and dendritic macromole, obtains temperature
Quick type high polymer coagulant.
2. a kind of chitosan/NIPA graft copolymerization temperature sensitive type high score according to claims 1
The preparation method of sub- flocculant, it is characterised in that comprise the following steps that：
（1）Hold the synthesis of amido dendritic macromole：
1., 3-5 parts by weight ethylenediamines are added in the three-necked bottle with magnetic stir bar, reflux condensing tube and thermometer, with
Ethylenediamine and methyl acrylate mol ratio are 1:8 amount adds methyl acrylate and 14-22 parts of methanol, is uniformly mixed,
In stirring reaction 5-7 hours at 20-30 DEG C, vacuum distillation obtained weak yellow liquid；
2., it will be added sequentially in above-mentioned weak yellow liquid with 16-25 parts of methanol, 32-46 parts of ethylenediamines in three-necked bottle, stirring is mixed
Close uniform, in stirring reaction 20-26 hours at 20-30 DEG C, vacuum distillation obtained pale yellow transparent viscous liquid product；
（2）The preparation of poly-N-isopropyl acrylamide carboxylic acid derivates：
80-150 parts of methanol are added in three-necked bottle, 60-70 DEG C is warming up under nitrogen protection, 55-70 parts of N- isopropyls are slowly added to
Base acrylamide, 1-4 part azodiisobutyronitrile and 10-21 parts of 2 mercaptopropionic acids, continue to be passed through nitrogen, and at 60-70 DEG C continue
Stirring 20-24 hours, vacuum distillation removes solvent, and n-hexane recrystallization, filtering, by solid is added dropwise in mixture acetone solution
Poly-N-isopropyl acrylamide carboxylic acid derivates are made in 35-45 DEG C of vacuum drying in product；
（3）Take 10-15 parts of chitosans to be dissolved in 65-80 parts of hydrochloric acid solutions, step is added under stirring condition（1）The end amine of preparation
Base dendritic macromole, sequentially adds the aqueous solution, the ring of 7-14 parts two of above-mentioned poly-N-isopropyl acrylamide carboxylic acid derivates
Hexyl carbodiimides, is added dropwise 0.02-0.1 parts of tetramethylethylenediamines afterwards, reaction 3-4 days is stirred at room temperature, by filtrate after filtering
It is placed in bag filter and is dialysed 4 days with distilled water, often crosses and change first water in 1 day, the solution that will be left in bag filter is freezed
Processing, is produced.
3. a kind of chitosan/NIPA graft copolymerization temperature sensitive type high score according to claims 2
The preparation method of sub- flocculant, it is characterised in that the step（3）The middle concentration of hydrochloric acid solution used is 1-3%, preferably 2%.
4. a kind of chitosan/NIPA graft copolymerization temperature sensitive type high score according to claims 2
The preparation method of sub- flocculant, it is characterised in that the step（3）Middle poly-N-isopropyl acrylamide carboxylic acid derivates it is water-soluble
The concentration of liquid is 20-40%.
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| CN201710506710.5A CN107162148B (en) | 2017-06-28 | 2017-06-28 | Chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant and preparation method thereof |
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| CN201710506710.5A CN107162148B (en) | 2017-06-28 | 2017-06-28 | Chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant and preparation method thereof |
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| CN107162148A true CN107162148A (en) | 2017-09-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776606A (en) * | 2019-10-31 | 2020-02-11 | 西南石油大学 | Modified chitosan/nitrogen-oxygen branched monomer functional polymer and preparation method and application thereof |
| CN113322073A (en) * | 2021-04-30 | 2021-08-31 | 上海工程技术大学 | Degradable dendritic soil conditioner and preparation method thereof |
| CN115010878A (en) * | 2022-06-30 | 2022-09-06 | 四川农业大学 | Hydrophilic-hydrophobic convertible flocculant and application thereof |
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| 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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2017
- 2017-06-28 CN CN201710506710.5A patent/CN107162148B/en active Active
Patent 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776606A (en) * | 2019-10-31 | 2020-02-11 | 西南石油大学 | Modified chitosan/nitrogen-oxygen branched monomer functional polymer and preparation method and application thereof |
| CN110776606B (en) * | 2019-10-31 | 2022-01-07 | 四川瑞冬科技有限公司 | Modified chitosan/nitrogen-oxygen branched monomer functional polymer and preparation method and application thereof |
| CN113322073A (en) * | 2021-04-30 | 2021-08-31 | 上海工程技术大学 | Degradable dendritic soil conditioner and preparation method thereof |
| CN113322073B (en) * | 2021-04-30 | 2022-07-01 | 上海工程技术大学 | Degradable dendritic soil conditioner and preparation method thereof |
| CN115010878A (en) * | 2022-06-30 | 2022-09-06 | 四川农业大学 | Hydrophilic-hydrophobic convertible flocculant and application thereof |
| CN115010878B (en) * | 2022-06-30 | 2023-05-16 | 四川农业大学 | Hydrophilic-hydrophobic switchable flocculant and application thereof |
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