CN103626916A - Method for preparing N-isopropylacrylamide-co-acylhydrazone adsorbent - Google Patents
Method for preparing N-isopropylacrylamide-co-acylhydrazone adsorbent Download PDFInfo
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- CN103626916A CN103626916A CN201310556755.5A CN201310556755A CN103626916A CN 103626916 A CN103626916 A CN 103626916A CN 201310556755 A CN201310556755 A CN 201310556755A CN 103626916 A CN103626916 A CN 103626916A
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Abstract
The invention relates to a method for preparing an N-isopropylacrylamide-co-acylhydrazone adsorbent. The method comprises the following steps: dispersing various reaction monomers in an organic solvent in a reaction kettle under gas protection, adding a radical initiator so as to carry out a polymerization reaction to generate a random copolymer, performing hydrazinolysis and grafting a micromolecule with an aldehyde group, thus synthesizing a final product; and controlling the conditions such as the reaction temperature, time and the ratio of various substances to finally obtain poly(N-isopropylacrylamide-co-acylhydrazone) with chelating properties. The method has the advantages that the chelate has excellent adsorption property to heavy metal ions, N-isopropylacrylamide with thermosensitivity serves as a monomer; and the polymer can be separated out in the case of temperature rise, so that the chelate is conveniently separated after adsorption.
Description
Technical field
The present invention relates to the numerous areas such as medicine, agricultural chemicals, analytical test and water treatment, especially relate to a kind of synthetic method of novel heavy metal ion sorbent material.
Background technology
Along with industrial expansion, the pollution of environment is more and more serious, and heavy metal is poisonous, is difficult for transforming in environment.Heavy metal ion in environment enters water body by all means, and the enrichment through various biologic chains in water body, finally enters human body by fishery products, and people's health is produced to harm.People attach great importance to the research of heavy metal containing wastewater treatment in recent years, develop many kinds for the treatment of processs and remove the heavy metal in waste water, to make it to reach emission standard.Macromolecular heavy metal chelating agent has the advantages such as cost is low, effect stability to the processing of heavy metal wastewater thereby.People attach great importance in the research aspect wastewater treatment macromolecular heavy metal chelating agent in recent years.
The method of removing the heavy metal ion in anhydrating is a lot.Traditional method has: the means such as charcoal absorption, ion precipitation, ion exchange resin absorption.In recent ten years, many investigators are exploring the sorbent material of Cheap highly effective, comprising: natural mineral, industrial by-products, tannins, chitosan, xanthate class, organic composite material and biological adsorption agent etc.According to practical situation, select suitable sorbent material, significant for processing containing the waste water of heavy metal ion economically.Macromolecular heavy metal chelating agent is water miscible a kind of, and macromolecule matrix has hydrophilic chelating and forms base, and it optionally reacts with the heavy metal ion in water, generates metal complex.
Acylhydrazone is a kind of novel heavy metal ion sorbent material, and it and heavy metal ion coordination form highly stable soluble chelating thing, to Cu
2+, Hg
2+, Cr
3+etc. heavy metal ion, all there is good adsorption effect.With traditional soluble chelating phase ratio, the present invention prepare owing to thering is Thermo-sensitive unit NIPA on Polymeric complexes main chain, can be by rising temperature, solubility Thermo-sensitive inner complex is separated out from solution with the change of temperature, and then facilitates separating-purifying.
Summary of the invention
Object of the present invention is intended to be to overcome the shortcoming of above-mentioned prior art, and a kind of preparation method of simple, efficient adsorbent for heavy metal is provided.
In the present invention, in adopting traditional radical polymerization, form high polymer main chain, by hydrazine, react, and then grafting has the monomer of adsorption function on diazanyl, thereby realize the adsorption function to heavy metal ion.And Polymeric complexes has Thermo-sensitive, facilitate separating-purifying.
The technical solution used in the present invention is in order to achieve the above object:
A synthetic method for NIPA-co-acylhydrazone sorbent material, concrete steps are as follows:
1), under nitrogen protection, in reactor, add mass fraction to be: 4～6 parts of monomer NIPAs, 1～3 part of monomer CALCIUM ACRYLATE, 20～30 parts of organic solvents, magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 2～4 parts of oil soluble radical initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 2～3 parts of the random copolymerss that make, be dissolved in 15～25 parts of organic solvents, magnetic agitation is even, adds 15～25 parts of hydrazine hydrates, keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get 3～7 parts of NIPA that step makes and propylene hydrazide copolymers, add 1～2 part 2,4-dinitrobenzal-dehyde, is dissolved in 50～60 parts of organic solvents, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
Wherein, step 1), 2) 3) in, the portion rate benchmark of each material is identical; Step 4), 5) in, the portion rate benchmark of each material is identical; Step 6), 7) in, the portion rate benchmark of each material is identical.
Described CALCIUM ACRYLATE is preferably a kind of in methyl acrylate or methyl methacrylate;
Described organic solvent is preferably a kind of in ethanol or acetone;
Described radical initiator is preferably a kind of in Diisopropyl azodicarboxylate or benzoyl peroxide.
In the present invention, employing has NIPA and the acrylic ester copolymer of Thermo-sensitive, make multipolymer have Thermo-sensitive have again simultaneously can with the unit of chelating monomer reaction, the adsorbent for heavy metal productive rate that this method makes is higher, and technique is simple, without too much aftertreatment.Adsorbent for heavy metal has good heavy metal ion adsorbed performance and water-soluble, and changing temperature inner complex can separate out from solution, facilitates separating-purifying.
Accompanying drawing explanation
Fig. 1: be the nuclear-magnetism figure of NIPA-co-acylhydrazone sorbent material of preparation.
Embodiment
Embodiment 1:
1), under nitrogen protection, in reactor, add mass fraction to be: 4 parts of monomer NIPAs (0.4g), 1 part of monomer CALCIUM ACRYLATE (0.1g), 30 parts of ethanol (3g), magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 2.5 parts of (0.25g) Diisopropyl azodicarboxylate initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 2 parts of the random copolymerss (0.2g) that make, be dissolved in 15 parts of (1.5g) ethanol, magnetic agitation is even, adds 15 parts of hydrazine hydrates (1.5g), keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get NIPA and 3 parts of the propylene hydrazide copolymers (0.3g) that step makes, add 1 part of (0.1g) 2,4-dinitrobenzal-dehyde, is dissolved in 55 parts of (5.5g) acetone, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
The acylhydrazone sample of preparation is faint yellow, and tasteless, relative molecular weight is lower.
Embodiment 2:
1), under nitrogen protection, in reactor, add mass fraction to be: 4 parts of monomer NIPAs (0.4g), 1 part of monomer methacrylate (0.1g), 30 parts, acetone (3g), magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 3 parts of (0.3g) benzoyl peroxide initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 2 parts of the random copolymerss (0.2g) that make, be dissolved in 15 parts of (1.5g) acetone, magnetic agitation is even, adds 15 parts of hydrazine hydrates (1.5g), keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get NIPA and 5 parts of the propylene hydrazide copolymers (0.5g) that step makes, add 1.5 parts of (0.15g) 2,4-dinitrobenzal-dehyde, is dissolved in 50 parts of (5g) ethanol, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
The acylhydrazone sample of preparation is faint yellow, and tasteless, relative molecular weight is lower.
Embodiment 3:
1), under nitrogen protection, in reactor, add mass fraction to be: 5 parts of monomer NIPAs (0.5g), 1 part of monomer CALCIUM ACRYLATE (0.1g), 25 parts of ethanol (2.5g), magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 2.5 parts of (0.25g) Diisopropyl azodicarboxylate initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 2.5 parts of the random copolymerss (0.25g) that make, be dissolved in 15 parts of (1.5g) ethanol, magnetic agitation is even, adds 20 parts of hydrazine hydrates (2g), keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get NIPA and 5 parts of the propylene hydrazide copolymers (0.5g) that step makes, add 1.5 parts of (0.15g) 2,4-dinitrobenzal-dehyde, is dissolved in 55 parts of (5.5g) ethanol, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
The acylhydrazone sample of preparation is faint yellow, and tasteless, relative molecular weight is lower.Fig. 1 is poly-(NIPA-co-propylene acylhydrazone) nuclear magnetic spectrogram.Chemical shift is the hydrocarbon characteristic peak of main chain in 1～2ppm left and right, the solvent peak that the spike of chemical shift at 7.26ppm place is deuterochloroform, chemical shift is characteristic peak hydrocarbon on phenyl ring at the assorted peak of 7～7.5ppm left and right, chemical shift is at broad peak (the peak a at 6～7ppm place, peak b, peak c) the proton characteristic peak on represent on acylhydrazone key-CH-and this ring, the proton characteristic peak of represent on acylhydrazone key at the fignal center (peak d) at 8.5～9ppm place-NH-of chemical shift, chemical shift is the methine protons peak on sec.-propyl at the characteristic peak (peak e) at 4ppm place.
Embodiment 4:
1), under nitrogen protection, in reactor, add mass fraction to be: 5 parts of monomer NIPAs (0.5g), 2 parts of monomer CALCIUM ACRYLATE (0.2g), 20 parts, acetone (2g), magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 3 parts of (0.3g) oil soluble radical initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 2.5 parts of the random copolymerss (0.25g) that make, be dissolved in 20 parts of (2g) ethanol, magnetic agitation is even, adds 20 parts of hydrazine hydrates (2g), keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get NIPA and 7 parts of the propylene hydrazide copolymers (0.7g) that step makes, add 2 parts of (0.2g) 2,4-dinitrobenzal-dehyde, is dissolved in 60 parts of (6g) acetone, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
The acylhydrazone sample of preparation is faint yellow, and tasteless, relative molecular weight is lower.
Embodiment 5:
1), under nitrogen protection, in reactor, add mass fraction to be: 5 parts of monomer NIPAs (0.5g), 2 parts of monomer methacrylate (0.2g), 20 parts of ethanol (2g), magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 4 parts of (0.4g) benzoyl peroxide initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 2.5 parts of the random copolymerss (0.25g) that make, be dissolved in 20 parts of (2g) acetone, magnetic agitation is even, adds 25 parts of hydrazine hydrates (2.5g), keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get NIPA and 7 parts of the propylene hydrazide copolymers (0.7g) that step makes, add 2 parts of (0.2g) 2,4-dinitrobenzal-dehyde, is dissolved in 60 parts of (6g) ethanol, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
The acylhydrazone sample of preparation is faint yellow, and tasteless, relative molecular weight is lower.
Embodiment 6:
1), under nitrogen protection, in reactor, add mass fraction to be: 6 parts of monomer NIPAs (0.6g), 3 parts of monomer CALCIUM ACRYLATE (0.3g), 25 parts, acetone (2.5g), magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 2 parts of (0.2g) benzoyl peroxide initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 3 parts of the random copolymerss (0.3g) that make, be dissolved in 25 parts of (2.5g) ethanol, magnetic agitation is even, adds 15 parts of hydrazine hydrates (1.5g), keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get NIPA and 3 parts of the propylene hydrazide copolymers (0.3g) that step makes, add 1.5 parts of (0.15g) 2,4-dinitrobenzal-dehyde, is dissolved in 50 parts of (5g) acetone, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
The acylhydrazone sample of preparation is faint yellow, and tasteless, relative molecular weight is lower.
Embodiment 7:
1), under nitrogen protection, in reactor, add mass fraction to be: 6 parts of monomer NIPAs (0.6g), 3 parts of monomer methacrylate (0.3g), 25 parts of ethanol (2.5g), magnetic agitation to monomer is uniformly dissolved in solvent;
2) after being uniformly dissolved, 2 parts of (0.2g) Diisopropyl azodicarboxylate initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 3 parts of the random copolymerss (0.3g) that make, be dissolved in 25 parts of (2.5g) acetone, magnetic agitation is even, adds 25 parts of hydrazine hydrates (2.5g), keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get NIPA and 3 parts of the propylene hydrazide copolymers (0.3g) that step makes, add 2 part 2,4-dinitrobenzal-dehyde, is dissolved in 55 parts of (5.5g) acetone, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly-(NIPA-co-acylhydrazone).
The acylhydrazone sample of preparation is faint yellow, and tasteless, relative molecular weight is lower.
Poly-(NIPA-co-acylhydrazone) that embodiment is made, for the absorption to heavy metal ion, tests it to Cu
2+and Cr
3+adsorption effect under specified temp, specific pH condition.Test discovery, heavy metal ion inner complex of the present invention is to having good adsorption effect.
Claims (4)
1. a synthetic method for NIPA-co-acylhydrazone sorbent material, concrete steps are as follows:
1), under nitrogen protection, in reactor, add mass fraction to be: 4～6 parts of monomer NIPAs, 1～3 part of monomer CALCIUM ACRYLATE, 20～30 parts of organic solvents, magnetic agitation 5min is uniformly dissolved monomer in solvent;
2) after being uniformly dissolved, 2～4 parts of oil soluble radical initiators are added in reactor, keep 70 ℃ of bath temperatures, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get 2～3 parts of the random copolymerss that make, be dissolved in 15～25 parts of organic solvents, magnetic agitation is even, adds 15～25 parts of hydrazine hydrates, keeps 90 ℃ of bath temperatures, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get 3～7 parts of NIPA that step makes and propylene hydrazide copolymers, add 1～2 part 2,4-dinitrobenzal-dehyde, is dissolved in 50～60 parts of organic solvents, and magnetic agitation is even;
7) keep 60 ℃ of bath temperatures, reaction 20h, dialysis freeze-drying obtains final product adsorbent for heavy metal poly N-isopropyl acrylamide-co-acylhydrazone.
2. the preparation method of sorbent material as claimed in claim 1, is characterized in that described CALCIUM ACRYLATE is a kind of in methyl acrylate or methyl methacrylate;
3. the preparation method of sorbent material as claimed in claim 1, is characterized in that described organic solvent is a kind of in ethanol or acetone;
4. the preparation method of sorbent material as claimed in claim 1, is characterized in that described radical initiator is a kind of in Diisopropyl azodicarboxylate or benzoyl peroxide.
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| CN105860104A (en) * | 2016-06-15 | 2016-08-17 | 河北大学 | Temperature-sensitive self-repairing hydrogel and preparation method and application thereof |
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| JP2006316151A (en) * | 2005-05-11 | 2006-11-24 | Kansai Paint Co Ltd | Hydrazide group-containing copolymer, manufacturing method thereof and resin composition containing the copolymer |
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| CN105860104A (en) * | 2016-06-15 | 2016-08-17 | 河北大学 | Temperature-sensitive self-repairing hydrogel and preparation method and application thereof |
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| CN106928414A (en) * | 2017-03-31 | 2017-07-07 | 天津大学 | A kind of preparation method of polymeric sorbent predecessor di-block copolymer |
| CN106905472A (en) * | 2017-04-18 | 2017-06-30 | 北京蛋白质组研究中心 | A kind of functionalization responsive to temperature type polymer and preparation method and application |
| CN110040833A (en) * | 2019-04-23 | 2019-07-23 | 襄阳先创环保科技有限公司 | A kind of preparation method of the heavy metal capturing agent for electroplating wastewater |
| CN110040833B (en) * | 2019-04-23 | 2021-09-03 | 襄阳先创环保科技有限公司 | Preparation method of heavy metal ion trapping agent for electroplating wastewater |
| CN110841599A (en) * | 2019-11-22 | 2020-02-28 | 山东农业大学 | Preparation method and application of bisphenol compound efficient adsorption material |
| CN113083240A (en) * | 2021-03-26 | 2021-07-09 | 西南石油大学 | Preparation and application of novel polymethacryloylhydrazone modified guar gum adsorbing material |
| CN113083241A (en) * | 2021-03-26 | 2021-07-09 | 西南石油大学 | Preparation of sulfonylhydrazone modified natural polymer for efficiently treating oil field wastewater and dye wastewater |
| CN113083240B (en) * | 2021-03-26 | 2022-04-15 | 西南石油大学 | Preparation method of polymethacrylhydrazone modified guar gum adsorbing material |
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